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WO1998036449A1 - Etching gas and cleaning gas - Google Patents

Etching gas and cleaning gas Download PDF

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Publication number
WO1998036449A1
WO1998036449A1 PCT/JP1998/000496 JP9800496W WO9836449A1 WO 1998036449 A1 WO1998036449 A1 WO 1998036449A1 JP 9800496 W JP9800496 W JP 9800496W WO 9836449 A1 WO9836449 A1 WO 9836449A1
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film
gas
general formula
integer
etching
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French (fr)
Japanese (ja)
Inventor
Mitsushi Itano
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Daikin Industries Ltd
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Daikin Industries Ltd
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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
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02046—Dry cleaning only
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only

Definitions

  • the present invention relates to an etching gas and a cleaning gas suitable for semiconductor manufacturing applications.
  • Perfluorinated compounds such as CF 4 , C 2 F 6 , C 4 F 8 ( ⁇ .-fluoro ⁇ sig ⁇ f, tan) and SF 6 are used in large quantities in the semiconductor production process as cleaning gas for cleaning gas and plasma CVD. Used for These are long life stable compounds in the air, fried infrared absorbance is high, global warming potential than carbon dioxide gas, 6300-fold with CF 4, Ji 2? 6 12500 times, C 4 F e but 9100-fold, SF 6 is very large as 24900 times, the development of low alternative gas global warming potential has become an urgent issue.
  • An object of the present invention is to provide an alternative gas which is suitable as an etching gas and a plasma CVD cleaning gas used in a semiconductor production process and has a small global warming effect.
  • the present invention provides the following etching gas and cleaning gas.
  • n and X each represent an integer of 1 to 5; m and y each represent an integer of 0 to 11 (however, m and y are not simultaneously 0); 1 and z each represent an integer of 0 to 11 (however, 1 and z are not simultaneously 0)];
  • a represents an integer of 1 to 3.
  • n, x, m, y, 1, and z are the same as above;
  • a represents an integer of 1 to 3.
  • the present invention relates to the following etching method and cleaning method.
  • At least one gas selected from the group consisting of the fluorine-based compounds represented by the general formulas (1), (2) and (3) can be used.
  • Preferred compounds among the fluorine compounds represented by the general formula (1) are HCF 20 CF 2 CF 3 , CF 3 OCF 2 CF 2 H, HCF 2 OCF 2 CF 2 H, CF 3 CF 2 OCFHCF 3 , CF 3 CF 2 Gases such as OCF 2 CF 2 H, CF 3 CFHCF 20 CH 3 , CF 3 CF 2 CF 2 OCFHCF 3 are also used, and these can be used alone or in combination of two. .
  • the etching gas of the invention He, N e, A r , single gas such as H 2> N 2, O 2 , C Compound gases such as H 4 , C 2 H 6 and NH 3 may be mixed and used at an appropriate ratio.
  • the etching method of the present invention is performed under various dry etching conditions such as plasma etching, reactive ion etching, and microphone mouth-wave etching.
  • Examples of the film to be processed on the substrate processed by the etching method of the present invention include a Si film, a SiO 2 film, a Si 3 N 4 film, and a refractory metal silicite film.
  • the etching gas of the present invention has high precision and high selectivity, and has reached a practical level as a substitute for CF "C 2 F 6 , C 4 F 8 , SF 6 which has been widely used as an etching gas in the past.
  • the etching gas of the present invention has a sufficiently low global warming potential as compared with CF 4 , C 2 F 6 , C 4 F 8 and SF 6 .
  • the gas of the general formulas (1) to (3) exemplified above as the etching gas or the gas specifically exemplified above. Regardless of which etching gas is used, the dimensional accuracy of the pattern is similarly high and the selectivity to the layer to be processed is high, so that it can be used without any practical problems.
  • At least one kind of gas selected from the group consisting of the fluorine compounds represented by the above general formulas (1), (2) and (3) can be used.
  • Preferred compounds among the fluorine compounds represented by the above general formula (1) are HCF 2 0 CF 2 CF 3 , CF3OCF2CF2H, HCF2OCF2CF2H.CF 3 C F2OC FHC F 3, CF 3 C F2OC F 2 CF 2 H, CF 3 Gases such as CFHCF 2 OCH 3 and CF 3 CF 2 CF 20 CFHCF 3 are also used for L and deviation, and these can be used alone or in combination of two. Monkey
  • CF3COOCH2CF3, CF 3 CF 2 COOCH 2 CF 3, CF 3 CF 2 CF 2 C 0 OCH 2 CF 3 use gas such that both t, is, they can be used singly or in combination of two or more.
  • Chamber cleaning gas of the present invention He, N e, A r , H 2, N 2, O 2 alone gas may be used in combination, such as.
  • a known material such as stainless steel and A1 alloy may be used as a material of the chamber.
  • the chamber cleaning gas of the present invention can quickly remove reaction by-products adhering to the chamber without damaging these materials used for the chamber.
  • the chamber cleaning gas of the present invention is at a level that can be used sufficiently as a substitute for CF 4 , C 2 F 6 , and SF 6 conventionally used as a chamber cleaning gas. Moreover, the chamber cleaning gas of the present invention has a sufficiently low global warming potential as compared with CF 4 , C 2 F 6 and SF 6 .
  • the object can be removed sufficiently and quickly, and the chamber can be used practically without damaging the chamber.

