WO2017000670A1 - 钨膜的沉积方法 - Google Patents

钨膜的沉积方法 Download PDF

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WO2017000670A1
WO2017000670A1 PCT/CN2016/081546 CN2016081546W WO2017000670A1 WO 2017000670 A1 WO2017000670 A1 WO 2017000670A1 CN 2016081546 W CN2016081546 W CN 2016081546W WO 2017000670 A1 WO2017000670 A1 WO 2017000670A1
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tungsten
silicon
gaseous compound
sccm
substrate
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French (fr)
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周君
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CSMC Technologies Fab2 Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C23C16/14—Deposition of only one other metal element
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/16—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal carbonyl compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/40—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials
    • H10P14/418—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials the conductive layers comprising transition metals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/40—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials
    • H10P14/42—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials using a gas or vapour
    • H10P14/43—Chemical deposition, e.g. chemical vapour deposition [CVD]
    • H10P14/432—Chemical deposition, e.g. chemical vapour deposition [CVD] using selective deposition

Definitions

  • the present invention relates to the field of chemical vapor deposition, and in particular to a method of depositing a tungsten film.
  • Chemical Vapor Deposition is a process in which a solid film is deposited on the surface of a silicon wafer by a chemical reaction of a gas.
  • the tungsten chemical vapor deposition (WCVD) process is the primary metallization technique for through-holes and contacts in aluminum processes due to its excellent void-filling capability.
  • an adhesion layer (Ti layer) and a barrier layer (TiN layer) are generally deposited on the surface of the silicon wafer.
  • Ti layer an adhesion layer
  • TiN layer a barrier layer
  • RTA Rapid Thermal Annealing
  • WF 6 diffuses and combines with Ti in a relatively weak place, and a chemical reaction occurs, which causes gaseous TiF x to escape outward, resulting in the deposition of tungsten film to form a volcanic eruption (Volcano), resulting in abnormal tungsten film.
  • a method of depositing a tungsten film comprising the steps of:
  • Chemical vapor deposition is performed using the gaseous compound of tungsten and hydrogen as a gas source to form a tungsten film deposited on the substrate.
  • the tungsten film deposition method is characterized in that a gaseous compound of silicon is used as a gas source for chemical vapor deposition to form a second silicon atom layer deposited on the tungsten core film, so that the gaseous compound of tungsten reaches the surface of the substrate and can be second.
  • the silicon in the silicon atom layer undergoes a displacement reaction to form tungsten, so that the tungsten core film can be repaired, thereby blocking the downward diffusion of the gaseous compound of tungsten, reducing the chemical reaction of the gaseous compound of tungsten with titanium to form a gaseous substance, and the conventional tungsten chemistry.
  • the above tungsten film deposition method reduces the deposition of the tungsten film to form a volcanic eruption.
  • FIG. 1 is a flow chart showing a method of depositing a tungsten film according to an embodiment
  • FIG. 2 is a schematic view showing the structural change of the surface of the wafer after the wafer is processed by the deposition method of the tungsten film as shown in FIG. 1.
  • a method for depositing a tungsten film includes the following steps:
  • the substrate 10 is uniformly heated by the back pressure adsorption on the surface of the electric resistance heater.
  • Substrate 10 can be a silicon wafer.
  • substrate 10 includes a body 110 and a protective layer 120 deposited on the surface of body 110.
  • the protective layer 120 may be a composite layer of a Ti layer and a TiN layer, and the Ti layer is in contact with the body 110.
  • the temperature of the chemical vapor deposition may be 390 ° C to 430 ° C, and the pressure may be 30 Torr to 50 Torr.
  • the time of chemical vapor deposition can be from 10 s to 30 s.
  • the flow rate of the gaseous compound of silicon may range from 40 sccm to 100 sccm.
  • the filling gas pressure is helium (He), and the flow rate of helium gas is 5000 sccm to 10000 sccm.
  • step (B) in FIG. 2 after the substrate 10 is subjected to S20 treatment, the gaseous compound of silicon is decomposed to form Si. Si is adsorbed on the surface of the substrate 10 to form a first silicon atomic layer 20.
  • the gaseous compound of silicon may be silicon methane (SiH 4 ).
  • SiH 4 is self-decomposed into Si and H 2 .
  • Si is adsorbed on the surface of the substrate 10 to form a first silicon atomic layer 20.
