TW201741484A - Method of forming Cu film - Google Patents

Method of forming Cu film Download PDF

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TW201741484A
TW201741484A TW106114912A TW106114912A TW201741484A TW 201741484 A TW201741484 A TW 201741484A TW 106114912 A TW106114912 A TW 106114912A TW 106114912 A TW106114912 A TW 106114912A TW 201741484 A TW201741484 A TW 201741484A
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film
degassing
temperature
forming
hydrogen
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TW106114912A
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TWI683919B (en
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原田雅通
猪狩晃
小風豊
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愛發科股份有限公司
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    • 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
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • 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
    • 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
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • 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
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H—ELECTRICITY
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    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]

Abstract

A method of implanting and forming a Cu film into a recess with a liner film interposed therebetween is provided. The recess is formed in an interlayer insulating film. The method includes: heat-treating the liner film after film formation; after the heat-treatment is carried out, causing a surface of the liner film to be subjected to a degassing treatment under a gas atmosphere including hydrogen; and after the degassing treatment is carried out, forming a Cu film on the post-heat treated liner film. The liner film is one selected from the group consisting of a Co film, a Ni film, and a CoNi film.

Description

Cu膜之形成方法Method for forming Cu film

本發明係關於一種於襯膜上形成Cu膜之方法。更詳細而言，係關於一種於Cu配線構造中於襯膜上形成Cu膜時所利用之方法。The present invention relates to a method of forming a Cu film on a liner film. More specifically, it relates to a method used in forming a Cu film on a liner film in a Cu wiring structure.

於半導體器件中，多使用將Cu用作導電材料之Cu配線構造。於此種Cu配線構造中，使用乾式法或濕式法於形成於層間絕緣膜1之凹部(孔洞或溝槽等)1a內埋入形成Cu配線層4。於層間絕緣膜1與Cu配線層4之間，設置有用以防止Cu向層間絕緣膜1擴散之障壁層(Ta系或Ti系)2、及形成於障壁層2上且成為Cu配線層4之基底之襯膜(Co或Ru)3(圖15A)。此種襯膜3係藉由PVD(Physical Vapor Deposition，物理氣相沈積)法或CVD(Chemical Vapor Deposition，化學氣相沈積)法而形成。 作為襯膜3，隨著半導體器件之速度及功能之改良，要求形態良好、對障壁層2之密接性優異且襯膜3本身電阻低之構件。又，對半導體器件要求低成本化，對襯膜3之構件亦要求低成本化。根據此種觀點，有望將Co作為襯膜3(例如，參照國際公開第2011/027835號公報)。 通常，為了作為襯膜3發揮功能，例如對藉由CVD法成膜之後之Co膜，為了自Co膜內去除雜質(C、N、O等)而實現Co膜之低電阻化，會進行如圖15A所示般之後退火處理(例如，參照日本專利特開2012-023152號公報)。其後，於處於經冷卻之狀態之Co膜上，例如藉由PVD法形成成為配線層4之Cu膜(圖15B)。繼而，藉由進行回焊處理而埋設內壁被Cu膜覆蓋之凹部4H，並且實現表面平坦化。然而，隨著凹部4H之開口直徑變窄、凹部4H之深度變深，有難以藉由回焊之Cu而穩定地填充凹部4H內之傾向，有於凹部4H內偶發性地產生孔隙(空隙)4V之虞(圖15C)。圖16係表示此種先前之製造流程圖之一例之圖。 若於Cu配線層4內存在孔隙4V，則會成為阻礙於Cu配線層4流動之電流之因素，而使信號傳輸或電力供給變得不穩定，因此，期待開發能夠穩定地形成不存在孔隙4V之Cu配線層4之製造方法。In a semiconductor device, a Cu wiring structure in which Cu is used as a conductive material is often used. In such a Cu wiring structure, the Cu wiring layer 4 is buried in a recess (a hole or a trench, etc.) 1a formed in the interlayer insulating film 1 by a dry method or a wet method. Between the interlayer insulating film 1 and the Cu wiring layer 4, a barrier layer (Ta-based or Ti-based) 2 for preventing Cu from diffusing into the interlayer insulating film 1 and a barrier layer 2 formed on the barrier layer 2 and serving as the Cu wiring layer 4 are provided. Substrate liner (Co or Ru) 3 (Fig. 15A). Such a liner 3 is formed by a PVD (Physical Vapor Deposition) method or a CVD (Chemical Vapor Deposition) method. As the lining film 3, as the speed and function of the semiconductor device are improved, a member having a good shape, excellent adhesion to the barrier layer 2, and low resistance of the lining film 3 itself is required. Further, the semiconductor device is required to be reduced in cost, and the member of the liner film 3 is also required to be reduced in cost. From this point of view, it is expected that Co is used as the backing film 3 (for example, refer to International Publication No. 2011/027835). In order to function as the lining film 3, for example, the Co film formed by the CVD method is used to remove the impurities (C, N, O, etc.) from the Co film to reduce the resistance of the Co film. The post-annealing treatment is shown in Fig. 15A (for example, refer to Japanese Laid-Open Patent Publication No. 2012-023152). Thereafter, a Cu film to be the wiring layer 4 is formed on the Co film in a cooled state, for example, by a PVD method (FIG. 15B). Then, the recessed portion 4H whose inner wall is covered with the Cu film is buried by performing the reflow process, and surface flattening is achieved. However, as the opening diameter of the concave portion 4H is narrowed and the depth of the concave portion 4H is deepened, there is a tendency that it is difficult to stably fill the inside of the concave portion 4H by reflowing Cu, and voids (voids) are occasionally generated in the concave portion 4H. After 4V (Figure 15C). Fig. 16 is a view showing an example of such a prior art manufacturing flow chart. When a hole of 4 V is present in the Cu wiring layer 4, the current flowing through the Cu wiring layer 4 is hindered, and signal transmission or power supply is unstable. Therefore, it is expected that the formation of the void 4V can be stably formed. A method of manufacturing the Cu wiring layer 4.

本發明係鑒於此種先前之實際情況而完成者，其目的在於提供一種Cu膜之形成方法，該Cu膜之形成方法能夠於在形成於層間絕緣膜之凹部內介隔襯膜埋入形成Cu配線層時，抑制Cu配線層內產生孔隙。 為了解決上述問題，本發明之一態樣之Cu膜之形成方法係於形成於層間絕緣膜之凹部內介隔襯膜埋入形成Cu膜之方法，且對成膜後之上述襯膜進行熱處理(後退火步驟)，進行上述熱處理之後，於包含氫之氣體環境下對上述襯膜之表面進行脫氣處理(改質步驟)，進行上述脫氣處理之後，於經上述熱處理之上述襯膜上形成Cu膜(成膜步驟)，上述襯膜係選自Co膜、Ni膜、CoNi膜中之一者。 於本發明之一態樣之Cu膜之形成方法中，上述脫氣處理亦可藉由氫還原使上述Co膜之表面成為以氫為終端之狀態。 於本發明之一態樣之Cu膜之形成方法中，上述脫氣處理之溫度亦可低於上述熱處理之溫度。 於本發明之一態樣之Cu膜之形成方法中，上述脫氣處理之溫度亦可為260℃以上且290℃以下。 於本發明之一態樣之Cu膜之形成方法中，亦可於進行上述熱處理之後，將上述Co膜暴露於大氣中，其後，進行上述脫氣處理(暴露步驟)。即，亦可於後退火步驟與脫氣處理(改質步驟)之間將上述Co膜暴露於大氣中。 [發明之效果] 本發明之一態樣之Cu膜之形成方法於在形成於層間絕緣膜之凹部內介隔Co膜埋入形成Cu膜時，於Co膜之後退火步驟與Cu膜之成膜步驟之間，進行對Co膜之表面進行脫氣處理之改質步驟。上述脫氣處理係於包含氫之氣體環境下進行。 根據該脫氣處理，藉由H2 還原而自Co膜之表面去除OH基或氧，Co膜之表面成為大致以氫為終端(吸附氫)之狀態。認為藉由以此方式使Co膜之表面以氫為終端(吸附氫)，而使沈積於其上之Cu膜之濡濕角θ變小。其結果，能夠藉由對Cu膜進行回焊而於形成於層間絕緣膜之凹部內介隔Co膜埋入形成Cu膜。 因此，本發明之一態樣有助於提供一種Cu膜之形成方法，其能夠抑制埋入形成Cu膜時之問題即Cu配線層內產生孔隙。The present invention has been made in view of such a prior art, and an object thereof is to provide a method for forming a Cu film which can be formed by interposing a liner film in a recess formed in an interlayer insulating film to form Cu. In the case of the wiring layer, generation of voids in the Cu wiring layer is suppressed. In order to solve the above problems, a method for forming a Cu film according to an aspect of the present invention is a method of forming a Cu film by interposing a liner film in a recess formed in an interlayer insulating film, and heat-treating the film after the film formation. (post-annealing step), after performing the above heat treatment, degassing (reforming step) the surface of the liner film in a gas atmosphere containing hydrogen, performing the above-described degassing treatment, and then applying the heat treatment to the liner film A Cu film (film formation step) is formed, and the liner film is selected from one of a Co film, a Ni film, and a CoNi film. In the method for forming a Cu film according to an aspect of the present invention, the degassing treatment may be such that the surface of the Co film is terminated by hydrogen by hydrogen reduction. In the method for forming a Cu film according to an aspect of the present invention, the temperature of the degassing treatment may be lower than the temperature of the heat treatment. In the method for forming a Cu film according to an aspect of the present invention, the temperature of the degassing treatment may be 260 ° C or higher and 290 ° C or lower. In the method for forming a Cu film according to an aspect of the present invention, after the heat treatment, the Co film may be exposed to the atmosphere, and then the degassing treatment (exposure step) may be performed. That is, the Co film may be exposed to the atmosphere between the post annealing step and the degassing treatment (modification step). [Effects of the Invention] The method for forming a Cu film according to an aspect of the present invention is to form a Cu film by interposing a Co film in a recess formed in the interlayer insulating film, and to form a film after the Co film is annealed and the Cu film is formed. Between the steps, a modification step of degassing the surface of the Co film is performed. The above degassing treatment is carried out in a gas atmosphere containing hydrogen. According to this degassing treatment, the OH group or oxygen is removed from the surface of the Co film by H 2 reduction, and the surface of the Co film is in a state of substantially hydrogen (end of hydrogen). It is considered that the surface of the Co film is terminated with hydrogen (hydrogen adsorption) in this manner, and the wet angle θ of the Cu film deposited thereon is made small. As a result, a Cu film can be formed by interposing a Co film in a recess formed in the interlayer insulating film by reflowing the Cu film. Therefore, an aspect of the present invention contributes to providing a method of forming a Cu film capable of suppressing generation of voids in a Cu wiring layer, which is a problem in embedding a Cu film.

