KR100458769B1 - Method for forming barrier metal layer of semiconductor device to guarantee step coverage and reduce contamination of carbon - Google Patents

Method for forming barrier metal layer of semiconductor device to guarantee step coverage and reduce contamination of carbon Download PDF

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KR100458769B1
KR100458769B1 KR1019970079301A KR19970079301A KR100458769B1 KR 100458769 B1 KR100458769 B1 KR 100458769B1 KR 1019970079301 A KR1019970079301 A KR 1019970079301A KR 19970079301 A KR19970079301 A KR 19970079301A KR 100458769 B1 KR100458769 B1 KR 100458769B1
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barrier metal
metal layer
layer
titanium
mole fraction
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KR19990059104A (en
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정철모
김우현
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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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
    • H01L21/76855—After-treatment introducing at least one additional element into the layer
    • H01L21/76856—After-treatment introducing at least one additional element into the layer by treatment in plasmas or gaseous environments, e.g. nitriding a refractory metal liner

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Abstract

PURPOSE: A method for forming a barrier metal layer of a semiconductor device is provided to guarantee step coverage and reduce contamination of carbon by adding hydrogen gas and ammonia gas during a barrier metal layer deposition process and by blocking chlorine ions from the barrier metal layer deposition process. CONSTITUTION: TiCl4 and NH3 having the first mole fraction smaller than the mole fraction of the TiCl4 are injected in an H2 plasma atmosphere to form a titanium layer. The introduction of H2 plasma is blocked by an in-situ process, and the TiCl4 and the NH3 having the second mole fraction greater than the first mole fraction are injected to form a titanium nitride layer.

Description

반도체 소자의 장벽 금속층 형성 방법Method of forming barrier metal layer of semiconductor device

본 발명은 반도체 소자의 장벽 금속층(barrier metal) 형성 방법에 관한 것으로, 특히 층덮힘(step coverage)을 확보하고 카본(corbon)의 오염을 감소시켜 장벽 금속층을 형성함으로써 콘택(contact) 저항이 감소되도록 하는 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a barrier metal layer of a semiconductor device. In particular, the contact resistance is reduced by forming a barrier metal layer by securing step coverage and reducing carbon contamination. It is about how to.

반도체 소자의 금속 배선 형성을 위한 장벽 금속층은 스퍼터링(sputtering) 방식이나 화학기상증착법(CVD)을 이용하여 형성하고 있다. 그러나 스퍼터링 방법을 이용하는 경우 메탈 콘택(metal contact) 하부면에서 층덮힘이 어렵울 뿐만 아니라 콘택의 오버 행잉(over hanging)에 의하여 금속 배선용 금속층의 콘택 매립이 어려운 문제점이 있다. 또한 타이타늄(Ti)층 및 타이타늄나이트라이드(TiN)층으로 이루어진 장벽 금속층의 타이타늄층 증착시 TiCl4를 사용할 경우에 증착 온도가 높은 단점이 있고, 타이타늄나이트라이드층 증착시 전구체로 TDMAT(Tetrakis- Dimethylamidotitanium)이나 TDEAT(Tetrakis-Diethylamidotitanium)를 사용하는 경우 층덮힘의 확보는 용이하나, 타이타늄나이트라이드층 대신 Ti(NC)가 형성되어 콘택 저항이 감소되는 단점이 있다. 이러한 현상이 나타나는 원인은 타이타늄층에 결합된 질소(nitrogen) 및 카본과 같은 유기 화합물(organic compound)이 타이타늄나이트라이드층을 형성하는 과정에서 타이타늄나이트라이드층과 함께 결합되기 때문이다. 질소와 카본의 타이타늄에 대한 반응성 및 이온결합 강도는 서로 비슷한데, 타이타늄과 질소의 이온결합 강도는 113.8 Kcal/mol. 이고, 타이타늄과 카본의 이온결합 강도는 101 Kcal/mol. 이다. 뿐만 아니라 활성화된 타이타늄-질소-카본의 결합은 분해 후, 카본 원자가 타이타늄에 직접 결합되거나 타이타늄-카본-질소의 결합으로 재정렬되어 타이타늄과 카본을 결합을 용이하게 한다.The barrier metal layer for forming the metal wiring of the semiconductor device is formed by the sputtering method or chemical vapor deposition (CVD). However, when the sputtering method is used, the layer covering is difficult on the lower surface of the metal contact, and the contact embedding of the metal layer for the metal wiring is difficult due to over hanging of the contact. In addition, when TiCl 4 is used to deposit a titanium layer of a barrier metal layer including a titanium (Ti) layer and a titanium nitride (TiN) layer, the deposition temperature is high. ) Or TDEAT (Tetrakis-Diethylamidotitanium), it is easy to secure the layer covering, but there is a disadvantage that the contact resistance is reduced because Ti (NC) is formed instead of the titanium nitride layer. This phenomenon occurs because organic compounds such as nitrogen and carbon bonded to the titanium layer are combined with the titanium nitride layer in the process of forming the titanium nitride layer. The reactivity and ionic bond strengths of nitrogen and carbon for titanium are similar, but the ionic bond strengths of titanium and nitrogen are 113.8 Kcal / mol. And the ionic bond strength of titanium and carbon is 101 Kcal / mol. to be. In addition, the activated titanium-nitrogen-carbon bond facilitates bonding of titanium and carbon after decomposition, with carbon atoms being directly bonded to titanium or rearranged to titanium-carbon-nitrogen bonds.

