TWI745559B - Method for processing target object - Google Patents

Method for processing target object Download PDF

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TWI745559B
TWI745559B TW107108356A TW107108356A TWI745559B TW I745559 B TWI745559 B TW I745559B TW 107108356 A TW107108356 A TW 107108356A TW 107108356 A TW107108356 A TW 107108356A TW I745559 B TWI745559 B TW I745559B
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barrier film
gas
film
insulating film
processing method
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TW201903900A (en
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濱康孝
橫山政司
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日商東京威力科創股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02312—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour
    • H01L21/02315—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • 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
    • H01L21/76801—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 dielectrics, e.g. smoothing
    • H01L21/76829—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 dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers

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Abstract

In a method for processing a target object including a conductive layer and an insulating film formed on the conductive layer, the insulating film is etched by plasma treatment of a fluorine-containing gas to form an opening in the insulating film. A barrier film is formed to cover a surface of the insulating film and a surface of the conductive layer which is exposed through the opening formed in the insulating film. The target object having the barrier film is placed in an atmospheric environment, and the barrier film is removed from the target object by isotropically etching the barrier film. The target object is maintained in a depressurized environment from start of etching the insulating film to end of forming the barrier film. The barrier film is conformally formed on the surfaces of the insulating film and the conductive layer exposed through the opening formed in the insulating film.

Description

被加工物之處理方法Processing method of processed objects

本案之實施形態，係有關於被加工物之處理方法。The implementation form of this case is related to the processing method of the processed object.

在半導體元件這類電子元件之製造，有時會為了在包含金屬的導電層上所形成之絶緣膜形成開口，而執行電漿蝕刻。於電漿蝕刻，會藉由含氟之氣體的電漿處理，以蝕刻絶緣膜。在執行電漿蝕刻後，從形成於絶緣膜之開口所露出的導電層之表面上，會形成含氟的殘留物。在執行電漿蝕刻後再把被加工物配置於大氣環境中，會在導電層之表面發生腐蝕。此腐蝕，會與金屬、氟、以及大氣中的水分反應，而形成水合物。此種導電層之表面腐蝕，應加以抑制。In the manufacture of electronic components such as semiconductor components, plasma etching is sometimes performed in order to form openings in the insulating film formed on the conductive layer containing metal. In plasma etching, the insulating film is etched by plasma treatment with a fluorine-containing gas. After plasma etching is performed, fluorine-containing residues are formed on the surface of the conductive layer exposed from the opening formed in the insulating film. After plasma etching is performed and the workpiece is placed in the atmosphere, corrosion will occur on the surface of the conductive layer. This corrosion will react with metals, fluorine, and moisture in the atmosphere to form hydrates. The surface corrosion of this conductive layer should be suppressed.

於專利文獻1，記載一種技術，係以含有氮及氫的氣體之電漿處理，來去除導電層表面上的殘留物。然而，即使藉由此處理，亦難以完全去除殘留物。Patent Document 1 describes a technique for removing residues on the surface of the conductive layer by plasma treatment of a gas containing nitrogen and hydrogen. However, even with this treatment, it is difficult to completely remove the residue.

於專利文獻2，則記載一種技術，係在對絶緣膜執行過電漿蝕刻之後、並且在將被加工物配置於大氣環境中之前，就以化學氣相沈積法（CVD法）形成氧化矽膜，以包覆絶緣膜及導電層之表面。 ［習知技術文獻］ ［專利文獻］Patent Document 2 describes a technique of forming a silicon oxide film by a chemical vapor deposition method (CVD method) after plasma etching is performed on the insulating film and before the workpiece is placed in the atmosphere. , To cover the surface of the insulating film and the conductive layer. [Related Technical Documents] [Patent Documents]

［專利文獻1］日本特開2006－156486號公報 ［專利文獻2］日本特開2012－124351號公報[Patent Document 1] Japanese Patent Application Publication No. 2006-156486 [Patent Document 2] Japanese Patent Application Publication No. 2012-124351

［發明所欲解決的問題］[The problem to be solved by the invention]

藉由上述之氧化矽膜，則即使將被加工物配置於大氣環境中，也能防止導電層的表面及殘留物接觸到大氣。此氧化矽膜，在被加工物配置於大氣環境中之後，會在下一製程受到去除。此去除，係進行氧化矽膜之濕蝕刻。然而，於去除氧化矽膜之際，絶緣膜會有局部受到大幅度的蝕刻。With the above-mentioned silicon oxide film, even if the workpiece is placed in the atmosphere, the surface of the conductive layer and residues can be prevented from contacting the atmosphere. The silicon oxide film will be removed in the next process after the object to be processed is placed in the atmosphere. This removal is performed by wet etching of the silicon oxide film. However, when the silicon oxide film is removed, the insulating film will be partially etched to a large extent.

因此，在對絶緣膜進行蝕刻之後、並且在將被加工物配置於大氣環境中之前，需要以阻障膜包覆絶緣膜之表面及導電層之表面。此外，在被加工物配置於大氣環境中之後所執行的阻障膜之去除，需要抑制絶緣膜有局部被大輻度蝕刻的問題。 ［解決問題之技術手段］Therefore, after the insulating film is etched and before the object to be processed is placed in the atmosphere, it is necessary to cover the surface of the insulating film and the surface of the conductive layer with a barrier film. In addition, the removal of the barrier film performed after the workpiece is placed in the atmospheric environment needs to suppress the problem of local large-radius etching of the insulating film. [Technical means to solve the problem]

於一態樣，係提供一種被加工物之處理方法。被加工物，具有導電層、以及設於該導電層上的絶緣膜。此處理方法包含以下步驟：（i）為了在絶緣膜形成開口，而藉由含氟氣體之電漿處理以蝕刻絶緣膜的步驟；（ii）為了包覆絶緣膜之表面、以及從形成於絶緣膜之開口所露出的導電層之表面，而形成阻障膜的步驟；（iii）將具有阻障膜之被加工物配置於大氣環境中的步驟；以及（iv）在將被加工物配置於大氣環境中的步驟之後，從被加工物去除阻障膜的步驟；於去除阻障膜的步驟，該阻障膜係等向性地受到蝕刻。於此方法，從蝕刻絶緣膜的步驟開始時、到形成阻障膜的步驟結束時為止的期間，被加工物係維持在減壓環境中。阻障膜，係在絶緣膜之表面、以及從形成於絶緣膜上之開口所露出的導電層之表面上，保形（conformal）地形成之膜層。In one aspect, it provides a processing method for processed objects. The object to be processed has a conductive layer and an insulating film provided on the conductive layer. This processing method includes the following steps: (i) in order to form an opening in the insulating film, a step of etching the insulating film by plasma treatment with a fluorine-containing gas; (ii) in order to cover the surface of the insulating film and from forming an insulating film The step of forming a barrier film on the surface of the conductive layer exposed by the opening of the film; (iii) the step of arranging the processed object with the barrier film in the atmospheric environment; and (iv) the step of arranging the processed object on After the step in the atmospheric environment, the step of removing the barrier film from the workpiece; in the step of removing the barrier film, the barrier film is etched isotropically. In this method, from the beginning of the step of etching the insulating film to the end of the step of forming the barrier film, the object to be processed is maintained in a reduced pressure environment. The barrier film is a film layer formed conformal on the surface of the insulating film and the surface of the conductive layer exposed from the opening formed on the insulating film.

若藉由上述方法，在對絶緣膜進行蝕刻之後、並且在將被加工物配置於大氣環境中之前，就以阻障膜包覆絶緣膜之表面及導電層之表面。由於導電層之表面受到此阻障膜保護，因此即使將被加工物配置於大氣環境中，也會抑制導電層之表面的腐蝕。再者，由於阻障膜係保形（conformal）地形成的膜層，所以藉由等向性蝕刻，會均勻地去除。因此，於去除阻障膜之際，能抑制絶緣膜有局部被大輻度蝕刻的問題。According to the above method, after the insulating film is etched and before the workpiece is placed in the atmosphere, the surface of the insulating film and the surface of the conductive layer are covered with a barrier film. Since the surface of the conductive layer is protected by the barrier film, even if the workpiece is placed in the atmosphere, the corrosion of the surface of the conductive layer will be suppressed. Furthermore, since the barrier film is a conformal film layer, it will be uniformly removed by isotropic etching. Therefore, when removing the barrier film, it is possible to suppress the problem of local large-radius etching of the insulating film.

於一實施形態，阻障膜係以原子層沈積法形成。形成阻障膜的步驟，包含以下步驟：為了使被加工物之表面吸附前驅體，而對被加工物供應前驅體氣體的步驟；以及為了從前驅體形成阻障膜，而對前驅體執行電漿處理的步驟。In one embodiment, the barrier film is formed by atomic layer deposition. The step of forming a barrier film includes the following steps: in order to make the surface of the processed object adsorb the precursor, the process of supplying a precursor gas to the processed object; and in order to form a barrier film from the precursor, the precursor is charged Pulp treatment steps.

於一實施形態，前驅體氣體，不含鹵素。若藉由不含鹵素的前驅體氣體，會抑制導電層之表面的損傷。In one embodiment, the precursor gas does not contain halogen. If halogen-free precursor gas is used, damage to the surface of the conductive layer will be suppressed.

於一實施形態，前驅體氣體，係胺基矽烷系氣體或矽醇鹽系氣體。In one embodiment, the precursor gas is an aminosilane-based gas or a silicon alkoxide-based gas.

於一實施形態，於對前驅體執行電漿處理的步驟，係對前驅體執行使用含氧氣體之電漿的電漿處理。In one embodiment, in the step of performing plasma processing on the precursor, plasma processing using plasma of oxygen-containing gas is performed on the precursor.

於一實施形態，被加工物之處理方法，更進一步地包含以下步驟：在形成阻障膜的步驟之後、並且在將被加工物配置於大氣環境中的步驟之前，對被加工物供應具有烷基矽烷基之胺基矽烷系氣體的步驟。若藉由使用含氧氣體之電漿的電漿處理，來使以胺基矽烷系氣體為基礎的前驅體氧化，會在阻障膜之表面形成OH基。該阻障膜之表面，會具有親水性。而具有烷基矽烷基的胺基矽烷系氣體，會在阻障膜之表面形成具有疏水性的膜層。因此，藉由此實施形態，會在將被加工物配置於大氣環境中之前，為被加工物之表面賦予疏水性。In one embodiment, the processing method of the workpiece further includes the following step: after the step of forming the barrier film and before the step of arranging the workpiece in the atmosphere, supplying the workpiece with alkane The step of the amine silane-based gas based on the silyl group. If the precursor based on the aminosilane gas is oxidized by the plasma treatment using the plasma of the oxygen-containing gas, OH groups will be formed on the surface of the barrier film. The surface of the barrier film will be hydrophilic. The aminosilane-based gas with alkylsilyl group will form a hydrophobic film on the surface of the barrier film. Therefore, with this embodiment, the surface of the workpiece is rendered hydrophobic before the workpiece is placed in the atmosphere.

於一實施形態，阻障膜係氧化矽膜。於另一實施形態，阻障膜亦可係氮化矽膜、或碳化矽膜。於再一種實施形態，阻障膜亦可係係金屬氧化膜。金屬氧化膜，可以係例如氧化鋁膜。In one embodiment, the barrier film is a silicon oxide film. In another embodiment, the barrier film may also be a silicon nitride film or a silicon carbide film. In another embodiment, the barrier film may also be a metal oxide film. The metal oxide film may be, for example, an aluminum oxide film.

於一實施形態，阻障膜的膜厚，係0.45nm以上。若藉由具有0.45nm以上之膜厚的阻障膜，可以更確實地抑制導電層之表面的腐蝕。又，阻障膜的膜厚，可以係不會堵塞絶緣膜之開口的膜厚，例如比該開口之寬度或直徑的1／2更薄的膜厚。In one embodiment, the thickness of the barrier film is 0.45 nm or more. If a barrier film having a film thickness of 0.45 nm or more is used, the corrosion of the surface of the conductive layer can be suppressed more reliably. In addition, the film thickness of the barrier film may be a film thickness that does not block the opening of the insulating film, for example, a film thickness thinner than 1/2 of the width or diameter of the opening.