以下，基於圖式對本發明之一實施形態之Cu膜之形成方法進行說明。此處，對襯膜包含Co膜之情形進行詳細說明。 圖1A～圖1D係表示本發明之一實施形態之Cu膜之形成方法之一例之模式剖視圖。如圖1A～圖1D所示，本發明之一實施形態之Cu膜之形成方法，可較佳地用作於形成於層間絕緣膜1上之凹部(孔洞或溝槽等)1a內介隔Co膜3埋入形成Cu配線層4(Cu膜)之方法。以下詳細說明之Cu膜之形成方法亦能夠用於與圖1A～圖1D相比Cu配線層非常厚之情形(圖2A～圖2D)。 該方法係用作例如構成圖6之流程圖所示之Cu配線膜形成製程之部分之步驟。將於下文中對圖6之流程圖所示之一連串之步驟及圖7所示之製造裝置一起進行說明。 於本發明之一實施形態之Cu膜之形成方法中，於層間絕緣膜1與Cu配線層4之間，設置有用以防止Cu向層間絕緣膜1擴散之障壁層(Ta或Ti系)2、及形成於障壁層2上且成為Cu配線層4之基底之襯膜(Co)3。 本發明之一實施形態特別包含對成膜後之Co膜3進行熱處理之後退火步驟S6、及於經過該後退火步驟S6之Co膜3上形成Cu配線層4之成膜步驟S10，且具有於後退火步驟S6與形成Cu配線層4之成膜步驟S10之間對Co膜4的表面進行脫氣處理之改質步驟S8。 後退火步驟S6係自成膜後之Co膜3之表面或內部向Co膜3之外部熱去除雜質(碳(C)、氮(N)、氧(O)等)而實現Co膜3的低電阻化之步驟。作為後退火步驟S6之具代表性之條件，可列舉製程溫度為260℃～380℃、製程氣體為NH3 與H2 之混合氣體、製程壓力為390 Pa、製程時間為120 sec。 於本發明之一實施形態中，對經過後退火步驟S6之Co膜3進行改質步驟S8之脫氣處理。再者，於後退火步驟S6與改質步驟S8之間，亦可視需要進行作為冷卻步驟之一例之例如空氣破壞(暴露於大氣中)。將於下文中對詳細內容進行說明。 藉由實施該脫氣處理，利用H2 還原自Co膜之表面去除OH基或氧，Co膜之表面成為大致以氫為終端(吸附氫)之狀態。因此，於本發明之一實施形態中，將脫氣處理亦稱為「H2 吸附處理」。 作為H2 吸附處理之具代表性之條件，可列舉製程溫度為RT(室溫)～300℃、製程氣體為包含氫(H)之氣體、製程壓力自10 Pa至1000 Pa、製程時間為120 sec。此處，所謂「包含氫(H)之氣體」，並不限定於僅由氫氣構成之氣體。代替此，例如亦可使用包含惰性氣體(例如，He氣體)及氫氣之混合氣體或藉由遠距電漿法或CAT(catalase，過氧化氫酶)法等產生之氫自由基。 圖1B表示藉由脫氣處理利用H2 還原自Co膜之表面去除OH基或氧而Co膜之表面大致以氫為終端(吸附氫)之狀態。於Co膜3之表面所示之「中空之○記號」表示所吸附之氫。於圖3A、圖3B及圖4A～圖4C中分別詳細地示出該脫氣處理前之狀態、處理中之狀態、處理後之狀態。 圖3A及圖3B係說明氫氣(H2 )脫氣效果與處理溫度之關係之圖，且圖3A表示脫氣處理前之狀態，圖3B表示脫氣處理中之狀態。圖4A～圖4C係說明氫氣(H2 )脫氣效果與處理溫度之關係之圖，且圖4A表示低溫處理後之狀態，圖4B表示中溫處理後之狀態，圖4C表示高溫處理後之狀態。 如圖3A所示，表示脫氣處理前之Co膜3之表面處於被氧或OH基覆蓋之狀態。圖3B表示正在對圖3A所示之Co膜3之表面使用包含氫氣(H2 )之氣體進行脫氣處理之狀態。覆蓋Co膜3之表面之氧或OH基藉由氫氣(H2 )而成為水(H2 O)並自Co膜3之表面脫離。 即，如圖4A～圖4C所示，根據上述脫氣處理，能夠藉由H2 還原而自Co膜之表面去除OH基或氧，使Co膜之表面成為大致以氫為終端(吸附氫)之狀態。但是，根據脫氣處理之溫度條件，該脫氣處理之作用、效果會發生變化。以下，按脫氣處理之每一溫度條件進行詳細說明。 圖4A表示低溫處理(200℃以上且未達260℃)之情形。於該情形時，雖然產生氫氣(H2 )還原，但氫氣(H2 )還原處於不充分之狀況。因此，處於在Co膜之表面殘存有未被去除之OH基或氧之狀態。 圖4B表示中溫處理(260℃以上且未達290℃)之情形。於該情形時，於Co膜之表面幾乎未殘存OH基或氧，Co膜之表面成為大致遍及全域被氫氣(H2 )還原之狀態。因此，氫終端之密度顯示出最大。 圖4C表示高溫處理(320℃以上)之情形。於該情形時，於Co膜之表面完全未殘存OH基或氧。Co膜之表面成為被氫氣(H2 )還原之狀態，但氫氣(H2 )亦開始脫離，氫終端之密度降低。 圖5係說明Cu膜表面之氫終端(氫吸附)與濡濕角之關係之圖。於圖5中，符號2為TaN膜，符號3為Co膜、符號4為經回焊之Cu。 於上述中溫處理(260℃以上且未達290℃)之情形(圖4B)時，Co膜表面以氫為終端(吸附氫)。藉此，形成於Co膜表面之上且成為熱熔融之狀態之Cu膜的相對於Co膜表面之濡濕角θ變小。 由以下之Young式表示該情況。此處，YS 係Co膜之表面張力，YL 係Cu膜之表面張力，YLS 係Cu膜與Co膜之界面之表面張力。 (數1)根據該式，可知為了減小濡濕角θ，要減小YL 或增大(YS -YLS )。Cu膜之表面張力YL 係由溫度決定，與Co膜之表面狀態無關，因此，不會因Co表面之氫終端而發生變化。 另一方面，由於YS 、YLS 均為受Co表面狀態影響之物理量，故而能夠容易推測會受到Co表面之氫終端之影響。因此，濡濕角θ變小之原因在於(YS -YLS )變大。 如此，Co膜之表面以氫為終端(吸附氫)，藉此，沈積於其上之Cu膜之濡濕角θ變小。本發明人等認為：其結果，能夠藉由對Cu膜進行回焊，而於形成於層間絕緣膜之凹部4H(圖1C、圖2C)內介隔Co膜埋入形成Cu膜。於圖1A～圖1D、圖2A～圖2D中，符號4C表示回焊後埋入Cu之部位。符號4A為回焊前之Cu膜。圖4B為回焊後之Cu膜。 因此，本發明之一實施形態有助於提供一種Cu膜之形成方法，其能夠抑制埋入形成Cu膜時之問題即Cu配線層內之孔隙之產生。 圖6係表示應用本發明之Cu配線膜形成製程之一例之流程圖。圖7係表示本發明之一實施形態之製造裝置之一例之圖。該製造裝置被設為能夠實施圖6之Cu配線膜形成製程之構成。 於圖6所示之例中，依序進行以下之S1～S13之步驟。但是，步驟S7係視需要設置之特殊之步驟。 S1係向裝入室C1之內部空間導入晶圓(被處理體)之步驟。 S2係於腔室C11中對晶圓進行熱處理而脫氣(脫氣體)之步驟。 S3係於腔室C7中將晶圓冷卻至較下一步驟之製程低之溫度之步驟。 S4係於腔室C10中於晶圓上形成TaN膜之步驟。 S5係於腔室C8中於TaN膜上形成Co膜之步驟。 S6係於腔室C3中對Co膜進行後退火之步驟。 S7係於腔室C2中將Co膜暴露於大氣中(空氣破壞)之步驟。 S8係於腔室C11中利用包含氫之氣體進行H2 吸附處理(脫氣)之步驟。 S9係於腔室C7中將晶圓冷卻至較下一步驟之製程低之溫度之步驟。 S10係於腔室C5中成膜Cu膜之步驟。 S11係於腔室C4中對Cu進行回焊之步驟。 S12係於腔室C7中為取出晶圓做準備而將晶圓冷卻之步驟。 S13係將晶圓自取出室C12之內部空間向裝置外部搬出之步驟。 藉由步驟S1向裝入室C1之內部導入晶圓(被處理體)，於步驟S2中，進行晶圓之脫氣體處理。其後，以低於下一步驟步驟S4之製程溫度將晶圓冷卻，為TaN膜之成膜做準備。 於步驟S4中，於將氧化矽膜(由SiO2 被覆之)晶圓用作基材並於其上形成TaN膜之情形時，較佳為使用例如以下所述之化學氣相沈積法(Chemical Vapor Deposition，CVD法)或原子層沈積法(Atomic Layer Deposition，ALD法)。 關於TaN膜，藉由CVD法或ALD法，使用例如有機系原料PDMAT(Ta(N(CH3 )2 )5 ，五(二甲氨基)鉭)或金屬鹵化物TaCl5 等作為原料，與H2 或NH3 或電漿化之H2 或NH3 熱反應，於成膜壓力數Pa～數十Pa、成膜溫度350℃之條件下，以1.5 nm～3.0 nm之厚度形成TaN膜。 此處，對於障壁膜為TaN膜之情形進行了詳細說明，但本發明之障壁膜並不限定於TaN膜。作為構成本發明之障壁膜之材料，除TaN以外，例如可列舉Ti、TiN、Ta、W、WN、及矽化物等。 於步驟S5中，於將TaN膜用作基材並於其上形成Co膜之情形時，較佳為使用例如以下所述之化學氣相沈積法(Chemical Vapor Deposition，CVD法)或原子層沈積法(Atomic Layer Deposition，ALD法)。 為了於作為障壁膜發揮功能之TaN膜上，將如2-烷基脒基鈷般之包含Co與烷基脒基(該烷基為乙基、丁基)之有機金屬材料還原而形成Co膜，使用還原氣體。作為此種還原氣體，使用選自作為公知之還原氣體之NH3 、N2 H4 、NH(CH3 )2 、N2 H3 CH、及N2 中之至少1種氣體、或將H2 氣體與上述還原氣體組合之氣體(其中，特佳為NH3 )。可將上述還原氣體供給至腔室內，使用CVD法或ALD法，於製程條件(例如，成膜壓力：50～1000 Pa；基材溫度(成膜溫度)：180～400℃、較佳為180～300℃、更佳為200～300℃；還原氣體(例如，NH3 等)之流量：100～1000 sccm)之下形成CVD(ALD)-Co膜。 藉此，使CVD-Co膜於TaN膜上沈積為1.5 nm～3.0 nm之厚度。藉由使用此種還原氣體，而可實現Co之成核時間之抑制或Co膜之沈積速度之控制、表面形態之改善、雜質濃度之抑制、低電阻化，而使於微細圖案中可於密接層、矽化物層、蓋層使用Co膜。作為包含上述烷基脒基鈷之有機金屬材料，例如可列舉Co(tBu-Et-Et-amd)2 。 Co膜之成膜法並不限定於CVD法，亦可採用PVD法。於採用PVD法之情形時，能夠於製程條件(成膜溫度：室溫；磁控濺鍍；DC功率：1000W；RF偏壓功率：100W；Ar：5 sccm；壓力：0.5 Pa等條件)下形成PVD-Co膜。 步驟S6係對步驟S5所形成之Co膜進行後退火之步驟。Co膜之後退火例如可於包含氨氣及氫氣之混合氣體環境中，換言之於還原氣體環境下以特定之溫度進行退火。藉此，能夠有效地去除所成膜之Co膜中之碳或氮等雜質，使Co膜本身低電阻化。又，可將Co膜表面中之碳之濃度抑制為較低。因此，藉由Cu配線構造之籽晶層之形成採用此種Co膜形成方法，而能夠提昇包含Co膜之籽晶層與障壁層之密接性。又，亦改善包含Co膜之籽晶層與Cu配線層之密接性。因此，亦與Co膜本身之低電阻化連動，而實現Cu配線之進一步低電阻化。 後退火時之溫度較佳為設定為高於Co膜之成膜時之溫度。藉由後退火時之溫度高於Co成膜時之溫度，而能夠於短時間內有效地去除Co膜中之雜質。後退火時之溫度較佳為250℃～350℃之範圍。若低於250℃，則無法充分地去除Co膜中之雜質，因此，無法獲得低電阻之Co膜。又，半導體器件之構造上、半導體器件之配線形成步驟中無法使用高於350℃之溫度。 於進行上述後退火之步驟中，可於僅包含氨氣及氫氣中任一者之氣體環境中進行退火。然而，於僅包含氨氣之情形時，未有效地去除Co膜中及Co膜表面之氮。又，於僅包含氫氣之情形時，不會有效地去除Co膜中及Co膜表面之碳。因此，後退火之步驟較佳為於包含氨氣及氫氣之兩者之氣體環境下進行。此時，後退火時之氫氣之分壓較佳為1～1000 Pa，更佳為100 Pa～1000 Pa。若氫氣之分壓偏離該範圍，則無法充分地去除雜質。 步驟S7係於腔室C2中將Co膜暴露於大氣中(空氣破壞)之步驟。此種將Co膜暴露於大氣中之步驟，即便存在於Co膜之成膜步驟與將於下文中進行說明之Cu膜之成膜步驟之間，只要Cu配線構造穩定地成立，則暴露於大氣中之步驟於量產面上極有效。例如，可使生產線於中途一端停止，對將處理之物品數量進行調整。即，可將製造步驟分為前步驟及後步驟進行管理，該前步驟進行自最初之步驟至Co膜之成膜步驟及後退火步驟之步驟，該後步驟包含Cu膜之成膜步驟。又，無需於真空原位(in-situ)下形成前步驟及後步驟，亦可導入前步驟或後步驟專用之製造裝置，亦可預料到製造裝置之小型化或佔據面積縮減等效果。 步驟S8係於腔室C11中利用包含氫之氣體進行H2 吸附處理(脫氣)之步驟。步驟S8係本發明之最特徵性之步驟，即，即便假設存在步驟S7(將Co膜暴露於大氣中(空氣破壞)之步驟)，亦會有效地有助於Cu配線構造穩定地成立。步驟S8不依賴於步驟S7之有無。如圖4A～圖4C所示，根據步驟S8之脫氣處理，能夠藉由H2 還原而自Co膜之表面去除OH基或氧，使Co膜之表面成為大致以氫為終端(氫吸附)之狀態。 此時，作為脫氣處理之溫度條件，如上所述，較佳為中溫處理(260℃以上且未達290℃)。於採用該溫度域之情形時，於Co膜之表面幾乎未殘存OH基或氧，Co膜之表面成為大致遍及全域被氫氣(H2 )還原之狀態。因此，氫終端之密度顯示出最大。如此Co膜之表面以氫為終端(氫吸附)，藉此，沈積於其上之Cu膜之濡濕角θ變小，因此，能夠藉由對Cu膜進行回焊而於形成於層間絕緣膜之凹部內介隔Co膜埋入形成Cu膜。 又，亦可於腔室內進行此種步驟S8中之脫氣處理及上述步驟S6中之熱處理。於該情形時，需要使脫氣處理之溫度低於後退火步驟之溫度。因此，作為晶圓加熱方法，較適宜為能夠使晶圓溫度升溫、降溫之利用紅外線燈或輻射等電磁波進行之加熱方式。 步驟S9係於腔室C7中將晶圓冷卻至較下一步驟之製程低之溫度之步驟。藉此，能夠於不依賴於前步驟之脫氣處理之溫度之情況下，以較佳之特定溫度進行下一步驟之Cu膜之成膜。 步驟S10係於腔室C5中成膜Cu膜之步驟。作為Cu膜之成膜法，例如可列舉CVD法或PVD法。於藉由CVD法形成Cu膜之情形時，例如，於成膜溫度200℃、成膜壓力500 Pa形成特定之膜厚即可。於藉由PVD法形成Cu膜之情形時，可於成膜溫度-20℃、成膜壓力0.5 Pa獲得特定之膜厚。此處，關於特定之膜厚，膜厚之最小值係埋入凹部所需之膜厚，膜厚之最大值根據所形成之Cu配線構造之條件而決定。Cu膜之成膜法並不限定於CVD法或PVD法，亦可視需要使用鍍覆等。 步驟S11係於腔室C4中對Cu進行回焊之步驟。於步驟S10中形成於在步驟S8中脫氣處理之Co膜上之Cu膜，於步驟S11中對該Cu膜進行回焊。藉此，能夠於不在凹部內產生空隙(孔隙)之情況下利用Cu膜埋入凹部內。如上所述，藉由脫氣處理，Co膜之表面成為以氫為終端(氫吸附)之狀態，藉此，沈積於其上之Cu膜之濡濕角θ變小。因此，其後，對Cu膜進行回焊，藉此，能夠實現於形成於層間絕緣膜之凹部內介隔Co膜穩定地埋入形成Cu膜。 步驟S12係於腔室C7中為取出晶圓做準備而將晶圓冷卻之步驟，步驟S13係將晶圓自取出室C12之內部空間向裝置外部搬出之步驟。 藉由經過此種一連串之步驟，而能夠提供一種可抑制Cu配線層內產生孔隙之Cu膜之形成方法。 圖7係表示本發明之一實施形態之製造裝置之一例之圖，可較佳地於進行上述一連串之步驟時使用。 圖7之製造裝置係安裝有複數個濺鍍模組等之集束型工具。於圖7中，C1係裝載室(搬入室)，C12係卸載室(搬出室)。藉由於大氣壓環境下設置之機器人31，作為被處理體之基板被搬入至裝載室C1及卸載室C12之中，或自裝載室C1及卸載室C12之中搬出。 裝載室C1及卸載室C12連接於第一搬送室FX及第二搬送室RX。搬送室FX、RX各自具備搬運基板之機器人32、33。2個搬送室FX、RX藉由中間室MX而連通。於第一搬送室FX，連接有6個腔室c1～c3、c10～c12。於第二搬送室RX，亦連接有6個腔室c4～c9。 於上述製造方法中，使用例如包含如下腔室之構成之製造裝置，即包含符號c2所表示之空氣破壞室、符號c3所表示之後退火室、符號c4所表示之回焊室、符號c5所表示之PVD-Cu成膜室、符號c7所表示之冷卻室、符號c8所表示之CVD-Co成膜室、符號c10所表示之PVD-TaN成膜室、及符號c11所表示之脫氣室。於在各室內進行各種處理時，以基板之上表面成為被處理面之方式進行配置。 例如，於上述製造方法中，於進行步驟S1～S13之情形時，依序實施c1→c11→c7→c10→c8→c3→(c2)→c11→c7→c5→c4→c7→c12，藉此，能夠提供一種本發明之一實施形態之Cu膜之形成方法。此處，本實施形態示出於各室內進行之各種處理之一例，但本發明並不限定於圖7所示之配置。 (實驗例1) 於本實驗例中，對Co膜之後退火溫度與填充(Filling)成功率之關係進行了研究。 圖8係表示後退火溫度與填充(Filling)成功率及比電阻之關係之曲線圖，符號◇記號表示填充(Filling)成功率，符號□記號表示比電阻。 圖9係表示後退火溫度與Co膜中之雜質濃度(O、C、N)之關係之曲線圖，符號□記號表示氧(O)，符號△記號表示碳(C)，符號◇記號表示氮(N)。 自圖8及圖9明確以下之方面。 (A1)伴隨後退火溫度之上升，Co膜之比電阻及Co膜所包含之雜質濃度(O、C、N)降低，膜質改善。 (A2)相對於此，伴隨後退火溫度之上升，填充(Filling)成功率(埋入率)降低。 根據以上之結果可知，僅藉由提高後退火溫度，難以應用於實際之配線形成步驟中。 (實驗例2) 於本實驗例中，改變Co膜之脫氣條件，對填充(Filling)成功率進行了研究。此時，準備人為地將Co膜之表面暴露於大氣中而得之試樣，對脫氣時之環境進行了調查。將其結果示於圖10。 圖10係表示脫氣時之環境與填充(Filling)成功率之關係之曲線圖。 於圖10之橫軸中，「high Vac」表示不供給H2 及He作為脫氣環境之真空狀態。「He 1000 sccm，57 Pa」表示將He氣體供給至腔室中作為脫氣環境之狀態。「H2 /He 500/1000 sccm，84 Pa」表示將氫氣與氦氣之混合氣體供給至腔室中作為脫氣環境之狀態。但是，於圖10中，脫氣處理時之基板溫度固定為260℃。 自圖10可明確以下之方面。 (B1)若將Co膜暴露於大氣中，則Co膜之表面被氧或OH基覆蓋。此後，於未供給H2 及He之真空狀態之情形(high Vac)時，填充(Filling)成功率成為10～20%，極低。 (B2)藉由將脫氣環境設為氦氣環境，而填充(Filling)成功率成為15～20%，雖然若干改善，但不實用。 (B3)藉由將脫氣環境設為氫氣與氦氣之混合氣體環境，而填充(Filling)成功率成為95～100%，能夠實現穩定之量產製程。不僅於基板(晶圓)之中央部(表示為「Center」)獲得實用之結果，於周緣部(表示為「Edge」)亦獲得實用之結果。 根據以上之結果可知，脫氣環境較佳為包含氫氣與氦氣之混合氣體。確認藉由採用此種脫氣環境，即便將Co膜暴露於大氣中，亦可獲得穩定之填充(Filling)成功率。 (實驗例3) 於本實驗例中，改變後退火溫度，對脫氣條件(真空排氣、He環境)與填充(Filling)成功率之關係進行了研究。此時，準備人為地將Co膜之表面暴露於大氣中而得之試樣，對脫氣條件進行了調查。將其結果示於圖11。 圖11係表示脫氣條件(真空排氣、H2 /He環境)與填充(Filling)成功率之關係之曲線圖。於圖11中，符號◇記號及符號□記號表示脫氣條件為氫氣與氦氣之混合氣體環境之情形。符號◇記號表示基板(晶圓)之中央部(表示為「Center」)之結果，符號□記號表示周緣部(表示為「Edge」)之結果。符號△記號表示於經真空排氣之狀態(不供給H2 及He之狀態)下進行脫氣之情形(high Vac)。 自圖11可明確以下之方面。 (C1)於在不供給H2 及He之狀態下進行脫氣之情形時，伴隨後退火溫度之上升，填充(Filling)成功率急遽減少。後退火溫度為320℃時，填充(Filling)成功率為數%，後退火溫度為350℃時，填充(Filling)成功率成為0%。 (C2)於在氫氣與氦氣之混合氣體環境下進行脫氣之情形時，即便後退火溫度為295℃，亦可獲得超過90%之填充(Filling)成功率。然而，若後退火溫度超過300℃，則填充(Filling)成功率急遽減少。後退火溫度為320℃時，填充(Filling)成功率減少為15～45%左右，後退火溫度為350℃時，填充(Filling)成功率減少為0～20%左右。 根據以上之結果，可知相較於「未供給氫氣及氦氣之狀態」，脫氣環境較佳為設為「氫氣與氦氣之混合氣體環境」。確認藉由採用此種脫氣環境，填充(Filling)成功率改善。 (實驗例4) 於本實驗例中，改變脫氣條件(H2 分壓)，對填充(Filling)成功率進行了研究。此時，準備人為地將Co膜之表面暴露於大氣中而得之試樣，對脫氣條件進行了調查。將其結果示於圖12。 圖12係表示脫氣條件(H2 分壓)與填充(Filling)成功率之關係之曲線圖。於圖12中，符號◇記號表示基板(晶圓)之中央部(表示為「Center」)之結果，符號□記號表示周緣部(表示為「Edge」)之結果。但是，脫氣溫度固定為260℃，後退火溫度固定為320℃。 自圖12可明確以下之方面。 (D1)伴隨氫氣(H2 )分壓之增加，填充(Filling)成功率急遽上升。即，回焊特性顯著改善。 (D2)由於嚴格之制約，圖12之曲線圖中填充(Filling)成功率之最高值成為80～90%，但只要能夠進一步增加氫氣(H2 )分壓，則填充(Filling)成功率會成為更高之數值。 根據以上之結果，確認脫氣環境較佳為設為「氫氣與氦氣之混合氣體」，於氫氣(H2 )分壓較高之情形時，會促進填充(Filling)成功率之改善效果。 (實驗例5) 於本實驗例中，改變脫氣溫度，對填充(Filling)成功率進行了研究。此時，準備人為地將Co膜之表面暴露於大氣中而得之試樣，對脫氣條件進行了調查。將其結果示於圖13。 圖13係表示脫氣條件(溫度)與填充(Filling)成功率之關係之曲線圖。於圖13中，符號◇記號表示基板(晶圓)之中央部(表示為「Center」)之結果，□記號表示周緣部(表示為「Edge」)之結果。但是，後退火溫度固定為320℃。 自圖13可明確以下之方面。 (E1)於脫氣溫度為260～290℃之範圍內，可獲得超過80%之填充(Filling)成功率。尤其是，於脫氣溫度為290℃之情形時，填充(Filling)成功率顯示出最大，於基板之中央部為100%，即便於基板之周緣部亦超過90%。 (E2)於脫氣溫度低於260℃之情形時，伴隨溫度之降低，填充(Filling)成功率急速減少。另一方面，於脫氣溫度高於290℃之情形時，伴隨溫度之上升，填充(Filling)成功率急速減少。尤其是，脫氣溫度為320℃時，填充(Filling)成功率變為0%。 根據以上之結果，確認：於後退火溫度為320℃之情形時，脫氣溫度較佳為260～290℃之範圍。脫氣溫度需要設定為低於後退火溫度。 圖14係表示應用本發明前後(亦稱為改善前後)之後退火溫度與填充(Filling)成功率及比電阻之關係之曲線圖。 於圖14中，符號◇記號及符號□記號係填充(Filling)成功率，符號◇記號表示改善前之結果，符號□記號表示改善後之結果。符號△記號係比電阻之結果。但是，Cu膜厚固定為20 nm。 自圖14可明確以下之方面。 (F1)伴隨後退火溫度之上升而Co膜之比電阻降低之傾向於改善前後未發生變化。 (F2)相對於此，填充(Filling)成功率於改善前後大幅變化。即，於改善前，伴隨後退火溫度之上升，填充(Filling)成功率銳減(符號◇記號)，相對於此，於改善後，填充(Filling)成功率能夠不受後退火溫度之上升之影響而維持100%。 根據以上之結果，確認根據本發明之一實施形態，能夠提供一種Cu膜之形成方法，其可於在形成於層間絕緣膜之凹部內介隔Co襯膜埋入形成Cu配線層時顯著地抑制Cu配線層內產生孔隙。 再者，亦確認即便使Cu膜厚度厚達80 nm，亦不會發生Cu自凹部之內部朝向外部往上吸引之情況(Cu被自凹部內部向Cu膜之厚膜部分拉伸之現象)，能夠向凹部內埋入Cu。因此，本發明之一實施形態之Cu膜之形成方法可廣範應用於各種Cu膜厚。 以上，對本發明之一實施形態之Cu膜之形成方法進行了說明，但本發明並不限定於此，可於不脫離發明之主旨之範圍內適當變更。 於上述各實驗例中，對襯膜包含Co膜之情形進行了詳細說明，但本發明之襯膜並不限定於Co膜。本發明之Cu膜之形成方法除Co膜以外，於使用Ni膜或CoNi膜之情形時亦可獲得相同之作用、效果。 又，H2 無論單獨使用，抑或與除He以外之N2 或Ar等惰性氣體一起導入，均可獲得相同之效果。 例如，於微細加工圖案中，能夠將Co膜或Ni膜、CoNi膜用作密接層、矽化物膜、蓋膜，因此，本發明可於半導體器件技術領域中使用。 [產業上之可利用性] 本發明之Cu膜之形成方法可廣泛用於半導體器件技術領域。Hereinafter, a method of forming a Cu film according to an embodiment of the present invention will be described based on the drawings. Here, the case where the liner film contains a Co film will be described in detail. 