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Drying Of Semiconductors (AREA)
  • ing And Chemical Polishing (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

An etching gas and chamber cleaning gas for Si films, SiO2 films, Si3N4 films or high-melting metal silicite films, which contains at least one gaseous fluorine compound selected from the group consisting of those of formulae (1) to (3): (1) CnFmH1OCxFyHz, wherein n and x each represents an integer of 1 to 5; m, y, 1 and z each represents an integer of 0 to 11; provided that m and y, or 1 and z do not represent 0 at the same time; (2) CaF2a+1OCF=CF2 and (3) CaF2a+1COOCH2CF3, wherein a represents an integer of 1 to 3. The etching gas and chamber cleaning gas do not cause global warming.

Description

明 細 書  Specification

エッチングガスおよびクリ一ニングガス  Etching gas and cleaning gas

技術分野  Technical field

本発明は、 半導体製造用途に適したエッチングガスおよびクリ一ニングガスに関する。  The present invention relates to an etching gas and a cleaning gas suitable for semiconductor manufacturing applications.

背景技術  Background art

CF4、 C2F6、 C4F8 (Λ。-フルォ πシク πフ、、タン） 、 S F 6などのパーフルォロ化合物は、 ェ ツチングガス、 プラズマ C VDのクリーニングガスとして半導体の生産工程で大量に使 用されている。 これらは大気中での寿命が長い安定な化合物であり、 赤外線吸収度が高 いため、 地球温暖化係数が炭酸ガスに比べ、 CF4で 6300倍、 じ2?6が12500倍、 C4Feが 9100倍、 SF 6が 24900倍と極めて大きく、 地球温暖化係数の低い代替 ガスの開発が緊急の課題となっている。 Perfluorinated compounds such as CF 4 , C 2 F 6 , C 4 F 8 (Λ.-fluoro π sig π f, tan) and SF 6 are used in large quantities in the semiconductor production process as cleaning gas for cleaning gas and plasma CVD. Used for These are long life stable compounds in the air, fried infrared absorbance is high, global warming potential than carbon dioxide gas, 6300-fold with CF 4, Ji 2? 6 12500 times, C 4 F e but 9100-fold, SF 6 is very large as 24900 times, the development of low alternative gas global warming potential has become an urgent issue.

本発明は、 半導体の生産工程で使用されるエツチングガスおよびプラズマ C V Dのク リーニングガスとして好適であり、 かつ、 地球温暖化作用の小さい代替ガスを提供する ことを目的とする。  An object of the present invention is to provide an alternative gas which is suitable as an etching gas and a plasma CVD cleaning gas used in a semiconductor production process and has a small global warming effect.

発明の開示  Disclosure of the invention

本発明は、 以下のエッチングガスおよびクリーニングガスを提供するものである。  The present invention provides the following etching gas and cleaning gas.

1. 下記一般式 （ 1 ) 、 一般式 （ 2 )及び一般式（ 3 ) のフッ素系化合物からなる群 から選ばれる少なくとも 1種のガスを含む S i膜、 S i O2膜、 S i 3N4膜または高融点 金属シリサイト膜用エツチングガス： 1. A Si film, a SiO 2 film, and a Si 3 film containing at least one gas selected from the group consisting of the fluorine compounds represented by the following general formulas (1), (2) and (3): Etching gas for N 4 film or high melting point metal silicide film:

一般式（ 1 ) General formula (1)

CnFmH,OCxFyHz (1) CnF m H, OCxFyHz (1)

〔式中、 n、 Xはいずれも 1〜5の整数を示し； m、 yはいずれも 0〜 1 1の整数を示 し （但し、 mと yが同時に 0であることはない） ；及び 1、 zはいずれも 0〜1 1の整 数を示す （但し、 1と zが同時に 0であることはない） 〕 ；  [Wherein, n and X each represent an integer of 1 to 5; m and y each represent an integer of 0 to 11 (however, m and y are not simultaneously 0); 1 and z each represent an integer of 0 to 11 (however, 1 and z are not simultaneously 0)];

一般式（ 2 )General formula (2)

Figure imgf000003_0001
Figure imgf000003_0001

〔式中、 aは 1〜 3の整数を示す。 〕 ；及び  [Wherein, a represents an integer of 1 to 3. 〕 ;as well as

一般式（ 3 ) General formula (3)

CaF2a + 1COOCH2CF3 (3) 〔式中、 aは前記に同じ。 〕 。 CaF2a + 1 COOCH 2 CF 3 (3) [Wherein a is as defined above. ].