於一實施形態，絶緣膜上設有遮罩。於蝕刻絶緣膜的該步驟，在形成於遮罩之開口所露出的部位，蝕刻絶緣膜。於此實施形態，被加工物之處理方法，於蝕刻絶緣膜的步驟與形成阻障膜的步驟之間，更進一步地包含藉由使用電漿之處理，以去除遮罩的步驟。用於去除遮罩的步驟之電漿，例如係含氮（N）及氫（H）之氣體的電漿、或含氧（O）氣體的電漿。In one embodiment, a mask is provided on the insulating film. In this step of etching the insulating film, the insulating film is etched at a portion exposed by the opening formed in the mask. In this embodiment, the processing method of the processed object further includes a step of removing the mask by processing using plasma between the step of etching the insulating film and the step of forming the barrier film. The plasma used in the step of removing the mask is, for example, a plasma containing nitrogen (N) and hydrogen (H) gas, or a plasma containing oxygen (O) gas.

於一實施形態，被加工物之處理方法，於蝕刻絶緣膜的步驟與形成阻障膜的步驟之間，更進一步地包含使用含氫（H）氣體之電漿，以執行導電層之表面處理的步驟。用於導電層的表面處理之氣體，除了氫以外，亦可包含氮（N）。藉由此表面處理，會減少導電層之表面的殘留物的量。再者，藉由此表面處理，則即使於蝕刻絶緣膜的步驟或去除遮罩的步驟中，導電層之表面有所氧化，亦會將該導電層之表面加以還原。In one embodiment, the processing method of the processed object further includes the use of a plasma containing hydrogen (H) gas between the step of etching the insulating film and the step of forming a barrier film to perform surface treatment of the conductive layer A step of. The gas used for the surface treatment of the conductive layer may contain nitrogen (N) in addition to hydrogen. With this surface treatment, the amount of residues on the surface of the conductive layer will be reduced. Furthermore, with this surface treatment, even if the surface of the conductive layer is oxidized in the step of etching the insulating film or the step of removing the mask, the surface of the conductive layer will be reduced.

於一實施形態之去除阻障膜的步驟，阻障膜係藉由濕蝕刻而去除。用於濕蝕刻的溶液包含氫氟酸（HF）或氟化銨（NH4 F）。In the step of removing the barrier film in one embodiment, the barrier film is removed by wet etching. The solution used for wet etching contains hydrofluoric acid (HF) or ammonium fluoride (NH 4 F).

於一實施形態，從蝕刻絶緣膜的步驟開始時、到形成阻障膜的步驟結束時為止，被加工物係維持在同一個處理室內。 ［發明之效果］In one embodiment, from the beginning of the step of etching the insulating film to the end of the step of forming the barrier film, the object to be processed is maintained in the same processing chamber. [Effects of Invention]

一如上文之說明，在對絶緣膜進行蝕刻之後、並且在將被加工物配置於大氣環境中之前，就以阻障膜包覆絶緣膜之表面及導電層之表面。此外，將被加工物配置於大氣環境中之後所執行的阻障膜之去除，會抑制絶緣膜有局部被大輻度蝕刻的問題。As explained above, after the insulating film is etched and before the object to be processed is placed in the atmosphere, the surface of the insulating film and the surface of the conductive layer are covered with a barrier film. In addition, the removal of the barrier film performed after the object to be processed is placed in an atmospheric environment can prevent the insulation film from being locally etched with large radiance.

以下將參照圖式，針對各種實施形態進行詳細說明。又，於各圖式中，對於相同或相當之部分，會標註相同的符號。Hereinafter, various embodiments will be described in detail with reference to the drawings. In addition, in each drawing, the same or equivalent parts are marked with the same symbols.

圖1為繪示一實施形態之被加工物之處理方法的流程圖。圖1所示之方法MT，適用於具有「導電層、以及設於該導電層上之絶緣膜」的被加工物。圖2為擴大繪示一案例中之被加工物局部的剖面圖。被加工物W具有：金屬層MTL、以及絶緣膜IL。金屬層MTL，係導電層之一例。圖2所示之一案例的被加工物W，更進一步地具有：基底層UL、遮罩層MKL、防止反射膜BL、以及光罩RM。Fig. 1 is a flowchart showing a processing method of a processed object according to an embodiment. The method MT shown in FIG. 1 is suitable for a workpiece having a "conductive layer and an insulating film provided on the conductive layer". Figure 2 is an enlarged drawing showing a partial cross-sectional view of the processed object in a case. The workpiece W has a metal layer MTL and an insulating film IL. The metal layer MTL is an example of a conductive layer. The workpiece W of one example shown in FIG. 2 further includes a base layer UL, a mask layer MKL, an anti-reflection film BL, and a photomask RM.

金屬層MTL，係設在基底層UL上。基底層UL，可以自下層依序具有矽層及氮化鈦層，但並不限定於此。金屬層MTL，係由金屬所形成之膜層。金屬層MTL，係例如構成半導體裝置中之配線層的膜層，可以由任意之配線金屬材料所形成。金屬層MTL，係例如由鈷或銅所形成。The metal layer MTL is provided on the base layer UL. The base layer UL may have a silicon layer and a titanium nitride layer in order from the lower layer, but it is not limited to this. The metal layer MTL is a film layer formed of metal. The metal layer MTL is, for example, a film layer constituting a wiring layer in a semiconductor device, and may be formed of any wiring metal material. The metal layer MTL is formed of cobalt or copper, for example.

絶緣膜IL，係設在金屬層MTL上。於一案例中，絶緣膜IL係多層膜，可以包含第1層IL1及第2層IL2。第1層IL1，係例如防止擴散膜，由氮化矽所形成。第2層IL2，係例如層間絶緣膜，由氧化矽所形成。The insulating film IL is provided on the metal layer MTL. In one case, the insulating film IL is a multilayer film, which may include a first layer IL1 and a second layer IL2. The first layer IL1 is, for example, an anti-diffusion film and is formed of silicon nitride. The second layer IL2 is, for example, an interlayer insulating film formed of silicon oxide.

遮罩層MKL，係設於絶緣膜IL上。遮罩層MKL，係用作絶緣膜IL之蝕刻遮罩的膜層。遮罩層MKL，係例如由非晶碳所形成。防止反射膜BL，係設於遮罩層MKL上。防止反射膜BL，係例如含有矽的防止反射膜。光罩RM，係設於防止反射膜BL上。於光罩RM，形成有一個以上的開口。光罩RM的圖案，係以光微影技術形成。The mask layer MKL is provided on the insulating film IL. The mask layer MKL is a film layer used as an etching mask for the insulating film IL. The mask layer MKL is formed of, for example, amorphous carbon. The anti-reflection film BL is arranged on the mask layer MKL. The anti-reflection film BL is, for example, an anti-reflection film containing silicon. The mask RM is set on the anti-reflection film BL. More than one opening is formed in the mask RM. The pattern of the mask RM is formed by photolithography technology.

方法MT，可用具備電漿處理裝置之處理系統及濕洗淨裝置來執行。圖3為繪示可用於執行一實施形態之方法的處理系統及濕洗淨裝置的圖式。圖3所示之處理系統110具備：載入模組112、載入鎖定模組141、載入鎖定模組142、移載模組116、複數之製程模組181～184、以及控制部130。The method MT can be performed by a processing system equipped with a plasma processing device and a wet cleaning device. FIG. 3 is a diagram showing a processing system and a wet cleaning device that can be used to perform the method of an embodiment. The processing system 110 shown in FIG. 3 includes: a load module 112, a load lock module 141, a load lock module 142, a transfer module 116, a plurality of process modules 181 to 184, and a control unit 130.

載入模組112，係於大氣環境下搬運被加工物W之裝置。於載入模組112，安裝有複數個載置台120。在複數個載置台120之各自的頂面，搭載有可容納複數個被加工物的容器122。容器122，例如可以係FOUP（Front-Opening Unified Pod；前開式晶圓傳送盒）。容器122係構成為以其內部來容納被加工物W。The loading module 112 is a device for conveying the workpiece W under the atmospheric environment. In the loading module 112, a plurality of loading tables 120 are installed. A container 122 capable of accommodating a plurality of objects to be processed is mounted on the top surface of each of the plurality of mounting tables 120. The container 122 may be, for example, a FOUP (Front-Opening Unified Pod; front-opening wafer transfer box). The container 122 is configured to accommodate the workpiece W in its inside.

載入模組112，提供其內部以作為搬運處理室112c。載入模組112，具有搬運機械臂（robot）112r。搬運機械臂112r，係設於搬運處理室112c內。載入模組112，連接著載入鎖定模組141及載入鎖定模組142。搬運機械臂112r，係構成為在容器122與載入鎖定模組141之間、或在容器122與載入鎖定模組142之間，搬運被加工物W。The loading module 112 is provided with its interior as a handling chamber 112c. The loading module 112 has a handling robot 112r. The conveyance robot 112r is installed in the conveyance processing chamber 112c. The loading module 112 is connected with the loading locking module 141 and the loading locking module 142. The transport robot 112r is configured to transport the workpiece W between the container 122 and the loading lock module 141, or between the container 122 and the loading lock module 142.

載入鎖定模組141及載入鎖定模組142，分別提供用以進行預備減壓的處理室141c及處理室142c。載入鎖定模組141及載入鎖定模組142，連接著移載模組116。移載模組116，提供可以減壓的搬運處理室116c。移載模組116，具有搬運機械臂116r。搬運機械臂116r，係設於搬運處理室116c內。移載模組116，連接著複數個製程模組181～184。移載模組116的搬運機械臂116r，可以在載入鎖定模組141及載入鎖定模組142中的任一個、與複數個製程模組181～184中的任一個之間，以及在複數個製程模組181～184中的任意二個製程模組之間，搬運被加工物W。The load lock module 141 and the load lock module 142 respectively provide a processing chamber 141c and a processing chamber 142c for preliminary decompression. The loading and locking module 141 and the loading and locking module 142 are connected to the transfer module 116. The transfer module 116 provides a transfer processing chamber 116c that can be decompressed. The transfer module 116 has a transfer robot 116r. The conveyance robot 116r is installed in the conveyance processing chamber 116c. The transfer module 116 is connected to a plurality of process modules 181-184. The transfer robot 116r of the transfer module 116 can be between any one of the load lock module 141 and the load lock module 142, and any one of the plurality of process modules 181 to 184, as well as between the plurality of process modules 181 to 184. Between any two process modules among the two process modules 181-184, the workpiece W is transported.

複數個製程模組181～184，分別係基板處理裝置。複數個製程模組181～184中的一個，係圖4所示之電漿處理裝置10。A plurality of process modules 181-184 are respectively a substrate processing device. One of the plurality of process modules 181 to 184 is the plasma processing device 10 shown in FIG. 4.

控制部130構成為控制：處理系統110之各部位、以及複數個製程模組之各部位。控制部130，係例如電腦裝置，具有處理器、記憶裝置、鍵盤等輸入裝置、顯示裝置、以及訊號之輸入輸出介面。記憶裝置，儲存有用以執行方法MT的控制程式及製程配方資料。處理器，依照控制程式及製程配方資料，而將控制訊號送出至處理系統110之各部位、以及複數個製程模組之各部位。The control unit 130 is configured to control: each part of the processing system 110 and each part of a plurality of process modules. The control unit 130 is, for example, a computer device, which has input devices such as a processor, a memory device, a keyboard, a display device, and a signal input and output interface. The memory device stores the control program and process recipe data useful for executing the method MT. The processor sends control signals to various parts of the processing system 110 and various parts of a plurality of process modules in accordance with the control program and process recipe data.

濕洗淨裝置210，係在方法MT中用以去除阻障膜的裝置。濕洗淨裝置210，構成為對於其內部所容納之被加工物，執行用以去除阻障膜的濕蝕刻。The wet cleaning device 210 is a device used to remove the barrier film in the method MT. The wet cleaning device 210 is configured to perform wet etching for removing the barrier film on the processed object contained therein.