1A to 1D are schematic cross-sectional views showing an example of a method of forming a Cu film according to an embodiment of the present invention. As shown in FIG. 1A to FIG. 1D, a method for forming a Cu film according to an embodiment of the present invention can be preferably used for interposing Co in a recess (a hole or a groove, etc.) 1a formed on the interlayer insulating film 1. The film 3 is buried in a method of forming a Cu wiring layer 4 (Cu film). The method of forming the Cu film described in detail below can also be applied to a case where the Cu wiring layer is extremely thick compared to FIGS. 1A to 1D (FIGS. 2A to 2D). This method is used as, for example, a step of forming a part of the Cu wiring film forming process shown in the flowchart of Fig. 6. A series of steps shown in the flow chart of Fig. 6 and the manufacturing apparatus shown in Fig. 7 will be described below. In the method for forming a Cu film according to an embodiment of the present invention, a barrier layer (Ta or Ti-based) for preventing diffusion of Cu to the interlayer insulating film 1 is provided between the interlayer insulating film 1 and the Cu wiring layer 4. And a liner film (Co) 3 formed on the barrier layer 2 and serving as a base of the Cu wiring layer 4. An embodiment of the present invention particularly includes a film forming step S10 of forming a Cu wiring layer 4 on the Co film 3 after the film formation of the Co film 3 after the film formation is performed, and the film forming step S10 is performed on the Co film 3 through the post annealing step S6. A modification step S8 of degassing the surface of the Co film 4 between the post-annealing step S6 and the film forming step S10 of forming the Cu wiring layer 4 is performed. The post-annealing step S6 is to remove impurities (carbon (C), nitrogen (N), oxygen (O), etc.) from the surface or inside of the Co film 3 after the film formation to the outside of the Co film 3 to achieve a low Co film 3. The step of resistance. Typical conditions of the post-annealing step S6 include a process temperature of 260 ° C to 380 ° C, a process gas of a mixed gas of NH 3 and H 2 , a process pressure of 390 Pa, and a process time of 120 sec. In one embodiment of the present invention, the Co film 3 subjected to the post annealing step S6 is subjected to a degassing treatment in the upgrading step S8. Further, between the post-annealing step S6 and the reforming step S8, for example, air destruction (exposure to the atmosphere) may be performed as an example of the cooling step. The details will be explained below. By performing this degassing treatment, the OH group or oxygen is removed from the surface of the Co film by H 2 reduction, and the surface of the Co film is in a state of substantially hydrogen (end of hydrogen). Therefore, in one embodiment of the present invention, the degassing treatment is also referred to as "H 2 adsorption treatment". Typical conditions for the H 2 adsorption treatment include a process temperature of RT (room temperature) to 300 ° C, a process gas of hydrogen containing hydrogen (H), a process pressure of from 10 Pa to 1000 Pa, and a process time of 120. Sec. Here, the "gas containing hydrogen (H)" is not limited to a gas composed only of hydrogen. Instead of this, for example, a mixed gas containing an inert gas (for example, He gas) and hydrogen or a hydrogen radical generated by a remote plasma method or a CAT (catalase) method may be used. Fig. 1B shows a state in which OH groups or oxygen are removed from the surface of the Co film by H 2 reduction by degassing treatment, and the surface of the Co film is substantially terminated by hydrogen (hydrogen adsorption). The "hollow mark" indicated on the surface of the Co film 3 indicates the hydrogen adsorbed. The state before the degassing process, the state during the process, and the state after the process are respectively shown in detail in FIGS. 3A, 3B, and 4A to 4C. 3A and 3B are views showing the relationship between the degassing effect of hydrogen gas (H 2 ) and the treatment temperature, and Fig. 3A shows the state before the degassing treatment, and Fig. 3B shows the state in the degassing treatment. 4A to 4C are views showing the relationship between the degassing effect of hydrogen gas (H 2 ) and the treatment temperature, and FIG. 4A shows the state after the low temperature treatment, FIG. 4B shows the state after the intermediate temperature treatment, and FIG. 4C shows the state after the high temperature treatment. status. As shown in Fig. 3A, the surface of the Co film 3 before the degassing treatment is in a state of being covered with oxygen or OH groups. Fig. 3B shows a state in which the surface of the Co film 3 shown in Fig. 3A is subjected to a degassing treatment using a gas containing hydrogen (H 2 ). The oxygen or OH group covering the surface of the Co film 3 becomes water (H 2 O) by hydrogen (H 2 ) and is detached from the surface of the Co film 3. That is, as shown in FIG. 4A to FIG. 4C, according to the above-described deaeration treatment, OH groups or oxygen can be removed from the surface of the Co film by H 2 reduction, and the surface of the Co film can be substantially terminated by hydrogen (hydrogen adsorption). State. However, depending on the temperature conditions of the degassing treatment, the action and effect of the degassing treatment may change. Hereinafter, each temperature condition of the degassing treatment will be described in detail. Fig. 4A shows the case of low temperature treatment (200 ° C or more and less than 260 ° C). In this case, although hydrogen (H 2 ) reduction occurs, hydrogen (H 2 ) reduction is in an insufficient state. Therefore, a state in which the OH group or oxygen which has not been removed remains on the surface of the Co film remains. Fig. 4B shows the case of a medium temperature treatment (260 ° C or more and less than 290 ° C). In this case, almost no OH group or oxygen remains on the surface of the Co film, and the surface of the Co film is substantially reduced throughout the entire region by hydrogen gas (H 2 ). Therefore, the density of the hydrogen terminal shows the largest. Fig. 4C shows the case of high temperature treatment (above 320 ° C). In this case, no OH group or oxygen remains on the surface of the Co film. The surface of the Co film is in a state of being reduced by hydrogen (H 2 ), but hydrogen (H 2 ) also starts to detach, and the density of the hydrogen terminal is lowered. Fig. 5 is a view showing the relationship between the hydrogen terminal (hydrogen adsorption) on the surface of the Cu film and the wetness angle. In Fig. 5, the symbol 2 is a TaN film, the symbol 3 is a Co film, and the symbol 4 is a reflowed Cu. In the case of the above intermediate temperature treatment (260 ° C or higher and less than 290 ° C) (Fig. 4B), the surface of the Co film is terminated with hydrogen (hydrogen adsorption). Thereby, the wettability angle θ of the Cu film formed on the surface of the Co film and in a state of being thermally melted with respect to the surface of the Co film becomes small. This case is represented by the following Young formula. Here, the surface tension of the Y S- based Co film, the surface tension of the Y L- based Cu film, and the surface tension of the interface between the Y LS- based Cu film and the Co film. (Number 1) According to this formula, it is understood that Y L is to be decreased or increased (Y S - Y LS ) in order to reduce the wetting angle θ. The surface tension Y L of the Cu film is determined by the temperature and is independent of the surface state of the Co film, and therefore does not change due to the hydrogen termination of the Co surface. On the other hand, since Y S and Y LS are both physical quantities affected by the surface state of Co, it can be easily estimated that they are affected by the hydrogen termination of the Co surface. Therefore, the reason why the wetness angle θ becomes small is that (Y S - Y LS ) becomes large. Thus, the surface of the Co film is terminated by hydrogen (hydrogen adsorption), whereby the wetness angle θ of the Cu film deposited thereon becomes small. As a result of the present invention, it is possible to form a Cu film by interposing a Co film in the recess 4H (FIG. 1C, FIG. 2C) formed in the interlayer insulating film by reflowing the Cu film. In FIGS. 1A to 1D and 2A to 2D, reference numeral 4C denotes a portion where Cu is buried after reflow. Symbol 4A is a Cu film before reflow. Fig. 4B shows the Cu film after reflow. Therefore, an embodiment of the present invention contributes to providing a method for forming a Cu film which can suppress the occurrence of voids in the Cu wiring layer, which is a problem when the Cu film is formed. Fig. 6 is a flow chart showing an example of a process for forming a Cu wiring film to which the present invention is applied. Fig. 7 is a view showing an example of a manufacturing apparatus according to an embodiment of the present invention. This manufacturing apparatus is configured to be able to carry out the Cu wiring film forming process of FIG. In the example shown in Fig. 6, the following steps S1 to S13 are sequentially performed. However, step S7 is a special step that needs to be set. S1 is a step of introducing a wafer (subject to be processed) into the internal space of the loading chamber C1. S2 is a step of heat-treating the wafer in the chamber C11 to degas (degas). S3 is the step of cooling the wafer in chamber C7 to a lower temperature than the process of the next step. S4 is a step of forming a TaN film on the wafer in the chamber C10. S5 is a step of forming a Co film on the TaN film in the chamber C8. S6 is a step of post-annealing the Co film in the chamber C3. S7 is a step of exposing the Co film to the atmosphere (air destruction) in the chamber C2. S8 is a step of performing H 2 adsorption treatment (degassing) by using a gas containing hydrogen in the chamber C11. S9 is the step of cooling the wafer in chamber C7 to a lower temperature than the process of the next step. S10 is a step of forming a Cu film in the chamber C5. S11 is a step of reflowing Cu in the chamber C4. S12 is a step of cooling the wafer in preparation for taking out the wafer in chamber C7. S13 is a step of moving the wafer out of the internal space of the take-out chamber C12 to the outside of the apparatus. The wafer (subject to be processed) is introduced into the interior of the loading chamber C1 in step S1, and the degassing treatment of the wafer is performed in step S2. Thereafter, the wafer is cooled at a temperature lower than the process temperature of the next step S4 to prepare for film formation of the TaN film. In the case where the yttrium oxide film (coated with SiO 2 ) is used as a substrate and a TaN film is formed thereon in step S4, it is preferable to use, for example, a chemical vapor deposition method as described below (Chemical) Vapor Deposition, CVD method or Atomic Layer Deposition (ALD method). Regarding the TaN film, for example, an organic material PDMAT (Ta(N(CH 3 ) 2 ) 5 , penta(dimethylamino) fluorene) or a metal halide TaCl 5 or the like is used as a raw material by a CVD method or an ALD method, and H is used. 2 or NH 3 or plasmad H 2 or NH 3 is thermally reacted to form a TaN film at a thickness of 1.5 nm to 3.0 nm under conditions of a film formation pressure of Pa to several tens of Pa and a film formation temperature of 350 °C. Here, the case where the barrier film is a TaN film has been described in detail, but the barrier film of the present invention is not limited to the TaN film. Examples of the material constituting the barrier film of the present invention include Ti, TiN, Ta, W, WN, and telluride. In the case where the TaN film is used as a substrate and a Co film is formed thereon in the step S5, it is preferable to use, for example, a chemical vapor deposition (CVD) method or atomic layer deposition as described below. Atomic Layer Deposition (ALD method). In order to form a Co film on a TaN film functioning as a barrier film, an organometallic material containing Co and an alkylsulfonyl group (the alkyl group is an ethyl group or a butyl group) such as 2-alkylsulfonyl cobalt is reduced to form a Co film. Use a reducing gas. As such a reducing gas, at least one selected from the group consisting of NH 3 , N 2 H 4 , NH(CH 3 ) 2 , N 2 H 3 CH, and N 2 as a known reducing gas, or H 2 is used. A gas in which a gas is combined with the above reducing gas (particularly, NH 3 ). The reducing gas may be supplied into the chamber by a CVD method or an ALD method in a process condition (for example, a film forming pressure: 50 to 