  • the temperature of the chemical vapor deposition may be 390 ° C to 430 ° C, and the pressure may be 30 Torr to 50 Torr.
  • the time of chemical vapor deposition can be from 10 s to 30 s.
  • the flow ratio of the gaseous compound of tungsten to the gaseous compound of silicon may be from 1:10 to 40.
  • the flow rate of the gaseous compound of tungsten is 1 sccm to 10 sccm, and the flow rate of the gaseous compound of silicon is 40 sccm to 100 sccm.
  • the gaseous compound of tungsten may be tungsten hexafluoride (WF 6 ), tungsten hexachloride (WCl 6 ) or tungsten carbonyl (W(CO) 6 ) or the like.
  • the gaseous compound of silicon may be silicon methane (SiH 4 ).
  • the gaseous compound of tungsten and the silicon of the first silicon atomic layer undergo a displacement reaction to form tungsten.
  • the gaseous compound of tungsten reacts with the gaseous compound of silicon to form tungsten.
  • the gaseous compound of tungsten and the silicon of the first silicon atomic layer undergo a displacement reaction to form tungsten and tungsten gas.
  • the tungsten formed by the reaction of the gaseous compound with the gaseous compound of silicon forms a tungsten core film deposited on the substrate.
  • the WF 6 and the Si of the first silicon atomic layer 20 undergo a displacement reaction to generate W.
  • WF 6 reacts with SiH 4 to form W.
  • the W formed by the above two reactions forms the W core film 30 deposited on the substrate 10.
  • a W core film 30 is deposited on the protective layer 120.
  • the temperature of the chemical vapor deposition may be 390 ° C to 430 ° C, and the pressure may be 30 Torr to 50 Torr.
  • the time of chemical vapor deposition can be from 10 s to 30 s.
  • the flow rate of the gaseous compound of silicon may range from 40 sccm to 100 sccm.
  • the filling gas pressure is helium (He), and the flow rate of helium gas is 5000 sccm to 10000 sccm.
  • the gaseous compound of silicon may be silicon methane (SiH 4 ).
  • the gaseous compound of silicon decomposes to form Si.
  • Si is adsorbed on the surface of the W core film 30 to form a second silicon atom layer 40, which can effectively block the diffusion of gaseous compounds of tungsten into the interior of the substrate 10.
  • SiH 4 is self-decomposed into Si and H 2 .
  • Si is adsorbed on the surface of the W core film 30 to form a second silicon atom layer 40, which can effectively block the diffusion of WF 6 into the interior of the substrate 10.
  • step (D) in FIG. 2 after the wafer shown in step (C) is subjected to S40 treatment, a second silicon atomic layer 40 is formed on the W core film 30.
  • the temperature of chemical vapor deposition may be 390 ° C ⁇ 430 ° C
  • the pressure can be 30 Torr to 50 Torr.
  • the time of chemical vapor deposition can be from 10 s to 30 s.
  • the flow rate of the gaseous compound of tungsten is from 1 sccm to 10 sccm.
  • the flow rate of hydrogen gas is from 80 sccm to 250 sccm.
  • the flow ratio of the gaseous compound of tungsten to hydrogen may be from 1:25 to 60.
  • the gaseous compound of tungsten undergoes a displacement reaction with the silicon of the second silicon atomic layer to form tungsten.
  • the gaseous compound of tungsten reacts with hydrogen to form tungsten.
  • the gaseous compound of tungsten and the tungsten of the second silicon atomic layer are reacted with tungsten formed by the reaction of gaseous compounds of tungsten and tungsten with hydrogen and tungsten in the tungsten core film to form a tungsten film deposited on the substrate.
  • the W formed by the reaction of the gaseous compound of tungsten with the silicon of the second silicon atomic layer can block the gaseous compound of the subsequent tungsten from diffusing downward along the weak region of the W core film 30, reducing the deposition of the W film 50 to form a volcanic eruption.
  • the gaseous compound of tungsten Since the reduction of Si atoms of the second silicon atom layer 40 is stronger than H 2 , and the gaseous compound of tungsten reaches the surface of the substrate 10 and does not react with H 2 , the gaseous compound of tungsten first reacts with the silicon of the second silicon atom layer to form W.
  • the gaseous compound of tungsten is WF 6 as an example.