2. 下記一般式（1) 、 一般式 （2)及び一般式 （3) のフッ素系化合物からなる群 から選ばれる少なくとも 1種のガスを含むチャンバクリ一ニングガス：  2. A chamber cleaning gas containing at least one gas selected from the group consisting of fluorine compounds represented by the following general formulas (1), (2) and (3):

一般式（ 1 ) General formula (1)

CnFmH!OCxFyHz (1)  CnFmH! OCxFyHz (1)

〔式中、 n、 x、 m、 y、 1、 zは前記に同じ〕 ；  Wherein n, x, m, y, 1, and z are the same as above;

一般式（ 2 )General formula (2)

Figure imgf000004_0001
Figure imgf000004_0001

〔式中、 aは 1〜3の整数を示す。 〕 ；及び  [Wherein, a represents an integer of 1 to 3. 〕 ;as well as

一般式 （ 3 ) General formula (3)

CaF2a + 1COOCH2CF3 (3) CaF 2 a + 1 COOCH 2 CF 3 (3)

〔式中、 aは前記に同じ。 〕 。  [Wherein a is as defined above. ].

さらに本発明は、 以下のエッチング方法およびクリーニング方法にも関する。  Further, the present invention relates to the following etching method and cleaning method.

•半導体集積回路製造のためのエッチング方法において、 （CF3) 2C = CFOCH3、 COF2、 （CF3) 2 (CH3) C— COF、 （ C F 3) 2 C H— C F 20 C H3、 C F 3 C F HCFH2、 CF3CHFCF3、 CF3CFHCF2H、 HCF2CF2CFH2、 CFsCH = CF2、 CF3CF = CFH、 C F 3 C H2 C H2 C F 3、 C F 3 C H2 C F 2 C F 3、 HC F 2CF2CF2CF2H, CF3CFHCFHCF2CF3, CF3CF = CFCF2CF3、 C 2 F 5 I , (CF3) 2CHC FHC F2C F3 (CF3) 2CFCFHCFHCF3、 2, 2， 3， 3—テトラフルォロォキセタン、 2, 2, 3, 4, 4—ペンタフルォロォキセタン、 1, 1, 1， 3, 3—ペンタフルォロプロパン （245 f a)からなる群から選ばれる 少なくとも 1種のガスを用いることを特徴とする S i膜、 S i O2膜、 S i 3N4膜または 高融点金属シリサイト膜のエツチング方法。 • In an etching method for manufacturing a semiconductor integrated circuit, (CF 3 ) 2 C = CFOCH 3 , COF 2 , (CF 3 ) 2 (CH 3 ) C—COF, (CF 3 ) 2 CH—CF 20 CH 3 , CF 3 CF HCFH 2 , CF 3 CHFCF 3 , CF 3 CFHCF 2 H, HCF 2 CF 2 CFH 2 , CFsCH = CF 2 , CF 3 CF = CFH, CF 3 CH 2 CH 2 CF 3 , CF 3 CH 2 CF 2 CF 3 , HC F 2CF2CF2CF2H, CF3CFHCFHCF2CF3, CF 3 CF = CFCF 2 CF 3 , C 2 F 5 I, (CF 3 ) 2 CHC FHC F 2 CF 3 (CF 3 ) 2 CFCFHCFHCF 3 , 2, 2, 3, Selected from the group consisting of 3-tetrafluoroxetane, 2, 2, 3, 4, 4-pentafluoroxetane and 1, 1, 1, 3, 3-pentafluoropropane (245 fa) A method for etching a Si film, a SiO 2 film, a Si 3 N 4 film or a refractory metal silicide film, characterized by using at least one kind of gas.

•半導体集積回路製造において、 チャンバクリーニングガスとして （CF3) 2C = CF OCH3、 COF2、 （CF3) 2 (CH3) C— COF、 (CF3) 2CH_CF2OCH3、 CF3CFHCFH2、 CF3CHFCF3, CF3CFHCF2H、 HCF2CF2CFH2、 CF3CH=CF2、 CF3CF = CFH、 C F 3 C H2 CH2 C F 3、 CF3CH2CF2CF• (CF 3 ) 2 C = CF OCH 3 , COF 2 , (CF 3 ) 2 (CH 3 ) C—COF, (CF 3 ) 2 CH_CF 2 OCH 3 , CF 3 CFHCFH 2, CF3CHFCF3, CF 3 CFHCF 2 H, HCF 2 CF 2 CFH 2, CF 3 CH = CF 2, CF 3 CF = CFH, CF 3 CH 2 CH 2 CF 3, CF3CH2CF2CF

3、 HCF2CF2CF2CF2H, CF3CFHCFHCF2CF3、 CF3CF = CFCF2 CF3、 C2F"、 （CF3) 2CHCFHCF2CF3、 (CF3) 2CFCFHCFHCF 3、 2, 2, 3, 3—テトラフルォロォキセタン、 2, 2， 3, 4, 4—ペン夕フルォロ ォキセタン、 1， 1， 1， 3, 3—ペンタフルォロプロパン （245 f a) からなる群 から選ばれる少なくとも 1種のガスを用いることを特徴とするチャンバクリーニング方 3, HCF2CF2CF2CF2H, CF 3 CFHCFHCF 2 CF 3, CF 3 CF = CFCF 2 CF 3, C 2 F ", (CF 3) 2 CHCFHCF 2 CF 3, (CF 3) 2CFCFHCFHCF 3,2,2,3,3-tetrafluoroxetane, 2,2,3,4,4-pentylfluoroxetane, 1,1,1,3,3-pentafluoropropane (245 fa ) Wherein at least one gas selected from the group consisting of

(A) エッチングガス及びエッチング方法 (A) Etching gas and etching method

エッチングに用いられるガスとしては、 上記一般式 （1) 、 一般式（2)及び一般式 (3) で表されるフッ素系化合物からなる群から選ばれる少なくとも 1種のガスを用い ることができる。  As the gas used for the etching, at least one gas selected from the group consisting of the fluorine-based compounds represented by the general formulas (1), (2) and (3) can be used. .