이러한 문제점과 같이 타이타늄나이트라이드층에 결합된 카본을 제거하기 위하여 과량의 질소(N2) 가스를 주입하면서 플라즈마 처리를 하여 카본의 농도를 감소시키려 하고 있으나, 이는 작업 처리량(through-put)을 현저하게 저하시키는 요인이되고 있다.In order to remove the carbon bound to the titanium nitride layer as described above, an attempt is made to reduce the concentration of carbon by injecting an excess of nitrogen (N 2 ) gas into the plasma treatment, but this significantly increases the throughput. Has become a depressing factor.

본 발명은 위와 같은 문제점을 해결하여 층덮힘의 확보가 이루어지고 콘택 저항이 개선되도록 장벽 금속층을 형성하는데 그 목적이 있다.The present invention has been made in view of solving the above problems to form a barrier metal layer to ensure layer covering and to improve contact resistance.

상술한 목적을 달성하기 위한 반도체 소자의 장벽 금속층 형성 방법은, H2플라즈마 분위기에서 TiCl4와 상기 TiCl4의 몰분율보다 작은 제 1 몰분율로 NH3를주입하여 타이타늄층을 형성시키는 단계와, 인 시투로 H2플라즈마의 유입을 차단하고 상기 TiCl4와 상기 제 1 몰분율보다 큰 몰분율로 NH3를 주입하여 타이타늄나이트라이드층을 형성시키는 단계를 포함하여 이루어지는 것을 특징으로 한다.A barrier metal layer forming a semiconductor device for achieving the above object is, H 2 plasma and the step of injecting the NH 3 with a small first mole fraction than the molar fraction of the TiCl 4 and TiCl 4 to form a titanium layer in an atmosphere, in situ Blocking the inflow of the H 2 plasma and injecting NH 3 at a mole fraction greater than the TiCl 4 and the first mole fraction to form a titanium nitride layer.

도 1(a) 및 도 1(b)는 본 발명에 따른 반도체 소자의 장벽 금속층 형성 방법을 설명하기 위해 도시한 화학 반응 순서도.1 (a) and 1 (b) are chemical reaction flowcharts for explaining a method of forming a barrier metal layer of a semiconductor device according to the present invention.

이하, 첨부된 도면을 참조하여 본 발명을 상세히 설명하기로 한다.Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.

도 1(a) 및 도 1(b)는 본 발명에 따른 반도체 소자의 장벽 금속층 형성 방법을 설명하기 위해 도시한 화학 반응 순서도이다.1 (a) and 1 (b) are flowcharts of chemical reactions shown for explaining a method of forming a barrier metal layer of a semiconductor device according to the present invention.