  • the chemical reaction equation for chemical vapor deposition of WF 6 and H 2 is as follows:
  • a W film 50 is formed on the protective layer 120.
  • the tungsten film deposition method is characterized in that a gaseous compound of silicon is used as a gas source for chemical vapor deposition to form a second silicon atom layer deposited on the tungsten core film, so that the gaseous compound of tungsten reaches the surface of the substrate and can be combined with the second silicon atom.
  • the layer of silicon undergoes a displacement reaction to form tungsten, thus repairing the weak tungsten membrane
  • the region which blocks the gaseous compound of tungsten from diffusing downward, reduces the chemical reaction between the gaseous compound of tungsten and titanium to form a gaseous substance.
  • the deposition method of the above tungsten film reduces the deposition of tungsten film. Volcanic eruption.
  • the silicon wafer is uniformly heated by a back pressure adsorption on the surface of the electric resistance heater.
  • SiH flow rate adjusted by the flow controller 4 is 40 sccm, SiH 4 and evenly distributed from the decomposition reaction occurs in the process chamber, the process chamber by adjusting the throttle valve of the internal chamber
  • the pressure is 30 Torr.
  • the temperature of the chemical vapor deposition was 390 °C.
  • the time for chemical vapor deposition was 15 s.
  • the filling gas pressure is helium gas, and the flow rate of helium gas is 5000 sccm.
  • a first silicon atomic layer is formed on the surface of the silicon wafer.
  • the set temperature was 390 ° C
  • the internal pressure of the process chamber was 30 Torr
  • WF 6 and SiH 4 were introduced into the process chamber for chemical vapor deposition.
  • the flow rate of the WF 6 is adjusted to 10 sccm by the flow controller, and the flow rate of the SiH 4 is 100 sccm.
  • the flow ratio of WF 6 to SiH 4 was 1:10.
  • the time for chemical vapor deposition is 10 s.
  • Si and WF 6 of the first silicon atomic layer undergo a displacement reaction to form W, WF 6 and SiH 4 react to form W, and W formed by the two reactions forms a W nuclear film.
  • SiH flow rate adjusted by the flow controller 4 is 70 sccm, SiH 4 and evenly distributed from the decomposition reaction occurs in the process chamber, the process chamber by adjusting the throttle valve of the internal chamber
  • the pressure is 30 Torr.
  • the temperature of the chemical vapor deposition was 390 °C.
  • the time for chemical vapor deposition is 30 s.
  • the filling gas pressure is helium gas, and the flow rate of helium gas is 10000 sccm.
  • a second layer of silicon atoms is formed on the surface of the W core film.
  • the set temperature was 390 ° C
  • the internal pressure of the process chamber was 30 Torr
  • WF 6 and H 2 were introduced into the process chamber for chemical vapor deposition.
  • the flow rate of the WF 6 was adjusted to 10 sccm by the flow controller, and the flow rate of the H 2 was 250 sccm.
  • the flow ratio of WF 6 and H 2 is 1:25.
  • the time for chemical vapor deposition is 10 s.
  • Si and WF 6 of the second silicon atomic layer undergo a displacement reaction to form W, and WF 6 and H 2 react to form W, and W in the above two reactions and W in the W core film together form a W film.
  • a wafer on which a W film is deposited is obtained.
  • the silicon wafer is uniformly heated by a back pressure adsorption on the surface of the electric resistance heater.
  • SiH flow rate adjusted by the flow controller 4 is 100 sccm, SiH 4 and evenly distributed from the decomposition reaction occurs in the process chamber, the process chamber by adjusting the throttle valve of the internal chamber
  • the pressure is 40 Torr.
  • the temperature of the chemical vapor deposition may be 430 °C.
  • the time for chemical vapor deposition is 10 s.
  • the filling gas pressure is helium gas, and the helium gas flow rate is 7000 sccm.
  • a first silicon atomic layer is formed on the surface of the silicon wafer.
  • the set temperature was 430 ° C
  • the internal pressure of the process chamber was 40 Torr
  • WCl 6 and SiH 4 were introduced into the process chamber for chemical vapor deposition.
  • the flow rate of the WCl 6 was adjusted to 1 sccm by the flow controller, and the flow rate of the SiH 4 was 40 sccm.
  • the flow ratio of WCl 6 to SiH 4 was 1:40.