1000 Pa; a substrate temperature (film forming temperature): 180 to 400 ° C, preferably 180 ～300° C., more preferably 200 to 300° C.; a CVD (ALD)-Co film is formed under a flow of a reducing gas (for example, NH 3 or the like: 100 to 1000 sccm). Thereby, the CVD-Co film is deposited on the TaN film to a thickness of 1.5 nm to 3.0 nm. By using such a reducing gas, it is possible to suppress the nucleation time of Co, control the deposition rate of the Co film, improve the surface morphology, suppress the impurity concentration, and reduce the resistance, so that the fine pattern can be closely adhered. A Co film was used for the layer, the telluride layer, and the cap layer. Examples of the organometallic material containing the above alkyl fluorenyl cobalt include Co(tBu-Et-Et-amd) 2 . The film formation method of the Co film is not limited to the CVD method, and the PVD method may also be employed. When using the PVD method, it can be used in process conditions (film formation temperature: room temperature; magnetron sputtering; DC power: 1000 W; RF bias power: 100 W; Ar: 5 sccm; pressure: 0.5 Pa, etc.) A PVD-Co film is formed. Step S6 is a step of post-annealing the Co film formed in the step S5. Annealing of the Co film may be performed, for example, in a mixed gas atmosphere containing ammonia gas and hydrogen gas, in other words, at a specific temperature in a reducing gas atmosphere. Thereby, impurities such as carbon or nitrogen in the formed Co film can be effectively removed, and the Co film itself can be reduced in resistance. Further, the concentration of carbon in the surface of the Co film can be suppressed to be low. Therefore, the formation of the seed layer by the Cu wiring structure employs such a Co film formation method, and the adhesion between the seed layer containing the Co film and the barrier layer can be improved. Moreover, the adhesion between the seed layer containing the Co film and the Cu wiring layer is also improved. Therefore, in conjunction with the low resistance of the Co film itself, the Cu wiring is further reduced in resistance. The temperature at the time of post-annealing is preferably set to be higher than the temperature at which the film of the Co film is formed. The impurities in the Co film can be effectively removed in a short time by the temperature at the time of post-annealing being higher than the temperature at which Co is formed. The temperature at the time of post-annealing is preferably in the range of 250 ° C to 350 ° C. If it is less than 250 ° C, the impurities in the Co film cannot be sufficiently removed, and therefore, a low-resistance Co film cannot be obtained. Further, in the structure of the semiconductor device, a temperature higher than 350 ° C cannot be used in the wiring forming step of the semiconductor device. In the step of performing the above post-annealing, annealing may be performed in a gas atmosphere containing only one of ammonia gas and hydrogen gas. However, in the case where only ammonia gas is contained, the nitrogen in the Co film and the surface of the Co film is not effectively removed. Further, in the case where only hydrogen gas is contained, carbon in the Co film and the surface of the Co film is not effectively removed. Therefore, the post-annealing step is preferably carried out in a gas atmosphere containing both ammonia gas and hydrogen gas. At this time, the partial pressure of hydrogen at the time of post-annealing is preferably from 1 to 1,000 Pa, more preferably from 100 Pa to 1,000 Pa. If the partial pressure of hydrogen deviates from this range, impurities cannot be sufficiently removed. Step S7 is a step of exposing the Co film to the atmosphere (air destruction) in the chamber C2. Such a step of exposing the Co film to the atmosphere, even if it exists between the film forming step of the Co film and the film forming step of the Cu film which will be described later, is exposed to the atmosphere as long as the Cu wiring structure is stably established. The steps in the process are extremely effective on the mass production surface. For example, the production line can be stopped at one end and the number of items to be processed can be adjusted. That is, the manufacturing step can be divided into a pre-step and a post-step, which are performed from the initial step to the film forming step and the post-annealing step of the Co film, and the subsequent step includes a film forming step of the Cu film. Further, it is not necessary to form the pre-step and the post-step in the vacuum in-situ, and it is also possible to introduce a manufacturing apparatus dedicated to the previous step or the subsequent step, and it is also expected that the manufacturing apparatus is miniaturized or the area is reduced. Step S8 is a step of performing H 2 adsorption treatment (degassing) by using a gas containing hydrogen in the chamber C11. Step S8 is the most characteristic step of the present invention, that is, even if the step S7 (the step of exposing the Co film to the atmosphere (air destruction)) is present, the Cu wiring structure is effectively contributed to stably. Step S8 does not depend on the presence or absence of step S7. As shown in FIG. 4A to FIG. 4C, according to the degassing treatment in the step S8, the OH group or the oxygen can be removed from the surface of the Co film by H 2 reduction, and the surface of the Co film is substantially terminated by hydrogen (hydrogen adsorption). State. At this time, as the temperature condition of the degassing treatment, as described above, the intermediate temperature treatment (260 ° C or higher and less than 290 ° C) is preferred. When the temperature range is employed, OH groups or oxygen are hardly left on the surface of the Co film, and the surface of the Co film is substantially reduced throughout the entire region by hydrogen gas (H 2 ). Therefore, the density of the hydrogen terminal shows the largest. Thus, the surface of the Co film is terminated by hydrogen (hydrogen adsorption), whereby the wet film θ of the Cu film deposited thereon becomes small, and therefore, the Cu film can be formed on the interlayer insulating film by reflowing the Cu film. A Co film is buried in the recess to form a Cu film. Further, the degassing treatment in the step S8 and the heat treatment in the above step S6 may be performed in the chamber. In this case, it is necessary to make the temperature of the degassing treatment lower than the temperature of the post annealing step. Therefore, as the wafer heating method, a heating method using an electromagnetic wave such as an infrared lamp or radiation, which can raise and lower the temperature of the wafer, is preferable. Step S9 is a step of cooling the wafer in the chamber C7 to a temperature lower than the process of the next step. Thereby, it is possible to carry out film formation of the Cu film of the next step at a specific temperature which is not dependent on the temperature of the degassing treatment of the previous step. Step S10 is a step of forming a Cu film in the chamber C5. As a film formation method of a Cu film, a CVD method or a PVD method is mentioned, for example. In the case where the Cu film is formed by the CVD method, for example, a specific film thickness may be formed at a film formation temperature of 200 ° C and a film formation pressure of 500 Pa. In the case where a Cu film is formed by the PVD method, a specific film thickness can be obtained at a film formation temperature of -20 ° C and a film formation pressure of 0.5 Pa. Here, regarding the specific film thickness, the minimum thickness of the film is the film thickness required to embed the concave portion, and the maximum thickness of the film is determined according to the conditions of the formed Cu wiring structure. The film formation method of the Cu film is not limited to the CVD method or the PVD method, and plating or the like may be used as needed. Step S11 is a step of re-welding Cu in the chamber C4. The Cu film formed on the Co film degassed in step S8 in step S10 is reflowed in step S11. Thereby, the Cu film can be buried in the concave portion without generating voids (pores) in the concave portion. As described above, the surface of the Co film is in a state of hydrogen termination (hydrogen adsorption) by the degassing treatment, whereby the wetness angle θ of the Cu film deposited thereon becomes small. Therefore, after the Cu film is reflowed, it is possible to stably form the Cu film by interposing the Co film in the concave portion formed in the interlayer insulating film. Step S12 is a step of cooling the wafer in preparation for taking out the wafer in the chamber C7, and step S13 is a step of moving the wafer from the internal space of the take-out chamber C12 to the outside of the apparatus. By such a series of steps, it is possible to provide a method of forming a Cu film which can suppress generation of voids in the Cu wiring layer. Fig. 7 is a view showing an example of a manufacturing apparatus according to an embodiment of the present invention, which can be preferably used in the above-described series of steps. The manufacturing apparatus of Fig. 7 is a cluster type tool in which a plurality of sputtering modules and the like are mounted. In Fig. 7, the C1 is a loading chamber (loading chamber) and the C12 is an unloading chamber (moving chamber). The substrate 31 as the object to be processed is carried into the loading chamber C1 and the unloading chamber C12, or is carried out from the loading chamber C1 and the unloading chamber C12 by the robot 31 installed in the atmospheric pressure environment. The loading chamber C1 and the unloading chamber C12 are connected to the first transfer chamber FX and the second transfer chamber RX. Each of the transfer chambers FX and RX includes robots 32 and 33 that transport substrates. The two transfer chambers FX and RX communicate with each other via the intermediate chamber MX. In the first transfer chamber FX, six chambers c1 to c3 and c10 to c12 are connected. In the second transfer chamber RX, six chambers c4 to c9 are also connected. In the above manufacturing method, for example, a manufacturing apparatus including a configuration of a chamber including the air destruction chamber indicated by symbol c2, the annealing chamber indicated by symbol c3, the reflow chamber indicated by symbol c4, and the symbol c5 are used. The PVD-Cu film forming chamber, the cooling chamber indicated by symbol c7, the CVD-Co film forming chamber indicated by symbol c8, the PVD-TaN film forming chamber indicated by symbol c10, and the degassing chamber indicated by symbol c11. When various processes are performed in each room, the upper surface of the substrate is placed as the surface to be processed. For example, in the above manufacturing method, in the case of performing steps S1 to S13, c1 → c11 → c7 → c10 → c8 → c3 → (c2) → c11 → c7 → c5 → c4 → c7 → c12 are sequentially performed, Thus, a method of forming a Cu film according to an embodiment of the present invention can be provided. Here, the present embodiment shows an example of various processes performed in each room, but the present invention is not limited to the arrangement shown in FIG. (Experimental Example 1) In this experimental example, the relationship between the annealing temperature after the Co film and the success rate of filling was investigated. Fig. 8 is a graph showing the relationship between the post-annealing temperature and the filling success rate and specific resistance. The symbol ◇ mark indicates the filling success rate, and the symbol □ symbol indicates the specific resistance. Figure 9 is a graph showing the relationship between the post-annealing temperature and the impurity concentration (O, C, N) in the Co film, the symbol □ mark indicates oxygen (O), the symbol △ mark indicates carbon (C), and the symbol ◇ mark indicates nitrogen. (N). The following aspects are clarified from FIGS. 8 and 9. (A1) With the increase in the post-annealing temperature, the specific resistance of the Co film and the impurity concentration (O, C, N) contained in the Co film are lowered, and the film quality is improved. (A2) In contrast, the filling success rate (buriing rate) is lowered as the post-annealing temperature is increased. From the above results, it is understood that it is difficult to apply it to the actual wiring forming step only by increasing the post-annealing temperature. (Experimental Example 2) In this experimental example, the degassing conditions of the Co film were changed, and the filling success rate of Filling was examined. At this time, a sample obtained by artificially exposing the surface of the Co film to the atmosphere was prepared, and the environment at the time of degassing was investigated. The result is shown in Fig. 10. Fig. 10 is a graph showing the relationship between the environment at the time of degassing and the success rate of filling. In the horizontal axis of Fig. 10, "high Vac" indicates a vacuum state in which H 2 and He are not supplied as a degassing environment. "He 1000 sccm, 57 Pa" indicates a state in which He gas is supplied to the chamber as a degassing environment. "H 2 /He 500/1000 sccm, 84 Pa" means a state in which a mixed gas of hydrogen gas and helium gas is supplied to the chamber as a degassing environment. However, in Fig. 10, the substrate temperature at the time of the degassing treatment was fixed at 260 °C. The following aspects can be clarified from Figure 10. (B1) When the Co film is exposed to the atmosphere, the surface of the Co film is covered with oxygen or OH groups. Thereafter, in the case where the vacuum state of H 2 and He is not supplied (high Vac), the filling success rate is 10 to 20%, which is extremely low. (B2) By setting the degassing environment to a helium atmosphere, the filling success rate is 15 to 20%, which is somewhat impractical, but is not practical. (B3) By setting the degassing environment to a mixed gas atmosphere of hydrogen gas and helium gas, the filling success rate is 95 to 100%, and a stable mass production process can be realized. Not only is the practical result obtained in the center portion (shown as "Center") of the substrate (wafer), but also practical results are obtained in the peripheral portion (shown as "Edge"). From the above results, it is understood that the degassing environment is preferably a mixed gas containing hydrogen and helium. It was confirmed that by using such a degassing environment, even if the Co film was exposed to the atmosphere, a stable filling success rate was obtained. (Experimental Example 3) In this experimental example, the relationship between the deaerating conditions (vacuum exhaust gas, He environment) and the filling success rate was examined by changing the post annealing temperature. At this time, a sample obtained by artificially exposing the surface of the Co film to the atmosphere was prepared, and the degassing conditions were investigated. The result is shown in Fig. 11. Figure 11 is a graph showing the relationship between degassing conditions (vacuum exhaust, H 2 /He environment) and filling success rate. In Fig. 11, the symbol ◇ mark and the symbol □ mark indicate the case where the degassing condition is a mixed gas atmosphere of hydrogen gas and helium gas. The symbol ◇ mark indicates the result of the center portion (shown as "Center") of the substrate (wafer), and the symbol □ mark indicates the result of the peripheral portion (shown as "Edge"). The symbol Δ symbol indicates a case where degassing is performed in a state of being evacuated by vacuum (a state in which H 2 and He are not supplied). The following aspects can be clarified from Figure 11. (C1) When degassing is performed in a state where H 2 and He are not supplied, the filling success rate is rapidly reduced as the post-annealing temperature rises. When the post-annealing temperature is 320 ° C, the filling success rate is several %, and when the post-annealing temperature is 350 ° C, the filling success rate becomes 0%. (C2) When degassing is carried out in a mixed gas atmosphere of hydrogen and helium, even if the post-annealing temperature is 295 ° C, a filling success rate of more than 90% can be obtained. However, if the post-annealing temperature exceeds 300 ° C, the filling success rate is drastically reduced. When the post-annealing temperature is 320 ° C, the filling success rate is reduced to about 15 to 45%, and when the post-annealing temperature is 350 ° C, the filling success rate is reduced to about 0 to 20%. From the above results, it is understood that the degassing environment is preferably "a mixed gas atmosphere of hydrogen gas and helium gas" compared to "the state in which hydrogen gas and helium gas are not supplied". It was confirmed that the filling success rate was improved by adopting such a degassing environment. (Experimental Example 4) In the present experimental example, the degassing condition (H 2 partial pressure) was changed, and the filling success rate was investigated. At this time, a sample obtained by artificially exposing the surface of the Co film to the atmosphere was prepared, and the degassing conditions were investigated. The result is shown in Fig. 12. Fig. 12 is a graph showing the relationship between the degassing condition (H 2 partial pressure) and the filling success rate. In FIG. 12, the symbol ◇ mark indicates the result of the center portion (shown as "Center") of the substrate (wafer), and the symbol □ mark indicates the result of the peripheral portion (shown as "Edge"). However, the degassing temperature was fixed at 260 ° C and the post annealing temperature was fixed at 320 ° C. The following aspects can be clarified from Figure 12. (D1) With the increase in the partial pressure of hydrogen (H 2 ), the filling success rate increases sharply. That is, the reflow characteristics are remarkably improved. (D2) Due to strict constraints, the highest value of Filling success rate in the graph of Fig. 12 is 80 to 90%, but as long as the hydrogen (H 2 ) partial pressure can be further increased, the filling success rate will be Become a higher value. From the above results, it is confirmed that the degassing environment is preferably "a mixed gas of hydrogen and helium", and when the partial pressure of hydrogen (H 2 ) is high, the effect of improving the filling success rate is promoted. (Experimental Example 5) In the present experimental example, the degassing temperature was changed, and the filling success rate was investigated. At this time, a sample obtained by artificially exposing the surface of the Co film to the atmosphere was prepared, and the degassing conditions were investigated. The result is shown in FIG. Fig. 13 is a graph showing the relationship between the degassing condition (temperature) and the filling success rate. In Fig. 13, the symbol ◇ mark indicates the result of the center portion (shown as "Center") of the substrate (wafer), and the □ mark indicates the result of the peripheral portion (shown as "Edge"). However, the post annealing temperature was fixed at 320 °C. The following aspects can be clarified from Figure 13. (E1) At a degassing temperature of 260 to 290 ° C, a filling success rate of more than 80% can be obtained. In particular, when the degassing temperature was 290 ° C, the filling success rate showed the maximum, which was 100% in the center portion of the substrate, and exceeded 90% even in the peripheral portion of the substrate. (E2) When the degassing temperature is lower than 260 ° C, the filling success rate decreases rapidly with a decrease in temperature. On the other hand, when the degassing temperature is higher than 290 ° C, the filling success rate decreases rapidly with an increase in temperature. In particular, when the degassing temperature was 320 ° C, the filling success rate became 0%. From the above results, it was confirmed that the degassing temperature is preferably in the range of 260 to 290 ° C when the post annealing temperature is 320 °C. The degassing temperature needs to be set lower than the post annealing temperature. Figure 14 is a graph showing the relationship between the annealing temperature and the filling success rate and specific resistance before and after application of the present invention (also referred to as before and after improvement). In Fig. 14, the symbol ◇ mark and the symbol □ mark are the filling success rate, the symbol ◇ mark indicates the result before the improvement, and the symbol □ mark indicates the improved result. The symbol Δ symbol is the result of the specific resistance. However, the Cu film thickness was fixed at 20 nm. The following aspects can be clarified from Figure 14. (F1) The decrease in the specific resistance of the Co film with an increase in the post-annealing temperature tends to be improved before and after the improvement. (F2) In contrast, the filling success rate greatly changes before and after improvement. That is, before the improvement, with the increase of the post-annealing temperature, the filling success rate is sharply reduced (symbol ◇ mark), whereas after the improvement, the filling success rate can be prevented from rising by the post-annealing temperature. The effect is maintained at 100%. According to the results of the above, it is possible to provide a method for forming a Cu film which can be remarkably suppressed when a Cu wiring layer is formed by interposing a Co liner film in a recess formed in the interlayer insulating film. Pores are generated in the Cu wiring layer. Furthermore, it has been confirmed that even if the thickness of the Cu film is as thick as 80 nm, the Cu is not attracted upward from the inside of the concave portion (the phenomenon that Cu is stretched from the inside of the concave portion to the thick film portion of the Cu film). Cu can be buried in the recess. Therefore, the method for forming a Cu film according to an embodiment of the present invention can be widely applied to various Cu film thicknesses. In the above, the method of forming the Cu film according to the embodiment of the present invention has been described, but the present invention is not limited thereto, and may be appropriately changed without departing from the scope of the invention. In each of the above experimental examples, the case where the liner film contains the Co film has been described in detail, but the liner film of the present invention is not limited to the Co film. In the method of forming a Cu film of the present invention, in addition to the Co film, the same action and effect can be obtained when a Ni film or a CoNi film is used. Further, the same effect can be obtained by using H 2 alone or in combination with an inert gas such as N 2 or Ar other than He. For example, in the fine processing pattern, the Co film, the Ni film, and the CoNi film can be used as the adhesion layer, the vaporized film, and the cap film. Therefore, the present invention can be used in the field of semiconductor device technology. [Industrial Applicability] The method for forming a Cu film of the present invention can be widely used in the field of semiconductor device technology.

