TWI781609B - Substrate processing method and substrate processing apparatus - Google Patents

Substrate processing method and substrate processing apparatus Download PDF

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TWI781609B
TWI781609B TW110116724A TW110116724A TWI781609B TW I781609 B TWI781609 B TW I781609B TW 110116724 A TW110116724 A TW 110116724A TW 110116724 A TW110116724 A TW 110116724A TW I781609 B TWI781609 B TW I781609B
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substrate
gas
sublimation
solidified body
flow rate
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TW202209419A (en
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尾辻正幸
加藤雅彦
山口佑
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日商斯庫林集團股份有限公司
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02057Cleaning during device manufacture
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26DRYING
    • F26BDRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
    • F26B21/06Controlling, e.g. regulating, parameters of gas supply
    • F26B21/12Velocity of flow; Quantity of flow, e.g. by varying fan speed, by modifying cross flow area
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26DRYING
    • F26BDRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00Drying solid materials or objects by processes not involving the application of heat
    • F26B5/04Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67011Apparatus for manufacture or treatment
    • H01L21/67017Apparatus for fluid treatment
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67011Apparatus for manufacture or treatment
    • H01L21/67017Apparatus for fluid treatment
    • H01L21/67028Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H01L21/67034Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for drying
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67242Apparatus for monitoring, sorting or marking
    • H01L21/67253Process monitoring, e.g. flow or thickness monitoring

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Computer Hardware Design (AREA)
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Abstract

本發明之基板處理方法之特徵在於具備:第1昇華工序,其向基板之表面中央部噴出第1氣體,使第1氣體經由整個凝固體流通至基板周邊而使整個凝固體昇華;及第2昇華工序,其向基板之表面周緣部噴出第2氣體,使第2氣體經由凝固體中之表面周緣部上之周緣區域流通至基板周邊而使周緣區域昇華;且第2昇華工序比第1昇華工序先開始,及/或第2氣體之流量多於第1氣體之流量。The substrate processing method of the present invention is characterized in that it includes: a first sublimation step, which sprays a first gas to the center of the surface of the substrate, and makes the first gas flow through the entire solidified body to the periphery of the substrate to sublimate the entire solidified body; and a second step. A sublimation process, which sprays a second gas to the surface peripheral portion of the substrate, so that the second gas flows through the peripheral area on the surface peripheral portion of the solidified body to the periphery of the substrate to sublimate the peripheral area; and the second sublimation process is more sublimated than the first sublimation process. The process starts first, and/or the flow rate of the second gas is greater than the flow rate of the first gas.

Description

基板處理方法及基板處理裝置Substrate processing method and substrate processing device

本發明係關於一種使基板乾燥之基板處理方法及基板處理裝置。基板包含半導體晶圓、液晶顯示裝置用基板、有機EL(electroluminescence,電致發光)顯示裝置等FPD(Flat Panel Display,平板顯示器)用基板、光碟用基板、磁碟用基板、磁光碟用基板、光罩用基板、陶瓷基板、太陽電池用基板等。The invention relates to a substrate processing method and a substrate processing device for drying a substrate. Substrates include semiconductor wafers, substrates for liquid crystal display devices, substrates for FPD (Flat Panel Display) such as organic EL (electroluminescence) display devices, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, Photomask substrates, ceramic substrates, solar cell substrates, etc.

半導體裝置、液晶顯示裝置等之電子零件之製造工序中,包含重複對基板表面實施成膜、蝕刻等處理而形成圖案之工序。此外,形成上述圖案後,依序進行利用藥液之清洗處理、利用沖洗液之沖洗處理及乾燥處理等,但隨著圖案微細化,乾燥處理之重要性尤為提高。即,於乾燥處理中抑制或防止圖案發生塌陷之技術變得重要。因此,例如日本專利特開2020-4948號公報所記載,提出一種利用不經過液體即變成氣體之昇華性物質使基板乾燥之基板處理方法及基板處理裝置。The manufacturing process of electronic components such as semiconductor devices and liquid crystal display devices includes the process of repeatedly applying film formation, etching, etc. to the surface of the substrate to form a pattern. In addition, after the above-mentioned pattern is formed, cleaning treatment with a chemical solution, rinsing treatment with a rinse solution, and drying treatment are sequentially performed, but the importance of the drying treatment is particularly increased as the pattern is miniaturized. That is, a technique for suppressing or preventing pattern collapse during the drying process becomes important. Therefore, for example, as described in Japanese Patent Application Laid-Open No. 2020-4948, a substrate processing method and a substrate processing apparatus for drying a substrate by using a sublimation substance that turns into a gas without passing through a liquid are proposed.

日本專利特開2020-4948號公報所記載之基板處理技術中,準備包含樟腦等昇華性物質及與該昇華性物質溶合之溶劑之溶液作為乾燥預處理液。乾燥預處理液被供給至形成有圖案之基板表面。使基板表面上之乾燥預處理液中之溶劑氣化,由此於整個基板表面形成包含昇華性物質之固體膜(相當於本發明之「凝固體」之一例)。其後,藉由昇華而從基板表面去除固體膜。In the substrate processing technology described in Japanese Patent Application Laid-Open No. 2020-4948, a solution containing a sublimable substance such as camphor and a solvent soluble in the sublimable substance is prepared as a dry pretreatment solution. The dry pretreatment liquid is supplied to the surface of the patterned substrate. The solvent in the dry pretreatment liquid on the surface of the substrate is vaporized, thereby forming a solid film (corresponding to an example of the "solidified body" of the present invention) containing a sublimable substance on the entire surface of the substrate. Thereafter, the solid film is removed from the substrate surface by sublimation.

以往技術中,藉由向基板之表面中央部噴出之氮氣而使固體膜昇華。更詳細而言,於基板之表面中央部上方配置噴嘴。而且,從該噴嘴向基板之表面中央部噴出氮氣。氮氣首先被供給至固體膜之中央區域,進而沿固體膜呈放射狀流動,從而流動至基板周邊。與該氮氣之流通並行地,昇華性物質之氣化從固體膜之中央區域向周緣區域推進。因此,從中央區域昇華之昇華性物質與氮氣一起流入固體膜之周緣區域之上方氛圍中,下文將參照圖8對此進行詳述。因此,該上方氛圍中之昇華性物質(氣體)之濃度升高,有時會抑制固體膜之周緣區域上之昇華。結果為,以往技術有時會於基板之表面周緣部發生圖案塌陷。In conventional techniques, the solid film is sublimated by blowing nitrogen gas toward the center of the surface of the substrate. More specifically, the nozzle is arranged above the central portion of the surface of the substrate. Then, nitrogen gas is sprayed from the nozzle toward the center of the surface of the substrate. Nitrogen gas is first supplied to the central region of the solid film, and then flows radially along the solid film, thereby flowing to the periphery of the substrate. Parallel to this flow of nitrogen gas, the vaporization of the sublimable substance proceeds from the central region of the solid film to the peripheral region. Thus, the sublimable species sublimated from the central region flows into the atmosphere above the peripheral region of the solid film together with the nitrogen gas, as will be described in detail below with reference to FIG. 8 . Therefore, the concentration of the sublimable substance (gas) in the upper atmosphere increases, and sublimation in the peripheral region of the solid film may be suppressed. As a result, in the prior art, pattern collapse sometimes occurred on the peripheral edge of the surface of the substrate.

本發明係鑒於上述問題而完成者,目的在於,於利用昇華性物質之昇華使基板乾燥之基板處理技術中改善基板之表面周緣部上之圖案塌陷。The present invention was made in view of the above problems, and an object of the present invention is to improve pattern collapse on the surface peripheral portion of a substrate in a substrate processing technique in which a substrate is dried by sublimation of a sublimation substance.

本發明之一實施方式係一種基板處理方法,其特徵在於,其係使包含不經過液體即變成氣體之昇華性物質的凝固體從基板昇華而使上述基板乾燥者,上述基板於整個表面上形成有上述凝固體;且上述基板處理方法具備:第1昇華工序,其向基板之表面中央部噴出第1氣體,使第1氣體經由整個凝固體流通至基板周邊而使整個凝固體昇華;及第2昇華工序,其向基板之表面周緣部噴出第2氣體,使第2氣體經由凝固體中之表面周緣部上之周緣區域流通至基板周邊而使周緣區域昇華;且第2昇華工序比第1昇華工序先開始,及/或第2氣體之流量多於第1氣體之流量。One embodiment of the present invention is a substrate processing method characterized by sublimating a solidified body including a sublimable substance that turns into a gas without passing through a liquid from a substrate to dry the substrate, and the substrate is formed on the entire surface. There is the above-mentioned solidified body; and the above-mentioned substrate processing method includes: a first sublimation step, which sprays a first gas to the central part of the surface of the substrate, and makes the first gas flow through the entire solidified body to the periphery of the substrate to sublimate the entire solidified body; and 2. The sublimation process, which sprays the second gas to the surface peripheral portion of the substrate, so that the second gas flows to the periphery of the substrate through the peripheral area on the surface peripheral portion in the solidified body to sublimate the peripheral area; and the second sublimation process is more efficient than the first The sublimation process starts first, and/or the flow rate of the second gas is greater than that of the first gas.

此外,本發明之另一實施方式係一種基板處理裝置,其特徵在於,其係使包含不經過液體即變成氣體之昇華性物質的凝固體從基板昇華而使基板乾燥者,該基板於整個表面上形成有凝固體;且該基板處理裝置具備:第1噴出部,其向基板之表面中央部噴出第1氣體;第2噴出部,其向基板之表面周緣部噴出第2氣體;及控制部,其使第1氣體從第1噴出部噴出,使第1氣體經由整個凝固體流通至基板周邊而使整個凝固體昇華,且使第2氣體從第2噴出部噴出,使第2氣體經由凝固體中之表面周緣部上之周緣區域流通至基板周邊而使周緣區域昇華;且控制部進行使第2氣體早於第1氣體開始噴出之噴出時序控制、以及使第2氣體之流量多於第1氣體之流量的流量控制中之至少一者。In addition, another embodiment of the present invention is a substrate processing apparatus characterized in that it dries the substrate by sublimating a solidified body containing a sublimable substance that turns into a gas without passing through a liquid, and the entire surface of the substrate is A solidified body is formed on the substrate; and the substrate processing apparatus includes: a first ejection part, which ejects the first gas to the central part of the surface of the substrate; a second ejection part, which ejects the second gas to the peripheral part of the surface of the substrate; and a control part , the first gas is ejected from the first ejection part, the first gas flows through the entire solidified body to the periphery of the substrate to sublimate the entire solidified body, and the second gas is ejected from the second ejection part, and the second gas passes through the solidified The peripheral area on the surface peripheral part of the body flows to the periphery of the substrate to sublimate the peripheral area; and the control part performs ejection timing control so that the second gas starts ejecting earlier than the first gas, and the flow rate of the second gas is greater than that of the first gas. 1. At least one of flow control of gas flow.

於以此種方式構成之發明中,將第2氣體先於第1氣體賦予給凝固體之周緣區域,或對凝固體中之周緣區域賦予大量第2氣體。因此,促進凝固體之周緣區域中之昇華。結果為,可有效改善基板之表面周緣部之圖案塌陷。In the invention constituted in this way, the second gas is supplied to the peripheral region of the solidified body prior to the first gas, or a large amount of the second gas is supplied to the peripheral region of the solidified body. Thus, sublimation in the peripheral region of the solidified body is promoted. As a result, the pattern collapse of the surface peripheral portion of the substrate can be effectively improved.