  • the time for chemical vapor deposition is 30 s.
  • a first layer of silicon atoms Si and WCl 6 by substitution reaction of W, WCl 6 and SiH 4 reacted W, generated by reaction of two nuclear membrane to form a W W.
  • SiH flow rate adjusted by the flow controller 4 is 100 sccm, SiH 4 and evenly distributed from the decomposition reaction occurs in the process chamber, the process chamber by adjusting the throttle valve of the internal chamber
  • the pressure is 40 Torr.
  • the temperature of the chemical vapor deposition may be 430 °C.
  • the time for chemical vapor deposition is 20 s.
  • the filling gas pressure is helium gas, and the flow rate of helium gas is 5000 sccm.
  • a second layer of silicon atoms is formed on the surface of the W core film.
  • the set temperature was 430 ° C
  • the internal pressure of the process chamber was 40 Torr
  • WCl 6 and H 2 were introduced into the process chamber for chemical vapor deposition.
  • the flow rate of the WCl 6 was adjusted to 1 sccm by the flow controller, and the flow rate of the H 2 was 60 sccm.
  • the flow ratio of WCl 6 to H 2 was 1:60.
  • the time for chemical vapor deposition is 30 s.
  • a second layer of silicon atoms Si and WCl 6 by substitution reaction of W, WCl 6 and H 2 reaction of W, W film is formed together with the generated two reactions in the nuclear membrane, and W W W.
  • a wafer on which a W film is deposited is obtained.
  • the silicon wafer is uniformly heated by a back pressure adsorption on the surface of the electric resistance heater.
  • SiH flow rate adjusted by the flow controller 4 is 80 sccm, SiH 4 and evenly distributed from the decomposition reaction occurs in the process chamber, the process chamber by adjusting the throttle valve of the internal chamber
  • the pressure is 50 Torr.
  • the temperature of the chemical vapor deposition may be 400 °C.
  • the time for chemical vapor deposition is 30 s.
  • the filling gas pressure is helium gas, and the flow rate of helium gas is 10000 sccm.
  • a first silicon atomic layer is formed on the surface of the silicon wafer.
  • the set temperature is 400 ° C
  • the internal pressure of the process chamber is 50 Torr
  • W (CO) 6 and SiH 4 are introduced into the process chamber for chemical vapor deposition.
  • the flow rate of W(CO) 6 was adjusted to 5 sccm by the flow controller, and the flow rate of SiH 4 was 80 sccm.
  • the flow ratio of W(CO) 6 to SiH 4 was 1:16.
  • the time for chemical vapor deposition is 20 s.
  • a first layer of silicon atoms Si and W (CO) 6 by substitution reaction of W, W (CO) 6 and SiH 4 reacted W, reaction of two nuclear membrane to form a W W.
  • SiH flow rate adjusted by the flow controller 4 is 40 sccm, SiH 4 and evenly distributed from the decomposition reaction occurs in the process chamber, the process chamber by adjusting the throttle valve of the internal chamber
  • the pressure is 50 Torr.
  • the temperature of the chemical vapor deposition may be 390 °C.
  • the time for chemical vapor deposition is 10 s.
  • the filling gas pressure is helium gas, and the helium gas flow rate is 7000 sccm.
  • a second layer of silicon atoms is formed on the surface of the W core film.
  • the set temperature was 400 ° C
  • the internal pressure of the process chamber was 50 Torr
  • W (CO) 6 and H 2 were introduced into the process chamber for chemical vapor deposition.
  • the flow rate of W(CO) 6 was adjusted to 8 sccm by the flow controller, and the flow rate of H 2 was 400 sccm.
  • the flow ratio of W(CO) 6 and H 2 was 1:50.
  • the time for chemical vapor deposition was 15 s.
  • a second layer of silicon atoms Si and W (CO) 6 by substitution reaction of W, W (CO) 6 and H 2 reaction of W, generated by the reaction of the two nuclear membranes of W and W W W film is formed together.
  • a wafer on which a W film is deposited is obtained.

