WO2022050099A1 - エッチング方法 - Google Patents
エッチング方法 Download PDFInfo
- Publication number
- WO2022050099A1 WO2022050099A1 PCT/JP2021/030739 JP2021030739W WO2022050099A1 WO 2022050099 A1 WO2022050099 A1 WO 2022050099A1 JP 2021030739 W JP2021030739 W JP 2021030739W WO 2022050099 A1 WO2022050099 A1 WO 2022050099A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- oxide film
- etching
- etching method
- metal oxide
- Prior art date
Links
- 238000005530 etching Methods 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000001590 oxidative effect Effects 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 36
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 36
- -1 alcohol compound Chemical class 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims description 58
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
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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
- H01L21/31122—Etching inorganic layers by chemical means by dry-etching of layers not containing Si, e.g. PZT, Al2O3
Definitions
- the present invention relates to a method of etching a metal oxide film by an atomic layer etching method.
- an atomic layer volumetric method (sometimes called an ALD (Atomic Layer Deposition) method) is used as a manufacturing process.
- ALD Atomic Layer Deposition
- Atomic layer etching method (also called ALE (Atomic Layer Etching) method) is attracting attention as a technology that enables such etching.
- the ALE method is a technique for etching a metal atom-containing film formed on a substrate by an etching gas at the atomic layer level. Such a technique based on the ALE method is described in, for example, Patent Documents 1 to 3.
- Patent Document 1 discloses an ALE method using chlorine gas as an etching gas.
- Patent Document 2 discloses an ALE method using a hydrogen fluoride gas and a boron-containing gas as etching gases.
- these etching gases often damage not only the metal atom-containing film formed on the substrate but also the substrate and surrounding members.
- stainless steel materials are often used in semiconductor manufacturing equipment, there is a problem that the etching gas corrodes such stainless steel materials.
- Patent Document 3 discloses an ALE method using formic acid vapor as an etching gas.
- formic acid vapor is also highly corrosive to metals and may damage the substrate and the stainless steel material of the semiconductor manufacturing apparatus.
- an object of the present invention is to provide a method for etching a metal oxide film by an ALE method without damaging a substrate, a stainless steel material of a semiconductor manufacturing apparatus, or the like.
- the present inventors have found that by adopting the ALE method having a specific process, it is possible to etch a metal oxide film without damaging the substrate or the stainless steel material of the semiconductor manufacturing apparatus. rice field.
- the present invention is a method of etching the metal oxide film in a laminate including a substrate and a metal oxide film formed on the surface thereof by an atomic layer etching method, in a processing atmosphere containing the laminate.
- the metal oxide film can be etched with high productivity without damaging the substrate or the stainless steel material of the semiconductor manufacturing apparatus.
- the etching method of the present invention is at least selected from the group consisting of an alcohol compound, an aldehyde compound and an ester compound in a treatment atmosphere such as a chamber containing a laminate containing a substrate and a metal oxide film formed on the surface thereof.
- the etching method of the present invention is a step of exhausting gas in a processing atmosphere such as a chamber (exhaust) between the oxidizing compound introduction step and the oxidizing gas introduction step and after the oxidizing gas introduction step, if necessary. Step).
- the oxidizing compound introduction step, the exhaust step, the oxidizing gas introduction step and the exhaust step are sequentially performed as one cycle, and by repeating this cycle, the metal oxide film is etched to a desired thickness. Can be done.
- the etching method of the present invention may be carried out in combination with the thin film formation by the ALD method, and in this case, it can be carried out without taking out the laminated body from the processing atmosphere such as a chamber.
- the amount of etching gas generated can be controlled by the amount of adsorption of the oxidizable compound, so that the etching method of the present invention can be suitably used for an etching process requiring microfabrication.
- each step of the etching method of the present invention will be described.
- the step of introducing an oxidizable compound is selected from the group consisting of an alcohol compound, an aldehyde compound and an ester compound in a treatment atmosphere such as a chamber containing a laminate containing a substrate and a metal oxide film formed on the surface thereof. This is a step of introducing at least one kind of oxidizing compound.
- the oxidizable compound may be introduced into the treatment atmosphere in either liquid or gaseous form, but after the introduction, the gaseous oxidizable compound acts (chemically adsorbs) on the metal oxide film. Is preferable.