圖1係表示裝備本發明之基板處理裝置之第1實施方式之基板處理系統之概略構成之俯視圖。此外,圖2係圖1所示之基板處理系統之側視圖。該些附圖並不是表示基板處理系統100之外觀,而是藉由去除基板處理系統100之外壁板或其他一部分構成而清晰易懂地表示其內部結構之模式圖。該基板處理系統100為單片式裝置,其設置於例如無塵室內,逐片地對僅於一主面形成有電路圖案等(以下稱為「圖案」)之基板W進行處理。而且,於基板處理系統100所裝備之處理單元1中執行本發明之基板處理方法。本說明書中,將基板之兩主面中形成有圖案(參照下文說明之圖6A中之符號PT)之圖案形成面(一主面)稱為「正面」,將其相反側之未形成圖案之另一主面稱為「背面」。此外,將朝向下方之面稱為「下表面」,將朝向上方之面稱為「上表面」。此外,本說明書中,「圖案形成面」係指基板中於任意區域形成有凹凸圖案之面。FIG. 1 is a plan view showing a schematic configuration of a substrate processing system equipped with a substrate processing apparatus according to a first embodiment of the present invention. In addition, FIG. 2 is a side view of the substrate processing system shown in FIG. 1 . These drawings do not show the appearance of the substrate processing system 100 , but are schematic diagrams showing the internal structure of the substrate processing system 100 clearly and intelligibly by removing the outer wall panels or other parts. The substrate processing system 100 is a single-chip device, which is installed in, for example, a clean room, and processes substrates W with circuit patterns (hereinafter referred to as "patterns") formed on only one main surface one by one. Moreover, the substrate processing method of the present invention is executed in the processing unit 1 equipped in the substrate processing system 100 . In this specification, the pattern forming surface (one main surface) on which patterns are formed (refer to the symbol PT in FIG. The other main face is called the "rear face". In addition, the surface facing downward is called "lower surface", and the surface facing upward is called "upper surface". In addition, in this specification, a "pattern formation surface" means the surface in which the uneven|corrugated pattern was formed in the arbitrary area|region among the board|substrates.

此處,作為本實施方式中之「基板」,能夠應用半導體晶圓、光罩用玻璃基板、液晶顯示用玻璃基板、電漿顯示用玻璃基板、FED(Field Emission Display,場發射顯示器)用基板、光碟用基板、磁碟用基板、磁光碟用基板等各種基板。以下主要以用於半導體晶圓之處理之基板處理裝置為例,參照附圖進行說明,但亦可同樣應用於以上例示之各種基板之處理。Here, as the "substrate" in this embodiment, semiconductor wafers, glass substrates for photomasks, glass substrates for liquid crystal displays, glass substrates for plasma displays, and substrates for FED (Field Emission Display) can be applied. , Substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, and other substrates. The following mainly takes a substrate processing apparatus for processing semiconductor wafers as an example, and will be described with reference to the drawings, but it can also be applied to the processing of various substrates exemplified above.

如圖1所示,基板處理系統100具備對基板W實施處理之基板處理部110、及與該基板處理部110結合之分度器部120。分度器部120具有容器保持部121,該容器保持部121可保持複數個用來收容基板W之容器C(將複數個基板W以密閉狀態收容之FOUP(Front Opening Unified Pod,前開式晶圓傳送盒)、SMIF(Standard Mechanical Interface,標準機械接口)盒、OC(Open Cassette,開放式晶圓匣)等)。此外,分度器部120具備分度機械手122,該分度機械手122用來對保持於容器保持部121之容器C進行存取,而從容器C取出未處理之基板W,或將處理完畢之基板W收納於容器C中。於各容器C中以大致水平姿勢收容著多片基板W。As shown in FIG. 1 , the substrate processing system 100 includes a substrate processing unit 110 that processes a substrate W, and an indexer unit 120 coupled to the substrate processing unit 110 . The indexer part 120 has a container holding part 121, and the container holding part 121 can hold a plurality of containers C for storing substrates W (FOUP (Front Opening Unified Pod, Front Opening Unified Pod) for storing a plurality of substrates W in a sealed state. ), SMIF (Standard Mechanical Interface, standard mechanical interface) box, OC (Open Cassette, open wafer box), etc.). In addition, the indexer unit 120 includes an indexing robot 122 for accessing the container C held in the container holding unit 121, and taking out the unprocessed substrate W from the container C, or removing the processed substrate W from the container C. The substrate W is housed in the container C. As shown in FIG. A plurality of substrates W are accommodated in each container C in a substantially horizontal posture.

分度機械手122具備固定於裝置殼體上之底座部122a、設置為能夠相對於底座部122a繞鉛直軸旋動之多關節臂122b、及安裝於多關節臂122b之前端之手部122c。手部122c成為可於其上表面載置並保持基板W之結構。具有此種多關節臂及基板保持用手部之分度機械手已為人們周知,因此省略其詳細說明。The indexing manipulator 122 has a base 122a fixed on the device housing, a multi-joint arm 122b rotatable relative to the base 122a around a vertical axis, and a hand 122c mounted on the front end of the multi-joint arm 122b. The hand 122c has a structure capable of placing and holding the substrate W on its upper surface. An indexing robot having such a multi-joint arm and a substrate holding hand is well known, and therefore detailed description thereof will be omitted.

基板處理部110具備供分度機械手122載置基板W之載置台112、俯視下配置於大致中央處之基板搬送機械手111、及以包圍該基板搬送機械手111之方式配置之複數個處理單元1。具體而言,面向配置有基板搬送機械手111之空間配置著複數個(該例中為8個)處理單元1。基板搬送機械手111針對該些處理單元1隨機地於載置台112上進行存取,從而於與載置台112之間交接基板W。另一方面,各處理單元1對基板W執行特定處理。本實施方式中,該些處理單元1具有相同功能。因此,能夠並行處理複數個基板W。另外,如果基板搬送機械手111能夠直接從分度機械手122交接基板W,則不必需要載置台112。作為各處理單元1,可使用以下說明之處理單元(1A~1C)等。The substrate processing unit 110 includes a mounting table 112 on which the index robot 122 mounts the substrate W, a substrate transfer robot 111 arranged approximately in the center in a plan view, and a plurality of processes arranged to surround the substrate transfer robot 111. Unit 1. Specifically, a plurality of (eight in this example) processing units 1 are arranged facing the space where the substrate transfer robot 111 is arranged. The substrate transfer robot 111 randomly accesses the processing units 1 on the mounting table 112 , and transfers the substrate W to the mounting table 112 . On the other hand, each processing unit 1 executes specific processing on the substrate W. As shown in FIG. In this embodiment, these processing units 1 have the same function. Therefore, a plurality of substrates W can be processed in parallel. In addition, if the substrate transfer robot 111 can directly deliver the substrate W from the index robot 122 , the mounting table 112 is not necessary. As each processing unit 1, processing units (1A to 1C) described below and the like can be used.

圖3係表示相當於本發明之基板處理裝置之第1實施方式之處理單元之構成之圖。此外,圖4係表示控制處理單元之控制系統之電氣構成之框圖。另外,本實施方式中,針對各處理單元1A而設置有控制部4,但亦可構成為由1台控制部控制複數個處理單元1A。此外,亦可構成為由控制整個基板處理系統100之控制單元(省略圖示)控制處理單元1A。3 is a diagram showing the configuration of a processing unit corresponding to the first embodiment of the substrate processing apparatus of the present invention. In addition, FIG. 4 is a block diagram showing the electrical configuration of the control system of the control processing unit. In addition, in the present embodiment, the control unit 4 is provided for each processing unit 1A, but a configuration may be adopted in which one control unit controls a plurality of processing units 1A. In addition, the processing unit 1A may be controlled by a control unit (not shown) that controls the entire substrate processing system 100 .

處理單元1A具備具有內部空間21之腔室20、及收容於腔室20之內部空間21中並保持基板W之旋轉夾頭30。如圖1及圖2所示,於腔室20之側面設置有擋閘23。擋閘開關機構22(圖4)連接於擋閘23,根據來自控制部4之開關指令使擋閘23開關。更具體而言,處理單元1A中,於將未處理之基板W搬入腔室20時擋閘開關機構22打開擋閘23,由基板搬送機械手111之手部將未處理之基板W以面朝上姿勢搬入旋轉夾頭30。即,基板W以正面Wf朝向上方之狀態載置於旋轉夾頭30上。而且,當搬入該基板後基板搬送機械手111之手部從腔室20退避出來時,擋閘開關機構22關閉擋閘23。然後,於腔室20之內部空間21內如下所述對基板W之正面Wf供給藥液、DIW(去離子水)、IPA(異丙醇)處理液、乾燥預處理液及氮氣而於常溫環境下執行所需之基板處理。此外,於基板處理結束後,擋閘開關機構22再次打開擋閘23,基板搬送機械手111之手部從旋轉夾頭30搬出處理完畢之基板W。如此,本實施方式中,腔室20之內部空間21作為保持為常溫環境進行基板處理之處理空間發揮功能。另外,本說明書中,「常溫」係指5℃~35℃之溫度範圍。The processing unit 1A includes a chamber 20 having an internal space 21 , and a spin chuck 30 that is housed in the internal space 21 of the chamber 20 and holds a substrate W. As shown in FIG. As shown in FIGS. 1 and 2 , a shutter 23 is provided on the side of the chamber 20 . The shutter switch mechanism 22 ( FIG. 4 ) is connected to the shutter 23 , and opens and closes the shutter 23 according to the switching command from the control unit 4 . More specifically, in the processing unit 1A, when the unprocessed substrate W is carried into the chamber 20, the shutter switch mechanism 22 opens the shutter 23, and the unprocessed substrate W is turned to face by the hand of the substrate transfer robot 111. The upper posture is moved into the rotary chuck 30. That is, the substrate W is placed on the spin chuck 30 with the front surface Wf facing upward. Then, when the hand of the substrate transfer robot 111 retreats from the chamber 20 after carrying in the substrate, the shutter switch mechanism 22 closes the shutter 23 . Then, in the internal space 21 of the chamber 20, the chemical solution, DIW (deionized water), IPA (isopropanol) treatment solution, dry pretreatment solution, and nitrogen gas are supplied to the front surface Wf of the substrate W as follows, and the substrate W is placed in a room temperature environment. Next, perform the required substrate processing. In addition, after the substrate processing is completed, the shutter switch mechanism 22 opens the shutter 23 again, and the hand of the substrate transfer robot 111 carries out the processed substrate W from the spin chuck 30 . In this manner, in the present embodiment, the internal space 21 of the chamber 20 functions as a processing space in which substrate processing is performed while maintaining an ambient temperature environment. In addition, in this specification, "normal temperature" means the temperature range of 5 degreeC - 35 degreeC.

旋轉夾頭30具有複數個夾頭銷31。旋轉夾頭30中,複數個夾頭銷31設置於圓盤形狀之旋轉底座32之上表面之周緣部。該實施方式中,夾頭銷31於旋轉底座32之圓周方向上隔開適當間隔(例如等間隔)配置並固持基板W之周緣部。由此,由旋轉夾頭30保持基板W。The rotary chuck 30 has a plurality of chuck pins 31 . In the rotary chuck 30 , a plurality of chuck pins 31 are provided on the peripheral portion of the upper surface of the disk-shaped rotary base 32 . In this embodiment, the chuck pins 31 are arranged at appropriate intervals (for example, equal intervals) in the circumferential direction of the rotating base 32 and hold the peripheral portion of the substrate W. As shown in FIG. Thus, the substrate W is held by the spin chuck 30 .