以下，針對電漿處理裝置10進行說明。圖4為概略繪示可用於執行圖1所示方法之電漿處理裝置的圖式。圖4所示之電漿處理裝置10，係電容耦合型電漿處理裝置。電漿處理裝置10，具備處理室本體12。處理室本體12，大致呈圓筒形。處理室本體12，提供其內部空間以作為處理室12c。於處理室本體12之內壁面，形成一層具有耐電漿性的覆膜。此覆膜，可以係藉由陽極氧化處理所形成之覆膜、或者由氧化釔所形成之覆膜。處理室本體12有接地。於處理室本體12之側壁，形成有開口12g。當被加工物W，從處理室本體12之外部搬入至處理室12c內時、以及從處理室12c內搬出至處理室本體12之外部時，會通過開口12g。於處理室本體12之側壁，安裝有閘閥14。閘閥14，係構成為使開口12g開閉。Hereinafter, the plasma processing apparatus 10 will be described. FIG. 4 is a schematic diagram showing a plasma processing apparatus that can be used to perform the method shown in FIG. 1. The plasma processing device 10 shown in FIG. 4 is a capacitive coupling type plasma processing device. The plasma processing apparatus 10 includes a processing chamber body 12. The processing chamber body 12 is substantially cylindrical. The processing chamber body 12 provides its internal space as a processing chamber 12c. On the inner wall surface of the main body 12 of the processing chamber, a coating film having plasma resistance is formed. This coating film may be a coating film formed by anodic oxidation treatment or a coating film formed of yttrium oxide. The processing chamber body 12 is grounded. On the side wall of the processing chamber body 12, an opening 12g is formed. When the workpiece W is carried into the processing chamber 12c from the outside of the processing chamber main body 12, and when it is carried out from the processing chamber 12c to the outside of the processing chamber main body 12, it passes through the opening 12g. A gate valve 14 is installed on the side wall of the processing chamber body 12. The gate valve 14 is configured to open and close the opening 12g.

於處理室本體12之底部上，設有支持部15。支持部15，係例如大致呈圓筒形，並由絶緣材料所形成。支持部15，係在處理室本體12內，從處理室本體12的底部朝向上方延伸。再者，於處理室12c內，設有工件台16。工件台16，係以支持部15所支撐。A supporting part 15 is provided on the bottom of the processing chamber body 12. The supporting portion 15 is, for example, substantially cylindrical and formed of an insulating material. The supporting part 15 is attached to the processing chamber main body 12 and extends upward from the bottom of the processing chamber main body 12. Furthermore, a work table 16 is provided in the processing chamber 12c. The work table 16 is supported by the supporting part 15.

工件台16，構成為支撐住載置於其頂面上的被加工物W。工件台16，具有下部電極18及靜電吸盤20。下部電極18，包含第1極板18a及第2極板18b。第1極板18a及第2極板18b，分別係由例如鋁等等的金屬所構成，大致呈圓盤狀。第2極板18b，係設在第1極板18a上，並與第1極板18a電性連接。The work table 16 is configured to support the workpiece W placed on the top surface thereof. The work table 16 has a lower electrode 18 and an electrostatic chuck 20. The lower electrode 18 includes a first electrode plate 18a and a second electrode plate 18b. The first electrode plate 18a and the second electrode plate 18b are each made of metal such as aluminum, and have a substantially disc shape. The second electrode plate 18b is provided on the first electrode plate 18a and is electrically connected to the first electrode plate 18a.

靜電吸盤20，係設於第2極板18b上。靜電吸盤20具有：絶緣層、以及設於該絶緣層內之導電膜所形成的電極。靜電吸盤20之電極，隔著開關23而與直流電源22電性連接。此靜電吸盤20，藉由來自直流電源22之直流電壓所產生的靜電力，而將被加工物W吸附至該靜電吸盤20，以固定該被加工物W。The electrostatic chuck 20 is arranged on the second electrode plate 18b. The electrostatic chuck 20 has an insulating layer and an electrode formed by a conductive film provided in the insulating layer. The electrodes of the electrostatic chuck 20 are electrically connected to the DC power supply 22 through the switch 23. The electrostatic chuck 20 attracts the processed object W to the electrostatic chuck 20 by the electrostatic force generated by the DC voltage from the DC power supply 22 to fix the processed object W.

在第2極板18b之周緣部上，配置有聚焦環24，其配置成包圍被加工物W之邊緣及靜電吸盤20。聚焦環24之設置，係用以提升對被加工物W之電漿處理的均勻性。聚焦環24，係由配合電漿處理而適當選擇的材料所形成。On the peripheral edge of the second electrode plate 18b, a focus ring 24 is arranged, which is arranged to surround the edge of the workpiece W and the electrostatic chuck 20. The setting of the focus ring 24 is used to improve the uniformity of the plasma treatment of the workpiece W. The focus ring 24 is formed of a material appropriately selected in accordance with plasma processing.

於第2極板18b之內部，形成有流路18f。對於流路18f，會經由配管26a，而從設在處理室本體12外部的冷卻單元供應冷媒過來。供應至流路18f的冷媒，會經由配管26b而回到冷卻單元。藉由使冷媒在流路18f與冷卻單元之間循環，來控制靜電吸盤20所支持之被加工物W的溫度。Inside the second electrode plate 18b, a flow path 18f is formed. For the flow path 18f, the refrigerant is supplied from the cooling unit provided outside the processing chamber body 12 via the pipe 26a. The refrigerant supplied to the flow path 18f returns to the cooling unit via the pipe 26b. By circulating a refrigerant between the flow path 18f and the cooling unit, the temperature of the workpiece W supported by the electrostatic chuck 20 is controlled.

於電漿處理裝置10，設有氣體供應管路28。氣體供應管路28，對於靜電吸盤20之頂面及被加工物W之背面之間，供應來自散熱氣體供應機構的散熱氣體，例如氦氣。The plasma processing device 10 is provided with a gas supply line 28. The gas supply pipe 28 supplies the heat dissipation gas from the heat dissipation gas supply mechanism between the top surface of the electrostatic chuck 20 and the back surface of the workpiece W, such as helium gas.

電漿處理裝置10，更進一步地具備上部電極30。上部電極30，係設於工件台16之上方。上部電極30，隔著構件32，而受到處理室本體12之上部所支撐。上部電極30，可包含頂棚板34及支持體36。頂棚板34，係面向處理室12c。於頂棚板34，形成有複數個氣體吐出孔34a。頂棚板34，係例如由矽所形成。或者，頂棚板34亦可以為表面形成有耐電漿性覆膜的鋁製構件。The plasma processing apparatus 10 further includes an upper electrode 30. The upper electrode 30 is arranged above the work table 16. The upper electrode 30 is supported by the upper part of the processing chamber body 12 with the member 32 interposed therebetween. The upper electrode 30 may include a ceiling plate 34 and a support 36. The ceiling plate 34 faces the processing chamber 12c. In the ceiling plate 34, a plurality of gas discharge holes 34a are formed. The ceiling plate 34 is formed of silicon, for example. Alternatively, the ceiling plate 34 may be an aluminum member with a plasma-resistant coating formed on the surface.

支持體36，裝卸自如支撐著頂棚板34。支持體36，係例如由鋁等等的導電性材料所形成。於支持體36之內部，形成有氣體擴散室36a。從氣體擴散室36a，有連通至氣體吐出孔34a之複數個氣體通流孔36b，朝向下方延伸。再者，於支持體36，形成有對氣體擴散室36a導入處理氣體的氣體導入口36c。氣體導入口36c，連接著氣體供應管38。The support body 36 supports the ceiling board 34 detachably. The support 36 is formed of, for example, a conductive material such as aluminum. Inside the support 36, a gas diffusion chamber 36a is formed. From the gas diffusion chamber 36a, there are a plurality of gas passage holes 36b that communicate with the gas discharge hole 34a, and extend downward. Furthermore, the support 36 is formed with a gas introduction port 36c for introducing a processing gas into the gas diffusion chamber 36a. A gas supply pipe 38 is connected to the gas inlet 36c.

氣體供應管38，隔著閥群42及流量控制器群44，而連接著氣體源群40。氣體源群40，具有複數個氣體源。於一案例中，氣體源群40具有：一個以上之含氟氣體源、N2 氣體源、H2 氣體源、稀有氣體源、前驅體氣體源、具有烷基矽烷基的胺基矽烷系氣體源、以及含氧氣體源。氣體源群40亦可更進一步地具有：含氮氣體（例如NH3 氣體）源、或烴氣（例如CH4 氣體、C2 H4 氣體、或C3 H8 氣體）源。The gas supply pipe 38 is connected to the gas source group 40 via the valve group 42 and the flow controller group 44. The gas source group 40 has a plurality of gas sources. In one case, the gas source group 40 has: one or more fluorine-containing gas sources, N 2 gas sources, H 2 gas sources, rare gas sources, precursor gas sources, and aminosilane gas sources with alkyl silyl groups , And a source of oxygen-containing gas. The gas source group 40 may further have: a source of nitrogen-containing gas (for example, NH 3 gas), or a source of hydrocarbon gas (for example, CH 4 gas, C 2 H 4 gas, or C 3 H 8 gas).

一個以上之含氟氣體源，可以包含：氟碳氣體源、氫氟碳氣體源、及NF3 氣體源中之一個以上。氟碳氣體源，例如包含CF4 氣體源、C4 F6 氣體源等等中之一個以上的氣體源。氫氟碳氣體源，係例如CH3 F氣體源。稀有氣體源，可以係氦氣、氖氣、氬氣、氪氣、氙氣等等任意之稀有氣體源。含氧氣體源，可以係氧（O2 ）氣、一氧化碳（CO）氣體、或二氧化碳（CO2 ）氣體源。The more than one fluorine-containing gas source may include more than one of a fluorocarbon gas source, a hydrofluorocarbon gas source, and an NF 3 gas source. The fluorocarbon gas source includes, for example , more than one of a CF 4 gas source, a C 4 F 6 gas source, and the like. The source of hydrofluorocarbon gas is, for example, a source of CH 3 F gas. The rare gas source can be any rare gas source such as helium, neon, argon, krypton, xenon, etc. The oxygen-containing gas source may be an oxygen (O 2 ) gas, carbon monoxide (CO) gas, or carbon dioxide (CO 2 ) gas source.

前驅體氣體源，係用於後述之步驟ST6。前驅體氣體源，可以係：含矽氣體源、或含金屬之氣體的氣體源。於一實施形態，前驅體氣體不含鹵素。用作前驅體氣體之含矽氣體，例如可以係胺基矽烷系氣體（於下文中，稱作「第1胺基矽烷系氣體」）。第1胺基矽烷系氣體，可以係任意之胺基矽烷系氣體。作為第1胺基矽烷系氣體，可以使用例如係單胺基矽烷（H3 －Si－R（R包含有機且可置換之胺基））。第1胺基矽烷系氣體，可以包含能具有1～3個矽原子的胺基矽烷，可以包含具有1～3個胺基的胺基矽烷。具有1～3個矽原子的胺基矽烷，可以為具有1～3個胺基的單矽烷、具有1～3個胺基的二矽烷、或具有1～3個胺基的三矽烷。更進一步地，上述之胺基矽烷，可以具有可置換之胺基。第1胺基矽烷系氣體，可以係：BTBAS（雙(第三丁基胺基)矽烷）、BDMAS（雙(二甲基胺基)矽烷）、BDEAS（雙(二乙基胺基)矽烷）、DMAS（二甲基胺基矽烷）、DEAS（二乙基胺基矽烷）、DPAS（二丙基胺基矽烷）、BAS（丁基胺基矽烷）、BEMAS（雙(乙基甲基胺基)矽烷）、或TDMAS（三(二甲基胺基)矽烷）。用作前驅體氣體之含矽氣體，亦可以係例如以TEOS（四乙氧基矽烷）為代表之矽醇鹽（silicon alkoxide）系氣體。用作前驅體氣體之含金屬之氣體，可以係三甲基鋁氣體。The precursor gas source is used in step ST6 described later. The precursor gas source may be: a silicon-containing gas source or a metal-containing gas source. In one embodiment, the precursor gas does not contain halogen. The silicon-containing gas used as the precursor gas may be, for example, an aminosilane-based gas (hereinafter, referred to as the "first aminosilane-based gas"). The first aminosilane-based gas may be any aminosilane-based gas. As the first aminosilane-based gas, for example, monoaminosilane (H 3 -Si-R (R contains an organic and replaceable amine group)) can be used. The first aminosilane-based gas may include an aminosilane capable of having 1 to 3 silicon atoms, and may include an aminosilane having 1 to 3 amino groups. The aminosilane having 1 to 3 silicon atoms may be monosilane having 1 to 3 amino groups, disilane having 1 to 3 amino groups, or trisilane having 1 to 3 amino groups. Furthermore, the aforementioned aminosilanes may have replaceable amino groups. The first aminosilane-based gas can be: BTBAS (bis(tertiary butylamino) silane), BDMAS (bis(dimethylamino) silane), BDEAS (bis(diethylamino) silane) , DMAS (dimethylaminosilane), DEAS (diethylaminosilane), DPAS (dipropylaminosilane), BAS (butylaminosilane), BEMAS (bis(ethylmethylaminosilane) ) Silane), or TDMAS (tris (dimethylamino) silane). The silicon-containing gas used as the precursor gas can also be a silicon alkoxide-based gas represented by TEOS (tetraethoxysilane), for example. The metal-containing gas used as the precursor gas may be trimethylaluminum gas.