본 발명에 따른 반도체 소자의 장벽 금속층 형성 방법은 종래의 화학기상증착 장비에 수소(H2) 플라즈마 장치와 NH3가스 라인을 설치하여 인-시투(in-situ) 방법으로 진행된다. 먼저, 반도체 소자를 형성하기 위한 여러 요소가 형성된 기판 상부에 장벽 금속층으로 타이타늄층을 증착한다. 타이타늄층을 증착하기 위해서는 400℃ 내지 900℃ 온도 영역의 반응 챔버(chamber) 내로 TiCl4및 NH3가스를 주입한다. 이 때 반응 챔버 내의 수소 플라즈마에 존재하는 H 레디칼(redical)은 TiCl4의 타이타늄-염소의 결합을 방지할 뿐 아니라, 부분적으로 NH3-H를 형성하여 염소 가스 포획을(capture)을 도와주어 NH4Cl 가스를 생성한다. 이러한 반응은 활성화(activation) 에너지가 낮아서 저온에서도 가능하다. 또한, NH4Cl의 생성은타이타늄층의 생성을 촉진하게 된다. 이 반응에서 NH3가스의 양은 TiCl4가스에 비하여 아주 작은 양, 즉 TiCl4의 몰분율보다 작은 몰분율이어야 한다.In the method of forming a barrier metal layer of a semiconductor device according to the present invention, a hydrogen (H 2 ) plasma apparatus and an NH 3 gas line are installed in a conventional chemical vapor deposition apparatus to proceed in an in-situ method. First, a titanium layer is deposited as a barrier metal layer on a substrate on which various elements for forming a semiconductor device are formed. In order to deposit the titanium layer, TiCl 4 and NH 3 gas are injected into the reaction chamber in the 400 ° C. to 900 ° C. temperature range. At this time, the H radical in the hydrogen plasma in the reaction chamber not only prevents titanium-chlorine binding of TiCl 4 , but also partially forms NH 3 -H to help capture chlorine gas. Produces 4 Cl gas. This reaction is possible at low temperatures due to the low activation energy. In addition, the production of NH 4 Cl promotes the production of the titanium layer. The amount of NH 3 gas in this reaction should be a very small amount compared to the TiCl 4 gas, ie less than the mole fraction of TiCl 4 .

타이타늄층의 증착이 완료되면 타이타늄나이트라이드층을 형성하기 위해, 반응 챕버 내의 수소 플라즈마 유입을 차단하고 TiCl4가스 및 NH3가스의 유입량을 증가시켜 유입시킨다. TiCl4는 표면에 흡착되게 되고, NH3가스는 표면에 흡착된 TiCl4와의 분해 반응에 기여한다. 또한 NH3가스는 타이타늄나이트라이드층을 형성하기 위한 질소 성분의 소오스(source)가 된다. 여기서, 타이타늄나이트라이드층을 형성하기 위해서는 TiCl4가스의 유입량은 타이타늄층을 형성할 때와 마찬가지로 유지하고, NH3가스의 유입량은 타이타늄층을 형성할 때보다 증가시켜 유입시킨다. 따라서, 타이타늄나이트라이드층을 형성할 때의 NH3의 몰분율은 타이타늄층을 형성할때의 NH3의 몰분율보다 크게 된다. 도 1(a)는 위와 같은 분해 반응으로 타이타늄나이트라이드층이 형성되는 반응 과정을 도시하고 있다.After the deposition of the titanium layer is completed, in order to form the titanium nitride layer, the flow of hydrogen plasma in the reaction chapter is blocked and the inflow of TiCl 4 gas and NH 3 gas is increased. TiCl 4 is adsorbed on the surface and NH 3 gas contributes to the decomposition reaction with TiCl 4 adsorbed on the surface. The NH 3 gas also serves as a source of nitrogen components for forming the titanium nitride layer. Here, in order to form the titanium nitride layer, the inflow amount of TiCl 4 gas is maintained as in the case of forming the titanium layer, and the inflow amount of NH 3 gas is increased and increased than in the case of forming the titanium layer. Therefore, the mole fraction of NH 3 in forming the titanium nitride layer is larger than the mole fraction of NH 3 in forming the titanium layer. Figure 1 (a) shows a reaction process in which the titanium nitride layer is formed by the above decomposition reaction.