上記一般式 （1) で表されるフッ素系化合物のうち好ましい化合物として、 HCF20 CF2CF3、 CF3OCF2CF2H、 H C F 2 O C F 2 C F 2H、 CF3CF2OCFHCF 3、 CF3CF2OCF2CF2H、 C F 3 C F H C F 20 C H3、 C F 3 C F 2 C F 2O C F H C F 3等のガスが 、ずれも用いられ、 これらは 1種又は 2種を組み合わせて用し、ることがで きる。 Preferred compounds among the fluorine compounds represented by the general formula (1) are HCF 20 CF 2 CF 3 , CF 3 OCF 2 CF 2 H, HCF 2 OCF 2 CF 2 H, CF 3 CF 2 OCFHCF 3 , CF 3 CF 2 Gases such as OCF 2 CF 2 H, CF 3 CFHCF 20 CH 3 , CF 3 CF 2 CF 2 OCFHCF 3 are also used, and these can be used alone or in combination of two. .

上記一般式 （2) で表されるフッ素系化合物のうち好ましい化合物として、  Preferred compounds among the fluorine compounds represented by the general formula (2) are

CF3OCF = CF2、 CF3CF2OCF = CF2、 C F3 C F 2 C F 2O C F = C F 2等のガ スが 、ずれも用いられ、 これらは 1種又は 2種を組み合わせて用いることができる。 上記一般式 （3) で表されるフッ素系化合物のうち好ましい化合物として、 CFaCO OCH2CF3, C F3C F2COOCH2C F3、 C F 3 C F 2 C F 2 C O 0 C H2 C F 3などの ガスがいずれも用いられ、 これらは 1種又は 2種を組み合わせて用いることができる。 具体的なエッチングガスとしては、 （CF3) 2C = CFOCH3、 COF2、 (CF3) 2 (CH3) C— COF、 (CF3) 2CH-CF2OCH3, CF3CFHCFH2, C FsC HFCF3、 CF3CFHCF2H, HCF2CF2CFH2, CF3CH = CF2、 CFsCF = CFH、 CF3CH2CH2CF3, CF3CH2CF2CF3, HCF2CF2CF2CF2H、 CF3CFHCFHCF2CF3, CF3CF = CFCF2CF3、 C2F5 I、 （CF3) 2C HCFHCF2CF3, (CF3) 2CFCFHCFHCF3, 2, 2， 3， 3—テトラフノレ ォロォキセタン、 2， 2, 3, 4, 4—ペンタフルォロォキセタン、 1, 1， 1, 3, 3—ペンタフルォロプロパン （245 f a)からなる群から選ばれる少なくとも 1種の ガスが挙げられる。 Gases such as CF 3 OCF = CF 2 , CF 3 CF 2 OCF = CF 2 , CF 3 CF 2 CF 2 OCF = CF 2, etc. are also used, and these may be used alone or in combination of two types. it can. Preferred compounds of the fluorine-based compound represented by the general formula (3), CFaCO OCH2CF3, CF 3 CF 2 COOCH 2 CF 3, CF 3 CF 2 CF 2 CO 0 CH 2 CF 3 gas, such that both used These can be used alone or in combination of two or more. Specific etching gases include (CF 3 ) 2 C = CFOCH 3 , COF 2 , (CF 3 ) 2 (CH 3 ) C—COF, (CF 3 ) 2CH-CF2OCH3, CF3CFHCFH2, C FsC HFCF 3 , CF3CFHCF2H , HCF2CF2CFH2, CF 3 CH = CF 2 , CFsCF = CFH, CF3CH2CH2CF3, CF3CH2CF2CF3, HCF 2 CF 2 CF 2 CF 2 H, CF3CFHCFHCF2CF3, CF 3 CF = CFCF 2 CF 3 , C 2 F 5 I, (CF 3 ) 2 C HCFHCF2CF3, (CF 3 ) 2CFCFHCFHCF3,2,2,3,3-tetrafluorophenol, 2,2,3,4-pentafluoroxetane, 1,1,1,3,3-pentafluoro At least one gas selected from the group consisting of lopropane (245 fa).

本発明のエッチングガスには、 He, N e, A r, H2> N2, O2などの単体ガス、 C H4, C2H6, NH3などの化合物ガスを適切な割合で混合して用いてもよい。 本発明のエッチング方法は、 プラズマエッチング、 反応性イオンエッチング、 マイク 口波エツチングなどの各種のドライエツチング条件下で行われる。 本発明のェッチング 方法で加工される基板上の被加工膜としては、 S i膜、 S i 02膜、 S i3N4膜または高 融点金属シリサイト膜が挙げられる。 The etching gas of the invention, He, N e, A r , single gas such as H 2> N 2, O 2 , C Compound gases such as H 4 , C 2 H 6 and NH 3 may be mixed and used at an appropriate ratio. The etching method of the present invention is performed under various dry etching conditions such as plasma etching, reactive ion etching, and microphone mouth-wave etching. Examples of the film to be processed on the substrate processed by the etching method of the present invention include a Si film, a SiO 2 film, a Si 3 N 4 film, and a refractory metal silicite film.