具有烷基矽烷基之胺基矽烷系氣體（於下文中，稱作「第2胺基矽烷系氣體」）源，可以係：HDMS（六甲基二矽氮烷）、DMSDMA（二甲矽基二甲胺）、TMSDMA（二甲基胺基三甲基矽胺）、TMMAS（三甲基(甲胺基)矽烷）、TMICS（三甲基（異氰酸基）矽烷）、TMSA（三甲基矽基乙炔）、或TMSC（三甲基氰矽烷）。The source of aminosilane-based gas with alkylsilyl group (hereinafter referred to as "second aminosilane-based gas") can be: HDMS (hexamethyldisilazane), DMSDMA (dimethysilyl) Dimethylamine), TMSDMA (dimethylamino trimethylsilylamine), TMMAS (trimethyl (methylamino) silane), TMICS (trimethyl (isocyanato) silane), TMSA (trimethyl Base silyl acetylene), or TMSC (trimethylsilyl cyanide).

閥群42包含複數個閥，而流量控制器群44則包含質量流動控制器之類的複數個流量控制器。氣體源群40的複數個氣體源，分別經由閥群42之對應的閥、以及流量控制器群44之對應的流量控制器，而連接著氣體供應管38。The valve group 42 includes a plurality of valves, and the flow controller group 44 includes a plurality of flow controllers such as mass flow controllers. The plural gas sources of the gas source group 40 are respectively connected to the gas supply pipe 38 via the corresponding valve of the valve group 42 and the corresponding flow controller of the flow controller group 44.

於處理室本體12之底部側、並且係於支持部15與處理室本體12的側壁之間，設有折流板48。於折流板48，形成有複數個於板厚方向延伸的貫穿孔。折流板48，可以係例如藉由在鋁製之母材上，被覆Y2 O3 等的陶瓷而形成。於折流板48之下方，有排氣管52連接至處理室本體12。排氣管52，連接至排氣裝置50。排氣裝置50具有：壓力調整閥這類的壓力調整器、以及渦輪分子泵這類的真空泵。排氣裝置50，係構成為將處理室12c減壓至指定之壓力。A baffle 48 is provided on the bottom side of the processing chamber body 12 and between the supporting portion 15 and the side wall of the processing chamber body 12. The baffle 48 is formed with a plurality of through holes extending in the plate thickness direction. The baffle 48 can be formed, for example, by coating a base material made of aluminum with ceramics such as Y 2 O 3. Below the baffle 48, there is an exhaust pipe 52 connected to the processing chamber body 12. The exhaust pipe 52 is connected to the exhaust device 50. The exhaust device 50 has a pressure regulator such as a pressure regulator valve and a vacuum pump such as a turbomolecular pump. The exhaust device 50 is configured to depressurize the processing chamber 12c to a predetermined pressure.

電漿處理裝置10，更進一步地具備第1高頻電源62及第2高頻電源64。第1高頻電源62，係發出第1高頻的電源，該第1高頻係用以產生電漿。第1高頻，係例如具有27～100MHz的頻率。第1高頻電源62，經由匹配器63而連接至上部電極30。匹配器63，具有用以將第1高頻電源62的輸出阻抗與負載側的阻抗加以匹配的電路。又，第1高頻電源62，亦可係經由匹配器63而連接至下部電極18。The plasma processing apparatus 10 further includes a first high-frequency power source 62 and a second high-frequency power source 64. The first high-frequency power source 62 is a power source that emits a first high-frequency, and the first high-frequency is used to generate plasma. The first high frequency has, for example, a frequency of 27 to 100 MHz. The first high-frequency power source 62 is connected to the upper electrode 30 via a matching device 63. The matching device 63 has a circuit for matching the output impedance of the first high-frequency power source 62 with the impedance on the load side. In addition, the first high-frequency power source 62 may be connected to the lower electrode 18 via the matching device 63.

第2高頻電源64，係發出第2高頻的電源，該第2高頻係用以對被加工物W引入離子，亦即偏壓用。第2高頻，例如具有400kHz～13.56MHz之範圍內的頻率。第2高頻電源64，經由匹配器65而連接至下部電極18。匹配器65，具有用以將第2高頻電源64的輸出阻抗與負載側的阻抗加以匹配的電路。The second high-frequency power source 64 is a power source that emits a second high-frequency, and the second high-frequency is used to introduce ions into the workpiece W, that is, for bias. The second high frequency has a frequency in the range of 400 kHz to 13.56 MHz, for example. The second high-frequency power source 64 is connected to the lower electrode 18 via a matching unit 65. The matching unit 65 has a circuit for matching the output impedance of the second high-frequency power source 64 with the impedance on the load side.

再度參照圖1，針對方法MT進行說明。於下文中，係套用以下情形來說明方法MT：使用處理系統110及濕洗淨裝置210以執行方法MT，並且使用電漿處理裝置10來執行方法MT的步驟ST1～步驟ST7。又，方法MT，未必要使用處理系統110及濕洗淨裝置210來執行。再者，方法MT的步驟ST1～步驟ST7，亦可使用包含電漿處理裝置10之一個以上的基板處理裝置、或電漿處理裝置10以外之一個以上的基板處理裝置來執行。Referring again to FIG. 1, the method MT will be described. In the following, the method MT will be described in the following situations: the processing system 110 and the wet cleaning device 210 are used to execute the method MT, and the plasma processing device 10 is used to execute the steps ST1 to ST7 of the method MT. In addition, the method MT does not need to be executed using the processing system 110 and the wet cleaning device 210. Furthermore, steps ST1 to ST7 of the method MT can also be executed using one or more substrate processing apparatuses including the plasma processing apparatus 10 or one or more substrate processing apparatuses other than the plasma processing apparatus 10.

以下，搭配圖1，一併參照圖5～圖14。圖5為繪示圖1所示方法之步驟ST3的流程圖。圖6為繪示圖1所示方法之步驟ST6的流程圖。圖7～圖13為擴大繪示圖1所示方法之中間階段所製得之被加工物局部的剖面圖。圖14為擴大繪示圖1所示方法結束時所製得之被加工物局部的剖面圖。Hereinafter, in conjunction with FIG. 1, refer to FIGS. 5 to 14 together. FIG. 5 is a flowchart showing step ST3 of the method shown in FIG. 1. FIG. 6 is a flowchart showing step ST6 of the method shown in FIG. 1. 7 to 13 are enlarged cross-sectional views showing a part of the processed object prepared in the intermediate stage of the method shown in FIG. 1. Fig. 14 is an enlarged drawing showing a partial cross-sectional view of the to-be-processed object obtained at the end of the method shown in Fig. 1.

如圖1所示，於一實施形態，以步驟ST1開始方法MT。於步驟ST1，進行防止反射膜BL之蝕刻。防止反射膜BL之蝕刻，係電漿蝕刻。在使用電漿處理裝置10的情況下，於步驟ST1，係將圖2所示之被加工物W，載置於工件台16的靜電吸盤20上，並以該靜電吸盤20加以保持。然後，從複數個氣體源之中所選出的一個以上之氣體源，對處理室12c供應用以蝕刻防止反射膜BL的氣體。於步驟ST1，供應至處理室12c的氣體，可以係氟碳氣體。再者，於步驟ST1，會以排氣裝置50將處理室12c加以減壓。更進一步地，於步驟ST1，對上部電極30供應來自第1高頻電源62的第1高頻，對下部電極18供應來自第2高頻電源64的第2高頻。As shown in Fig. 1, in one embodiment, the method MT is started with step ST1. In step ST1, the anti-reflective film BL is etched. The etching of the anti-reflective film BL is plasma etching. In the case of using the plasma processing apparatus 10, in step ST1, the workpiece W shown in FIG. 2 is placed on the electrostatic chuck 20 of the work table 16 and held by the electrostatic chuck 20. Then, one or more gas sources selected from a plurality of gas sources supply the gas for etching the anti-reflection film BL to the processing chamber 12c. In step ST1, the gas supplied to the processing chamber 12c may be a fluorocarbon gas. Furthermore, in step ST1, the processing chamber 12c is decompressed by the exhaust device 50. Furthermore, in step ST1, the upper electrode 30 is supplied with the first high frequency from the first high-frequency power source 62, and the lower electrode 18 is supplied with the second high frequency from the second high-frequency power source 64.

於步驟ST1，供應至處理室12c的氣體產生電漿，並藉由該電漿中的離子及／或自由基這類的活性物種，以蝕刻防止反射膜BL。藉由執行此步驟ST1，如圖7所示，光罩RM的圖案會轉印至防止反射膜BL，而在防止反射膜BL形成開口，此開口會連續至光罩RM之開口。In step ST1, the gas supplied to the processing chamber 12c generates plasma, and the anti-reflection film BL is etched by active species such as ions and/or radicals in the plasma. By performing this step ST1, as shown in FIG. 7, the pattern of the photomask RM is transferred to the anti-reflective film BL, and an opening is formed in the anti-reflective film BL, and the opening is continuous to the opening of the photomask RM.

如圖1所示，於一實施形態之方法MT，接下來就執行步驟ST2。於步驟ST2，進行圖7所示之被加工物W的遮罩層MKL之蝕刻。遮罩層MKL之蝕刻，係電漿蝕刻。在使用電漿處理裝置10的情況下，於步驟ST2，係將圖7所示之被加工物W，載置於工件台16的靜電吸盤20上，並以該靜電吸盤20加以保持。然後，於步驟ST2，從複數個氣體源之中所選出的一個以上之氣體源，對處理室12c供應用以蝕刻遮罩層MKL的氣體。於步驟ST2，供應至處理室12c的氣體，係例如N2 氣體及H2 氣體的混合氣體。再者，於步驟ST2，會以排氣裝置50將處理室12c加以減壓。更進一步地，於步驟ST2，對上部電極30供應來自第1高頻電源62的第1高頻，對下部電極18供應來自第2高頻電源64的第2高頻。As shown in FIG. 1, in the method MT of an embodiment, step ST2 is executed next. In step ST2, the mask layer MKL of the workpiece W shown in FIG. 7 is etched. The etching of the mask layer MKL is plasma etching. In the case of using the plasma processing apparatus 10, in step ST2, the workpiece W shown in FIG. 7 is placed on the electrostatic chuck 20 of the work table 16 and held by the electrostatic chuck 20. Then, in step ST2, one or more gas sources selected from a plurality of gas sources supply the gas for etching the mask layer MKL to the processing chamber 12c. In step ST2, the gas supplied to the processing chamber 12c is, for example, a mixed gas of N 2 gas and H 2 gas. Furthermore, in step ST2, the processing chamber 12c is decompressed by the exhaust device 50. Furthermore, in step ST2, the upper electrode 30 is supplied with the first high frequency from the first high-frequency power supply 62, and the lower electrode 18 is supplied with the second high frequency from the second high-frequency power supply 64.

於步驟ST2，供應至處理室12c的氣體產生電漿，並藉由該電漿中的離子及／或自由基這類的活性物種，以蝕刻遮罩層MKL。藉由執行此步驟ST2，如圖8所示，防止反射膜BL的圖案會轉印至遮罩層MKL，而在遮罩層MKL形成開口，此開口會連續至防止反射膜BL之開口。藉此，從遮罩層MKL製得遮罩MK。In step ST2, the gas supplied to the processing chamber 12c generates plasma, and the mask layer MKL is etched by active species such as ions and/or radicals in the plasma. By performing this step ST2, as shown in FIG. 8, the pattern of the anti-reflective film BL is transferred to the mask layer MKL, and an opening is formed in the mask layer MKL, and the opening is continuous to the opening of the anti-reflective film BL. In this way, the mask MK is produced from the mask layer MKL.

