KR20020045898A - Etching method of insulating layer using a gas containing fluoride-ether - Google Patents

Etching method of insulating layer using a gas containing fluoride-ether Download PDF

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KR20020045898A
KR20020045898A KR1020000075315A KR20000075315A KR20020045898A KR 20020045898 A KR20020045898 A KR 20020045898A KR 1020000075315 A KR1020000075315 A KR 1020000075315A KR 20000075315 A KR20000075315 A KR 20000075315A KR 20020045898 A KR20020045898 A KR 20020045898A
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etching
gas
etching method
ether
formula
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KR1020000075315A
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Korean (ko)
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최창주
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박종섭
주식회사 하이닉스반도체
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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

Abstract

PURPOSE: An etch method using fluoride-ether based etch gas is provided to remarkably reduce the quantity of exhausted contaminant, by preventing a microloading effect, residue, particles and an etch stop phenomenon. CONSTITUTION: A layer on a semiconductor substrate is etched by using fluoride-ether so that a global warming phenomenon is minimized. The etch process is performed by adding Ar, N2, O2 or CO to the fluoride-ether gas. A silicon oxide layer, a silicon oxynitride layer, a silicon nitride layer or a low-k layer is used in a contact etch process, an insulation layer trench etch process, a spacer etch process, a hard mask etch process and a planarization-etch process.

Description

불화 에테르 계 식각가스를 이용한 식각방법{Etching method of insulating layer using a gas containing fluoride-ether}Etching method of insulating layer using a gas containing fluoride-ether

본 발명은 불화 에테르 ( fluoride-ether ) 계 식각가스를 이용한 식각방법에 관한 것으로, 기존에 식각가스로 널리 사용되고 있지만 지구온난화에 크게 영향을 미치기 때문에 전세계적으로 감축의 노력을 기울이고 있는 과불화 화합물 (perfluoro compound; 이하 "PFC"라 약칭함)의 대체가스로 유용하게 사용될 수 있는 불화 에테르계 ( fluoride-ether ) 계 식각가스를 이용한 식각방법에 관한 것이다.The present invention relates to an etching method using a fluoride ether-based etching gas, which is widely used as an etching gas, but because it greatly affects global warming, the perfluorinated compound that is making efforts to reduce globally ( It relates to an etching method using a fluoride-ether-based etching gas that can be usefully used as a replacement gas of a perfluoro compound (hereinafter abbreviated as "PFC").

반도체 소자의 제조공정에서 층간 절연막으로 주로 이용되는 산화막은 콘택 (contact) 등의 패턴을 형성하기 위하여 식각 공정을 반드시 거쳐야 하는데, 산화막 식각에 주로 사용되는 가스는 CHF3, C2F6, C3F8및 C4F8등의 PFC 계열이다.The oxide film mainly used as an interlayer insulating film in the manufacturing process of a semiconductor device must go through an etching process in order to form a pattern such as a contact, and the gas mainly used for etching an oxide film is CHF 3 , C 2 F 6 , C 3. PFC series such as F 8 and C 4 F 8 .

이산화탄소에 비해 지구온난화지수 (Global Warming Potential; GWP) 값이 수천∼수만배 이상 높은, 상기 PFC계열의 식각가스는 환경에 매우 나쁜 영향을 미치기 때문에 전세계적으로 이의 사용을 규제하려는 움직임이 확산되다.Since the Global Warming Potential (GWP) value of thousands to tens of thousands of times higher than that of carbon dioxide, the PFC-based etching gas has a very bad effect on the environment, so the movement to regulate its use worldwide is spreading.

지난 1999년 3월에 있었던 세계 반도체협회에서 한국은 PFC 계열의 식각가스를 MMTCE (Million Metric Tons of Carbon Equivalent)기준으로 2010년부터 1997년에 비하여 10%를 감축하기로 합의하였는데, 이는 매년 PFC 계열의 식각가스의 사용이 증가하는 점과 감축공정의 수가 한정되어 있다는 점에 비추어 볼 때, 시기적으로나 기술적으로 PFC 계열의 식각가스 감축 공정의 개발이 중요하다는 것을 알 수 있다.At the World Semiconductor Association in March 1999, Korea agreed to reduce PFC-based etching gas by 10% compared to 2010-1997 on the basis of Million Metric Tons of Carbon Equivalent (MMTCE). In view of the increasing use of etch gas and the limited number of reduction processes, it is important to develop PFC-based etching gas reduction processes in a timely and technical manner.