- the laminate may be heated or the inside of the treatment atmosphere may be heated to apply heat.
- the oxidizable compound is vaporized by heating and / or depressurizing in a container in which the oxidizable compound is stored or a connecting portion connecting the container and the chamber. Let it be introduced into the processing atmosphere.
- an inert gas such as argon, nitrogen, or helium may be used as the carrier gas, if necessary.
- the introduced liquid oxidizable compound may be vaporized by heating and / or reducing the pressure in the treatment atmosphere.
- the pressure in the treatment atmosphere when carrying out the oxidizable compound introduction step is preferably 1 Pa to 10,000 Pa, and more preferably 10 Pa to 1,000 Pa.
- the temperature in the treatment atmosphere is preferably 100 ° C. to 500 ° C., and more preferably 150 ° C. to 400 ° C. It is preferably 200 ° C. to 350 ° C., and particularly preferably 200 ° C. to 350 ° C.
- Examples of the alcohol compound include alkyl alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, secondary butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, pentyl alcohol, isopentyl alcohol, and tertiary pentyl alcohol; 2-methoxyethanol.
- alkyl alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, secondary butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, pentyl alcohol, isopentyl alcohol, and tertiary pentyl alcohol; 2-methoxyethanol.
- aldehyde compound examples include formaldehyde, acetaldehyde, propionaldehyde, butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, and benzaldehyde.
- ester compound examples include methyl butyrate, methyl salicylate, ethyl formate, ethyl butyrate, ethyl acetate, ethyl caproate, pentyl acetate, isopentyl acetate, pentyl pentanoate, pentyl butyrate, octyl acetate and the like.
- an alcohol compound is preferable, an alcohol compound having 1 to 5 carbon atoms is more preferable, and methanol, ethanol, and the first Tributyl alcohol is particularly preferred. Further, from the viewpoint of not damaging the substrate or the stainless steel material of the semiconductor manufacturing apparatus, it is preferable that the oxidizing compound does not contain a fluorine atom.
- the method for synthesizing the above-mentioned alcohol compound, aldehyde compound and ester compound is not particularly limited, and can be synthesized by using a well-known and general method for synthesizing an alcohol compound, an aldehyde compound and an ester compound.
- commercially available reagents can also be used.
- the oxidizable compound used in the present invention should contain as little impurity metal elements, impurity halogens such as fluorine, and impurity organics as possible.
- the impurity metal element content is preferably 100 ppb or less for each element, more preferably 10 ppb or less, and the total amount is preferably 1 ppm or less, more preferably 100 ppb or less.
- the impurity halogen content is preferably 100 ppm or less, more preferably 10 ppm or less, and most preferably 1 ppm or less.
- the total amount of the impurity organic content is preferably 500 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less.
- the oxidizable compound used in the present invention contains as little particles as possible in order to reduce or prevent particle contamination of the etched metal oxide film.
- the number of particles larger than 0.3 ⁇ m is preferably 100 or less in 1 mL of the liquid phase, and is larger than 0.2 ⁇ m.
- the number of particles is more preferably 1000 or less in 1 mL of the liquid phase, and most preferably the number of particles larger than 0.2 ⁇ m is 100 or less in 1 mL of the liquid phase.
- the material of the substrate is not particularly limited, and examples thereof include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass; and metal. ..
- Examples of the shape of the substrate include plate-like, spherical, fibrous, and scaly shapes.
- the surface of the substrate may be flat or may have a three-dimensional structure such as a trench structure.
- the method for forming the metal oxide film is not particularly limited, and examples thereof include a sputtering method, an ion plating method, a MOD method such as a coating pyrolysis method and a sol-gel method, a CVD method, and an ALD method.
- a metal oxide film formed by the ALD method is preferable from the viewpoint that there are few impurities in the film and the etching rate is stable.
- a laminate containing the metal film formed on the surface of the substrate by the above-mentioned method may be used.
- the metal film is pre-oxidized with an oxidizing gas such as oxygen or ozone before the step of introducing the oxidizable compound.
- oxygen or ozone is preferable.
- an inert gas such as argon or nitrogen to remove the oxidizing gas from the treatment atmosphere as much as possible, and then carry out the step of introducing the oxidizing compound.