本発明のエッチングガスは、 高精度かつ高選択性であり、 従来エッチングガスとして 汎用されていた CF" C2F6、 C4F8、 SF6の代替品として実用的なレベルに達して いる。 また、 本発明のエッチングガスは CF4、 C2F6、 C4F8、 SF6に比較して地球 温暖化係数が十分低い。 The etching gas of the present invention has high precision and high selectivity, and has reached a practical level as a substitute for CF "C 2 F 6 , C 4 F 8 , SF 6 which has been widely used as an etching gas in the past. The etching gas of the present invention has a sufficiently low global warming potential as compared with CF 4 , C 2 F 6 , C 4 F 8 and SF 6 .

具体的には、 例えば本発明の 2, 2, 3， 3—テトラフルォロォキセタンを公知の反 応性イオンエッチングの条件下 （例えば、 圧力 =50mTo r r、 入力高周波電力 = 2 00W、 ガス流量 =25 c cZm i n) に S i膜、 S i O2膜、 S i 3N4膜または高融点 金属シリサイト膜に使用すると、 パターンの寸法精度が高く、 かつ、 被加工層に対する 選択性も高い。 Specifically, for example, the 2,2,3,3-tetrafluoroxetane of the present invention is subjected to a known reactive ion etching condition (for example, pressure = 50 mTorr, input high frequency power = 200 W, gas flow rate). = 25 c cZm in) when used for Si film, SiO 2 film, Si 3 N 4 film or refractory metal silicide film, the pattern dimensional accuracy is high and the selectivity to the layer to be processed is high. high.

2, 2， 3, 3—テトラフルォロォキセタンに代えて 1 , 1, 1, 3， 3—ペンタフ ルォロプロパン （245 f a)を使用しても、 同様にパターンの寸法精度が高く、 かつ、 被加工層に対する選択性も高いため、 実用上の支障なく使用することができる。  Similarly, when 1,1,1,3,3-pentafluoropropane (245fa) is used instead of 2,2,3,3-tetrafluoroxetane, the dimensional accuracy of the pattern is also high, and Since it has high selectivity to the layer to be processed, it can be used without practical problems.

さらに、 2， 2, 3, 3—テトラフルォロォキセタンに代えて、 エッチングガスとし て上記に例示された一般式 （1)〜 （3)のガス、 或いは上記に具体的に例示されたェ ツチングガスのいずれを使用しても、 同様にパターンの寸法精度が高く、 かつ、 被加工 層に対する選択性も高いため、 実用上の支障なく使用することができる。  Further, in place of 2,2,3,3-tetrafluoroxetane, the gas of the general formulas (1) to (3) exemplified above as the etching gas, or the gas specifically exemplified above. Regardless of which etching gas is used, the dimensional accuracy of the pattern is similarly high and the selectivity to the layer to be processed is high, so that it can be used without any practical problems.

( B ) チャンバクリ一ニングガス及びチャンバクリ一ニング方法  (B) Chamber cleaning gas and chamber cleaning method

チャンバクリーニングに用いられるガスとしては、 上記一般式 （1)、 一般式 （2) 及び一般式 （3)で表されるフッ素系化合物からなる群から選ばれる少なくとも 1種の ガスを用いることができる。  As the gas used for the chamber cleaning, at least one kind of gas selected from the group consisting of the fluorine compounds represented by the above general formulas (1), (2) and (3) can be used. .

上記一般式 （1)で表されるフッ素系化合物のうち好ましい化合物として、 HCF20 CF2CF3、 CF3OCF2CF2H, HCF2OCF2CF2H. C F3C F2OC FHC F 3、 C F3C F2OC F2C F2H, CF3CFHCF2OCH3、 C F 3 C F 2 C F 20 C F H C F 3等のガスが L、ずれも用いられ、 これらは 1種又は 2種を組み合わせて用 、ることがで さる。 Preferred compounds among the fluorine compounds represented by the above general formula (1) are HCF 2 0 CF 2 CF 3 , CF3OCF2CF2H, HCF2OCF2CF2H.CF 3 C F2OC FHC F 3, CF 3 C F2OC F 2 CF 2 H, CF 3 Gases such as CFHCF 2 OCH 3 and CF 3 CF 2 CF 20 CFHCF 3 are also used for L and deviation, and these can be used alone or in combination of two. Monkey

上記一般式（2)で表されるフッ素系化合物のうち好ましい化合物として、 CF3OC F = CF2、 CF3CF2OCF = CF2、 C F 3 C F 2 C F 2O C F = C F 2等のガスがいず れも用いられ、 これらは 1種又は 2種を組み合わせて用 L、ることができる。 Preferred compounds of the fluorine-based compound represented by the above general formula (2), CF 3 OC F = CF 2, CF 3 CF 2 OCF = CF 2, CF 3 CF 2 CF 2 OCF = CF 2 , etc. Gasugai of These are also used, and these can be used alone or in combination of two or more.