於旋轉底座32連結著旋轉軸33。該旋轉軸33繞旋轉軸線AX1旋轉自由地設置,該旋轉軸線AX1與從旋轉夾頭30所支撐之基板W之表面中心延伸之面法線平行。旋轉軸33連結於包含馬達等之基板旋轉驅動機構34。因此,當於由夾頭銷31保持著載置於旋轉夾頭30上之基板W之狀態下,根據來自控制部4之旋轉指令而基板旋轉驅動機構34之馬達作動時,基板W以與上述旋轉指令對應之旋轉速度繞旋轉軸線AX1旋轉。此外,於使基板W如此旋轉之狀態下,根據來自控制部4之供給指令而從於鉛直方向上插通對向構件50之中心軸噴嘴60對基板W之正面Wf供給藥液、IPA處理液、DIW、乾燥預處理液及氮氣。The rotation shaft 33 is connected to the rotation base 32 . The rotation shaft 33 is rotatably provided about a rotation axis AX1 parallel to a surface normal extending from the center of the surface of the substrate W supported by the spin chuck 30 . The rotation shaft 33 is connected to a substrate rotation drive mechanism 34 including a motor and the like. Therefore, when the motor of the substrate rotation drive mechanism 34 is activated in response to a rotation command from the control unit 4 in a state where the substrate W placed on the rotary chuck 30 is held by the chuck pin 31, the substrate W will be rotated in the same manner as described above. The rotation speed corresponding to the rotation command rotates around the rotation axis AX1. In addition, in the state where the substrate W is rotated in this way, the chemical solution and the IPA treatment solution are supplied to the front surface Wf of the substrate W from the central axis nozzle 60 inserted through the opposing member 50 in the vertical direction according to a supply command from the control unit 4 . , DIW, dry pretreatment liquid and nitrogen.

圖5係模式性地表示對向構件位於對向位置時之旋轉底座、基板及對向構件之位置關係之圖。如圖3及圖5所示,對向構件50係隨著旋轉夾頭30旋轉之從動型對向構件。即,關於對向構件50,於基板處理中,對向構件50係可與旋轉夾頭30一體旋轉地被旋轉夾頭30支撐。為了能夠如此,對向構件50具有對向板51、可一同升降地設置於對向板51之卡合構件52、及用以與卡合構件52卡合而從上方支撐對向板51之支撐部53。FIG. 5 is a diagram schematically showing the positional relationship among the rotating base, the base plate, and the opposing member when the opposing member is at the opposing position. As shown in FIGS. 3 and 5 , the opposing member 50 is a driven opposing member that rotates with the rotary chuck 30 . That is, the opposing member 50 is supported by the spin chuck 30 so as to be rotatable integrally with the spin chuck 30 during substrate processing. In order to do this, the opposing member 50 has an opposing plate 51, an engaging member 52 that can be raised and lowered on the opposing plate 51, and a support for engaging with the engaging member 52 to support the opposing plate 51 from above. Section 53.

對向板51係較基板W之直徑大之圓板狀,具有從鉛直上方覆蓋基板W之蓋帽形狀。更詳細而言,對向板51具有被以水平姿勢保持之圓板部511、及從圓板部511之外周部向下方延伸之圓筒部512。對向板51之內表面513成為向下凹陷之杯面。內表面513具有基板對向面513a、中央傾斜面513b及內周面513c。The opposing plate 51 is disc-shaped with a diameter larger than that of the substrate W, and has a cap shape covering the substrate W from vertically above. More specifically, the facing plate 51 has a circular plate portion 511 held in a horizontal posture, and a cylindrical portion 512 extending downward from the outer peripheral portion of the circular plate portion 511 . The inner surface 513 of the facing plate 51 becomes a downwardly concave cup surface. The inner surface 513 has a substrate-facing surface 513a, a central inclined surface 513b, and an inner peripheral surface 513c.

基板對向面513a相當於圓板部511之下表面。更具體而言,基板對向面513a被精加工成與基板W之上表面平行之平坦面,與基板W之正面Wf對向。The substrate facing surface 513 a corresponds to the lower surface of the disc portion 511 . More specifically, the substrate-facing surface 513a is finished to be a flat surface parallel to the upper surface of the substrate W, and faces the front surface Wf of the substrate W.

此外,中央傾斜面513b具有被基板對向面513a包圍之傾斜面。更具體而言,中央傾斜面513b具有從基板對向面513a向斜上方朝旋轉軸線AX1延伸之環狀之中央傾斜部,且具有以下特徵。中央傾斜部具有相對於旋轉軸線AX1之傾斜角固定之緩斜面。中央傾斜部之截面向下開放。中央傾斜面513b之內徑隨著靠近中央傾斜面513b之下端而增加。中央傾斜面513b之下端與基板對向面513a相連。因此,於對向構件50位於對向位置之狀態下,中心軸噴嘴60之下端部被中央傾斜面513b包圍,並且於下方露出(參照下文說明之圖6A及圖6B)。In addition, the central inclined surface 513b has an inclined surface surrounded by the substrate facing surface 513a. More specifically, the central inclined surface 513b has an annular central inclined portion extending obliquely upward from the substrate-facing surface 513a toward the rotation axis AX1, and has the following characteristics. The central inclined portion has a gentle inclined surface with a fixed inclination angle relative to the rotation axis AX1. The cross-section of the central inclined portion is open downward. The inner diameter of the central inclined surface 513b increases as the lower end of the central inclined surface 513b approaches. The lower end of the central inclined surface 513b is connected to the substrate facing surface 513a. Therefore, when the facing member 50 is at the facing position, the lower end of the central axis nozzle 60 is surrounded by the central inclined surface 513b and exposed below (see FIGS. 6A and 6B described below).

進而,內周面513c相當於圓筒部512之內側面。更具體而言,內周面513c具有從基板對向面513a向斜下方朝外側延伸之環狀之內傾斜部,且具有以下特徵。內傾斜部具有相對於旋轉軸線AX1之傾斜角連續變化之圓弧狀截面。內傾斜部之截面向下開放。內周面513c之內徑隨著靠近內周面513c之下端而增加。內周面513c之下端具有較旋轉底座32之外徑大之內徑。因此,如圖3之單點劃線所示,於對向構件50位於對向位置之狀態下,內周面513c與基板W之外周端及旋轉底座32之外周面(外周端)32b對向。Furthermore, the inner peripheral surface 513c corresponds to the inner surface of the cylindrical portion 512 . More specifically, the inner peripheral surface 513c has an annular inner inclined portion extending obliquely downward and outward from the substrate-facing surface 513a, and has the following characteristics. The inner inclined portion has an arc-shaped cross-section whose inclination angle with respect to the rotation axis AX1 changes continuously. The section of the inner inclined part is opened downward. The inner diameter of the inner peripheral surface 513c increases as it approaches the lower end of the inner peripheral surface 513c. The lower end of the inner peripheral surface 513c has an inner diameter larger than the outer diameter of the rotating base 32 . Therefore, as shown by the dashed-dotted line in FIG. 3 , in the state where the facing member 50 is located at the facing position, the inner peripheral surface 513c faces the outer peripheral end of the substrate W and the outer peripheral surface (outer peripheral end) 32b of the rotary base 32. .

對向板51還具有設置於基板對向面513a且用以與第1卡合構件35卡合之複數個第2卡合構件514。於基板對向面513a之中央部形成有上下貫通對向構件50之貫通孔515。貫通孔515由圓筒狀之內周面劃分。第2卡合構件514之數量與第1卡合構件35相同,與第1卡合構件35一一對應地設置。另外,第1卡合構件35及第2卡合構件514之構成一直以來就被人們所周知。例如可將日本專利特開2019-57599號記載之構成用作本實施方式之卡合構件35、514。藉由第1卡合構件35與第2卡合構件514卡合,經由該卡合體而將對向構件50支撐於旋轉底座32。而且,當藉由馬達之作動而使旋轉底座32旋轉時,對向構件50與該旋轉底座32一體地繞旋轉軸線AX1旋轉。The facing plate 51 also has a plurality of second engaging members 514 disposed on the substrate facing surface 513 a and configured to engage with the first engaging member 35 . A through-hole 515 penetrating up and down through the opposing member 50 is formed in the central portion of the board-facing surface 513a. The through hole 515 is defined by a cylindrical inner peripheral surface. The number of the second engaging members 514 is the same as that of the first engaging members 35 , and they are provided in one-to-one correspondence with the first engaging members 35 . In addition, the configurations of the first engagement member 35 and the second engagement member 514 are conventionally known. For example, the structure described in Japanese Patent Application Laid-Open No. 2019-57599 can be used as the engagement members 35 and 514 of this embodiment. When the first engaging member 35 is engaged with the second engaging member 514 , the facing member 50 is supported by the rotating base 32 via the engaging body. Then, when the rotating base 32 is rotated by the operation of the motor, the facing member 50 is integrally rotated around the rotating axis AX1 with the rotating base 32 .

如圖3所示,卡合構件52具有於對向板51之上表面包圍貫通孔515周圍之圓筒部521、及從圓筒部521之上端向直徑方向外側擴展之凸緣部522。凸緣部522較作為支撐部53之一構成零件之凸緣支撐部531位於更上方,凸緣部522外周之直徑設為大於凸緣支撐部531內周之直徑。As shown in FIG. 3 , the engaging member 52 has a cylindrical portion 521 surrounding the through hole 515 on the upper surface of the opposing plate 51 , and a flange portion 522 extending radially outward from the upper end of the cylindrical portion 521 . The flange part 522 is located above the flange support part 531 which is a component part of the support part 53, and the diameter of the outer periphery of the flange part 522 is set larger than the diameter of the inner periphery of the flange support part 531.