- the thickness of the metal oxide film is not particularly limited, but is usually 0.1 nm to 100 nm.
- the type of metal constituting the metal oxide film is not particularly limited, but for example, titanium, aluminum, zirconium, copper, cobalt, molybdenum, ruthenium, germanium, magnesium, tin, hafnium, scandium, gallium, iron and Zinc is mentioned.
- the metal constituting the metal oxide film may be one kind or two or more kinds.
- the gaseous oxidizable compound that has not been adsorbed on the surface of the metal oxide film is exhausted from the chamber.
- the gaseous oxidizing compound is completely exhausted from the chamber, but it is not always necessary to completely exhaust the gas.
- the exhaust method include a method of purging the inside of the chamber with an inert gas such as helium, nitrogen, and argon, a method of exhausting by depressurizing the inside of the chamber, and a method of combining these.
- the degree of decompression in the case of depressurization is preferably in the range of 0.01 Pa to 300 Pa, more preferably in the range of 0.01 Pa to 100 Pa.
- the oxidizing gas introduction step is a step of introducing an oxidizing gas into the treatment atmosphere after the above-mentioned exhaust step.
- the mechanism of etching is unknown, but it is thought that the oxidizing gas reacts with the oxidizing compound chemically adsorbed on the metal oxide film to generate etching gas on the spot, and the metal oxide film is etched. ..
- the laminate may be heated or the inside of the treatment atmosphere may be heated to apply heat.
- an inert gas such as argon, nitrogen or helium may be used as the carrier gas.
- the pressure in the treatment atmosphere when carrying out the oxidizing gas introduction step is preferably 1 Pa to 10,000 Pa, and more preferably 10 Pa to 1,000 Pa.
- the temperature in the treatment atmosphere is preferably 100 ° C. to 500 ° C., more preferably 150 ° C. to 400 ° C., and 200 ° C. to 350 ° C. It is particularly preferable to do so.
- Examples of the oxidizing gas used in the present invention include oxygen, ozone, steam, hydrogen peroxide, nitric oxide and nitrous oxide.
- the oxidizing gas used in the present invention may be one kind or two or more kinds. Further, from the viewpoint of not damaging the substrate or the stainless steel material of the semiconductor manufacturing apparatus, it is preferable that the oxidizing gas does not contain a fluorine atom.
- the oxidizing gas used in the present invention is one kind, oxygen, ozone or water vapor is preferable, and ozone is more preferable from the viewpoint that the metal oxide film can be etched with high productivity.
- oxygen, ozone or water vapor is preferable, and ozone is more preferable from the viewpoint that the metal oxide film can be etched with high productivity.
- two or more kinds of oxidizing gases are used in the present invention, it is preferable to contain ozone and other oxidizing gases from the viewpoint that the metal oxide film can be etched with high productivity.
- the apparatus for carrying out the etching method of the present invention can introduce an oxidizing gas, a gaseous oxidizing compound and a carrier gas into the system and exhaust the system with a purge gas as shown in FIG.
- a device with a capable chamber can be used.
- the etching method of the present invention may be carried out in a film forming chamber in a well-known ALD apparatus.
- the oxidizing gas and the gaseous oxidizing compound may be introduced into the film forming chamber of the ALD apparatus from separate ports or through a shower head.
- the metal oxide film of the present invention can be suitably used for manufacturing various semiconductor devices that require a high-purity metal oxide film.
- Example 1 Using methanol as the oxidizing compound and ozone gas as the oxidizing gas, the atomic layer etching of the molybdenum oxide film formed on the silicon wafer was performed using the apparatus shown in FIG. 1 under the following conditions and steps. .. The change in film thickness before and after atomic layer etching was confirmed by fluorescent X-ray analysis and scanning electron microscope. When the change in the film thickness before and after etching was measured, it was found that the film thickness of the molybdenum oxide film was 20.5 nm thinner, and the film thickness that could be etched per cycle was 0.68 nm. In addition, no corrosion of the stainless steel used in the device was confirmed.