上記一般式（3)で表されるフッ素系化合物のうち好ましい化合物として、  As preferred compounds among the fluorine-based compounds represented by the general formula (3),

CF3COOCH2CF3, CF3CF2COOCH2CF3、 C F 3 C F 2 C F 2C 0 O C H2 C F 3などのガスがいずれも用 t、られ、 これらは 1種又は 2種を組み合わせて用いることが できる。 CF3COOCH2CF3, CF 3 CF 2 COOCH 2 CF 3, CF 3 CF 2 CF 2 C 0 OCH 2 CF 3 use gas such that both t, is, they can be used singly or in combination of two or more.

具体的なチャンバクリーニングガスとしては、 （CF3) 2C = CFOCH3、 COF2、 (CF3) 2 (CH3) C— COF、 (CF3) 2CH-CF2OCH3, CF3CFHCFH 2、 CF3CHFCF3、 CF3CFHCF2H、 HCF2CF2CFH2、 CF3CH = CF2、 CF3CF = CFH、 CF3CH2CH2CF3、 C F 3 C H2 C F 2 C F 3、 HCF2CF2CF 2CF2H, CF3CFHCFHCF2CF3, CF3CF = CFCF2CF3、 C2F5I、 (CF3) 2CHCFHCF2CF3, (CF3) 2CFCFHCFHCF3, 2, 2, 3, 3 —テトラフルォロォキセタン、 2， 2, 3, 4, 4—ペンタフルォロォキセタン、 1， 1， 1， 3, 3—ペンタフルォロプロパン （245 f a)からなる群から選ばれる少な くとも 1種のガスが挙げられる。 Specific chamber cleaning gases include (CF 3 ) 2 C = CFOCH 3 , COF 2 , (CF 3 ) 2 (CH 3 ) C—COF, (CF 3 ) 2CH-CF2OCH3, CF3CFHCFH 2 , CF 3 CHFCF 3 , CF 3 CFHCF 2 H, HCF 2 CF 2 CFH 2 , CF 3 CH = CF 2 , CF 3 CF = CFH, CF 3 CH 2 CH 2 CF 3 , CF 3 CH 2 CF 2 CF 3 , HCF2CF2CF 2CF2H, CF3CFHCFHCF2CF3, CF 3 CF = CFCF 2 CF 3 , C 2 F 5 I, (CF 3 ) 2CHCFHCF2CF3, (CF 3 ) 2CFCFHCFHCF3, 2, 2, 3, 3 —tetrafluorooxetane, 2, 2, 3, 4, At least one gas selected from the group consisting of 4-pentafluoroxetane and 1,1,1,3,3-pentafluoropropane (245 fa).

本発明のチャンバクリーニングガスは、 He, N e, A r, H2， N2， O2などの単体 ガスと併用してもよい。 Chamber cleaning gas of the present invention, He, N e, A r , H 2, N 2, O 2 alone gas may be used in combination, such as.

チャンバの素材としては、 ステンレス、 A 1合金等の公知の材料が挙げられる。 本発 明のチャンバクリーニングガスは、 チャンバに用いられるこれら材料にダメージを与え ることなく、 チャンバに付着した反応副生成物を迅速に除去することができる。  As a material of the chamber, a known material such as stainless steel and A1 alloy may be used. The chamber cleaning gas of the present invention can quickly remove reaction by-products adhering to the chamber without damaging these materials used for the chamber.

従って、 本発明のチャンバクリーニングガスは、 従来チャンバクリーニングガスとし て用いられている CF4、 C2F6、 SF 6の代替品として十分実用的に使用できるレベル にある。 しかも、 本発明のチャンバクリーニングガスは、 CF4、 C2F6、 SF6に比較 して地球温暖化係数が十分低 、。 Therefore, the chamber cleaning gas of the present invention is at a level that can be used sufficiently as a substitute for CF 4 , C 2 F 6 , and SF 6 conventionally used as a chamber cleaning gas. Moreover, the chamber cleaning gas of the present invention has a sufficiently low global warming potential as compared with CF 4 , C 2 F 6 and SF 6 .

具体的には、 例えば本発明の 2， 2， 3， 3—テトラフルォロォキセタンを公知のチ ヤンバクリーニングの条件下 （圧力 = 10 OmTo r r ；入力高周波電力 =300W； ガス流量 =50 c c/m i n) に 30分間使用すると、 チャンバに付着した反応副生成 物を十分かつ迅速に取り除くことができ、 かつ、 チャンバにダメージを与えることはな く、 十分実用的に使用できる。 Specifically, for example, 2,2,3,3-tetrafluoroxetane of the present invention is subjected to known chamber cleaning conditions (pressure = 10 OmTorr; input high-frequency power = 300 W; gas flow rate = 50 cc). / min) for 30 minutes. The object can be removed sufficiently and quickly, and the chamber can be used practically without damaging the chamber.