支撐部53具有水平凸緣支撐部531、大致圓板狀之支撐部主體532、及連接凸緣支撐部531與支撐部主體532之連接部533。而且,中心軸噴嘴60以插通支撐部53及對向板51之內部空間之方式,沿藉由對向板51及基板W之中心之鉛直軸線、即旋轉軸線AX1於上下方向延伸。此外,中心軸噴嘴60與支撐部53一起藉由對向板升降驅動機構56而升降。例如圖3之實線所示,當中心軸噴嘴60及對向構件50定位於向鉛直上方離開基板W之退避位置時,中心軸噴嘴60之前端部向上方離開保持於旋轉夾頭30上之基板W之正面Wf。然後,對向板升降驅動機構56根據來自控制部4之下降指令使中心軸噴嘴60及支撐部53向下方下降,如圖3之單點劃線或圖5所示,將對向構件50定位於對向位置。由此,對向構件50之對向板51接近於基板W之正面Wf。結果為,由基板對向面(第1對向面)513a、內周面(第2對向面)513c及旋轉底座32之外周面(外周端)32b形成包圍保持於旋轉夾頭30上之基板W之半密閉狀空間SP。然後,於將基板W封入半密閉狀空間SP中而與周邊氛圍遮斷之狀態下,如圖6A及圖6B所示,從中心軸噴嘴60對該基板W之正面Wf供給藥液、IPA處理液、DIW、乾燥預處理液及氮氣。The supporting part 53 has a horizontal flange supporting part 531 , a substantially disc-shaped supporting part main body 532 , and a connection part 533 connecting the flange supporting part 531 and the supporting part main body 532 . Furthermore, the center axis nozzle 60 extends vertically along the vertical axis passing through the centers of the opposing plate 51 and the substrate W, that is, the rotation axis AX1 , so as to penetrate the inner space of the supporting portion 53 and the opposing plate 51 . In addition, the central axis nozzle 60 is raised and lowered by the opposing plate lifting and lowering drive mechanism 56 together with the supporting portion 53 . For example, as shown by the solid line in FIG. 3 , when the central axis nozzle 60 and the opposing member 50 are positioned at a retracted position away from the substrate W vertically upward, the front end of the central axis nozzle 60 is upwardly separated from the surface held on the rotary chuck 30. The front side Wf of the substrate W. Then, the opposing plate lifting drive mechanism 56 makes the central axis nozzle 60 and the supporting portion 53 descend downward according to the descending command from the control unit 4, as shown in the single-dot dash line in FIG. 3 or in FIG. 5 , and the opposing member 50 is positioned in the opposite position. Accordingly, the facing plate 51 of the facing member 50 is brought close to the front surface Wf of the substrate W. As shown in FIG. As a result, the substrate facing surface (first facing surface) 513a, the inner peripheral surface (second facing surface) 513c, and the outer peripheral surface (outer peripheral end) 32b of the spin base 32 form a circle that is surrounded and held on the spin chuck 30. The semi-closed space SP of the substrate W. Next, in a state where the substrate W is enclosed in the semi-closed space SP and shielded from the surrounding atmosphere, as shown in FIG. 6A and FIG. liquid, DIW, dry pretreatment liquid and nitrogen.

圖6A係對向構件及中心軸噴嘴之局部剖視圖。圖6B係從下方觀察中心軸噴嘴之下端部附近之模式圖。圖6A中之虛線區域為基板W之正面Wf之局部放大圖,圖示出形成於正面Wf上之圖案PT之一例。中心軸噴嘴60具有沿旋轉軸線AX1於上下方向延伸設置之噴嘴主體61。於該噴嘴主體61之中央部,從噴嘴主體61之上端面貫通至下端面而設置有5根中央配管部(省略圖示)。此5根中央配管部之下端面側開口分別作為藥液噴出口62a、DIW噴出口63a、IPA噴出口64a、乾燥預處理液噴出口65a及中央氣體噴出口66a發揮功能。Fig. 6A is a partial sectional view of the opposing member and the central axis nozzle. Fig. 6B is a schematic view of the vicinity of the lower end of the central axis nozzle viewed from below. The dotted line area in FIG. 6A is a partially enlarged view of the front surface Wf of the substrate W, showing an example of the pattern PT formed on the front surface Wf. The central axis nozzle 60 has a nozzle body 61 extending in the vertical direction along the rotation axis AX1. In the central portion of the nozzle body 61 , five central piping portions (not shown) are provided penetrating from the upper end surface to the lower end surface of the nozzle body 61 . The openings on the lower end faces of the five central pipes function as the chemical liquid discharge port 62a, the DIW discharge port 63a, the IPA discharge port 64a, the dry pretreatment liquid discharge port 65a, and the central gas discharge port 66a, respectively.

具有藥液噴出口62a之中央配管部如圖3所示經由配管62b與藥液供給部(省略圖示)連接。於該配管62b上插裝有閥門62c。因此,當根據來自控制部4之開關指令而打開閥門62c時,藥液經由配管62b被供給至中心軸噴嘴60,從藥液噴出口62a向基板W之表面中央部噴出。本實施方式中,藥液只要具有清洗基板W之正面Wf之功能即可,例如可為包含硫酸、硝酸、鹽酸、氫氟酸、磷酸、醋酸、氨水、過氧化氫水、有機酸(例如檸檬酸、草酸等)、有機鹼(例如TMAH:氫氧化四甲基銨等)、界面活性劑、及防腐劑中之至少一種之液體,亦可為除此以外之液體。As shown in FIG. 3 , the central piping section having the chemical liquid discharge port 62 a is connected to a chemical liquid supply section (not shown) via a pipe 62 b. A valve 62c is inserted into the piping 62b. Therefore, when the valve 62c is opened according to the switch command from the control unit 4, the chemical solution is supplied to the center axis nozzle 60 through the pipe 62b, and is sprayed toward the center of the surface of the substrate W from the chemical solution discharge port 62a. In this embodiment, as long as the chemical solution has the function of cleaning the front surface Wf of the substrate W, for example, it may contain sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia water, hydrogen peroxide water, organic acid (such as lemon acid, oxalic acid, etc.), organic base (such as TMAH: tetramethylammonium hydroxide, etc.), surfactant, and preservative at least one of the liquid, and other liquids may also be used.

具有DIW噴出口63a之中央配管部如圖3所示經由配管63b與DIW供給部(省略圖示)連接。於該配管63b上插裝有閥門63c。因此,當根據來自控制部4之開關指令而打開閥門63c時,DIW經由配管63b被供給至中心軸噴嘴60,從DIW噴出口63a向基板W之表面中央部噴出。本實施方式中,如下文所說明,使用DIW作為對藥液處理後之基板W之正面Wf進行沖洗處理之沖洗液,但亦可使用其他沖洗液。例如可將碳酸水、電解離子水、氫水、臭氧水、及稀釋濃度(例如10~100 ppm左右)之鹽酸水中之任一種用作沖洗液。As shown in FIG. 3, the central piping part which has the DIW discharge port 63a is connected to the DIW supply part (not shown) via the piping 63b. A valve 63c is inserted into the piping 63b. Therefore, when the valve 63c is opened according to the switch command from the control unit 4, DIW is supplied to the center axis nozzle 60 through the pipe 63b, and is discharged to the center of the surface of the substrate W from the DIW discharge port 63a. In this embodiment, as described below, DIW is used as the rinse solution for rinsing the front surface Wf of the substrate W after chemical treatment, but other rinse solutions may also be used. For example, any one of carbonated water, electrolyzed ionized water, hydrogen water, ozone water, and hydrochloric acid water at a diluted concentration (for example, about 10-100 ppm) can be used as the rinse solution.

具有IPA噴出口64a之中央配管部如圖3所示經由配管64b與IPA處理液供給部(省略圖示)連接。於該配管64b上插裝有閥門64c。因此,當根據來自控制部4之開關指令而打開閥門64c時,IPA處理液經由配管64b被供給至中心軸噴嘴60,從IPA噴出口64a向基板W之表面中央部噴出。本實施方式中,使用IPA處理液作為置換沖洗處理後附著於基板W之正面Wf之沖洗液(DIW)之置換液,但亦可使用其他液體。更詳細而言,可將與沖洗液及乾燥預處理液此兩種液體溶合之液體用作置換液。例如可為HFE(氫氟醚)或IPA與HFE之混合液,亦可包含IPA及HFE中之至少一者與除此以外之成分。As shown in FIG. 3, the central piping part which has the IPA discharge port 64a is connected to the IPA processing liquid supply part (illustration omitted) via the piping 64b. A valve 64c is inserted in the piping 64b. Therefore, when the valve 64c is opened according to the switch command from the control unit 4, the IPA treatment liquid is supplied to the center axis nozzle 60 through the pipe 64b, and is sprayed toward the center of the surface of the substrate W from the IPA discharge port 64a. In this embodiment, the IPA treatment liquid is used as a replacement liquid for replacing the rinsing liquid (DIW) adhering to the front surface Wf of the substrate W after the rinsing process, but other liquids may also be used. In more detail, a liquid mixed with two liquids, the rinse liquid and the dry pretreatment liquid, can be used as the replacement liquid. For example, it may be HFE (hydrofluoroether) or a mixed solution of IPA and HFE, and may contain at least one of IPA and HFE and other components.

具有乾燥預處理液噴出口65a之中央配管部如圖3所示經由配管65b與乾燥預處理液供給部(省略圖示)連接。於該配管65b上插裝有閥門65c。因此,當根據來自控制部4之開關指令而打開閥門65c時,乾燥預處理液經由配管65b被供給至中心軸噴嘴60,從乾燥預處理液噴出口65a向基板W之表面中央部噴出。本實施方式中,使用包含相當於溶質之昇華性物質及與昇華性物質溶合之溶劑之溶液作為乾燥預處理液。此處,昇華性物質亦可為於常溫(與室溫同義)或常壓(處理單元1A內之壓力,例如1氣壓或其附近值)下不經過液體便從固體變成氣體之物質。溶劑可為上述物質,亦可為除此以外之物質。即,乾燥預處理液亦可包含常溫或常壓下不經過液體便從固體變成氣體之2種以上之物質。As shown in FIG. 3, the central piping part which has the dry pretreatment liquid discharge port 65a is connected to the dry pretreatment liquid supply part (not shown) via the pipe 65b. A valve 65c is inserted in the piping 65b. Therefore, when the valve 65c is opened according to the switch command from the control unit 4, the dry pretreatment liquid is supplied to the center axis nozzle 60 through the pipe 65b, and is sprayed toward the center of the surface of the substrate W from the dry pretreatment liquid discharge port 65a. In this embodiment, a solution containing a sublimable substance corresponding to a solute and a solvent fused with the sublimable substance is used as a dry pretreatment liquid. Here, the sublimable substance may also be a substance that changes from a solid to a gas without passing through a liquid at normal temperature (synonymous with room temperature) or normal pressure (the pressure in the processing unit 1A, such as 1 atmosphere or its vicinity). The solvent may be those mentioned above, or other substances may be used. That is, the dry pretreatment liquid may contain two or more substances that change from solid to gas without passing through liquid at normal temperature or normal pressure.

昇華性物質例如可為2-甲基-2-丙醇(別名:tert-丁醇、t-丁醇、第三丁醇)或環己醇等醇類、氫氟碳化合物、1,3,5-三氧雜環己烷(別名:三聚甲醛)、樟腦(別名:camphor)、萘、碘、環己酮肟、及環己烷中之任一者,亦可為除此以外之物質。Sublimable substances can be, for example, 2-methyl-2-propanol (alias: tert-butanol, t-butanol, tert-butanol) or alcohols such as cyclohexanol, hydrofluorocarbons, 1,3, Any one of 5-trioxane (alias: paraformaldehyde), camphor (alias: camphor), naphthalene, iodine, cyclohexanone oxime, and cyclohexane, or other substances .

溶劑例如可為選自由純水、IPA、HFE、丙酮、PGMEA(丙二醇單甲醚乙酸酯)、PGEE(丙二醇單***、1-乙氧基-2-丙醇)、乙二醇、及氫氟碳(hydrofluorocarbon)所組成之群中之至少一種。The solvent, for example, can be selected from pure water, IPA, HFE, acetone, PGMEA (propylene glycol monomethyl ether acetate), PGEE (propylene glycol monoethyl ether, 1-ethoxy-2-propanol), ethylene glycol, and hydrogen At least one of the group consisting of hydrofluorocarbons.