상기 PFC 계열의 식각가스는 분자의 구조적인 측면에서 산소원자나 불포화 이중결합을 함유하지 않은 불소에 의해 포화된 상태로서, 지구 대기 중에 방출될 경우 지구 복사 열 에너지를 적외선 영역에서 강하게 흡수하여 지구온난화를 야기시켜 왔다.The etching gas of the PFC series is saturated with fluorine that does not contain oxygen atoms or unsaturated double bonds in terms of molecular structure, and when it is released into the earth's atmosphere, global warming is strongly absorbed in the infrared region. Has caused.

또한, 상기 PFC계열의 식각가스는 수천에서 수만의 지구온난화지수 (GWP)를 갖기 때문에 환경에 매우 나쁜 영향을 끼친다. 지구온난화지수는 이산화탄소를 1로 하였을 때 지구온난화에 영향을 미치는 정도를 나타내는 수치로서, 큰 값을 가질수록 지구온난화에 크게 영향을 미친다는 것을 나타낸다. 지구 온난화 지수가 환경에 끼치는 영향을 나타낸 수치라면, MMTCE 는 하기 식과 같이 계산되며, 오염물질의 방출량까지 고려한 것으로서 실질적으로 지구온난화에 영향을 미치는 정도를 수치화한 것이다.In addition, the etching gas of the PFC series has a global warming potential (GWP) of several thousands to tens of thousands, which has a very bad effect on the environment. The global warming index is a figure that indicates the degree to which global warming is affected when carbon dioxide is 1, and the larger the value, the greater the impact on global warming. If the global warming index shows the impact on the environment, the MMTCE is calculated as the following equation, and the amount of pollutant emissions is taken into consideration and quantifies the extent to which the global warming is actually affected.

MMTCE = 가스방출량(㎏) × GWP × 10-9× (12/44)MMTCE = amount of gas released (kg) × GWP × 10 -9 × (12/44)

예를 들어 종래의 PFC 계열의 식각가스 중에서 C2F6를 사용한 식각공정을 진행할 때 웨이퍼 한 장당 MMTCE 가 보통 1×10-9정도 산정될 수 있는데, 이것은 본 공정의 지구온난화효과가 CO2가스 기준으로 약 3.6㎏ 방출되는 것과 같은 효과로서, 일반적으로 반도체 한 개의 칩을 생산하는 데에는 PFC 를 20∼30번 사용해서 식각을 한다는 것을 생각할 때 지구온난화에 막대한 영향을 미치는 문제점이 있다.For example, when performing an etching process using C 2 F 6 among conventional PFC-based etching gases, MMTCE can be estimated to be about 1 × 10 -9 per wafer, which is a global warming effect of CO 2 gas. As an effect of emitting about 3.6 kg as a reference, there is a problem that the global warming is considerably considered when etching a PFC is used 20 to 30 times to produce a single chip.

본 발명은, 상기한 종래기술의 문제점을 해결하기 위하여, 지구온난화 물질로 세계적으로 감축하고 있는 PFC 가스의 대체가스인 불화 에테르계 ( fluoride-ether ) 계 식각가스로 피식각층을 식각함으로써 MMTCE를 감소시켜 지구 온난화를 최소화시키는 불화 에테르계 ( fluoride-ether ) 계 식각가스를 이용한 식각방법을 제공하는 것을 그 목적으로 한다.The present invention, in order to solve the above problems of the prior art, by reducing the MMTCE by etching the etched layer with a fluoride-ether-based etching gas, which is a replacement gas of PFC gas is reduced globally as a global warming material The aim is to provide an etching method using a fluoride ether-based etching gas that minimizes global warming.

상기 목적을 달성하기 위하여 본 발명에 따라 불화 에테르계 ( fluoride-ether ) 계 식각가스를 이용한 식각방법은,Etching method using a fluoride ether-based etching gas in accordance with the present invention to achieve the above object,

불화에테르계 식각가스를 이용한 식각방법에 있어서,In the etching method using an fluorine ether-based etching gas,

반도체기판 상의 피식각층을 불화에테르계 가스 ( fluoride-ether ) 로 식각하여 지구온난화 현상을 최소화시키는 것을 특징으로 한다.The etching target layer on the semiconductor substrate is etched with fluoride-ether gas to minimize global warming.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에서는 우선, 불화 에테르계 ( fluoride-ether ) 계 식각가스를 제공하는데, 상기 불화 에테르 계 식각가스는 하기 화학식 1 내지 화학식 7 의 화합물로 이루어진 군으로부터 선택되는 화합물을 단독으로 또는 혼합한 가스이다.In the present invention, first, a fluoride ether-based etching gas is provided, wherein the fluoride ether-based etching gas is a gas alone or mixed with a compound selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 7 .