2, 2, 3, 3—テトラフルォロォキセタンに代えて 1, 1, 1, 3, 3—ペンタフ ルォロプロパン （245 f a) を使用しても、 同様にチャンバに付着した反応副生成物 を十分かつ迅速に取り除くことができ、 かつ、 チャンバにダメージを与えることはなく、 実用上の支障なく使用することができる。  Similarly, when 1,1,1,3,3-pentafluoropropane (245 fa) was used instead of 2,2,3,3-tetrafluorooxetane, the reaction by-product adhering to the chamber was also reduced. It can be removed sufficiently and quickly, does not damage the chamber, and can be used without practical problems.

さらに、 2, 2， 3, 3—テトラフノレォロォキセタンに代えてチャンバクリーニング ガスとして上記に例示された一般式 （1)〜 （3) のガス、 或いは上記に具体的に例示 されたチャンバクリーニングガスのいずれを使用しても、 同様にチャンバに付着した反 応副生成物を十分かつ迅速に取り除くことができ、 かつ、 チャンバにダメージを与える ことはなく、 実用上の支障なく使用することができる。  Further, the gases of the general formulas (1) to (3) exemplified above as the chamber cleaning gas in place of 2,2,3,3-tetraphlorenoloxetane, or the chamber specifically exemplified above Regardless of which cleaning gas is used, similarly, reaction by-products adhering to the chamber can be sufficiently and promptly removed, and the chamber can be used without any damage without damaging the chamber. Can be.

本発明によれば、 地球温暖化係数が炭酸ガスに比べ極めて高い CF 4、 C2F6、 C4F 8、 SF6を用いることなく、 良好なエッチング及びチャンバクリーニングを行うことが できる。 According to the present invention, global warming is extremely high compared with the carbon dioxide gas CF 4, C 2 F 6, without using a C 4 F 8, SF 6, it is possible to perform good etching and chamber cleaning.