具有中央氣體噴出口66a之中央配管部如圖3所示經由配管66b與氮氣供給部(省略圖示)連接。於該配管66b上插裝有閥門66c。因此,當根據來自控制部4之開關指令而打開閥門66c時,氮氣經由配管66b被供給至中心軸噴嘴60,如圖6A中之單點劃線箭頭所示,從中央氣體噴出口66a向基板W之表面中央部噴出。如此,本實施方式中,中央氣體噴出口66a相當於本發明之「第1噴出部」之一例。此外,從中央氣體噴出口66a噴出之氮氣相當於本發明之「第1氣體」之一例,以下適當地稱為「垂直N2」。As shown in FIG. 3, the central piping part which has the central gas discharge port 66a is connected to the nitrogen gas supply part (not shown) via the piping 66b. A valve 66c is inserted in the piping 66b. Therefore, when the valve 66c is opened according to the switching command from the control unit 4, nitrogen gas is supplied to the central axis nozzle 60 through the piping 66b, and as shown by the single-dot chain arrow in FIG. The center part of the surface of W is ejected. Thus, in this embodiment, the center gas discharge port 66a corresponds to an example of the "1st discharge part" of this invention. In addition, the nitrogen gas ejected from the central gas ejection port 66a corresponds to an example of the "first gas" of the present invention, and is hereinafter appropriately referred to as "vertical N2".

如此設置有5個噴出口62a~66a之下端面61a如圖3之實線所示,於非遮斷狀態下向較基板對向面513a及中央傾斜面513b更上方側後退。另一方面,於遮斷狀態下,如圖6A及圖6B所示,下端面61a與基板對向面513a於上下方向上位於相同高度,噴嘴主體61之下端部61b以被中央傾斜面513b包圍之狀態從貫通孔515向下方露出。As shown by the solid line in FIG. 3 , the bottom end surface 61a provided with the five ejection ports 62a to 66a recedes upward from the substrate-facing surface 513a and the central inclined surface 513b in the non-blocking state. On the other hand, in the off state, as shown in FIGS. 6A and 6B , the lower end surface 61a and the substrate facing surface 513a are at the same height in the vertical direction, and the lower end portion 61b of the nozzle body 61 is surrounded by the central inclined surface 513b. The state is exposed downward from the through hole 515 .

於該下端部61b之側面,以旋轉軸線AX1為中心大致等角度間隔地設置著6個周緣氣體噴出口67。從噴嘴主體61之側面延伸至噴嘴主體61之上端面之周緣配管部68連接於該些周緣氣體噴出口67。周緣配管部68如圖3所示經由配管68b與氮氣供給部(省略圖示)連接。於該配管68b上插裝有閥門68c。因此,當根據來自控制部4之開關指令而打開閥門68c時,氮氣經由配管68b被供給至中心軸噴嘴60,從周緣氣體噴出口67以旋轉軸線AX1為中心沿大致水平方向噴出。如此,本實施方式中,周緣氣體噴出口67相當於本發明之「第2噴出部」之一例。此外,從周緣氣體噴出口67噴出之氮氣相當於本發明之「第2氣體」之一例,為了區別於垂直N2,以下適當地稱為「水平N2」。如圖6A中之虛線箭頭所示,該水平N2沿中央傾斜面513b及基板對向面513a被導向基板W之表面周緣部。On the side surface of the lower end portion 61b, six peripheral gas ejection ports 67 are provided at substantially equal angular intervals around the rotation axis AX1. The peripheral piping portion 68 extending from the side surface of the nozzle main body 61 to the upper end surface of the nozzle main body 61 is connected to the peripheral gas ejection ports 67 . The peripheral piping portion 68 is connected to a nitrogen gas supply portion (not shown) via a piping 68 b as shown in FIG. 3 . A valve 68c is inserted in the piping 68b. Therefore, when the valve 68c is opened according to the switch command from the control unit 4, nitrogen gas is supplied to the central axis nozzle 60 through the pipe 68b, and is ejected from the peripheral gas ejection port 67 in a substantially horizontal direction centered on the rotation axis AX1. Thus, in the present embodiment, the peripheral gas ejection port 67 corresponds to an example of the "second ejection part" of the present invention. In addition, the nitrogen gas ejected from the peripheral gas ejection port 67 corresponds to an example of the "second gas" of the present invention, and is hereinafter appropriately referred to as "horizontal N2" in order to distinguish it from vertical N2. As shown by the dotted arrow in FIG. 6A , the level N2 is guided to the surface peripheral portion of the substrate W along the central inclined surface 513 b and the substrate-facing surface 513 a.

如上所述,本實施方式中,如圖6A所示,作為向基板W供給氮氣之供給方式,存在如下兩種方式,即:As described above, in this embodiment, as shown in FIG. 6A , there are the following two methods for supplying nitrogen gas to the substrate W, namely:

• 第1供給方式(該圖中之單點劃線箭頭),經由基板W之表面中央部供給至基板W之表面周緣部;• The first supply method (the dot-and-dash line arrow in the figure) is to supply to the surface peripheral part of the substrate W through the central part of the surface of the substrate W;

• 第2供給方式(該圖中之虛線箭頭),不經由基板W之表面中央部而供給至基板W之表面周緣部。而且,藉由控制部4控制閥門66c、68c之開關,而選擇性地切換停止供給氮氣之模式、僅執行第1供給方式之模式、僅執行第2供給方式之模式、及同時執行第1供給方式及第2供給方式之模式。此外,能夠根據來自控制部4之指令分別獨立地可變控制以第1供給方式及第2供給方式供給之氮氣之流量,但於該圖中省略了圖示。另外,本實施方式中,將氮氣用作本發明之「惰性氣體」,但除此以外,亦可使用經去濕之氬氣等惰性氣體。• In the second supply method (dotted arrow in the figure), the substrate W is supplied to the surface peripheral portion of the substrate W without passing through the central portion of the surface of the substrate W. Moreover, by controlling the switches of the valves 66c and 68c by the controller 4, the mode of stopping the supply of nitrogen gas, the mode of only the first supply mode, the mode of only the second supply mode, and the simultaneous execution of the first supply can be selectively switched. mode and the mode of the second supply mode. In addition, the flow rates of the nitrogen gas supplied in the first supply mode and the second supply mode can be independently and variablely controlled according to commands from the control unit 4 , but are not shown in this figure. In addition, in the present embodiment, nitrogen is used as the "inert gas" in the present invention, but inert gases such as dehumidified argon may also be used.

在處理單元1A中,以包圍旋轉夾頭30之方式設置著排氣桶70。此外,處理單元1A中設置有:複數個承杯72,其配置於旋轉夾頭30與排氣桶70之間;及複數個擋板73,其擋住飛濺到基板W周圍之藥液、沖洗液(DIW)、IPA處理液、乾燥預處理液。此外,擋板升降驅動機構71連結於擋板73。擋板升降驅動機構71根據來自控制部4之升降指令,使擋板73獨立地升降。進而,排氣機構74經由配管75連接於排氣桶70。該排氣機構74對由腔室20之內底面、排氣桶70及擋板73包圍之空間進行排氣。In the processing unit 1A, an exhaust barrel 70 is provided so as to surround the rotary chuck 30 . In addition, the processing unit 1A is provided with: a plurality of cups 72, which are arranged between the rotary chuck 30 and the exhaust barrel 70; (DIW), IPA treatment solution, dry pretreatment solution. In addition, the shutter lift drive mechanism 71 is connected to the shutter 73 . The baffle plate lifting drive mechanism 71 independently lifts the baffle plate 73 according to the lift instruction from the control unit 4 . Furthermore, the exhaust mechanism 74 is connected to the exhaust tub 70 via a pipe 75 . The exhaust mechanism 74 exhausts the space surrounded by the inner bottom surface of the chamber 20 , the exhaust barrel 70 and the baffle 73 .

進而,在處理單元1A中,設置著3個流量計81~83,監控裝置各部中之氣體成分之流量。更具體而言,第1流量計81以面向半密閉狀空間SP之方式安裝於圓板部511。第1流量計81測量空間SP內之氣體成分之流量,並將其測量結果輸出至控制部4。第2流量計82以面向旋轉夾頭30之周邊空間之方式安裝於旋轉夾頭30。第2流量計82測量旋轉夾頭30之周邊氛圍中之氣體成分之流量,並將其測量結果輸出至控制部4。於從排氣桶70延伸至排氣機構74之配管75上安裝著第1流量計81。第3流量計83測量流經上述配管75之氣體成分之流量,並將其測量結果輸出至控制部4。Furthermore, in the processing unit 1A, three flow meters 81 to 83 are installed to monitor the flow rate of the gas components in each part of the apparatus. More specifically, the first flowmeter 81 is attached to the disc portion 511 so as to face the semi-sealed space SP. The first flowmeter 81 measures the flow rate of the gas component in the space SP, and outputs the measurement result to the control unit 4 . The second flowmeter 82 is attached to the spin chuck 30 so as to face the peripheral space of the spin chuck 30 . The second flowmeter 82 measures the flow rate of the gas component in the surrounding atmosphere of the spin chuck 30 and outputs the measurement result to the control unit 4 . A first flow meter 81 is attached to the pipe 75 extending from the exhaust barrel 70 to the exhaust mechanism 74 . The third flow meter 83 measures the flow rate of the gas component flowing through the pipe 75 and outputs the measurement result to the control unit 4 .

控制部4具有CPU(Central Processing Unit,中央處理單元)等運算單元、固定記憶體器件、硬碟驅動器等記憶單元、及輸入輸出單元。於記憶單元中記憶著運算單元所要執行之程式。而且,控制部4藉由按照上述程式控制裝置各部,而執行圖7所示之基板處理。尤其,控制部4如以下所說明般,藉由於昇華處理中進行使水平N2早於垂直N2開始噴出之噴出時序控制、以及使水平N2之流量多於垂直N2之流量的流量控制,而謀求改善基板W之表面周緣部處之圖案塌陷。The control unit 4 has an arithmetic unit such as a CPU (Central Processing Unit, central processing unit), a memory unit such as a fixed memory device, a hard disk drive, and an input/output unit. The program to be executed by the arithmetic unit is stored in the memory unit. And the control part 4 executes the substrate process shown in FIG. 7 by controlling each part of an apparatus according to the said program. In particular, as described below, the control unit 4 seeks improvement by performing discharge timing control such that the horizontal N2 starts to discharge earlier than the vertical N2, and flow control such that the flow rate of the horizontal N2 is greater than the flow rate of the vertical N2 during the sublimation process. The pattern at the peripheral portion of the surface of the substrate W is collapsed.