如圖1所示，於一實施形態之方法MT，接下來就執行步驟ST3。於步驟ST3，藉由含氟氣體之電漿處理以蝕刻絶緣膜IL。於一案例中，絶緣膜IL包含第1層IL1及第2層IL2；步驟ST3如圖5所示，包含步驟ST31及步驟ST32。As shown in FIG. 1, in the method MT of one embodiment, step ST3 is executed next. In step ST3, the insulating film IL is etched by plasma treatment of a fluorine-containing gas. In one case, the insulating film IL includes a first layer IL1 and a second layer IL2; as shown in FIG. 5, step ST3 includes steps ST31 and ST32.

於步驟ST31，進行第2層IL2之蝕刻。在使用電漿處理裝置10的情況下，於步驟ST31，係將圖8所示之被加工物W，載置於工件台16的靜電吸盤20上，並以該靜電吸盤20加以保持。然後，於步驟ST31，從複數個氣體源之中所選出的一個以上之氣體源，對處理室12c供應用以蝕刻第2層IL2的氣體。於步驟ST31，供應至處理室12c的氣體，係例如氟碳氣體、O2 氣體、以及稀有氣體的混合氣體。再者，於步驟ST31，會以排氣裝置50將處理室12c加以減壓。更進一步地，於步驟ST31，對上部電極30供應來自第1高頻電源62的第1高頻，對下部電極18供應來自第2高頻電源64的第2高頻。於步驟ST31，供應至處理室12c的氣體產生電漿，並藉由該電漿中的離子及／或自由基這類的活性物種，以蝕刻第2層IL2。藉由執行此步驟ST31，如圖9所示，在第2層IL2形成開口，此開口會連續至遮罩MK之開口。In step ST31, the second layer IL2 is etched. In the case of using the plasma processing apparatus 10, in step ST31, the workpiece W shown in FIG. 8 is placed on the electrostatic chuck 20 of the work table 16 and held by the electrostatic chuck 20. Then, in step ST31, one or more gas sources selected from a plurality of gas sources supply the gas for etching the second layer IL2 to the processing chamber 12c. In step ST31, the gas supplied to the processing chamber 12c is, for example, a mixed gas of fluorocarbon gas, O 2 gas, and rare gas. Furthermore, in step ST31, the processing chamber 12c is decompressed by the exhaust device 50. Furthermore, in step ST31, the upper electrode 30 is supplied with the first high frequency from the first high-frequency power supply 62, and the lower electrode 18 is supplied with the second high frequency from the second high-frequency power supply 64. In step ST31, the gas supplied to the processing chamber 12c generates plasma, and the second layer IL2 is etched by active species such as ions and/or radicals in the plasma. By performing this step ST31, as shown in FIG. 9, an opening is formed in the second layer IL2, and the opening will continue to the opening of the mask MK.

於步驟ST32，進行第1層IL1之蝕刻。在使用電漿處理裝置10的情況下，於步驟ST32，係將被加工物W，載置於工件台16的靜電吸盤20上，並以該靜電吸盤20加以保持。然後，於步驟ST32，從複數個氣體源之中所選出的一個以上之氣體源，對處理室12c供應用以蝕刻第1層IL1的氣體。於步驟ST32，供應至處理室12c的氣體，係例如氫氟碳氣體及稀有氣體的混合氣體。再者，於步驟ST32，會以排氣裝置50將處理室12c加以減壓。更進一步地，於步驟ST32，對上部電極30供應來自第1高頻電源62的第1高頻，對下部電極18供應來自第2高頻電源64的第2高頻。於步驟ST32，供應至處理室12c的氣體產生電漿，並藉由該電漿中的離子及／或自由基這類的活性物種，以蝕刻第1層IL1。藉由執行此步驟ST32，如圖10所示，在第1層IL1形成開口，此開口會連續至遮罩MK之開口及第2層IL2之開口。藉由步驟ST3之執行，而使形成在絶緣膜IL的開口，延伸至金屬層MTL之表面。於此種絶緣膜IL之蝕刻，會在金屬層MTL之表面上形成含氟殘留物。In step ST32, the first layer IL1 is etched. In the case of using the plasma processing apparatus 10, in step ST32, the workpiece W is placed on the electrostatic chuck 20 of the work table 16 and held by the electrostatic chuck 20. Then, in step ST32, one or more gas sources selected from a plurality of gas sources supply the gas for etching the first layer IL1 to the processing chamber 12c. In step ST32, the gas supplied to the processing chamber 12c is, for example, a mixed gas of hydrofluorocarbon gas and rare gas. Furthermore, in step ST32, the processing chamber 12c is decompressed by the exhaust device 50. Furthermore, in step ST32, the upper electrode 30 is supplied with the first high frequency from the first high-frequency power supply 62, and the lower electrode 18 is supplied with the second high frequency from the second high-frequency power supply 64. In step ST32, the gas supplied to the processing chamber 12c generates plasma, and the first layer IL1 is etched by active species such as ions and/or radicals in the plasma. By performing this step ST32, as shown in FIG. 10, an opening is formed in the first layer IL1, and this opening will continue to the opening of the mask MK and the opening of the second layer IL2. By performing step ST3, the opening formed in the insulating film IL extends to the surface of the metal layer MTL. The etching of this insulating film IL will form fluorine-containing residues on the surface of the metal layer MTL.

如圖1所示，於一實施形態之方法MT，接下來就執行步驟ST4。於步驟ST4，去除圖10所示之被加工物W的遮罩MK。為了去除遮罩MK，於步驟ST4，會執行電漿蝕刻。在使用電漿處理裝置10的情況下，於步驟ST4，係將圖10所示之被加工物W，載置於工件台16的靜電吸盤20上，並以該靜電吸盤20加以保持。然後，於步驟ST4，從複數個氣體源之中所選出的一個以上之氣體源，對處理室12c供應用以蝕刻遮罩MK的氣體。於步驟ST4，供應至處理室12c的氣體，係含氮（N）及／或氫（H）的氣體，例如N2 氣體與H2 氣體的混合氣體。再者，於步驟ST4，會以排氣裝置50將處理室12c加以減壓。更進一步地，於步驟ST4，會對上部電極30供應來自第1高頻電源62的第1高頻。於步驟ST4，亦可對下部電極18供應來自第2高頻電源64的第2高頻。又，於步驟ST4供應至處理室12c的氣體，亦可係O2 、CO、CO2 等等的含氧（O）氣體。As shown in FIG. 1, in the method MT of one embodiment, step ST4 is executed next. In step ST4, the mask MK of the workpiece W shown in FIG. 10 is removed. In order to remove the mask MK, in step ST4, plasma etching is performed. In the case of using the plasma processing apparatus 10, in step ST4, the workpiece W shown in FIG. 10 is placed on the electrostatic chuck 20 of the work table 16 and held by the electrostatic chuck 20. Then, in step ST4, one or more gas sources selected from a plurality of gas sources supply the gas for etching the mask MK to the processing chamber 12c. In step ST4, the gas supplied to the processing chamber 12c is a gas containing nitrogen (N) and/or hydrogen (H), such as a mixed gas of N 2 gas and H 2 gas. Furthermore, in step ST4, the processing chamber 12c is decompressed by the exhaust device 50. Furthermore, in step ST4, the upper electrode 30 is supplied with the first high frequency from the first high frequency power supply 62. In step ST4, the second high frequency from the second high frequency power supply 64 may be supplied to the lower electrode 18. In addition, the gas supplied to the processing chamber 12c in step ST4 may also be an oxygen (O) -containing gas such as O 2 , CO, CO 2 and the like.

於步驟ST4，供應至處理室12c的氣體產生電漿，並藉由該電漿中的離子及／或自由基這類的活性物種，以蝕刻遮罩MK。藉由執行此步驟ST4，如圖11所示，遮罩MK就會去除。In step ST4, the gas supplied to the processing chamber 12c generates plasma, and the active species such as ions and/or radicals in the plasma are used to etch the mask MK. By performing this step ST4, as shown in FIG. 11, the mask MK will be removed.

於一實施形態，方法MT，在步驟ST4與步驟ST6之間，亦可更進一步地包含步驟ST5。於步驟ST5，會對於施行過步驟ST4的被加工物W之金屬層MTL，執行表面處理（treatment）。步驟ST5中之表面處理，係例如含N2 及H2 之氣體的電漿所進行的電漿處理。在使用電漿處理裝置10的情況下，於步驟ST5，係將被加工物W，載置於工件台16的靜電吸盤20上，並以該靜電吸盤20加以保持。然後，於步驟ST5，從複數個氣體源對處理室12c供應含N2 及H2 的氣體（混合氣體）。再者，於步驟ST5，會以排氣裝置50將處理室12c加以減壓。更進一步地，於步驟ST5，亦可對上部電極30供應來自第1高頻電源62的第1高頻，對下部電極18供應來自第2高頻電源64的第2高頻。又，步驟ST5中之表面處理所使用的氣體，並不限定於含N2 及H2 之氣體，亦可係含氫（H）氣體。用於步驟ST5之表面處理的氣體，除了氫（H）以外，亦可包含氮（N）。再者，用於步驟ST5之表面處理的氣體，亦可係還原性氣體。In one embodiment, the method MT may further include step ST5 between step ST4 and step ST6. In step ST5, surface treatment is performed on the metal layer MTL of the workpiece W that has been subjected to step ST4. The surface treatment in step ST5 is, for example, plasma treatment performed by plasma containing N 2 and H 2 gases. In the case of using the plasma processing apparatus 10, in step ST5, the workpiece W is placed on the electrostatic chuck 20 of the work table 16 and held by the electrostatic chuck 20. Then, in step ST5, a gas (mixed gas) containing N 2 and H 2 is supplied to the processing chamber 12 c from a plurality of gas sources. Furthermore, in step ST5, the processing chamber 12c is decompressed by the exhaust device 50. Furthermore, in step ST5, the first high frequency from the first high frequency power supply 62 may be supplied to the upper electrode 30 and the second high frequency from the second high frequency power supply 64 may be supplied to the lower electrode 18. In addition, the gas used for the surface treatment in step ST5 is not limited to a gas containing N 2 and H 2 , and may be a gas containing hydrogen (H). The gas used for the surface treatment in step ST5 may contain nitrogen (N) in addition to hydrogen (H). Furthermore, the gas used for the surface treatment in step ST5 may also be a reducing gas.

於步驟ST5，供應至處理室12c的氣體產生電漿，並藉由該電漿中的離子及／或自由基這類的活性物種，以處理金屬層MTL之表面。亦即，減少存在於金屬層MTL之表面的殘留物的量。再者，步驟ST5中之表面處理用的氣體，若係還原性氣體，例如含氫（H）氣體，則即使於步驟ST3或步驟ST4中，金屬層MTL之表面有所氧化，也能藉由該表面處理，而使該金屬層MTL之表面還原。In step ST5, the gas supplied to the processing chamber 12c generates plasma, and the surface of the metal layer MTL is processed by active species such as ions and/or free radicals in the plasma. That is, the amount of residue existing on the surface of the metal layer MTL is reduced. Furthermore, if the surface treatment gas in step ST5 is a reducing gas, such as hydrogen (H) gas, even if the surface of the metal layer MTL is oxidized in step ST3 or step ST4, it can be The surface treatment reduces the surface of the metal layer MTL.

於方法MT，接下來就執行步驟ST6。於步驟ST6，如圖12所示，形成阻障膜BF，以包覆絶緣膜IL之表面、以及形成於絶緣膜IL之開口所露出的金屬層MTL之表面。於步驟ST6所形成的阻障膜BF，係於絶緣膜IL之表面、以及形成於絶緣膜IL之開口所露出的金屬層MTL之表面上，保形地形成之膜層。亦即，阻障膜BF，係相對於被加工物W表面上之形成位置的膜厚依存性較小的膜層。例如，相對於阻障膜BF之膜厚的平均値，該阻障膜BF中之膜厚的偏差係±10％以下。阻障膜BF的膜厚，可以是比形成於絶緣膜IL之開口的寬度或直徑之1／2或1／4還要薄的膜厚。於一實施形態，阻障膜BF的膜厚，係0.45nm以上。In the method MT, step ST6 is executed next. In step ST6, as shown in FIG. 12, a barrier film BF is formed to cover the surface of the insulating film IL and the surface of the metal layer MTL exposed by the opening formed in the insulating film IL. The barrier film BF formed in step ST6 is a film layer formed conformally on the surface of the insulating film IL and the surface of the metal layer MTL exposed by the opening of the insulating film IL. That is, the barrier film BF is a film layer that has a small dependence on the film thickness of the formation position on the surface of the workpiece W. For example, with respect to the average value of the film thickness of the barrier film BF, the deviation of the film thickness in the barrier film BF is ±10% or less. The film thickness of the barrier film BF may be thinner than 1/2 or 1/4 of the width or diameter of the opening formed in the insulating film IL. In one embodiment, the thickness of the barrier film BF is 0.45 nm or more.