1‧‧‧層間絕緣膜
1a‧‧‧凹部(坑或溝槽等)
2‧‧‧障壁層
3‧‧‧襯膜
4‧‧‧配線層(Cu膜)
4A‧‧‧回焊前之Cu膜
4B‧‧‧回焊後之Cu膜
4C‧‧‧回焊後埋入Cu之部位
4H‧‧‧凹部
4V‧‧‧孔隙(空隙)
31‧‧‧機器人
32‧‧‧機器人
33‧‧‧機器人
c1‧‧‧腔室
c2‧‧‧腔室
c3‧‧‧腔室
c4‧‧‧腔室
c5‧‧‧腔室
c6‧‧‧腔室
c7‧‧‧腔室
c8‧‧‧腔室
c9‧‧‧腔室
c10‧‧‧腔室
c11‧‧‧腔室
c12‧‧‧腔室
C‧‧‧碳
H‧‧‧氫
N‧‧‧氮
O‧‧‧氧
FX‧‧‧第一搬送室
RX‧‧‧第二搬送室
MX‧‧‧中間室
YL‧‧‧Co膜之表面張力
YS‧‧‧Cu膜之表面張力
YLS‧‧‧Cu膜與Co膜之界面之表面張力
θ‧‧‧Cu膜之濡濕角1‧‧‧Interlayer insulating film
1a‧‧‧ recesses (pits or grooves, etc.)
2‧‧ ‧ barrier layer
3‧‧‧ lining film
4‧‧‧Wiring layer (Cu film)
4A‧‧‧Cu film before reflow
4B‧‧‧Cu film after reflow
4C‧‧‧A part of Cu buried after reflow
4H‧‧‧ recess
4V‧‧‧ pores (voids)
31‧‧‧ Robot
32‧‧‧ Robot
33‧‧‧ Robot
C1‧‧‧ chamber
C2‧‧‧ chamber
C3‧‧‧ chamber
C4‧‧‧ chamber
C5‧‧‧ chamber
C6‧‧‧ chamber
C7‧‧‧ chamber
C8‧‧‧ chamber
C9‧‧‧ chamber
C10‧‧‧ chamber
C11‧‧‧ chamber
C12‧‧‧ chamber
C‧‧‧carbon
H‧‧‧ hydrogen
N‧‧‧Nitrate
O‧‧‧Oxygen
FX‧‧‧First Transfer Room
RX‧‧‧Second transfer room
MX‧‧‧ intermediate room
Surface tension of YL‧‧‧Co film
Surface tension of YS‧‧‧Cu film
The surface tension of the interface between the YLS‧‧Cu film and the Co film is the wet angle of the θ‧‧‧Cu film