- Laminated body Molybdenum oxide film formed on a silicon wafer Reaction temperature (silicon wafer temperature): 275 ° C
- Oxidizing compound Methanol Oxidizing gas: Ozone
- Example 2 Atomic layer etching was performed in the same manner as in Example 1 except that ethanol was used as an oxidizing compound instead of methanol. When the change in the film thickness before and after the atomic layer etching was measured, it was found that the film thickness of the molybdenum oxide film was 17.0 nm thinner, and the film thickness that could be etched per cycle was 0.57 nm. In addition, no corrosion of the stainless steel used in the device was confirmed.
- Example 3 Atomic layer etching was performed in the same manner as in Example 1 except that a silicon wafer having a cobalt oxide film formed on the silicon wafer was used as a laminate and tert-butyl alcohol was used as an oxidizable compound instead of methanol. .. When the change in the film thickness before and after the atomic layer etching was measured, it was found that the film thickness of the cobalt oxide film was 15.5 nm thinner, and the film thickness that could be etched per cycle was 0.52 nm. In addition, no corrosion of the stainless steel used in the device was confirmed.
- Example 4 Atomic layer etching was performed in the same manner as in Example 1 except that acetaldehyde was used as an oxidizable compound instead of methanol. When the change in the film thickness before and after the atomic layer etching was measured, it was found that the film thickness of the molybdenum oxide film was 14.5 nm thinner and the film thickness that could be etched per cycle was 0.48 nm. In addition, no corrosion of the stainless steel used in the device was confirmed.
- Example 5 Atomic layer etching was performed in the same manner as in Example 1 except that a titanium oxide film formed on a silicon wafer was used as a laminate and ethyl acetate was used as an oxidizable compound instead of methanol.
- a titanium oxide film formed on a silicon wafer was used as a laminate and ethyl acetate was used as an oxidizable compound instead of methanol.
- the film thickness of the titanium oxide film was 14.0 nm thinner, and the film thickness that could be etched per cycle was 0.47 nm. In addition, no corrosion of the stainless steel used in the device was confirmed.
- Example 6 Atomic layer etching was performed in the same manner as in Example 1 except that a silicon wafer having a copper oxide film formed on the silicon wafer was used as a laminate and tert-butyl alcohol was used as an oxidizable compound instead of methanol. .. When the change in the film thickness before and after the atomic layer etching was measured, it was found that the film thickness of the copper oxide film was 15.0 nm thinner and the film thickness that could be etched per cycle was 0.50 nm. In addition, no corrosion of the stainless steel used in the device was confirmed.
- Laminated body Molybdenum oxide film formed on a silicon wafer Reaction temperature (silicon wafer temperature): 275 ° C
- Etching gas Hydrogen fluoride
- Comparative Example 2 Atomic layer etching was performed in the same manner as in Comparative Example 1 except that formic acid vapor was used as the etching gas instead of hydrogen fluoride. When the change in the film thickness before and after the atomic layer etching was measured, it was found that the film thickness of the molybdenum oxide film was 7.5 nm thinner, and the film thickness that could be etched per cycle was 0.25 nm. However, corrosion of the stainless steel used in the equipment was confirmed.
- the metal oxide film formed on the substrate can be etched with high productivity without damaging the stainless steel material used in the semiconductor manufacturing apparatus or the like. ..