阻障膜BF，可以係含矽膜、或金屬氧化膜。含矽膜，係例如氧化矽膜、氮化矽膜、或碳化矽膜。金屬氧化膜，係例如氧化鋁膜。阻障膜BF之成膜法，可以係原子層沈積法、或循環電漿輔助化學氣相沈積（cyclic plasma enhanced CVD）法這類的循環式成膜（cyclic deposition）法。The barrier film BF may be a silicon-containing film or a metal oxide film. The silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, or a silicon carbide film. The metal oxide film is, for example, an aluminum oxide film. The film formation method of the barrier film BF may be a cyclic deposition method such as atomic layer deposition method or cyclic plasma enhanced chemical vapor deposition (cyclic plasma enhanced CVD) method.

若於步驟ST6係使用原子層沈積法，則步驟ST6如圖6所示，會包含步驟ST61～步驟ST65。於步驟ST61，會對於容納在處理室內的被加工物W，供應前驅體氣體。於一實施形態，前驅體氣體不含鹵素。一旦執行步驟ST61，就會在被加工物W之表面吸附前驅體。在後續的步驟ST62，會進行處理室的吹洗（purge）。在後續的步驟ST63，會在處理室內對被加工物執行電漿處理。於步驟ST63，吸附於被加工物W的前驅體，會與電漿中的離子及／或自由基反應。在後續的步驟ST64，會判定是否已滿足結束條件。若包含步驟ST61及步驟ST63在內的排序流程（sequence）之執行次數達到既定次數，就滿足結束條件。若未滿足結束條件，則會在後續的步驟ST65，進行處理室的吹洗，再使處理回到步驟ST61。另一方面，若已滿足結束條件，步驟ST6就會結束。其結果，會形成阻障膜BF。又，步驟ST6，亦可不包含步驟ST62及步驟ST65。If the atomic layer deposition method is used in step ST6, step ST6 will include steps ST61 to ST65 as shown in FIG. 6. In step ST61, the precursor gas is supplied to the workpiece W contained in the processing chamber. In one embodiment, the precursor gas does not contain halogen. Once step ST61 is executed, the precursor is adsorbed on the surface of the workpiece W. In the subsequent step ST62, the processing chamber will be purged. In the subsequent step ST63, plasma processing is performed on the workpiece in the processing chamber. In step ST63, the precursor adsorbed on the workpiece W will react with ions and/or free radicals in the plasma. In the subsequent step ST64, it is determined whether the end condition has been satisfied. If the number of executions of the sequence including step ST61 and step ST63 reaches a predetermined number of times, the end condition is satisfied. If the end condition is not satisfied, the processing chamber will be purged in the subsequent step ST65, and the processing will be returned to step ST61. On the other hand, if the end condition has been satisfied, step ST6 will end. As a result, a barrier film BF is formed. In addition, step ST6 may not include step ST62 and step ST65.

若阻障膜BF為含矽膜，則在步驟ST61，會使用含矽氣體以作為前驅體氣體。用作為前驅體氣體之含矽氣體，係例如上述之第1胺基矽烷系氣體或矽醇鹽系氣體。若阻障膜BF為金屬氧化膜，則在步驟ST61，會使用含金屬之氣體以作為前驅體氣體。含金屬之氣體，係例如三甲基鋁氣體。若阻障膜BF為氧化矽膜或金屬氧化膜，則在步驟ST63的電漿處理，會使用含氧氣體。含氧氣體，係例如氧（O2 ）氣、CO氣體、或CO2 氣體。若阻障膜BF為氮化矽膜，則在步驟ST63的電漿處理，會使用含氮氣體（例如NH3 氣體）。若阻障膜BF為碳化矽膜，則在步驟ST63的電漿處理，會使用烴氣（例如CH4 氣體、C2 H4 氣體、或C3 H8 氣體）。If the barrier film BF is a silicon-containing film, in step ST61, a silicon-containing gas is used as the precursor gas. The silicon-containing gas used as the precursor gas is, for example, the above-mentioned first aminosilane-based gas or silicon alkoxide-based gas. If the barrier film BF is a metal oxide film, in step ST61, a metal-containing gas is used as the precursor gas. The metal-containing gas is, for example, trimethylaluminum gas. If the barrier film BF is a silicon oxide film or a metal oxide film, the plasma treatment in step ST63 will use an oxygen-containing gas. The oxygen-containing gas is, for example, oxygen (O 2 ) gas, CO gas, or CO 2 gas. If the barrier film BF is a silicon nitride film, the plasma treatment in step ST63 will use a nitrogen-containing gas (for example, NH 3 gas). If the barrier film BF is a silicon carbide film, a hydrocarbon gas (for example, CH 4 gas, C 2 H 4 gas, or C 3 H 8 gas) will be used in the plasma treatment in step ST63.

於步驟ST6所使用的原子層沈積法，相較於化學氣相沈積法（CVD），更能夠形成保形的膜層，並且可以形成少有微孔的膜層。因此，原子層沈積法所形成之膜層，具有非常低的通透性。亦即，若藉由原子層沈積法，得以形成具有高屏障性的阻障膜。再者，若藉由原子層沈積法，由於可以形成保形、且具有高深寬比（high aspect ratio）的膜層，因此即使被加工物W之遮罩MK的開口尺寸微細化，亦可在金屬層MTL之表面形成阻障膜BF。更進一步地，由於原子層沈積法相較於化學氣相沈積法（CVD），係可以在低處理溫度成膜，因此可以壓低成膜處理對被加工物W內含之半導體元件所造成的影響。Compared with chemical vapor deposition (CVD), the atomic layer deposition method used in step ST6 can form a conformal film layer and can form a film layer with few micropores. Therefore, the film formed by the atomic layer deposition method has very low permeability. That is, if the atomic layer deposition method is used, a barrier film with high barrier properties can be formed. Furthermore, if the atomic layer deposition method is used, since a conformal and high aspect ratio film can be formed, even if the opening size of the mask MK of the workpiece W is made finer, it can be A barrier film BF is formed on the surface of the metal layer MTL. Furthermore, since the atomic layer deposition method can form a film at a lower processing temperature than the chemical vapor deposition (CVD) method, the influence of the film formation process on the semiconductor elements contained in the workpiece W can be suppressed.

從步驟ST3開始時、到步驟ST6結束時為止，被加工物W都維持在減壓環境中。於一實施形態，係於步驟ST3開始時、到步驟ST6結束時為止，被加工物W都維持在同一個處理室內。例如，從步驟ST3開始時、到步驟ST6結束時為止，被加工物W都維持在電漿處理裝置10的處理室12c內。亦即，步驟ST3與步驟ST6，都在同一個電漿處理裝置10執行。或者，執行步驟ST6所使用的基板處理裝置，亦可不同於步驟ST3所使用的基板處理裝置。但是，從步驟ST3開始時、到步驟ST6結束時為止，被加工物W都要維持在減壓環境中。例如，亦可係步驟ST3、或步驟ST3～步驟ST5使用電漿處理裝置10來執行，而在執行步驟ST6前，使被加工物W僅經由移載模組116搬運到作為處理系統110之另一製程模組的成膜裝置。From the beginning of step ST3 to the end of step ST6, the workpiece W is maintained in a reduced pressure environment. In one embodiment, the workpiece W is maintained in the same processing chamber at the beginning of step ST3 and until the end of step ST6. For example, from the beginning of step ST3 to the end of step ST6, the workpiece W is maintained in the processing chamber 12c of the plasma processing apparatus 10. That is, step ST3 and step ST6 are both performed in the same plasma processing device 10. Alternatively, the substrate processing apparatus used in step ST6 may be different from the substrate processing apparatus used in step ST3. However, from the beginning of step ST3 to the end of step ST6, the workpiece W is maintained in a reduced pressure environment. For example, step ST3 or steps ST3 to ST5 may be executed using the plasma processing apparatus 10, and before step ST6 is executed, the workpiece W may be transported to another processing system 110 through the transfer module 116 only. A film forming device of a process module.

方法MT，在步驟ST6與步驟ST8之間，亦可更進一步地包含步驟ST7。於步驟ST7，會對於圖12所示之被加工物W，供應上述之第2胺基矽烷系氣體。藉由步驟ST7之執行，如圖13所示，會在阻障膜BF上形成第2胺基矽烷系氣體所構成的保護膜PF。此步驟ST7，可使用電漿處理裝置10來執行。或者，步驟ST7，亦可使用不同於電漿處理裝置10之處理系統110的基板處理裝置來執行。The method MT, between step ST6 and step ST8, may further include step ST7. In step ST7, the above-mentioned second aminosilane-based gas is supplied to the workpiece W shown in FIG. 12. By the execution of step ST7, as shown in FIG. 13, a protective film PF made of a second aminosilane-based gas is formed on the barrier film BF. This step ST7 can be performed using the plasma processing apparatus 10. Alternatively, step ST7 can also be performed using a substrate processing apparatus other than the processing system 110 of the plasma processing apparatus 10.

於方法MT，接下來就執行步驟ST8。於步驟ST8，會將圖13所示之被加工物W（若不執行步驟ST7，則係圖12所示之被加工物）配置於大氣環境中。若使用處理系統110，則被加工物W會從步驟ST7所用過的基板處理裝置（若不執行步驟ST7，則係步驟ST6所用過的基板處理裝置），經由移載模組116、載入鎖定模組141或載入鎖定模組142、以及載入模組112，而搬運至大氣環境。然後，直到執行步驟ST9為止的期間，被加工物W會在大氣環境中保管。In the method MT, step ST8 is executed next. In step ST8, the workpiece W shown in FIG. 13 (if step ST7 is not performed, it is the workpiece shown in FIG. 12) is placed in the atmosphere. If the processing system 110 is used, the workpiece W will be transferred from the substrate processing apparatus used in step ST7 (if step ST7 is not performed, it is the substrate processing apparatus used in step ST6), through the transfer module 116, load lock The module 141 or the load lock module 142 and the load module 112 are transported to the atmosphere. Then, until step ST9 is executed, the workpiece W is stored in an atmospheric environment.

於方法MT，接下來就執行步驟ST9。於步驟ST9，如圖14所示，會去除阻障膜BF。若有執行過步驟ST7，則會將保護膜PF與阻障膜BF一同去除。於步驟ST9，會藉由等向性蝕刻來去除阻障膜BF。於一實施形態，等向性蝕刻係濕蝕刻。用於濕蝕刻的溶液，包含氫氟酸（HF）或氟化銨（NH4 F）。此濕蝕刻，可使用濕洗淨裝置210。In the method MT, step ST9 is executed next. In step ST9, as shown in FIG. 14, the barrier film BF is removed. If step ST7 has been performed, the protective film PF and the barrier film BF will be removed together. In step ST9, the barrier film BF is removed by isotropic etching. In one embodiment, the isotropic etching is wet etching. The solution used for wet etching contains hydrofluoric acid (HF) or ammonium fluoride (NH 4 F). For this wet etching, a wet cleaning device 210 can be used.