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Abstract

一种钨膜的沉积方法，包括以下步骤：提供基底；以硅的气态化合物作为气源进行化学气相沉积，形成沉积在基底上的第一硅原子层；以钨的气态化合物和硅的气态化合物作为气源进行化学气相沉积，形成沉积在基底上的钨核膜；以硅的气态化合物作为气源进行化学气相沉积，形成沉积在钨核膜上的第二硅原子层；以钨的气态化合物和氢气作为气源进行化学气相沉积，形成沉积在基底上的钨膜。

Description

钨膜的沉积方法 技术领域：
本发明涉及化学气相沉积领域，特别是涉及一种钨膜的沉积方法。
背景技术：
化学气相沉积(Chemical Vapor Deposition，CVD)是通过气体的化学反应，在硅片表面沉积一层固体膜的工艺。钨化学气相沉积(WCVD)工艺因其优异的空隙填充能力成为铝工艺通孔和接触的主要金属化技术。
WCVD前，一般在会硅片表面沉积一层粘着层(Ti层)和一层阻挡层(TiN层)。然而，硅片表面的粘着层和阻挡层层存在较薄弱的区域，经过快速热退火(Rapid Thermal Annealing，RTA)后，这种薄弱被放大。WCVD沉积时，WF6沿着比较薄弱的地方扩散与Ti结合，发生化学反应，产生气态的TiFx物向外逸出，导致钨薄膜沉积形成火山喷发状(Volcano)，导致钨薄膜异常。
发明内容：
基于此，有必要提供一种能够减少钨膜沉积时形成火山喷发状的钨膜的沉积方法。
一种钨膜的沉积方法，包括以下步骤：
提供基底；
以硅的气态化合物作为气源进行化学气相沉积，形成沉积在所述基底上的第一硅原子层；
以钨的气态化合物和所述硅的气态化合物作为气源进行化学气相沉积，形成沉积在所述基底上的钨核膜；
以所述硅的气态化合物作为气源进行化学气相沉积，形成沉积在所述钨 核膜上的第二硅原子层；
以所述钨的气态化合物和氢气作为气源进行化学气相沉积，形成沉积在所述基底上的钨膜。
上述钨膜的沉积方法，以硅的气态化合物作为气源进行化学气相沉积，形成沉积在所述钨核膜上的第二硅原子层，从而使钨的气态化合物到达基底表面时能够和第二硅原子层的硅发生置换反应生成钨，因此可以修复钨核膜薄弱的地区，从而阻挡钨的气态化合物向下扩散，减少钨的气态化合物与钛发生化学反应生成气态物质，和传统的钨化学气相沉积方法相比，上述钨膜的沉积方法减少了钨膜沉积形成火山喷发状。
附图说明
图1为一实施方式的钨膜的沉积方法的流程图；
图2为如图1所示的钨膜的沉积方法处理晶圆后晶圆表面的结构变化示意图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。
请参考图1和图2，一实施方式的钨膜的沉积方法，包括以下步骤：
S10、提供基底10。
在钨化学气相沉积系统内，基底10由背压吸附在电阻加热器表面均匀加热。
基底10可以为硅片。
结合图2中的步骤(A)，基底10包括本体110以及沉积在本体110表面的保护层120。保护层120可以为Ti层和TiN层的复合层，Ti层和本体110接触。
S20、以硅的气态化合物作为气源进行化学气相沉积，形成沉积在基底10上的第一硅原子层20。
S20中，化学气相沉积的温度可以为390℃～430℃，压强可以为30Torr～50Torr。化学气相沉积的时间可以为10s～30s。硅的气态化合物的流量可以为40sccm～100sccm。填充气压气体为氦气(He)，氦气的流量为5000sccm～10000sccm。
结合图2中的步骤(B)，将基底10经过S20处理后，硅的气态化合物分解生成Si。Si吸附在基底10表面，形成第一硅原子层20。
硅的气态化合物可以为硅甲烷(SiH4)。
硅的气态化合物为SiH4时，化学气相沉积的反应方程式如下：
SiH4→Si+2H2。
SiH4自分解为Si和H2。Si吸附在基底10表面，形成第一硅原子层20。
S30、以钨的气态化合物和硅的气态化合物作为气源进行化学气相沉积，形成沉积在基底10上的钨核膜30。