[화학식 1][Formula 1]

CF3-O-CF3 CF 3 -O-CF 3

[화학식 2][Formula 2]

CF3-CF2-O-CF3 CF 3 -CF 2 -O-CF 3

[화학식 3][Formula 3]

CF3-CF2-CF2-O-CF3 CF 3 -CF 2 -CF 2 -O-CF 3

[화학식 4][Formula 4]

CF3-CF2-O-CF2-CF3 CF 3 -CF 2 -O-CF 2 -CF 3

[화학식 5][Formula 5]

CF3-CF2-CF2-CF2-O-CF3 CF 3 -CF 2 -CF 2 -CF 2 -O-CF 3

[화학식 6][Formula 6]

CF3-CF2-CF2-O-CF2-CF3 CF 3 -CF 2 -CF 2 -O-CF 2 -CF 3

[화학식 7][Formula 7]

또한, 본 발명에서는 상기 불화에테르계 식각가스를 이용한 식각방법을 제공한다.In addition, the present invention provides an etching method using the fluorinated ether etching gas.

이때, 식각방법은 상기 화학식 1 내지 화학식 7 로 이루어지는 군에서 선택되는 한가지 가스 또는 이들이 조합된 혼합가스를 식각가스로 이용하여 실시한다.In this case, the etching method is performed using one gas selected from the group consisting of Chemical Formulas 1 to 7 or a mixed gas thereof as an etching gas.

그리고, 상기 식각가스는 Ar, N2, O2, CO 등의 첨가가스를 혼합하여 사용할 수 있다.The etching gas may be used by mixing additive gases such as Ar, N 2 , O 2 , and CO.

그리고, 상기 식각공정은 실리콘산화막, 실리콘산화질화막, 실리콘질화막 또는 로우-케이층(low-k layer)이 피식각층으로 구성되는 콘택식각, 절연막 트렌치 식각, 스페이서 식각, 하드마스크층식각, 평탄화 식각 등에 사용된다.The etching process may include contact etching, insulating film trench etching, spacer etching, hard mask layer etching, planarization etching, etc., in which a silicon oxide film, a silicon oxynitride film, a silicon nitride film, or a low-k layer is formed of an etched layer. Used.

또한, 상기 식각방법은 단소와 산소 간의 결합에 의하여 높은 전자 에너지 꼬리 ( high energy tail in electron energy distribution ) 부분의 에너지는 일반적으로 고밀도 플라즈마에서 20 eV를 넘기 때문에 1eV 전후의 낮은 에너지를 요구하는 가스의 분해반응을 활발하게 하여 플라즈마 내의 활성 라디칼을 형성함으로써 식각속도를 향상시킨다. 이때, 상기 식각방법은 플라즈마 내(內) 전자의 평균 여기 에너지를 3 ∼ 10 전자볼트(eV)로 유지하여 식각속도를 유지하도록 한다.In addition, since the energy of the portion of the high energy tail in electron energy distribution is generally greater than 20 eV in a high density plasma, the etching method requires a low energy around 1 eV. The etching rate is enhanced by actively decomposing the reaction to form active radicals in the plasma. At this time, the etching method is to maintain the etching rate by maintaining the average excitation energy of electrons in the plasma to 3 to 10 electron volts (eV).

그리고, 상기 불화에테르계 식각가스의 구조적인 특성상 O 라디칼을 부가적으로 생성시켜 재결함 형성된 안정한 F2및 CF4등의 분자들을 체인 리액션 ( chain reaction ) 시킴으로써 활성 F 라디칼을 형성할 수 있도록 한다. 이때, 상기 O 라디칼은 식각공정시 발생되는 테프론계 식각 폴리머를 제거하는 역할을 한다.In addition, due to the structural characteristics of the fluorinated ether etching gas, O radicals are additionally generated to form active F radicals by chain reaction of stable F 2 and CF 4 molecules formed by defects. In this case, the O radical serves to remove the teflon-based etching polymer generated during the etching process.

한편, 상기 식각공정은 다음과 같은 조건으로 실시한다.On the other hand, the etching process is carried out under the following conditions.

먼저, 불화에테르계 가스를 2∼200 sccm 정도 플로우(Flow)시켜 실시한다. 이때, 상기 불화에테르계 가스는 상기 화학식 1 내지 화학식 7 로 이루어지는 군에서 선택되는 한가지 가스 또는 이들이 조합된 혼합가스를 식각가스를 말한다.First, the fluoride ether gas is flowed by about 2 to 200 sccm. In this case, the fluorinated ether gas refers to an etching gas of one gas selected from the group consisting of Chemical Formulas 1 to 7 or a mixed gas thereof.