한편, 도 1(b)에 도시된 것과 같이, NH3는 NH3및 TiCl4의 반응으로 생성된 HCl과 반응하여 NH4Cl을 형성한다.On the other hand, as shown in Figure 1 (b), NH 3 reacts with HCl produced by the reaction of NH 3 and TiCl 4 to form NH 4 Cl.

그러므로 본 발명에서는 수소와 NH3가스를 이용하여 타이타늄층 및 타이타늄나이트라이드층을 인-시투로 증착시키면서 타이타늄층의 증착 온도를 낮추고, 증착 공정의 부산물인 HCl을 NH3와 결합시켜서 NH4Cl 염(salt)을 형성하여 제거한다. 따라서 반응 속도가 증가되고 HCl이 용이하게 제거된다. 종래의 단순한 증착 방식으로는 타이타늄층이나 타이타늄나이트라이드층 대신에 Ti(NCl)이 형성되는 반응을 피할 수 없었다. 그러나 수소나 암모니아 가스를 적절히 첨가하여 활성화 에너지를 낮추고, NH3를 불순물 제거제(scavenger)로 작용하게 하여 HCl을 제거하면서 염소 이온을 타이타늄층 및 타이타늄나이트라이드층의 증착 반응으로부터 차단시킨다.Therefore, in the present invention, the deposition temperature of the titanium layer is lowered by in-situ deposition of the titanium layer and the titanium nitride layer using hydrogen and NH 3 gas, and the NH 4 Cl salt by combining HCl, a byproduct of the deposition process, with NH 3. It forms and removes salt. The reaction rate is thus increased and HCl is easily removed. In the conventional simple deposition method, a reaction in which Ti (NCl) is formed in place of the titanium layer or the titanium nitride layer is inevitable. However, by appropriately adding hydrogen or ammonia gas, the activation energy is lowered, and NH 3 acts as a scavenger to remove chlorine ions from the deposition reaction of the titanium layer and the titanium nitride layer while removing HCl.

반도체 소자의 집적도가 증가함으로써 소자의 디자인 룰이 감소하고 콘택 사이즈가 작아져 콘택 홀은 높이 대 폭의 비율이 증가하게 된다. 따라서 장벽 금속층의 층덮힘 확보가 어려워지고 있다. 그러나 상술한 바와 같이 본 발명에 의하면, 장벽 금속층 증착시 층덮힘을 확보하면서 콘택 저항 문제를 해결할 수 있을 뿐만 아니라 콘택 홀의 오버 행잉을 피할 수 있어 이후 금속 배선 형성시 콘택 매립을 용이하게 진행 할 수 있는 탁월한 효과가 있다.As the degree of integration of the semiconductor device increases, the design rule of the device decreases and the contact size decreases, resulting in a height-to-width ratio of the contact hole. Therefore, it is difficult to secure the layer covering of the barrier metal layer. However, as described above, according to the present invention, it is possible not only to solve the contact resistance problem while securing the layer covering when depositing the barrier metal layer, but also to avoid overhanging of the contact hole, so that the contact filling can be easily performed when forming the metal wiring. Excellent effect

Claims (1)

H2플라즈마 분위기에서 TiCl4와 상기 TiCl4의 몰분율보다 작은 제 1 몰분율로 NH3를 주입하여 타이타늄층을 형성시키는 단계와,The step of injecting the NH 3 with a small mole fraction than the first TiCl 4 and the mole fraction of said TiCl 4 to form a titanium dioxide layer in H 2 atmosphere with the plasma, 인 시투로 H2플라즈마의 유입을 차단하고, 상기 TiCl4와 상기 제 1 몰분율보다 큰 제 2 몰분율로 NH3를 주입하여 타이타늄나이트라이드층을 형성시키는 단계를 포함하여 이루어지는 것을 특징으로 하는 반도체 소자의 장벽 금속층 형성 방법.Blocking the inflow of H 2 plasma by in-situ, and injecting NH 3 at a second mole fraction greater than the TiCl 4 and the first mole fraction to form a titanium nitride layer. Method of forming a barrier metal layer.
KR1019970079301A 1997-12-30 1997-12-30 Method for forming barrier metal layer of semiconductor device to guarantee step coverage and reduce contamination of carbon KR100458769B1 (en)

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