若藉由該方法MT，則在步驟ST3中對絶緣膜進行蝕刻之後、並且在將被加工物W配置於大氣環境中之前，絶緣膜IL之表面及金屬層MTL之表面，係受到阻障膜BF所包覆。由於金屬層MTL之表面受到此阻障膜BF保護，因此即使將被加工物W配置於大氣環境中，也會抑制金屬層MTL之腐蝕。此阻障膜BF，會在步驟ST9受到去除。在阻障膜BF之膜厚偏差大的情況下，會由於步驟ST9的等向性蝕刻，而使得以膜厚較薄之部分所包覆的部位，有絶緣膜IL被局部性大輻度蝕刻的問題。以方法MT所形成之阻障膜BF，由於係保形地形成之膜層，所以在步驟ST9的等向性蝕刻，會均勻地去除。因此，若藉由方法MT，於去除阻障膜BF之際，能抑制絶緣膜IL有局部被大輻度蝕刻的問題。According to the method MT, after the insulating film is etched in step ST3 and before the workpiece W is placed in the atmosphere, the surface of the insulating film IL and the surface of the metal layer MTL are subjected to the barrier film Covered by BF. Since the surface of the metal layer MTL is protected by the barrier film BF, even if the workpiece W is arranged in the atmosphere, the corrosion of the metal layer MTL will be suppressed. The barrier film BF will be removed in step ST9. In the case where the thickness deviation of the barrier film BF is large, due to the isotropic etching in step ST9, the insulating film IL is locally etched to a large extent in the area covered by the thinner film thickness. The problem. Since the barrier film BF formed by the method MT is a conformal film layer, the isotropic etching in step ST9 will be uniformly removed. Therefore, if the method MT is used to remove the barrier film BF, it is possible to prevent the insulating film IL from being locally etched to a large extent.

於一實施形態之步驟ST3，係使用不含鹵素的前驅體氣體。若藉由該前驅體氣體，會抑制金屬層MTL之表面的損傷。In step ST3 of an embodiment, a halogen-free precursor gas is used. If the precursor gas is used, damage to the surface of the metal layer MTL can be suppressed.

於一實施形態，方法MT包含步驟ST7。藉由使用第1胺基矽烷系氣體以作為前驅體氣體，並以氧氣電漿處理來使前驅體氧化，而形成氧化矽膜以作為阻障膜BF，如此一來會在該阻障膜BF之表面形成OH基。該阻障膜BF之表面，會具有親水性。由於在步驟ST7所使用的第2胺基矽烷系氣體，係具有烷基矽烷基的胺基矽烷系氣體，因此藉由步驟ST7之執行，會在阻障膜BF之表面形成具有疏水性的保護膜PF。從而，藉由在將被加工物W配置於大氣環境中之前就執行步驟ST7，而對被加工物W之表面賦予疏水性。其結果，會抑制在大氣環境中被加工物W吸附水分的情形。In one embodiment, the method MT includes step ST7. By using the first aminosilane-based gas as the precursor gas, and oxidizing the precursor with oxygen plasma treatment, a silicon oxide film is formed as a barrier film BF, so that the barrier film BF OH groups are formed on the surface. The surface of the barrier film BF will be hydrophilic. Since the second aminosilane-based gas used in step ST7 is an aminosilane-based gas having an alkylsilyl group, by performing step ST7, a hydrophobic protection is formed on the surface of the barrier film BF膜PF. Therefore, by performing step ST7 before arranging the workpiece W in the atmosphere, the surface of the workpiece W is rendered hydrophobic. As a result, it is suppressed that the processed material W absorbs moisture in the atmospheric environment.

於一實施形態，阻障膜BF之膜厚，係0.45nm以上。若藉由具有該膜厚的阻障膜BF，會更進一步地抑制金屬層MTL之表面的腐蝕。In one embodiment, the thickness of the barrier film BF is 0.45 nm or more. If the barrier film BF with this film thickness is used, the corrosion of the surface of the metal layer MTL will be further suppressed.

以下，針對第1～第6實驗例及比較實驗例來進行說明。於第1～第6實驗例，係使用電漿處理裝置10，對於具有圖2所示構造的被加工物，執行步驟ST1、步驟ST2、步驟ST3、步驟ST4、以及步驟ST6，接下來再執行步驟ST8，並使用濕洗淨裝置210來執行步驟ST9。被加工物，具有鈷所形成的金屬層、以及設於該金屬層上的氧化矽膜所構成之絶緣膜。絶緣膜的膜厚為80nm。於步驟ST3，在絶緣膜上形成複數個直徑30nm的開口。於步驟ST6，使用圖6所示之原子層沈積法。於包含步驟ST61及步驟ST63之每一輪排序流程（sequence）的步驟ST61，將處理室12c的壓力設定為100mTorr（13.33Pa），並以具有包含有機之1個胺基的單矽烷氣體作為前驅體氣體，以50sccm的流量，對被加工物供應10秒鐘。在每一輪排序流程的步驟ST63，係將處理室12c的壓力設定為200mTorr（26.66Pa），並以300sccm的流量，對處理室12c供應CO氣體。再者，在每一輪排序流程的步驟ST63，對上部電極30供應60MHz、300W的第1高頻。每一輪排序流程的步驟ST63之執行時間為5秒。於第1～第6實驗例中，排序流程的執行次數分別為1～6次。於步驟ST8，將被加工物配置於大氣環境中，共6小時。然後，於步驟ST9，使用含有氫氟酸的溶液，以去除阻障膜。再者，作為比較實驗例，係以不執行步驟ST6而作為不同於實驗例1～6的條件，來處理同樣的被加工物。Hereinafter, the first to sixth experimental examples and comparative experimental examples will be described. In the first to sixth experimental examples, the plasma processing apparatus 10 was used, and for the workpiece having the structure shown in FIG. 2, step ST1, step ST2, step ST3, step ST4, and step ST6 were performed, and then performed Step ST8, and use the wet cleaning device 210 to execute step ST9. The object to be processed has a metal layer formed of cobalt and an insulating film formed of a silicon oxide film provided on the metal layer. The thickness of the insulating film is 80 nm. In step ST3, a plurality of openings with a diameter of 30 nm are formed on the insulating film. In step ST6, the atomic layer deposition method shown in FIG. 6 is used. In step ST61 of each sequence including step ST61 and step ST63, the pressure of the processing chamber 12c is set to 100mTorr (13.33Pa), and a monosilane gas containing an organic amine group is used as a precursor The gas is supplied to the workpiece for 10 seconds at a flow rate of 50 sccm. In step ST63 of each round of the sequencing process, the pressure of the processing chamber 12c is set to 200 mTorr (26.66 Pa), and CO gas is supplied to the processing chamber 12c at a flow rate of 300 sccm. Furthermore, in step ST63 of each round of the sequencing flow, the upper electrode 30 is supplied with the first high frequency of 60 MHz and 300 W. The execution time of step ST63 in each round of the sequencing process is 5 seconds. In the first to sixth experimental examples, the number of executions of the sorting process is 1 to 6 times, respectively. In step ST8, the object to be processed is placed in the atmosphere for a total of 6 hours. Then, in step ST9, a solution containing hydrofluoric acid is used to remove the barrier film. In addition, as a comparative experiment example, step ST6 was not performed, and the same processing object was processed as a condition different from experiment examples 1 to 6.

然後，取得第1～第6實驗例及比較實驗例所分別製得之被加工物的SEM（掃描式電子顯微鏡）照片（俯視圖）。然後，從各被加工物的SEM照片，求取相對於絶緣膜所形成之開口的總數，由該處露出腐蝕之金屬表面的開口個數之比例。其結果，比較實驗例所求出之比例為97.8％。第1實驗例所求出之比例為31.6％。第2實驗例所求出之比例為30.0％。第3～第6實驗例所求出之比例為0％。因此確認到，藉由在蝕刻絶緣膜後就形成阻障膜，則即使將被加工物配置於大氣環境中，亦能抑制金屬層表面之腐蝕。再者，確認到由於在原子層沈積法，平均一輪排序流程所形成之氧化矽膜的膜厚為0.15nm，因此藉由具有0.45nm以上膜厚的阻障膜，則即使將被加工物配置於大氣環境中，亦能大輻抑制金屬層表面之腐蝕。Then, SEM (scanning electron microscope) photographs (plan view) of the processed objects prepared in the first to sixth experimental examples and the comparative experimental examples were obtained. Then, from the SEM photograph of each workpiece, the ratio of the number of openings that exposed the corroded metal surface to the total number of openings formed in the insulating film was determined. As a result, the ratio calculated in the comparative experiment example was 97.8%. The ratio calculated in the first experimental example was 31.6%. The ratio calculated in the second experimental example was 30.0%. The ratio calculated in the third to sixth experimental examples is 0%. Therefore, it was confirmed that by forming the barrier film after etching the insulating film, the corrosion of the metal layer surface can be suppressed even if the workpiece is placed in an atmospheric environment. Furthermore, it was confirmed that the thickness of the silicon oxide film formed by an average round of sequencing process in the atomic layer deposition method is 0.15nm. Therefore, the barrier film with a film thickness of 0.45nm or more, even if the workpiece is arranged In the atmospheric environment, it can also greatly inhibit the corrosion of the surface of the metal layer.

以上，針對各種實施形態進行了說明，但並不限定於上述實施形態，可以構成各種變形態樣。例如，於上述說明中，在方法MT係使用電容耦合型的電漿處理裝置10，但在方法MT所使用的電漿處理裝置，亦可係感應耦合型的電漿處理裝置、或藉由微波之類的表面波來激發氣體的電漿處理裝置。As mentioned above, although various embodiments have been described, it is not limited to the above-mentioned embodiments, and various modifications can be made. For example, in the above description, the capacitive coupling type plasma processing device 10 is used in the method MT, but the plasma processing device used in the method MT may also be an inductively coupled plasma processing device or by microwave Such as surface waves to excite gas plasma processing device.

再者，於上述說明中，作為適用方法MT之基板的導電層，係以鈷或銅所形成之金屬層為例。然而，適用方法MT之基板的導電層，並不限定於此種金屬層。導電層，亦可係釕（Ru）或鎳（Ni）所形成的金屬層。或者，導電層亦可係具有導電性的含矽層。此種含矽層，係例如添加了硼（B）、砷（As）這類導電性雜質的矽層，多晶矽層，非晶矽層，或矽鍺（SiGe）層。Furthermore, in the above description, as the conductive layer of the substrate to which the method MT is applied, a metal layer formed of cobalt or copper is taken as an example. However, the conductive layer of the substrate to which the method MT is applied is not limited to this metal layer. The conductive layer may also be a metal layer formed of ruthenium (Ru) or nickel (Ni). Alternatively, the conductive layer may be a silicon-containing layer having conductivity. Such a silicon-containing layer is, for example, a silicon layer added with conductive impurities such as boron (B) and arsenic (As), a polycrystalline silicon layer, an amorphous silicon layer, or a silicon germanium (SiGe) layer.

110‧‧‧處理系統112‧‧‧載入模組112c‧‧‧搬運處理室112r‧‧‧搬運機械臂116‧‧‧移載模組116c‧‧‧搬運處理室116r‧‧‧搬運機械臂120‧‧‧載置台122‧‧‧容器130‧‧‧控制部141‧‧‧載入鎖定模組141c‧‧‧處理室142‧‧‧載入鎖定模組142c‧‧‧處理室181、182、183、184‧‧‧製程模組210‧‧‧濕洗淨裝置10‧‧‧電漿處理裝置12‧‧‧處理室本體12c‧‧‧處理室12g‧‧‧開口14‧‧‧閘閥15‧‧‧支持部16‧‧‧工件台18‧‧‧下部電極18a‧‧‧第1極板18b‧‧‧第2極板18f‧‧‧流路20‧‧‧靜電吸盤22‧‧‧直流電源23‧‧‧開關24‧‧‧聚焦環26a‧‧‧配管26b‧‧‧配管28‧‧‧氣體供應管路30‧‧‧上部電極32‧‧‧構件34‧‧‧頂棚板34a‧‧‧氣體吐出孔36‧‧‧支持體36a‧‧‧氣體擴散室36b‧‧‧氣體通流孔36c‧‧‧氣體導入口38‧‧‧氣體供應管40‧‧‧氣體源群42‧‧‧閥群44‧‧‧流量控制器群48‧‧‧折流板50‧‧‧排氣裝置52‧‧‧排氣管62‧‧‧第1高頻電源63‧‧‧匹配器64‧‧‧第2高頻電源65‧‧‧匹配器W‧‧‧被加工物MTL‧‧‧金屬層IL‧‧‧絶緣膜IL1‧‧‧第1層IL2‧‧‧第2層BF‧‧‧阻障膜MK‧‧‧遮罩UL‧‧‧基底層MKL‧‧‧遮罩層BL‧‧‧防止反射膜RM‧‧‧光罩PF‧‧‧保護膜MT‧‧‧方法ST1～ST9、ST31～ST32、ST61～ST65‧‧‧步驟110‧‧‧Processing system 112‧‧‧Loading module 112c‧‧‧Transportation processing room 112r‧‧‧Transporting robot 116‧‧‧Transferring module 116c‧‧‧Transportation processing room 116r‧‧‧Transporting robot 120‧‧‧Mounting table 122‧‧‧Container 130‧‧‧Control part 141‧‧‧Loading lock module 141c‧‧‧Processing chamber 142‧‧‧Loading locking module 142c‧‧‧Processing chambers 181, 182 , 183, 184‧‧‧Process module 210‧‧‧Wet cleaning device 10‧‧‧Plasma processing device 12‧‧‧Processing chamber body 12c‧‧‧Processing chamber 12g‧‧‧Opening 14‧‧‧Gate valve 15 ‧‧‧Support 16‧‧‧Workpiece table 18‧‧‧Bottom electrode 18a‧‧‧First plate 18b‧‧‧Second plate 18f‧‧Flow path 20‧‧‧Electrostatic chuck 22‧‧‧DC Power supply 23‧‧‧switch 24‧‧‧focus ring 26a‧‧‧piping 26b‧‧‧piping 28‧‧‧gas supply line 30‧‧‧upper electrode 32‧‧‧member 34‧‧‧ceiling plate 34a‧‧ ‧Gas discharge hole 36‧‧‧Support 36a‧‧‧Gas diffusion chamber 36b‧‧‧Gas through hole 36c‧‧‧Gas inlet 38‧‧‧Gas supply pipe 40‧‧‧Gas source group 42‧‧‧ Valve group 44‧‧‧Flow controller group 48‧‧‧Baffle plate 50‧‧‧Exhaust device 52‧‧‧Exhaust pipe 62‧‧‧First high frequency power supply 63‧‧‧Matching device 64‧‧‧ Second high-frequency power supply 65‧‧‧Matching device W‧‧‧Working object MTL‧‧‧Metal layer IL‧‧‧Insulation film IL1‧‧‧The first layer IL2‧‧‧The second layer BF‧‧‧Barrier Film MK‧‧‧Mask UL‧‧‧Base layer MKL‧‧‧Mask layer BL‧‧‧Anti-reflection film RM‧‧‧Mask PF‧‧‧Protection film MT‧‧‧Method ST1～ST9, ST31～ ST32, ST61～ST65‧‧‧Step