여기서, 상기 불화에테르계 가스와 Ar, N2또는 H2의 첨가가스를 10∼300 sccm 첨가하여 식각 장비 내의 전자밀도를 균일하게 하고 적절한 전자 밀도를 유지하게 한다.Here, 10 to 300 sccm of the fluorinated ether gas and the additive gas of Ar, N 2 or H 2 are added to make the electron density uniform in the etching equipment and maintain the proper electron density.

그리고, 상기 불화에테르계 가스의 구조적 특성에 의하여 생성되는 O 라디칼의 생성을 조절하여 식각공정시 식각되는 폴리머의 양을 조절함으로써 산화막의 식각공정시 마이크로로딩 효과 ( microloading effect )를 감소시키고 식각정지 현상을 감소시킨다.In addition, by controlling the generation of O radicals generated by the structural characteristics of the fluorinated ether gas by controlling the amount of polymer etched during the etching process to reduce the microloading effect (etching phenomenon) during the etching process of the oxide film Decreases.

그리고, 상기 식각공정은 I 라인용 감광막, DUV 용 감광막 또는 전자빔용 감광막을 사용하여 실시할 수 있다.The etching process may be performed using a photosensitive film for I line, a photosensitive film for DUV, or a photosensitive film for electron beam.

그리고, 공정 압력을 1∼100 mTorr 로 유지하고, 알.에프. 소오스 전력(RF source power)을 300∼3000 와트(Watt)의 범위 내에서 조절하여 플라즈마 밀도를 유지한다.Then, the process pressure is maintained at 1 to 100 mTorr, and R.F. RF source power is adjusted within the range of 300-3000 Watts to maintain plasma density.

그리고, 상기 알.에프. 바이어스 전력(RF bias power)을 100∼3000 와트의 범위 내에서 조절하여 1000∼15000 Å/min 의 식각 속도를 확보한다.And R. F. The RF bias power is adjusted within the range of 100 to 3000 watts to secure an etching rate of 1000 to 15000 Å / min.

그리고, 상기 피식각층이 구비되는 반도체기판의 온도를 0∼200 ℃ 로 유지한다.The temperature of the semiconductor substrate on which the etched layer is provided is maintained at 0 to 200 ° C.

이상에서 살펴본 바와 같이, 본 발명에 따른 불화에테르계 가스를 이용한 식각방법은, 식각공정시 마이크로로딩 효과, 잔류물, 파티클 및 식각정지 등의 현상을 방지하여 식각 특성을 향상시키고 지구온난화 현상을 최소화시켜 오염물질의 배출량을 크게 감소시키고 식각장비의 오염을 감소시키는 효과를 제공한다.As described above, the etching method using the fluorinated ether gas according to the present invention, by preventing the phenomenon of micro-loading effect, residue, particles and etch stop during the etching process to improve the etching characteristics and minimize the global warming phenomenon This greatly reduces the emissions of pollutants and reduces the contamination of etching equipment.

Claims (11)