圖1A係表示本發明之一實施形態之Cu膜之形成方法之一例之模式剖視圖。 圖1B係表示本發明之一實施形態之Cu膜之形成方法之一例之模式剖視圖。 圖1C係表示本發明之一實施形態之Cu膜之形成方法之一例之模式剖視圖。 圖1D係表示本發明之一實施形態之Cu膜之形成方法之一例之模式剖視圖。 圖2A係表示本發明之一實施形態之Cu膜之形成方法之另一例之模式剖視圖。 圖2B係表示本發明之一實施形態之Cu膜之形成方法之另一例之模式剖視圖。 圖2C係表示本發明之一實施形態之Cu膜之形成方法之另一例之模式剖視圖。 圖2D係表示本發明之一實施形態之Cu膜之形成方法之另一例之模式剖視圖。 圖3A係說明氫氣(H2 )脫氣效果與處理溫度之關係之圖且表示脫氣處理前之狀態之圖。 圖3B係說明氫氣(H2 )脫氣效果與處理溫度之關係之圖且表示脫氣處理中之狀態之圖。 圖4A係說明氫氣(H2 )脫氣效果與處理溫度之關係之圖且表示低溫處理後之狀態之圖。 圖4B係說明氫氣(H2 )脫氣效果與處理溫度之關係之圖且表示中溫處理後之狀態之圖。 圖4C係說明氫氣(H2 )脫氣效果與處理溫度之關係之圖且表示高溫處理後之狀態之圖。 圖5係說明Cu膜表面之氫終端(氫吸附)與濡濕角之關係之圖。 圖6係表示應用本發明之一實施形態之Cu配線膜形成製程之一例之流程圖。 圖7係表示本發明之一實施形態之製造裝置之一例之圖。 圖8係表示後退火溫度與填充(Filling)成功率及比電阻之關係之曲線圖。 圖9係表示後退火溫度與Co膜中之雜質濃度(O、C、N)之關係之曲線圖。 圖10係表示脫氣條件(環境氣體)與填充(Filling)成功率之關係之曲線圖。 圖11係表示脫氣條件(真空排氣、He環境)與填充(Filling)成功率之關係之曲線圖。 圖12係表示脫氣條件(H2 分壓)與填充(Filling)成功率之關係之曲線圖。 圖13係表示脫氣條件(溫度)與填充(Filling)成功率之關係之曲線圖。 圖14係表示改善前後之後退火溫度與填充(Filling)成功率及比電阻之關係之曲線圖。 圖15A係表示先前之Cu膜之形成方法之一例之模式剖視圖。 圖15B係表示先前之Cu膜之形成方法之一例之模式剖視圖。 圖15C係表示先前之Cu膜之形成方法之一例之模式剖視圖。 圖16係表示先前之製造流程圖之一例之圖。Fig. 1A is a schematic cross-sectional view showing an example of a method of forming a Cu film according to an embodiment of the present invention. Fig. 1B is a schematic cross-sectional view showing an example of a method of forming a Cu film according to an embodiment of the present invention. Fig. 1C is a schematic cross-sectional view showing an example of a method of forming a Cu film according to an embodiment of the present invention. Fig. 1D is a schematic cross-sectional view showing an example of a method of forming a Cu film according to an embodiment of the present invention. Fig. 2A is a schematic cross-sectional view showing another example of a method of forming a Cu film according to an embodiment of the present invention. Fig. 2B is a schematic cross-sectional view showing another example of a method of forming a Cu film according to an embodiment of the present invention. Fig. 2C is a schematic cross-sectional view showing another example of a method of forming a Cu film according to an embodiment of the present invention. Fig. 2D is a schematic cross-sectional view showing another example of a method of forming a Cu film according to an embodiment of the present invention. Fig. 3A is a view showing the relationship between the degassing effect of hydrogen (H 2 ) and the treatment temperature and showing the state before the degassing treatment. Fig. 3B is a view showing the relationship between the degassing effect of hydrogen gas (H 2 ) and the treatment temperature and showing a state in the degassing treatment. Fig. 4A is a view showing the relationship between the degassing effect of hydrogen (H 2 ) and the treatment temperature and showing the state after the low temperature treatment. Fig. 4B is a view showing the relationship between the degassing effect of hydrogen gas (H 2 ) and the treatment temperature and showing the state after the intermediate temperature treatment. Fig. 4C is a view showing the relationship between the degassing effect of hydrogen (H 2 ) and the treatment temperature and showing the state after the high temperature treatment. Fig. 5 is a view showing the relationship between the hydrogen terminal (hydrogen adsorption) on the surface of the Cu film and the wetness angle. Fig. 6 is a flow chart showing an example of a process for forming a Cu wiring film according to an embodiment of the present invention. Fig. 7 is a view showing an example of a manufacturing apparatus according to an embodiment of the present invention. Fig. 8 is a graph showing the relationship between the post-annealing temperature and the filling success rate and specific resistance. Fig. 9 is a graph showing the relationship between the post-annealing temperature and the impurity concentration (O, C, N) in the Co film. Fig. 10 is a graph showing the relationship between the degassing condition (ambient gas) and the filling success rate. Fig. 11 is a graph showing the relationship between the degassing conditions (vacuum exhaust, He environment) and the filling success rate. Fig. 12 is a graph showing the relationship between the degassing condition (H 2 partial pressure) and the filling success rate. Fig. 13 is a graph showing the relationship between the degassing condition (temperature) and the filling success rate. Fig. 14 is a graph showing the relationship between the annealing temperature and the filling success rate and the specific resistance after the improvement. Fig. 15A is a schematic cross-sectional view showing an example of a method of forming a conventional Cu film. Fig. 15B is a schematic cross-sectional view showing an example of a method of forming a conventional Cu film. Fig. 15C is a schematic cross-sectional view showing an example of a method of forming a conventional Cu film. Fig. 16 is a view showing an example of a prior art manufacturing flow chart.