圖7係表示處理單元中執行之基板處理之內容之流程圖。基板處理系統100之處理對象例如為矽晶圓,該矽晶圓於作為圖案形成面之正面Wf上形成有凹凸狀之圖案PT(參照圖6A)。圖案PT可為構成邏輯電路、DRAM(Dynamic Random Access Memory,動態隨機存取記憶體)或使用硫屬化物系合金之特異性質之PRAM(Phase-change Random Access Memory,相變隨機存取記憶體)者。圖案PT亦可為將由微細溝槽形成之線狀圖案重複排列而成之圖案。此外,圖案PT亦可藉由對薄膜設置複數個微細孔(空隙(void)或孔洞(pore))而形成。圖案PT例如包含絕緣膜。此外,圖案PT亦可包含導體膜。更具體而言,圖案PT由積層複數個膜而成之積層膜形成,進而,亦可包含絕緣膜與導體膜。圖案PT亦可為由單層膜構成之圖案PT。絕緣膜可為氧化矽膜或氮化矽膜。此外,導體膜可為經導入用於低電阻化之雜質的非晶矽膜,亦可為金屬膜(例如TiN膜)。此外,圖案PT可於前道工序中形成,亦可於後道工序中形成。進而,圖案PT可為疏水性膜,亦可為親水性膜。作為親水性膜,例如包含TEOS(tetraethoxysilane,四乙氧基矽烷)膜(氧化矽膜之一種)。FIG. 7 is a flowchart showing the contents of substrate processing performed in the processing unit. The object to be processed by the substrate processing system 100 is, for example, a silicon wafer on which a concave-convex pattern PT is formed on the front surface Wf as a pattern forming surface (see FIG. 6A ). The pattern PT can be a logic circuit, DRAM (Dynamic Random Access Memory, dynamic random access memory) or PRAM (Phase-change Random Access Memory, phase-change random access memory) using the specific properties of chalcogenide alloys By. The pattern PT may be a pattern obtained by repeatedly arranging linear patterns formed by fine grooves. In addition, the pattern PT can also be formed by providing a plurality of microscopic holes (voids or pores) in the thin film. Pattern PT includes, for example, an insulating film. In addition, the pattern PT may also include a conductive film. More specifically, the pattern PT is formed of a laminated film obtained by laminating a plurality of films, and may further include an insulating film and a conductive film. The pattern PT may also be a pattern PT composed of a single-layer film. The insulating film can be a silicon oxide film or a silicon nitride film. In addition, the conductive film may be an amorphous silicon film into which impurities for low resistance have been introduced, or may be a metal film (such as a TiN film). In addition, the pattern PT may be formed in a previous process, or may be formed in a subsequent process. Furthermore, the pattern PT may be a hydrophobic film or a hydrophilic film. The hydrophilic film includes, for example, a TEOS (tetraethoxysilane, tetraethoxysilane) film (a type of silicon oxide film).

此外,圖7所示之各工序只要未特別明示,均為於大氣壓環境下進行處理。此處,大氣壓環境是指以標準大氣壓(1個氣壓,1013 hPa)為中心之0.7個氣壓以上、1.3個氣壓以下之環境。尤其,於基板處理系統100配置於正壓之無塵室內時,基板W之正面Wf之環境高於1個氣壓。In addition, each process shown in FIG. 7 was processed under atmospheric pressure environment unless otherwise indicated. Here, the atmospheric pressure environment refers to an environment above 0.7 atmospheric pressure and below 1.3 atmospheric pressure around the standard atmospheric pressure (1 atmospheric pressure, 1013 hPa). In particular, when the substrate processing system 100 is arranged in a positive pressure clean room, the environment of the front surface Wf of the substrate W is higher than 1 atmosphere.

將未處理之基板W搬入處理單元1A之前,控制部4對裝置各部賦予指令而將處理單元1A設置為初始狀態。即,藉由擋閘開關機構22關閉擋閘23(圖1至圖3)。藉由基板旋轉驅動機構34將旋轉夾頭30定位並停在適合於裝載基板W之位置,並且藉由未圖示之夾頭開關機構使夾頭銷31為打開狀態。對向板51藉由對向板升降驅動機構56而定位於退避位置。由此,解除旋轉底座32給予對向板51之支撐,對向板51停止旋轉。擋板73均向下方移動並定位。進而,閥門62c~66c、68c均關閉。Before loading the unprocessed substrate W into the processing unit 1A, the control unit 4 gives instructions to each part of the apparatus to set the processing unit 1A to an initial state. That is, the shutter 23 is closed by the shutter switch mechanism 22 ( FIGS. 1 to 3 ). The rotary chuck 30 is positioned and stopped at a position suitable for loading the substrate W by the substrate rotation driving mechanism 34 , and the chuck pin 31 is opened by the chuck switch mechanism not shown. The facing plate 51 is positioned at the withdrawn position by the facing plate lift drive mechanism 56 . As a result, the support given by the rotating base 32 to the opposing plate 51 is released, and the opposing plate 51 stops rotating. The baffles 73 all move downward and are positioned. Furthermore, valves 62c-66c, 68c are all closed.

當未處理之基板W由基板搬送機械手111搬送來時,擋閘23打開。與擋閘23之打開相應地,基板W由基板搬送機械手111搬入至腔室20之內部空間21中,以正面Wf朝上方之面朝上狀態被交接給旋轉夾頭30。然後,夾頭銷31成為關閉狀態,基板W被保持於旋轉夾頭30上(步驟S1:基板搬入)。When the unprocessed substrate W is transported by the substrate transport robot 111 , the shutter 23 is opened. Corresponding to the opening of the shutter 23, the substrate W is carried into the inner space 21 of the chamber 20 by the substrate transfer robot 111, and is handed over to the spin chuck 30 with the front surface Wf facing upward. Then, the chuck pin 31 is in the closed state, and the substrate W is held on the spin chuck 30 (step S1: substrate loading).

於搬入基板W之後,基板搬送機械手111退避至腔室20外,進而擋閘23再次關閉。然後,控制部4控制對向板升降驅動機構56,將對向板51配置於對向位置。由此,如圖5所示設置於對向板51之卡合構件514由卡合構件35承接,對向板51及中心軸噴嘴60支撐於旋轉底座32上。此外,對向板51與旋轉底座32相互接近而形成半密閉狀空間SP。結果為,保持於旋轉夾頭30上之基板W被封入空間SP中而與周邊氛圍遮斷。另外,本實施方式中,於下文說明之昇華工序(步驟S8)完成之前,對向板51定位於對向位置上。After loading the substrate W, the substrate transfer robot 111 retreats to the outside of the chamber 20 , and the shutter 23 is closed again. Then, the control unit 4 controls the facing plate elevation drive mechanism 56 to arrange the facing plate 51 at the facing position. As a result, the engaging member 514 provided on the facing plate 51 is received by the engaging member 35 as shown in FIG. In addition, the opposing plate 51 and the rotating base 32 approach each other to form a semi-closed space SP. As a result, the substrate W held on the spin chuck 30 is enclosed in the space SP and shielded from the surrounding atmosphere. In addition, in the present embodiment, the facing plate 51 is positioned at the facing position before the sublimation step (step S8 ) described below is completed.

於完成將基板W封入到空間SP中之後,控制部4控制基板旋轉驅動機構34之馬達(省略圖示),使旋轉底座32之旋轉速度上升到特定之藥液處理速度(於約10~1200 rpm之範圍內,例如約800 rpm)並維持於該藥液處理速度。與該旋轉底座32之旋轉一同地,對向板51繞旋轉軸線AX1旋轉,並且基板W繞旋轉軸線AX1旋轉(步驟S2:基板旋轉開始)。另外,於進入下一藥液處理之前,控制部4藉由使與藥液處理對應之擋板73上升,而使該擋板73與間隙GP對向,上述間隙GP係對向板51之內周面513c與旋轉底座32之外周面32b之間隙。After the substrate W is sealed into the space SP, the control unit 4 controls the motor (not shown) of the substrate rotation drive mechanism 34 to increase the rotation speed of the rotary base 32 to a specific chemical solution processing speed (about 10-1200 within the range of rpm, such as about 800 rpm) and maintained at the liquid treatment speed. Along with the rotation of the rotary base 32, the opposing plate 51 rotates around the rotation axis AX1, and the substrate W rotates around the rotation axis AX1 (step S2: substrate rotation start). In addition, before entering the next chemical solution treatment, the control unit 4 raises the baffle plate 73 corresponding to the chemical solution treatment, so that the baffle plate 73 faces the gap GP, which is inside the facing plate 51. The gap between the peripheral surface 513c and the outer peripheral surface 32b of the rotating base 32 .

當基板W之旋轉速度達到藥液處理速度時,接下來,控制部4打開閥門62c。由此,從中心軸噴嘴60之藥液噴出口62a噴出藥液並供給至基板W之正面Wf。於基板W之正面Wf上,藥液受到基板W之旋轉所產生之離心力而移動至基板W之周緣部。由此,基板W之整個正面Wf受到藥液之清洗(步驟S3)。此時,到達基板W之周緣部之藥液被從基板W之周緣部向基板W之側方排出,並經由擋板73送出至設備外之廢液處理設備。藉由供給該藥液而進行之藥液清洗持續進行預先規定之清洗時間,於經過該時間後,控制部4關閉閥門62c,停止從中心軸噴嘴60噴出藥液。When the rotation speed of the substrate W reaches the chemical solution processing speed, next, the control unit 4 opens the valve 62c. As a result, the chemical liquid is ejected from the chemical liquid ejection port 62 a of the center axis nozzle 60 and supplied to the front surface Wf of the substrate W. As shown in FIG. On the front surface Wf of the substrate W, the chemical solution is moved to the peripheral edge of the substrate W by the centrifugal force generated by the rotation of the substrate W. Thus, the entire front surface Wf of the substrate W is cleaned with the chemical solution (step S3). At this time, the chemical solution reaching the peripheral portion of the substrate W is discharged from the peripheral portion of the substrate W to the side of the substrate W, and sent to the waste liquid treatment equipment outside the equipment through the baffle plate 73 . The cleaning of the chemical solution by supplying the chemical solution continues for a predetermined cleaning time, and after the elapse of the time, the control unit 4 closes the valve 62c to stop spraying of the chemical solution from the central axis nozzle 60 .

於藥液清洗之後,利用沖洗液(DIW)執行沖洗處理(步驟S4)。於該DIW沖洗中,控制部4打開閥門63c。由此,從中心軸噴嘴60之DIW噴出口63a對經藥液清洗處理後之基板W之正面Wf之中央部供給DIW作為沖洗液。如此一來,DIW受到基板W之旋轉所產生之離心力而移動至基板W之周緣部。由此,附著於基板W上之藥液被DIW沖走。此時,從基板W之周緣部排出之DIW從基板W之周緣部向基板W之側方排出,與藥液相同被送出至設備外之廢液處理設備。該DIW沖洗持續預先規定之沖洗時間,於經過該時間後,控制部4關閉閥門63c,停止從中心軸噴嘴60噴出DIW。After cleaning with the chemical solution, a rinse process is performed with a rinse solution (DIW) (step S4). During this DIW flushing, the control unit 4 opens the valve 63c. Thus, DIW is supplied as a rinse liquid from the DIW discharge port 63a of the center axis nozzle 60 to the central portion of the front surface Wf of the substrate W after the chemical liquid cleaning process. In this way, the DIW moves to the peripheral edge of the substrate W by the centrifugal force generated by the rotation of the substrate W. As shown in FIG. Accordingly, the chemical solution adhering to the substrate W is washed away by the DIW. At this time, the DIW discharged from the peripheral portion of the substrate W is discharged from the peripheral portion of the substrate W to the side of the substrate W, and sent to the waste liquid treatment facility outside the facility like the chemical solution. This DIW flushing continues for a predetermined flushing time, and after the elapse of the time, the control unit 4 closes the valve 63c to stop DIW ejection from the central axis nozzle 60 .