S30中，化学气相沉积的温度可以为390℃～430℃，压强可以为30Torr～50Torr。化学气相沉积的时间可以为10s～30s。钨的气态化合物和硅的气态化合物的流量比可以为1∶10～40。钨的气态化合物的流量为1sccm～10sccm，硅的气态化合物的流量为40sccm～100sccm。
钨的气态化合物可以为六氟化钨(WF6)、六氯化钨(WCl6)或羰基钨(W(CO)6)等。
硅的气态化合物可以为硅甲烷(SiH4)。
钨的气态化合物和第一硅原子层的硅发生置换反应生成钨。同时，钨的气态化合物和硅的气态化合物反应也生成钨。
钨的气态化合物和第一硅原子层的硅发生置换反应生成的钨以及钨的气 态化合物和硅的气态化合物反应生成的钨一起形成沉积在基底上的钨核膜。
下面以钨的气态化合物为WF6，硅的气态化合物为SiH4为例进行说明。WF6和SiH4进行化学气相沉积的反应方程式如下：
2WF6+3SiH4→2W+3SiF4+6H2
WF6+Si→W+SiF4
WF6和第一硅原子层20的Si发生置换反应生成W。WF6和SiH4发生反应生成W。上述两个反应生成的W形成沉积在基底10上的W核膜30。
结合图2中的步骤(C)，将如步骤(B)所示的晶圆进行S30处理后，保护层120上沉积有一层W核膜30。
S40、以硅的气态化合物作为气源进行化学气相沉积，形成沉积在钨核膜30上的第二硅原子层40。
S40中，化学气相沉积的温度可以为390℃～430℃，压强可以为30Torr～50Torr。化学气相沉积的时间可以为10s～30s。硅的气态化合物的流量可以为40sccm～100sccm。填充气压气体为氦气(He)，氦气的流量为5000sccm～10000sccm。
硅的气态化合物可以为硅甲烷(SiH4)。
硅的气态化合物分解生成Si。Si吸附在W核膜30表面，形成第二硅原子层40，能够有效阻挡钨的气态化合物向基底10内部扩散。
硅的气态化合物为SiH4时，化学气相沉积的反应方程式如下：
SiH4→Si+2H2
SiH4自分解为Si和H2。Si吸附在W核膜30表面，形成第二硅原子层40，能够有效阻挡WF6向基底10内部扩散。
结合图2中的步骤(D)，将如步骤(C)所示的晶圆进行S40处理后，W核膜30上形成有一层第二硅原子层40。
S50、以钨的气态化合物和氢气作为气源进行化学气相沉积，形成沉积在基底10上的钨膜50。
S50中，化学气相沉积的温度可以为390℃～430℃，压强可以为 30Torr～50Torr。化学气相沉积的时间可以为10s～30s。钨的气态化合物的流量为1sccm～10sccm。氢气的流量为80sccm～250sccm。钨的气态化合物和氢气的流量比可以为1∶25～60。
钨的气态化合物与第二硅原子层的硅发生置换反应生成钨。钨的气态化合物和氢气反应生成钨。
钨的气态化合物与第二硅原子层的硅发生置换反应生成的钨、钨的气态化合物和氢气反应生成的钨以及钨核膜中的钨一起形成沉积在基底上的钨膜。
钨的气态化合物与第二硅原子层的硅反应生成的W能够阻挡后续钨的气态化合物沿W核膜30的薄弱区域向下扩散，减少W膜50沉积形成火山喷发状。
由于第二硅原子层40的Si原子的还原性比H2强，钨的气态化合物到达基底10表面还未与H2发生反应时，钨的气态化合物先与第二硅原子层的硅反应生成W。
钨的气态化合物以WF6为例，WF6和H2进行化学气相沉积的化学反应方程式如下：
WF6+3H2→W+6HF
由于第二硅原子层40的Si原子的还原性比H2强，所以WF6到达基底10表面还未与H2发生反应时，WF6优先与W核膜30表面的第二硅原子层40的Si发生置换反应生成硅，并阻挡后续WF6沿W核膜30的薄弱区域向下扩散，减少W膜50沉积形成火山喷发状。之后，WF6和H2反应生成W。上述两个反应生成的W和W核膜30中的W形成W膜50。
结合图2中的步骤(E)，将如步骤(D)所示的晶圆进行S50处理后，保护层120上形成有一层W膜50。