불화에테르계 식각가스를 이용한 식각방법에 있어서,In the etching method using an fluorine ether-based etching gas, 반도체기판 상의 피식각층을 불화에테르계 가스 ( fluoride-ether ) 로 식각하여 지구온난화 현상을 최소화시키는 것을 특징으로하는 식각방법.An etching method, characterized in that to minimize the global warming phenomenon by etching the etched layer on the semiconductor substrate with a fluoride ether (fluoride-ether). 제 1 항에 있어서,The method of claim 1, 상기 불화에테르계 가스는, 하기 화학식 1 내지 화학식 7 로 이루어진 군으로부터 선택되는 화합물이나 이들의 조합으로 사용하는 것을 특징으로 하는 식각방법.The etching method, characterized in that the fluorinated ether gas is used as a compound selected from the group consisting of the following formulas (1) to (7) or a combination thereof. [화학식 1][Formula 1] CF3-O-CF3 CF 3 -O-CF 3 [화학식 2][Formula 2] CF3-CF2-O-CF3 CF 3 -CF 2 -O-CF 3 [화학식 3][Formula 3] CF3-CF2-CF2-O-CF3 CF 3 -CF 2 -CF 2 -O-CF 3 [화학식 4][Formula 4] CF3-CF2-O-CF2-CF3 CF 3 -CF 2 -O-CF 2 -CF 3 [화학식 5][Formula 5] CF3-CF2-CF2-CF2-O-CF3 CF 3 -CF 2 -CF 2 -CF 2 -O-CF 3 [화학식 6][Formula 6] CF3-CF2-CF2-O-CF2-CF3 CF 3 -CF 2 -CF 2 -O-CF 2 -CF 3 [화학식 7][Formula 7] 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 불화에테르계 가스에 Ar, N2, O2또는 CO 첨가가스를 혼합하여 실시하는 것을 특징으로하는 식각방법.The etching method may be performed by mixing Ar, N 2 , O 2 or CO addition gas to the fluorinated ether gas. 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 실리콘산화막, 실리콘산화질화막, 실리콘질화막 또는 로우-케이층(low-k layer)이 피식각층으로 구성되는 콘택식각, 절연막 트렌치 식각, 스페이서 식각, 하드마스크 식각, 평탄화 식각에 사용되는 것을 특징으로하는 식각방법.The etching method may be used for contact etching, insulating film trench etching, spacer etching, hard mask etching, and planarization etching, in which a silicon oxide film, a silicon oxynitride film, a silicon nitride film, or a low-k layer is formed of an etched layer. Etching method characterized by. 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 불화에테르계 가스를 2∼200 sccm 정도 플로우(Flow)시키며 실시하는 것을 특징으로하는 식각방법.The etching method is characterized in that the fluorinated ether gas is flowed by about 2 to 200 sccm. 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 상기 불화에테르계 가스에 Ar, N2 또는 H2 의 첨가가스를 10∼300 sccm 첨가하여 식각 장비 내의 전자밀도를 균일하게 유지하는 것을 특징으로하는 식각방법.The etching method is an etching method, characterized in that to maintain a uniform electron density in the etching equipment by adding 10 to 300 sccm of the addition gas of Ar, N2 or H2 to the fluorinated ether gas. 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 압력을 1∼100 mTorr 로 유지하고, 알.에프. 소오스 전력(RF source power)을 300∼3000 와트(Watt)로 조절하여 플라즈마 밀도를 유지하는 것을 특징으로하는 식각방법.The etching method maintains the pressure at 1 to 100 mTorr, R. F. Etching method characterized in that to maintain the plasma density by adjusting the source power (RF source power) to 300 ~ 3000 Watt (Watt). 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 알.에프. 바이어스 전력(RF bias power)을 100∼3000 와트로 조절하여 1000∼15000 Å/min 의 식각 속도를 확보하는 것을 특징으로하는 식각방법.The etching method is R. F .. Etching method characterized in that the etching speed of 1000 ~ 15000 Å / min is secured by adjusting the bias power (RF bias power) to 100 ~ 3000 watts. 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 피식각층이 구비되는 반도체기판의 온도를 0∼200 ℃ 로 유지하는 것을 특징으로하는 식각방법.The etching method is characterized in that for maintaining the temperature of the semiconductor substrate is provided with an etching target layer at 0 ~ 200 ℃. 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 I 라인용 감광막, DUV 용 감광막 또는 전자빔용 감광막을 마스크로 하여 수행하는 것을 특징으로하는 식각방법.The etching method may be performed using a photosensitive film for I line, a photosensitive film for DUV, or a photosensitive film for electron beam as a mask. 제 1 항에 있어서,The method of claim 1, 상기 식각방법은 플라즈마 내의 전자의 평균 여기 에너지를 3 ∼ 10 eV 유지하여 불소반응물을 유지하고 빠른 식각속도를 유지하는 것을 특징으로하는 식각방법.The etching method is characterized in that to maintain the fluorine reactant and maintain a fast etching rate by maintaining the average excitation energy of electrons in the plasma 3 to 10 eV.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07169738A (en) * 1993-12-13 1995-07-04 Sony Corp Dry etching method
JPH07183274A (en) * 1993-12-24 1995-07-21 Sony Corp Dry etching
JPH08291299A (en) * 1995-04-21 1996-11-05 Central Glass Co Ltd Cleaning or etching gas
KR20000053068A (en) * 1996-11-05 2000-08-25 고교기쥬쯔잉초가다이효스루니혼고쿠 Dry etching gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07169738A (en) * 1993-12-13 1995-07-04 Sony Corp Dry etching method
JPH07183274A (en) * 1993-12-24 1995-07-21 Sony Corp Dry etching
JPH08291299A (en) * 1995-04-21 1996-11-05 Central Glass Co Ltd Cleaning or etching gas
KR20000053068A (en) * 1996-11-05 2000-08-25 고교기쥬쯔잉초가다이효스루니혼고쿠 Dry etching gas

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