1‧‧‧層間絕緣膜 1‧‧‧Interlayer insulating film

1a‧‧‧凹部(坑或溝槽等) 1a‧‧‧ recesses (pits or grooves, etc.)

2‧‧‧障壁層 2‧‧ ‧ barrier layer

3‧‧‧襯膜 3‧‧‧ lining film

4‧‧‧配線層(Cu膜) 4‧‧‧Wiring layer (Cu film)

4A‧‧‧回焊前之Cu膜 4A‧‧‧Cu film before reflow

4H‧‧‧凹部 4H‧‧‧ recess

H‧‧‧氫 H‧‧‧ hydrogen

Claims (5)

一種Cu膜之形成方法，其係於形成於層間絕緣膜之凹部內介隔襯膜埋入形成Cu膜之方法，且 對成膜後之上述襯膜進行熱處理， 進行上述熱處理之後，於包含氫之氣體環境下，對上述襯膜之表面進行脫氣處理， 進行上述脫氣處理之後，於經上述熱處理之上述襯膜上形成Cu膜， 上述襯膜係選自Co膜、Ni膜、CoNi膜中之一者。A method for forming a Cu film, which is formed by embedding a liner film in a recess formed in an interlayer insulating film to form a Cu film, and heat-treating the film after the film formation, and after performing the heat treatment, containing hydrogen In the gas atmosphere, the surface of the lining film is subjected to a degassing treatment, and after the degassing treatment, a Cu film is formed on the lining film subjected to the heat treatment, and the lining film is selected from a Co film, a Ni film, and a CoNi film. One of them. 如請求項1之Cu膜之形成方法，其中上述脫氣處理係藉由氫還原而使上述Co膜之表面成為以氫為終端之狀態。The method for forming a Cu film according to claim 1, wherein the degassing treatment is such that the surface of the Co film is terminated by hydrogen by hydrogen reduction. 如請求項1或2之Cu膜之形成方法，其中上述脫氣處理之溫度低於上述熱處理之溫度。The method for forming a Cu film according to claim 1 or 2, wherein the temperature of the degassing treatment is lower than the temperature of the heat treatment. 如請求項1或2之Cu膜之形成方法，其中上述脫氣處理之溫度為260℃以上且290℃以下。The method for forming a Cu film according to claim 1 or 2, wherein the temperature of the degassing treatment is 260 ° C or higher and 290 ° C or lower. 如請求項1之Cu膜之形成方法，其中於進行上述熱處理之後，將上述Co膜暴露於大氣中，其後進行上述脫氣處理。The method for forming a Cu film according to claim 1, wherein after the heat treatment is performed, the Co film is exposed to the atmosphere, and then the degassing treatment is performed.
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