上述钨膜的沉积方法，以硅的气态化合物作为气源进行化学气相沉积，形成沉积在钨核膜上的第二硅原子层，从而使钨的气态化合物到达基底表面时能够和第二硅原子层的硅发生置换反应生成钨，因此可以修复钨核膜薄弱 的地区，从而阻挡钨的气态化合物向下扩散，减少钨的气态化合物与钛发生化学反应生成气态物质，和传统的钨化学气相沉积方法相比，上述钨膜的沉积方法减少了钨膜沉积形成火山喷发状。
下面为具体实施例部分。
实施例1
在钨化学气相沉积系统内，硅片由背压吸附在电阻加热器表面均匀加热。
往工艺腔体内通入SiH4进行化学气相沉积，用流量控制器调节SiH4的流量为40sccm，SiH4在工艺腔体均匀分布并发生自分解反应，通过节流阀调节工艺腔腔体的内部压强为30Torr。化学气相沉积的温度为390℃。化学气相沉积的时间为15s。填充气压气体为氦气，氦气的流量为5000sccm。在硅片表面形成第一硅原子层。
设定温度为390℃，工艺腔腔体的内部压强为30Torr，往工艺腔体内通入WF6和SiH4进行化学气相沉积。通过流量控制器分别调节WF6的流量为10sccm，SiH4的流量为100sccm。WF6和SiH4的流量比为1∶10。化学气相沉积的时间为10s。第一硅原子层的Si和WF6发生置换反应生成W，WF6和SiH4反应生成W，两个反应生成的W形成W核膜。
往工艺腔体内通入SiH4进行化学气相沉积，用流量控制器调节SiH4的流量为70sccm，SiH4在工艺腔体均匀分布并发生自分解反应，通过节流阀调节工艺腔腔体的内部压强为30Torr。化学气相沉积的温度为390℃。化学气相沉积的时间为30s。填充气压气体为氦气，氦气的流量为10000sccm。在W核膜表面形成第二硅原子层。
设定温度为390℃，工艺腔腔体的内部压强为30Torr，往工艺腔体内通入WF6和H2进行化学气相沉积。通过流量控制器分别调节WF6的流量为10sccm，H2的流量为250sccm。WF6和H2的流量比为1∶25。化学气相沉积的时间为10s。第二硅原子层的Si和WF6发生置换反应生成W，WF6和H2反应生成W，上述两个反应生成的W和W核膜中的W一起形成W膜。得到沉积有W膜的晶圆。
实施例2
在钨化学气相沉积系统内，硅片由背压吸附在电阻加热器表面均匀加热。
往工艺腔体内通入SiH4进行化学气相沉积，用流量控制器调节SiH4的流量为100sccm，SiH4在工艺腔体均匀分布并发生自分解反应，通过节流阀调节工艺腔腔体的内部压强为40Torr。化学气相沉积的温度可以为430℃。化学气相沉积的时间为10s。填充气压气体为氦气，氦气的流量为7000sccm。在硅片表面形成第一硅原子层。
设定温度为430℃，工艺腔腔体的内部压强为40Torr，往工艺腔体内通入WCl6和SiH4进行化学气相沉积。通过流量控制器分别调节WCl6的流量为1sccm，SiH4的流量为40sccm。WCl6和SiH4的流量比为1∶40。化学气相沉积的时间为30s。第一硅原子层的Si和WCl6发生置换反应生成W，WCl6和SiH4反应生成W，两个反应生成的W形成W核膜。
往工艺腔体内通入SiH4进行化学气相沉积，用流量控制器调节SiH4的流量为100sccm，SiH4在工艺腔体均匀分布并发生自分解反应，通过节流阀调节工艺腔腔体的内部压强为40Torr。化学气相沉积的温度可以为430℃。化学气相沉积的时间为20s。填充气压气体为氦气，氦气的流量为5000sccm。在W核膜表面形成第二硅原子层。
设定温度为430℃，工艺腔腔体的内部压强为40Torr，往工艺腔体内通入WCl6和H2进行化学气相沉积。通过流量控制器分别调节WCl6的流量为1sccm，，H2的流量为60sccm。WCl6和H2的流量比为1∶60。化学气相沉积的时间为30s。第二硅原子层的Si和WCl6发生置换反应生成W，WCl6和H2反应生成W，上述两个反应生成的W和W核膜中的W一起形成W膜。得到沉积有W膜的晶圆。
实施例3
在钨化学气相沉积系统内，硅片由背压吸附在电阻加热器表面均匀加热。
往工艺腔体内通入SiH4进行化学气相沉积，用流量控制器调节SiH4的流量为80sccm，SiH4在工艺腔体均匀分布并发生自分解反应，通过节流阀调节 工艺腔腔体的内部压强为50Torr。化学气相沉积的温度可以为400℃。化学气相沉积的时间为30s。填充气压气体为氦气，氦气的流量为10000sccm。在硅片表面形成第一硅原子层。