於完成DIW沖洗之後,進行置換處理(步驟S5)。置換處理(步驟S5)中,控制部4控制基板旋轉驅動機構34之馬達(省略圖示),將基板W之旋轉速度調整為特定之置換旋轉速度並維持於該置換旋轉速度。此外,控制部4分別調整來自中央氣體噴出口66a及周緣氣體噴出口67之氮氣、亦即垂直N2及水平N2之流量。由此,對半密閉狀空間SP供給氮氣,於空間SP內氮富集。此外,可有效防止外部氣體經由作為連通空間SP與周邊氛圍之唯一部位之間隙GP(參照圖5)從周邊氛圍侵入空間SP中。由此,空間SP成為低氧環境。此處,「低氧」係指氧濃度為100 ppm以下。After the DIW flushing is completed, a replacement process is performed (step S5). In the replacement process (step S5 ), the control unit 4 controls the motor (not shown) of the substrate rotation drive mechanism 34 to adjust and maintain the rotation speed of the substrate W to a specific replacement rotation speed. In addition, the control unit 4 adjusts the nitrogen gas from the central gas ejection port 66 a and the peripheral gas ejection port 67 , that is, the flow rates of vertical N2 and horizontal N2 . Thus, nitrogen gas is supplied to the semi-closed space SP, and nitrogen is enriched in the space SP. In addition, it is possible to effectively prevent external air from entering the space SP from the surrounding atmosphere through the gap GP (refer to FIG. 5 ), which is the only part communicating the space SP and the surrounding atmosphere. Accordingly, the space SP becomes a hypoxic environment. Here, "hypoxia" means that the oxygen concentration is 100 ppm or less.

此外,控制部4使與置換處理對應之擋板73與間隙GP對向。然後,控制部4打開閥門64c。由此,從中心軸噴嘴60之IPA噴出口64a向附著有DIW之基板W之正面Wf之中央部噴出IPA處理液作為低表面張力液體。供給至基板W之正面Wf之IPA處理液受到基板W之旋轉所產生之離心力而擴展至基板W之整個正面Wf。由此,於基板W之整個正面Wf,附著於該正面Wf上之DIW(沖洗液)被IPA處理液置換。另外,於基板W之正面Wf上移動之IPA處理液從基板W之周緣部向基板W之側方排出並被上述擋板73擋住,沿省略圖示之回收路徑被送出至回收設備中。該IPA置換持續預先規定之置換時間,於經過該時間後,控制部4關閉閥門64c,停止從中心軸噴嘴60噴出IPA處理液。In addition, the control unit 4 makes the baffle 73 corresponding to the replacement process face the gap GP. Then, the control unit 4 opens the valve 64c. As a result, the IPA treatment liquid is ejected as a low surface tension liquid from the IPA ejection port 64a of the center axis nozzle 60 toward the central portion of the front surface Wf of the substrate W on which the DIW is attached. The IPA treatment liquid supplied to the front surface Wf of the substrate W is spread to the entire front surface Wf of the substrate W by the centrifugal force generated by the rotation of the substrate W. Thereby, the DIW (rinsing liquid) adhering to the front surface Wf of the substrate W is replaced by the IPA treatment solution on the entire front surface Wf of the substrate W. In addition, the IPA treatment solution moving on the front surface Wf of the substrate W is discharged from the peripheral portion of the substrate W to the side of the substrate W and blocked by the baffle plate 73, and sent to the recovery equipment along the recovery path not shown. This IPA replacement continues for a predetermined replacement time, and after the elapse of the time, the control unit 4 closes the valve 64c, and stops spraying of the IPA treatment liquid from the central axis nozzle 60 .

於IPA置換之後,執行乾燥預處理液供給處理(步驟S6)。該乾燥預處理液供給處理中,控制部4將基板W之旋轉速度、垂直N2之流量及水平N2之流量分別維持為置換處理中之值。控制部4使與乾燥預處理液供給處理對應之擋板73與間隙GP對向。控制部4打開閥門65c。由此,從中心軸噴嘴60之乾燥預處理液噴出口65a向附著有置換液之基板W之正面Wf之中央部噴出乾燥預處理液。供給至基板W之正面Wf之乾燥預處理液受到基板W之旋轉所產生之離心力而擴展至基板W之整個正面Wf。由此,於基板W之整個正面Wf進行從IPA處理液向乾燥預處理液之置換,並且形成相對較厚之乾燥預處理液之液膜。乾燥預處理液之噴出持續預先規定之時間,於經過該時間後,控制部4關閉閥門65c,停止從中心軸噴嘴60噴出乾燥預處理液。After the IPA replacement, dry pretreatment liquid supply processing is performed (step S6). In this dry pretreatment liquid supply process, the control unit 4 maintains the rotation speed of the substrate W, the flow rate of the vertical N2, and the flow rate of the horizontal N2 respectively at the values in the replacement process. The control unit 4 makes the baffle plate 73 corresponding to the dry pretreatment liquid supply process face the gap GP. The control unit 4 opens the valve 65c. As a result, the dry pretreatment liquid is sprayed from the dry pretreatment liquid discharge port 65a of the central axis nozzle 60 toward the center of the front surface Wf of the substrate W to which the replacement liquid is attached. The dry pretreatment liquid supplied to the front surface Wf of the substrate W is spread to the entire front surface Wf of the substrate W by the centrifugal force generated by the rotation of the substrate W. Thus, the replacement of the IPA treatment solution to the dry pretreatment solution is performed on the entire front surface Wf of the substrate W, and a relatively thick liquid film of the dry pretreatment solution is formed. The spraying of the dry pretreatment liquid continues for a predetermined time, and after the elapse of the time, the control unit 4 closes the valve 65c to stop spraying of the dry pretreatment liquid from the central axis nozzle 60 .

為了將以此種方式形成之液膜減薄至所需厚度而執行膜厚減少處理(步驟S7)。膜厚減少處理中,控制部4關閉閥門66c、68c而使垂直N2及水平N2之噴出停止,並且控制基板旋轉驅動機構34之馬達(省略圖示)使基板W之旋轉速度增速至較置換旋轉速度高之旋轉甩脫速度。而且,控制部4將基板W之旋轉速度維持於旋轉甩脫速度預先規定之時間。由此,從基板W之正面Wf去除多餘之乾燥預處理液而將乾燥預處理液之液膜厚度調整為所需厚度。另外,本實施方式中,於膜厚減少處理中之期間停止向空間SP供給氮氣,但亦可供給氮氣。A film thickness reduction process is performed in order to thin the liquid film formed in this way to a desired thickness (step S7). During the film thickness reduction process, the control unit 4 closes the valves 66c and 68c to stop the discharge of the vertical N2 and the horizontal N2, and controls the motor (not shown) of the substrate rotation drive mechanism 34 to increase the rotation speed of the substrate W to a relatively high speed. The spin-off speed with high spin speed. And the control part 4 maintains the rotation speed of the board|substrate W at the spin-off speed predetermined time. In this way, excess dry pretreatment liquid is removed from the front surface Wf of the substrate W, and the liquid film thickness of the dry pretreatment liquid is adjusted to a desired thickness. In addition, in the present embodiment, the supply of nitrogen gas to the space SP is stopped during the film thickness reduction process, but nitrogen gas may be supplied.

接下來,執行凝固體形成處理(步驟S8),即,使基板W上之乾燥預處理液凝固,於基板W之正面Wf上形成包含昇華性物質之凝固體。該凝固體形成處理中,控制部4控制基板旋轉驅動機構34之馬達(省略圖示)將基板W之旋轉速度調整為凝固體形成速度。該凝固體形成速度可與置換旋轉速度相同,亦可為該置換旋轉速度以上。此外,為了促進形成凝固體,控制部4打開閥門66c、68c中之至少一者而噴出氮氣。藉由該凝固體形成處理而促進乾燥預處理液之蒸發,從而基板W上之乾燥預處理液之一部分得以蒸發。液膜中之昇華性物質之濃度慢慢增加,同時液膜之膜厚慢慢減少。而且,形成相當於覆蓋基板W之整個表面之上表面之固化膜之凝固體(圖8~圖11、圖15中之符號SB)。Next, a solidified body forming process (step S8 ) is performed, that is, the dry pretreatment liquid on the substrate W is solidified to form a solidified body containing a sublimable substance on the front surface Wf of the substrate W. In this solidified body forming process, the control unit 4 controls the motor (not shown) of the substrate rotation driving mechanism 34 to adjust the rotation speed of the substrate W to the solidified body forming speed. The solidified body formation speed may be the same as the replacement rotation speed, or may be higher than the replacement rotation speed. In addition, in order to promote the formation of solidified matter, the controller 4 opens at least one of the valves 66c and 68c to blow nitrogen gas. Evaporation of the dry pretreatment liquid is promoted by this solidified body forming process, and a part of the dry pretreatment liquid on the substrate W is evaporated. The concentration of the sublimable substance in the liquid film increases slowly, while the film thickness of the liquid film decreases slowly. Then, a solidified body corresponding to a cured film covering the entire upper surface of the substrate W is formed (symbol SB in FIGS. 8 to 11 and FIG. 15 ).

於該凝固體形成處理之後,執行使基板W之正面Wf上之凝固體昇華而將凝固體從基板W之正面Wf去除之昇華處理(步驟S9)。控制部4將基板W之旋轉速度調整為昇華速度。該昇華速度可與凝固體形成工序之最終速度相同,亦可不同。此外,控制部4對凝固體SB供給氮氣。此處,例如圖8所示,當利用與以往技術相同之方法,即僅藉由垂直N2之供給來進行昇華處理時,會產生上文所述之問題。After the solidified body forming process, a sublimation process for sublimating the solidified body on the front surface Wf of the substrate W to remove the solidified body from the front surface Wf of the substrate W is performed (step S9 ). The control unit 4 adjusts the rotation speed of the substrate W to the sublimation speed. This sublimation rate may be the same as or different from the final rate in the solidified body forming step. In addition, the control unit 4 supplies nitrogen gas to the solidified body SB. Here, as shown in FIG. 8, for example, when the sublimation process is performed by the same method as in the prior art, that is, only by supplying vertical N2, the above-mentioned problems arise.

圖8係表示以往技術中執行之昇華處理之圖。該圖中之上段曲線圖(及下文說明之相同之曲線圖)之橫軸表示昇華開始後之經過時間,縱軸表示垂直N2之流量。以往技術中,僅藉由圖6A中之單點劃線箭頭所示之第1供給方式對基板W之正面Wf供給氮氣。即,垂直N2經由基板W之表面中央部而遍佈基板W之整個表面。因此,如圖8之下段模式圖所示,於昇華處理之初始階段(時序T01)中,凝固體SB之表層部分中昇華之氣體狀昇華性物質SS與氮氣一起被從基板W之正面Wf排除。然而,於經過某程度之時間後之時序T02,始終對位於基板W之表面周緣部上之凝固體SB之中央區域SB1供給新鮮之氮氣,相對於此,昇華性物質SS之濃度較高之氮氣流向位於基板W之表面周緣部上之凝固體SB之周緣區域SB2。因此,於凝固體SB之中央區域SB1與周緣區域SB2中,昇華處理之推進度不同。更具體而言,存在周緣區域SB2之昇華受到抑制之情形,此成為基板W之表面周緣部中之圖案塌陷之主要原因之一。因此,本實施方式中,準備兩種氮氣供給方式,藉由適當控制該些供給方式之開啟/關閉來消除上述問題。Fig. 8 is a diagram showing a sublimation process performed in the prior art. The horizontal axis of the upper graph in the figure (and the same graph described below) represents the elapsed time after the start of sublimation, and the vertical axis represents the flow rate of vertical N2. In the prior art, nitrogen gas is supplied to the front surface Wf of the substrate W only by the first supply method indicated by the dashed-dotted line arrow in FIG. 6A . That is, the vertical N2 extends over the entire surface of the substrate W via the central portion of the surface of the substrate W. Therefore, as shown in the lower schematic diagram of FIG. 8, in the initial stage (sequence T01) of the sublimation process, the gaseous sublimable substance SS sublimated in the surface layer portion of the solidified body SB is exhausted from the front surface Wf of the substrate W together with nitrogen gas. . However, at sequence T02 after a certain amount of time has elapsed, fresh nitrogen gas is always supplied to the central region SB1 of the solidified body SB located on the peripheral portion of the surface of the substrate W, whereas nitrogen gas having a higher concentration of the sublimable substance SS is used. The flow is directed to the peripheral region SB2 of the solidified body SB located on the surface peripheral portion of the substrate W. Therefore, the degree of advancement of the sublimation process differs between the central region SB1 and the peripheral region SB2 of the solidified body SB. More specifically, there are cases where the sublimation of the peripheral region SB2 is suppressed, which becomes one of the main causes of pattern collapse in the surface peripheral portion of the substrate W. Therefore, in the present embodiment, two kinds of nitrogen gas supply methods are prepared, and the above-mentioned problems are solved by appropriately controlling ON/OFF of these supply methods.