［圖1］繪示一實施形態之被加工物之處理方法的流程圖。 ［圖2］擴大繪示一案例中之被加工物局部的剖面圖。 ［圖3］繪示可用於執行一實施形態之方法的處理系統及濕洗淨裝置的圖式。 ［圖4］概略繪示可用於執行圖1所示方法之電漿處理裝置的圖式。 ［圖5］繪示圖1所示方法之步驟ST3的流程圖。 ［圖6］繪示圖1所示方法之步驟ST6的流程圖。 ［圖7］擴大繪示圖1所示方法之中間階段所製得之被加工物局部的剖面圖。 ［圖8］擴大繪示圖1所示方法之中間階段所製得之被加工物局部的剖面圖。 ［圖9］擴大繪示圖1所示方法之中間階段所製得之被加工物局部的剖面圖。 ［圖10］擴大繪示圖1所示方法之中間階段所製得之被加工物局部的剖面圖。 ［圖11］擴大繪示圖1所示方法之中間階段所製得之被加工物局部的剖面圖。 ［圖12］擴大繪示圖1所示方法之中間階段所製得之被加工物局部的剖面圖。 ［圖13］擴大繪示圖1所示方法之中間階段所製得之被加工物局部的剖面圖。 ［圖14］擴大繪示圖1所示方法結束時所製得之被加工物局部的剖面圖。[Figure 1] shows a flow chart of the processing method of the processed object in one embodiment. [Figure 2] Enlarged drawing of a partial cross-sectional view of the processed object in a case. [Figure 3] shows a schematic diagram of a processing system and a wet cleaning device that can be used to implement the method of an embodiment. [Figure 4] A schematic diagram of a plasma processing device that can be used to implement the method shown in Figure 1. [Fig. 5] A flowchart of step ST3 of the method shown in Fig. 1 is shown. [Fig. 6] A flowchart of step ST6 of the method shown in Fig. 1 is shown. [Figure 7] Enlarged drawing shows a partial cross-sectional view of the processed object prepared in the intermediate stage of the method shown in Figure 1. [Figure 8] Enlarged drawing shows a partial cross-sectional view of the processed object prepared in the intermediate stage of the method shown in Figure 1. [Figure 9] Enlarged drawing shows a partial cross-sectional view of the processed object prepared in the intermediate stage of the method shown in Figure 1. [Figure 10] Enlarged drawing shows a partial cross-sectional view of the processed object prepared in the intermediate stage of the method shown in Figure 1. [Figure 11] Enlarged drawing shows a partial cross-sectional view of the processed object prepared in the intermediate stage of the method shown in Figure 1. [Figure 12] Enlarged drawing shows a partial cross-sectional view of the processed object prepared in the intermediate stage of the method shown in Figure 1. [Figure 13] Enlarged drawing shows a partial cross-sectional view of the processed object prepared in the intermediate stage of the method shown in Figure 1. [Figure 14] Enlarged drawing shows a partial cross-sectional view of the processed object obtained at the end of the method shown in Figure 1.

MT‧‧‧方法 MT‧‧‧Method

ST1~ST9‧‧‧步驟 ST1~ST9‧‧‧Step

Claims (15)

一種被加工物之處理方法，該被加工物具有導電層、以及設於該導電層上的絶緣膜；該處理方法包括以下步驟：絶緣膜蝕刻步驟，為了在該絶緣膜形成開口，而藉由含氟氣體之電漿處理以蝕刻該絶緣膜；阻障膜形成步驟，形成阻障膜以包覆該絶緣膜之表面、以及從形成於該絶緣膜之該開口所露出的該導電層之表面；被加工物配置步驟，將具有該阻障膜之該被加工物配置於大氣環境中；及阻障膜去除步驟，在將該被加工物配置於大氣環境中的步驟之後，從該被加工物去除該阻障膜；於該阻障膜去除步驟中，該阻障膜係等向性地受到蝕刻；從該絶緣膜蝕刻步驟開始時到該阻障膜形成步驟結束時為止的期間，該被加工物係維持在減壓環境中；該阻障膜，係在該絶緣膜之表面、以及從形成於該絶緣膜上之該開口所露出的該導電層之表面上，保形地形成之膜層。 A processing method of a processed object, the processed object having a conductive layer and an insulating film provided on the conductive layer; the processing method includes the following steps: an insulating film etching step, in order to form an opening in the insulating film, by Plasma treatment of a fluorine-containing gas to etch the insulating film; a barrier film forming step, forming a barrier film to cover the surface of the insulating film, and the surface of the conductive layer exposed from the opening formed in the insulating film Arranging the object to be processed, the object to be processed with the barrier film is placed in an atmospheric environment; and the barrier film removal step, after the step of arranging the object to be processed in the atmospheric environment, from the processed object In the barrier film removal step, the barrier film is etched isotropically; from the beginning of the insulating film etching step to the end of the barrier film forming step, the The object to be processed is maintained in a reduced pressure environment; the barrier film is conformally formed on the surface of the insulating film and the surface of the conductive layer exposed from the opening formed on the insulating film膜层。 Film layer. 如申請專利範圍第1項之被加工物之處理方法，其中，該阻障膜係以原子層沈積法形成；該阻障膜形成步驟，包括以下步驟：為了使該被加工物之表面吸附前驅體，而對該被加工物供應前驅體氣體的步驟；以及為了從該前驅體形成該阻障膜，而對該前驅體執行電漿處理的步驟。 For example, the processing method of the processed object in the scope of the patent application, wherein the barrier film is formed by atomic layer deposition; the barrier film formation step includes the following steps: in order to make the surface of the processed object adsorb the precursor A step of supplying a precursor gas to the workpiece; and a step of performing plasma treatment on the precursor in order to form the barrier film from the precursor. 如申請專利範圍第2項之被加工物之處理方法，其中， 該前驅體氣體不包含鹵素。 For example, the processing method of the processed object in item 2 of the scope of patent application, among which, The precursor gas does not contain halogen. 如申請專利範圍第2或3項之被加工物之處理方法，其中，該前驅體氣體，係胺基矽烷系氣體或矽醇鹽系氣體。 For example, the processing method of the processed object of the second or third item of the scope of patent application, wherein the precursor gas is an aminosilane-based gas or a silicon alkoxide-based gas. 如申請專利範圍第4項之被加工物之處理方法，其中，於對該前驅體執行電漿處理的步驟，係對該前驅體執行使用含氧氣體之電漿的電漿處理。 For example, the processing method of the processed object in the scope of patent application, wherein, in the step of performing plasma treatment on the precursor, plasma treatment using plasma of oxygen-containing gas is performed on the precursor. 如申請專利範圍第5項之被加工物之處理方法，其中，更包括以下步驟：在該阻障膜形成步驟之後、並且在將該被加工物配置於大氣環境中的步驟之前，對該被加工物供應具有烷基矽烷基之胺基矽烷系氣體的步驟。 For example, the processing method of the processed object in the scope of the patent application, which further includes the following steps: after the barrier film formation step and before the step of arranging the processed object in the atmospheric environment, the processing method The process of supplying an amine silane-based gas with an alkyl silyl group to the processed product. 如申請專利範圍第1至3項中任一項之被加工物之處理方法，其中，該阻障膜係氧化矽膜。 For example, the processing method of any one of items 1 to 3 in the scope of patent application, wherein the barrier film is a silicon oxide film. 如申請專利範圍第1至3項中任一項之被加工物之處理方法，其中，該阻障膜，係氮化矽膜、或碳化矽膜。 For example, in the processing method of any one of items 1 to 3 in the scope of patent application, the barrier film is a silicon nitride film or a silicon carbide film. 如申請專利範圍第1至3項中任一項之被加工物之處理方法，其中，該阻障膜，係金屬氧化膜。 For example, the processing method of any one of items 1 to 3 in the scope of patent application, wherein the barrier film is a metal oxide film. 如申請專利範圍第1至3項中任一項之被加工物之處理方法，其中，該阻障膜的膜厚，係0.45nm以上。 For example, in the processing method of any one of items 1 to 3 in the scope of patent application, the film thickness of the barrier film is 0.45 nm or more. 如申請專利範圍第1至3項中任一項之被加工物之處理方法，其中，於該絶緣膜上，設有遮罩；於該絶緣膜蝕刻步驟中，在從形成於該遮罩之開口所露出的部位，蝕刻該絶緣膜；在該絶緣膜蝕刻步驟與該阻障膜形成步驟之間，更包括藉由使用電漿之處理，以去除該遮罩的步驟。 For example, the processing method of any one of items 1 to 3 in the scope of the patent application, wherein a mask is provided on the insulating film; in the etching step of the insulating film, a The portion exposed by the opening is etched on the insulating film; between the insulating film etching step and the barrier film forming step, a step of removing the mask by using plasma is further included. 如申請專利範圍第11項之被加工物之處理方法，其中，在該絶緣膜蝕刻步驟與該阻障膜形成步驟之間，更包括：使用含氫氣體之電漿，以執行該導電層之表面處理的步驟。 For example, the processing method of the processed object in the scope of patent application, wherein, between the insulating film etching step and the barrier film forming step, it further includes: using a plasma containing hydrogen gas to perform the conductive layer Surface treatment steps. 如申請專利範圍第1至3項中任一項之被加工物之處理方法，其中，於該阻障膜去除步驟，係藉由濕蝕刻而去除該阻障膜，用於該濕蝕刻的溶液包含氟化氫或氟化銨。 For example, the processing method of any one of items 1 to 3 in the scope of patent application, wherein, in the barrier film removal step, the barrier film is removed by wet etching, and the solution is used for the wet etching Contains hydrogen fluoride or ammonium fluoride. 如申請專利範圍第1至3項中任一項之被加工物之處理方法，其中，從該絶緣膜蝕刻步驟開始時到該阻障膜形成步驟結束時為止，將該被加工物維持在同一個處理室內。 For example, the processing method of any one of items 1 to 3 in the scope of patent application, wherein from the beginning of the insulating film etching step to the end of the barrier film forming step, the processed object is maintained in the same A processing room. 如申請專利範圍第1至3項中任一項之被加工物之處理方法，其中，該導電層，係金屬層、或具有導電性的含矽層。 For example, in the processing method of any one of items 1 to 3 in the scope of the patent application, the conductive layer is a metal layer or a conductive silicon-containing layer.
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