设定温度为400℃，工艺腔腔体的内部压强为50Torr，往工艺腔体内通入W(CO)6和SiH4进行化学气相沉积。通过流量控制器分别调节W(CO)6的流量为5sccm，SiH4的流量为80sccm。W(CO)6和SiH4的流量比为1∶16。化学气相沉积的时间为20s。第一硅原子层的Si和W(CO)6发生置换反应生成W，W(CO)6和SiH4反应生成W，两个反应生成的W形成W核膜。
往工艺腔体内通入SiH4进行化学气相沉积，用流量控制器调节SiH4的流量为40sccm，SiH4在工艺腔体均匀分布并发生自分解反应，通过节流阀调节工艺腔腔体的内部压强为50Torr。化学气相沉积的温度可以为390℃。化学气相沉积的时间为10s。填充气压气体为氦气，氦气的流量为7000sccm。在W核膜表面形成第二硅原子层。
设定温度为400℃，工艺腔腔体的内部压强为50Torr，往工艺腔体内通入W(CO)6和H2进行化学气相沉积。通过流量控制器分别调节W(CO)6的流量为8sccm，H2的流量为400sccm。W(CO)6和H2的流量比为1∶50。化学气相沉积的时间为15s。第二硅原子层的Si和W(CO)6发生置换反应生成W，W(CO)6和H2反应生成W，上述两个反应生成的W和W核膜中的W一起形成W膜。得到沉积有W膜的晶圆。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种钨膜的沉积方法，包括以下步骤：
    提供基底；
    以硅的气态化合物作为气源进行化学气相沉积，形成沉积在所述基底上的第一硅原子层；
    以钨的气态化合物和所述硅的气态化合物作为气源进行化学气相沉积，形成沉积在所述基底上的钨核膜；
    以所述硅的气态化合物作为气源进行化学气相沉积，形成沉积在所述钨核膜上的第二硅原子层；及
    以所述钨的气态化合物和氢气作为气源进行化学气相沉积，形成沉积在所述基底上的钨膜。
  2. 根据权利要求1所述的方法，其特征在于，所述硅的气态化合物为硅甲烷。
  3. 根据权利要求1中所述的方法，其特征在于，所述钨的气态化合物为六氟化钨、六氯化钨或羰基钨。
  4. 根据权利要求1～3中任一项所述的方法，其特征在于，所述形成沉积在所述基底上的第一硅原子层的操作中，所述硅的气态化合物的流量为40sccm～100sccm，反应的温度为390℃～430℃，压强为30Torr～50Torr。
  5. 根据权利要求1～3中任一项所述的方法，其特征在于，所述形成沉积在所述基底上的第一硅原子层的操作中，反应的时间为10s～30s。
  6. 根据权利要求1～3中任一项所述的方法，其特征在于，所述形成沉积在所述基底上的钨核膜的操作中，所述钨的气态化合物的流量为1sccm～10sccm，所述硅的气态化合物的流量为40sccm～100sccm，反应的温度为390℃～430℃，压强为30Torr～50Torr。
  7. 根据权利要求6所述的方法，其特征在于，所述形成沉积在所述基底上的钨核膜的操作中，所述钨的气态化合物和所述硅的气态化合物的流量比为1∶10～40。
  8. 根据权利要求1～3中任一项所述的方法，其特征在于，所述形成沉积在所述钨核膜上的第二硅原子层的操作中，所述硅的气态化合物的流量为40sccm～100sccm，反应的温度为390℃～430℃，压强为30Torr～50Torr。
  9. 根据权利要求1～3中任一项所述的方法，其特征在于，所述形成沉积在所述基底上的钨膜的操作中，所述钨的气态化合物的流量为1sccm～10sccm，所述氢气的流量为80sccm～250sccm，反应的温度为390℃～430℃，压强为30Torr～50Torr。
  10. 根据权利要求9所述的方法，其特征在于，所述形成沉积在所述基底上的钨膜的操作中，所述钨的气态化合物和所述氢气的流量比为1∶25～60。
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