Abstract
Description
以下、本発明のエッチング方法の各工程について説明する。
被酸化性化合物導入工程は、基体とその表面に形成された金属酸化膜とを含む積層体を収容したチャンバーなどの処理雰囲気内に、アルコール化合物、アルデヒド化合物及びエステル化合物からなる群より選択される少なくとも1種の被酸化性化合物を導入する工程である。
被酸化性化合物導入工程後、金属酸化膜の表面に吸着しなかった気体状の被酸化性化合物をチャンバー内から排気する。この際、気体状の被酸化性化合物がチャンバー内から完全に排気されるのが理想的であるが、必ずしも完全に排気する必要はない。排気方法としては、例えば、ヘリウム、窒素、アルゴン等の不活性ガスによりチャンバー内をパージする方法、チャンバー内を減圧することで排気する方法、これらを組み合わせた方法等が挙げられる。減圧する場合の減圧度は、0.01Pa~300Paの範囲が好ましく、0.01Pa~100Paの範囲がより好ましい。
酸化性ガス導入工程は、上述の排気工程後、処理雰囲気内に酸化性ガスを導入する工程である。エッチングのメカニズムは不明であるが、酸化性ガスが、金属酸化膜に化学的に吸着した被酸化性化合物と反応してエッチングガスをその場で生成し、金属酸化膜がエッチングされると考えられる。このとき、積層体を加熱するか又は処理雰囲気内を加熱して熱を加えてもよい。酸化性ガスを導入する際に、必要に応じて、アルゴン、窒素、ヘリウム等の不活性ガスをキャリアガスとして用いてもよい。
上述の酸化性ガス導入工程後、未反応の酸化性ガス及び副生ガスをチャンバー内から排気する。この際、酸化性ガス及び副生ガスがチャンバー内から完全に排気されるのが理想的であるが、必ずしも完全に排気する必要はない。排気方法及び減圧する場合の減圧度は、上述した被酸化性化合物導入工程後の排気工程と同様である。
被酸化性化合物としてメタノールを用い、酸化性ガスとしてオゾンガスを用いて、図1に示す装置を用いて以下の条件及び工程で、シリコンウェハ上に形成された酸化モリブデン膜の原子層エッチングを行った。原子層エッチング前後の膜厚変化は、蛍光X線分析法及び走査型電子顕微鏡によって確認した。エッチング前後の膜厚の変化を測定したところ、酸化モリブデン膜の膜厚は20.5nm薄くなっており、1サイクル当たりにエッチングできる膜厚は0.68nmであることがわかった。また、装置に用いられているステンレス材の腐食は全く確認されなかった。
積層体:シリコンウェハ上に酸化モリブデン膜が形成されたもの
反応温度(シリコンウェハ温度):275℃
被酸化性化合物:メタノール
酸化性ガス:オゾン
下記(1)~(4)からなる一連の工程を1サイクルとして、30サイクル繰り返した。
(1)23℃、100Paの条件で気化させた被酸化性化合物をチャンバー内に導入し、系圧力100Paで5秒間、酸化モリブデン膜の表面に被酸化性化合物を吸着させる。
(2)60秒間のアルゴンパージにより、吸着しなかった被酸化性化合物をチャンバー内から排気する。
(3)酸化性ガスをチャンバー内に導入し、系圧力100Paで20秒間エッチングする。
(4)60秒間のアルゴンパージにより、未反応の酸化性ガス及び副生ガスをチャンバー内から排気する。
メタノールの代わりにエタノールを被酸化性化合物として用いたこと以外は、実施例1と同様に原子層エッチングを行った。原子層エッチング前後の膜厚の変化を測定したところ、酸化モリブデン膜の膜厚は17.0nm薄くなっており、1サイクル当たりにエッチングできる膜厚は0.57nmであることがわかった。また、装置に用いられているステンレス材の腐食は全く確認されなかった。
シリコンウェハ上に酸化コバルト膜が形成されたものを積層体として用い、メタノールの代わりに第三ブチルアルコールを被酸化性化合物として用いたこと以外は、実施例1と同様に原子層エッチングを行った。原子層エッチング前後の膜厚の変化を測定したところ、酸化コバルト膜の膜厚は15.5nm薄くなっており、1サイクル当たりにエッチングできる膜厚は0.52nmであることがわかった。また、装置に用いられているステンレス材の腐食は全く確認されなかった。
メタノールの代わりにアセトアルデヒドを被酸化性化合物として用いたこと以外は、実施例1と同様に原子層エッチングを行った。原子層エッチング前後の膜厚の変化を測定したところ、酸化モリブデン膜の膜厚は14.5nm薄くなっており、1サイクル当たりにエッチングできる膜厚は0.48nmであることがわかった。また、装置に用いられているステンレス材の腐食は全く確認されなかった。
シリコンウェハ上に酸化チタン膜が形成されたものを積層体として用い、メタノールの代わりに酢酸エチルを被酸化性化合物として用いたこと以外は、実施例1と同様に原子層エッチングを行った。原子層エッチング前後の膜厚の変化を測定したところ、酸化チタン膜の膜厚は14.0nm薄くなっており、1サイクル当たりにエッチングできる膜厚は0.47nmであることがわかった。また、装置に用いられているステンレス材の腐食は全く確認されなかった。