Claims

請求の範囲 The scope of the claims 1. 下記一般式（ 1 ) 、 一般式（ 2 )及び一般式（ 3 ) のフッ素系化合物からなる群 から選ばれる少なくとも 1種のガスを含む S i膜、 S i 02膜、 S i 3N4膜または高融点 金属シリサイト膜用エッチングガス： 1. the following general formula (1), the general formula (2) and the general formula (3) S i film containing at least one gas selected from the group consisting of fluorine-based compound of, S i 0 2 film, S i 3 Etching gas for N 4 film or high melting point metal silicide film: 一般式（ 1 ) General formula (1) C„FmH,OCxFyHz (1) C „F m H, OCxF y H z (1) 〔式中、 n、 Xはいずれも 1〜5の整数を示し； m、 yはいずれも 0〜 11の整数を示 し （但し、 mと yが同時に 0であることはない） ；及び 1、 zはいずれも 0〜11の整 数を示す （但し、 1と zが同時に 0であることはない） 〕 ；  Wherein n and X each represent an integer of 1 to 5; m and y each represent an integer of 0 to 11 (provided that m and y are not simultaneously 0); and 1 , Z each represent an integer of 0 to 11 (however, 1 and z are not simultaneously 0)]; 一般式（ 2 )General formula (2)
Figure imgf000009_0001
Figure imgf000009_0001
 〔式中、 aは 1〜 3の整数を示す。 〕 ；及び  [Wherein, a represents an integer of 1 to 3. 〕 ;as well as 一般式 ( 3 ) General formula (3) CaF2a+lCOOCH2CF3 (3) CaF2a + lCOOCH 2 CF 3 (3) 〔式中、 aは前記に同じ。 〕 。  [Wherein a is as defined above. ]. 2. (CF3) 2C = CFOCH3、 COF2、 (CF3) 2 (CH3) C— COF、 (C F 3) 2CH-C F2OCH3, CF3CFHCFH2, CF3CHFCF3, CF3CFHCF2 H、 HCF2CF2CFH2、 CF3CH = CF2、 CF3CF = CFH、 CF3CH2CH2C F3、 C F3CH2C F2CF3. HCF2CF2CF2CF2H、 C F 3 C F H C F H C F 2 C F2. (CF 3 ) 2 C = CFOCH 3 , COF 2 , (CF 3 ) 2 (CH 3 ) C—COF, (CF 3 ) 2 CH-C F2OCH3, CF3CFHCFH2, CF3CHFCF3, CF3CFHCF2 H, HCF 2 CF 2 CFH 2 , CF 3 CH = CF 2 , CF 3 CF = CFH, CF 3 CH 2 CH 2 CF 3 , C F3CH2C F2CF3. HCF 2 CF 2 CF 2 CF 2 H, CF 3 CFHCFHCF 2 CF 3、 CF3CF = CFCF2CF3、 C2F5 I、 （ C F 3) 2 C H C F H C F 2 C F 3、 (C F 3) 2CFCFHCFHCF3. 2, 2, 3， 3—テトラフルォロォキセタン、 2, 2， 3, 3, CF 3 CF = CFCF 2 CF 3, C 2 F 5 I, (CF 3) 2 CHCFHCF 2 CF 3, (CF 3) 2CFCFHCFHCF3. 2, 2, 3, 3- tetrafluoropropoxy O Roo xenon Tan, 2, twenty three, 4, 4—ペンタフルォロォキセタン、 1, 1， 1, 3, 3—ペンタフルォロプロパン4, 4-pentafluoroxetane, 1, 1, 1, 3, 3-pentafluoropropane (245 f a)からなる群から選ばれる少なくとも 1種のガスを含む S i膜、 S i 02膜、 S i 3 N 4膜または高融点金属シリサイト膜用のエッチングガス。 S i film containing at least one gas selected from the group consisting of (245 fa), S i 0 2 film, S i 3 N 4 film, or a refractory metal silicide film etching gas for. 3. 下記一般式 （1)、 一般式 （2)及び一般式 （3)のフッ素系化合物からなる群 から選ばれる少なくとも 1種のガスを含むチャンバクリーニングガス：  3. A chamber cleaning gas containing at least one gas selected from the group consisting of fluorine compounds represented by the following general formulas (1), (2) and (3): 一般式（ 1 )General formula (1)
Figure imgf000009_0002
Figure imgf000009_0002
 〔式中、 n、 Xはいずれも 1〜5の整数を示し； m、 yはいずれも 0〜 11の整数を示 し （但し、 mと yが同時に 0であることはない） ；及び 1、 zはいずれも 0〜1 1の整 数を示す （但し、 1と zが同時に 0であることはない） 〕 ； [Wherein, n and X each represent an integer of 1 to 5; m and y each represent an integer of 0 to 11] (However, m and y are not 0 at the same time); and 1 and z both represent integers from 0 to 11 (however, 1 and z are not 0 at the same time)]; 一般式（ 2 )General formula (2)
Figure imgf000010_0001
Figure imgf000010_0001
 〔式中、 aは 1〜 3の整数を示す。 〕 ；及び  [Wherein, a represents an integer of 1 to 3. 〕 ;as well as 一般式（ 3 ) General formula (3) CaF2a + iCOOCH2C F3 (3) CaF 2 a + iCOOCH 2 CF 3 (3) 〔式中、 aは前記に同じ。 〕 。  [Wherein a is as defined above. ]. 4. (CF3) 2C = CFOCH3、 COF2、 (CF3) 2 (CH3) C— COF、 (C F 3) 2CH— CF2OCH3、 CF3CFHCFH2, CF3CHF C F3、 CF3CFHCF2 H、 HCF2CF2C FH2, C F3CH = CF2、 C F3C F = C FH、 CF3CH2CH2C F3、 CF3CH2CF2CF3、 H C F 2 C F 2 C F 2 C F 2H、 C F 3 C F H C F H C F 2 C F 3、 CF3CF = CF C F2CF3、 C2F5 I、 （ C F 3) 2 C H C F H C F 2 C F 3、 (C F 3) 2CFCFHCFHCF3, 2, 2, 3, 3—テトラフルォロォキセタン、 2, 2, 3， 4， 4一ペンタフルォロォキセタン、 1, 1, 1 , 3, 3—ペンタフルォロプロノヽ。ン4. (CF 3 ) 2 C = CFOCH 3 , COF 2 , (CF 3 ) 2 (CH 3 ) C—COF, (CF 3 ) 2 CH—CF 2 OCH 3 , CF3CFHCFH2, CF 3 CHF CF 3 , CF3CFHCF2 H , HCF2CF2C FH2, CF 3 CH = CF 2 , CF 3 CF = C FH, CF 3 CH 2 CH 2 CF 3 , CF 3 CH 2 CF 2 CF 3 , HCF 2 CF 2 CF 2 CF 2 H, CF 3 CFHCFHCF 2 CF 3 , CF 3 CF = CF CF 2 CF 3 , C 2 F 5 I, (CF 3 ) 2 CHCFHCF 2 CF 3 , (CF 3) 2 CFCFHCFHCF3, 2, 2, 3, 3-tetrafluorooxetane, 2,2,3,4,4-Pentafluoroxetane, 1,1,1,3,3-Pentafluoroprono ヽ. In (24 5 f a) からなる群から選ばれる少なくとも 1種のガスを含むチャンバクリー二 ングガス。 (24 5 f a) A chamber cleaning gas containing at least one gas selected from the group consisting of: 5. 請求項 1又は 2に記載のエッチングガスを用いて S i膜、 S i 02膜、 S i 3N4膜 または高融点金属シリサイト膜をドライエッチング条件下でエッチングする工程を含む S i膜、 S i O2膜、 S i 3N4膜または高融点金属シリサイト膜のエッチング方法。 5. A step of etching the Si film, the SiO 2 film, the Si 3 N 4 film, or the refractory metal silicide film under dry etching conditions using the etching gas according to claim 1 or 2 An etching method for an i film, a SiO 2 film, a Si 3 N 4 film, or a refractory metal silicide film. 6. 請求項 3又は 4に記載のチャンバクリーニングガスを用いてチャンバをクリー二 ングする工程を含む集積回路製造用のチャンバのクリ一ニング方法。  6. A method of cleaning a chamber for manufacturing an integrated circuit, comprising a step of cleaning the chamber using the chamber cleaning gas according to claim 3 or 4.
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