シリコンウェハ上に酸化銅膜が形成されたものを積層体として用い、メタノールの代わりに第三ブチルアルコールを被酸化性化合物として用いたこと以外は、実施例1と同様に原子層エッチングを行った。原子層エッチング前後の膜厚の変化を測定したところ、酸化銅膜の膜厚は15.0nm薄くなっており、1サイクル当たりにエッチングできる膜厚は0.50nmであることがわかった。また、装置に用いられているステンレス材の腐食は全く確認されなかった。
エッチングガスとしてフッ化水素を用い、図2に示す装置を用いて以下の条件及び工程で、シリコンウェハ上に形成された酸化モリブデン膜の原子層エッチングを行った。原子層エッチング前後の膜厚変化は、蛍光X線分析法及び走査型電子顕微鏡によって確認した。原子層エッチング前後の膜厚の変化を測定したところ、酸化モリブデン膜の膜厚は8.5nm薄くなっており、1サイクル当たりにエッチングできる膜厚は0.28nmであることがわかった。ただし、装置に用いられているステンレス材の腐食が確認された。
積層体:シリコンウェハ上に酸化モリブデン膜が形成されたもの
反応温度(シリコンウェハ温度):275℃
エッチングガス:フッ化水素
下記(1)~(2)からなる一連の工程を1サイクルとして、30サイクル繰り返した。
(1)エッチングガスをチャンバー内に導入し、系圧力100Paで20秒間エッチングする。
(2)60秒間のアルゴンパージにより、未反応のエッチングガス及び副生ガスをチャンバー内から排気する。
フッ化水素の代わりにギ酸蒸気をエッチングガスとして用いたこと以外は、比較例1と同様に原子層エッチングを行った。原子層エッチング前後の膜厚の変化を測定したところ、酸化モリブデン膜の膜厚は7.5nm薄くなっており、1サイクル当たりにエッチングできる膜厚は0.25nmであることがわかった。ただし、装置に用いられているステンレス材の腐食が確認された。
Claims (7)
- 基体とその表面に形成された金属酸化膜とを含む積層体における該金属酸化膜を原子層エッチング法によりエッチングする方法であって、
該積層体を収容した処理雰囲気内に、アルコール化合物、アルデヒド化合物及びエステル化合物からなる群より選択される少なくとも1種の被酸化性化合物を導入する第1の工程と、
該第1の工程後、該処理雰囲気内に、酸化性ガスを導入する第2の工程と
を有する、エッチング方法。 - 前記第1の工程又は前記第2の工程において、前記処理雰囲気内の温度を150℃以上にする、請求項1に記載のエッチング方法。
- 前記酸化性ガスが、酸素、オゾン、水蒸気、過酸化水素、一酸化窒素及び亜酸化窒素からなる群より選択される少なくとも1種のガスである、請求項1又は2に記載のエッチング方法。
- 前記金属酸化膜を構成する金属が、チタン、アルミニウム、ジルコニウム、銅、コバルト、モリブデン、ルテニウム、ゲルマニウム、マグネシウム、錫、ハフニウム、スカンジウム、ガリウム、鉄及び亜鉛からなる群より選択される少なくとも1種の金属である、請求項1~3のいずれか一項に記載のエッチング方法。
- 前記被酸化性化合物が、炭素原子数1~5のアルコール化合物である、請求項1~4のいずれか一項に記載のエッチング方法。
- 前記被酸化性化合物及び前記酸化性ガスが、フッ素原子を含有しない、請求項1~5のいずれか一項に記載のエッチング方法。
- 請求項1~6のいずれか一項に記載のエッチング方法によりエッチングされた金属酸化膜。
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JP2004091829A (ja) * | 2002-08-30 | 2004-03-25 | Tokyo Electron Ltd | エッチング方法及びエッチング装置 |
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JP2020501373A (ja) * | 2016-12-09 | 2020-01-16 | エーエスエム アイピー ホールディング ビー.ブイ. | 熱原子層エッチングプロセス |
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US10283369B2 (en) | 2016-08-10 | 2019-05-07 | Tokyo Electron Limited | Atomic layer etching using a boron-containing gas and hydrogen fluoride gas |
US10832909B2 (en) | 2017-04-24 | 2020-11-10 | Lam Research Corporation | Atomic layer etch, reactive precursors and energetic sources for patterning applications |
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