圖9使表示本發明之第1實施方式中執行之昇華處理之圖。本實施方式中,於昇華處理(步驟S9)之開始時點,控制部4關閉閥門66c而使垂直N2之噴出停止,另一方面,打開閥門68c而以流量F2開始噴出水平N2。由此,於僅供給水平N2之期間,始終對周緣區域SB2供給不包含昇華性物質SS之新鮮氮氣。結果為,例如於時序T11,周緣區域SB2之昇華推進。另一方面,由於不對凝固體SB之中央區域SB1供給氮氣,因此中央區域SB1之昇華被限制。Fig. 9 is a diagram showing a sublimation process performed in the first embodiment of the present invention. In this embodiment, at the start of the sublimation process (step S9), the controller 4 closes the valve 66c to stop the vertical N2 discharge, and opens the valve 68c to start the horizontal N2 discharge at the flow rate F2. Thereby, while supplying only level N2, the fresh nitrogen gas which does not contain the sublimable substance SS is always supplied to peripheral area SB2. As a result, for example, at time sequence T11, the sublimation of the peripheral region SB2 advances. On the other hand, since the nitrogen gas is not supplied to the central region SB1 of the solidified body SB, the sublimation of the central region SB1 is restricted.

如此,於相當於本發明之「第2昇華工序」之一例之周緣區域SB2之昇華優先推進、或該昇華完成之時序Tsw,控制部4於保持閥門68c打開之狀態下打開閥門66c,而以流量F1(<F2)開始噴出垂直N2。由此,例如時序T12下之模式圖(該圖之下段右圖)所示,對中央區域SB1供給新鮮之氮氣,使得包含中央區域SB1在內之凝固體SB之整體昇華逐漸推進。此相當於本發明之「第1昇華工序」之一例。此外,對周緣區域SB2持續供給新鮮之水平N2,將昇華性物質SS之濃度抑制得較低。因此,即便於時序Tsw時點周緣區域SB2之昇華未完成之情形時,周緣區域SB2之昇華亦會逐漸推進。其結果為,藉由昇華處理(步驟S9)而切實地將整個凝固體SB昇華去除。In this way, at the time sequence Tsw at which the sublimation of the peripheral region SB2 which corresponds to an example of the "second sublimation process" of the present invention advances preferentially, or the sublimation is completed, the control part 4 opens the valve 66c while keeping the valve 68c open, and thereby The flow rate F1 (<F2) starts to spray vertical N2. Thus, for example, as shown in the schematic diagram (lower right diagram of the figure) at the time sequence T12, fresh nitrogen gas is supplied to the central region SB1, and the sublimation of the whole solidified body SB including the central region SB1 is gradually promoted. This corresponds to an example of the "first sublimation step" of the present invention. In addition, the concentration of the sublimable substance SS is kept low by continuously supplying fresh level N2 to the peripheral region SB2. Therefore, even when the sublimation of the peripheral region SB2 is not completed at the time sequence Tsw, the sublimation of the peripheral region SB2 will gradually advance. As a result, the entire solidified body SB is surely removed by sublimation by the sublimation treatment (step S9).

返回圖7繼續進行說明。於昇華處理之後,控制部4對基板旋轉驅動機構34之馬達進行停止控制而使基板W停止旋轉(步驟S10:基板旋轉停止)。繼而,控制部4控制對向板升降驅動機構56使對向板51從對向位置上升並定位於退避位置。進而,控制部4使所有擋板73從間隙GP向下方退避。Return to FIG. 7 to continue the description. After the sublimation process, the control unit 4 controls the stop of the motor of the substrate rotation drive mechanism 34 to stop the rotation of the substrate W (step S10: substrate rotation stop). Next, the control unit 4 controls the facing plate elevation drive mechanism 56 to raise the facing plate 51 from the facing position and position it at the retracted position. Furthermore, the control unit 4 retracts all the shutters 73 downward from the gap GP.

然後,控制部4控制擋閘開關機構22打開擋閘23(圖1~圖3)後,基板搬送機械手111進入腔室20之內部空間中,將已解除夾頭銷31給予之保持之處理完畢之基板W搬出至腔室20外(步驟S11)。另外,當基板搬送機械手111完成基板W之搬出而離開處理單元1A後,控制部4控制擋閘開關機構22而關閉擋閘23。Then, after the control unit 4 controls the shutter switch mechanism 22 to open the shutter 23 (Figs. 1-3), the substrate transfer manipulator 111 enters the inner space of the chamber 20, and releases the holding process given by the chuck pin 31. The finished substrate W is carried out to the outside of the chamber 20 (step S11 ). In addition, after the substrate transfer robot 111 completes unloading the substrate W and leaves the processing unit 1A, the control unit 4 controls the shutter switch mechanism 22 to close the shutter 23 .

如上所述,第1實施方式中,於藉由供給垂直N2而使整個凝固體SB昇華之前,將水平N2供給至凝固體SB之周緣區域SB2而優先進行周緣區域SB2之昇華。此外,於開始供給垂直N2之後,將水平N2之流量F2設定得多於垂直N2之流量F1。因此,於開始供給垂直N2之後,流入周緣區域SB2之氮氣(=垂直N2+水平N2)中之昇華性物質SS之濃度較低。因此,即便係於開始供給垂直N2之時點周緣區域SB2之一部分未昇華,亦會與中央區域SB1之昇華並行地進行該未昇華部分之昇華。由此,根據第1實施方式,可改善基板W之表面周緣部上之圖案塌陷。As described above, in the first embodiment, before the entire solidified body SB is sublimated by supplying the vertical N2, the horizontal N2 is supplied to the peripheral region SB2 of the solidified body SB, and the sublimation of the peripheral region SB2 is performed preferentially. In addition, after the supply of the vertical N2 is started, the flow rate F2 of the horizontal N2 is set much more than the flow rate F1 of the vertical N2. Therefore, after the vertical N2 supply is started, the concentration of the sublimable substance SS in the nitrogen gas (=vertical N2+horizontal N2 ) flowing into the peripheral region SB2 is low. Therefore, even if a part of the peripheral region SB2 is not sublimated when the supply of the vertical N2 is started, the sublimation of the non-sublimated part proceeds in parallel with the sublimation of the central region SB1. Thus, according to the first embodiment, pattern sinking on the surface peripheral portion of the substrate W can be improved.

圖10係表示本發明之第2實施方式中執行之昇華處理之圖。第2實施方式與第1實施方式較大地不同點僅在於,於開始噴出垂直N2後控制垂直N2(第1氣體)及水平N2(第2氣體)之流量。其他構成與第1實施方式相同。因此,以下以不同點為中心進行說明,對相同構成附上相同符號並省略說明。Fig. 10 is a diagram showing sublimation processing performed in the second embodiment of the present invention. The only major difference between the second embodiment and the first embodiment is that the flow rate of vertical N2 (first gas) and horizontal N2 (second gas) is controlled after the vertical N2 is started to be sprayed. Other configurations are the same as those of the first embodiment. Therefore, the following description will focus on different points, and the same components will be given the same symbols and their descriptions will be omitted.

第2實施方式中,於昇華處理(步驟S9)中,於周緣區域SB2之昇華優先推進、或昇華完成之時序Tsw,控制部4打開閥門66c,並且慢慢增加垂直N2之流量,同時慢慢減少水平N2之流量後,關閉閥門68c而停止供給水平N2。In the second embodiment, in the sublimation process (step S9), the sublimation in the peripheral area SB2 is advanced preferentially, or at the time sequence Tsw when the sublimation is completed, the control unit 4 opens the valve 66c, and gradually increases the flow rate of the vertical N2 while gradually After reducing the flow rate of the level N2, the supply of the level N2 is stopped by closing the valve 68c.

根據該第2實施方式,可獲得以下作用效果。優先進行凝固體SB之周緣區域SB2之昇華,於時序Tsw以後應昇華之周緣區域SB2為零或少量。因此,於時序Tsw以後藉由減少於幫助周緣區域SB2之昇華中為主體之水平N2之流量,可抑制氮氣之消耗量及排氣機構74之排氣量。結果為,可謀求降低運轉成本。According to this second embodiment, the following effects can be obtained. The sublimation of the peripheral region SB2 of the solidified body SB is preferentially performed, and the peripheral region SB2 to be sublimated after the time sequence Tsw is zero or a small amount. Therefore, by reducing the flow rate of the horizontal N2 that mainly assists the sublimation of the peripheral region SB2 after the time sequence Tsw, the consumption amount of nitrogen gas and the exhaust amount of the exhaust mechanism 74 can be suppressed. As a result, running cost can be reduced.

圖11係表示本發明之第3實施方式中執行之昇華處理之圖。第3實施方式與第1實施方式較大地不同點在於開始噴出垂直N2之時序。其他構成與第1實施方式相同。因此,以下以不同點為中心進行說明,對相同構成附上相同符號並省略說明。Fig. 11 is a diagram showing sublimation processing performed in the third embodiment of the present invention. The third embodiment is largely different from the first embodiment in the timing of starting to discharge the vertical N2. Other configurations are the same as those of the first embodiment. Therefore, the following description will focus on different points, and the same components will be given the same symbols and their descriptions will be omitted.

第3實施方式中,控制部4從開始昇華處理(步驟S9)之時點起打開閥門66c,開始以流量F1噴出垂直N2,並且打開閥門68c而開始以流量F2噴出水平N2。由此,將垂直N2供給至基板W之表面中央部,而逐漸推進凝固體SB之中央區域SB1之昇華。此時產生之氣體狀昇華性物質SS包含於氮氣中向表面周緣部流動。因此,於該表面周緣部存在昇華性物質SS。然而,第3實施方式中,從開始昇華處理之時點起以較垂直N2之流量F1多之流量F2向基板W之表面周緣部供給水平N2。因此,表面周緣部上之氮氣(=垂直N2+水平N2)中之昇華性物質濃度相對較低,藉由該氮氣而與中央區域SB1之昇華並行地進行周緣區域SB2之昇華。In the third embodiment, the control unit 4 opens the valve 66c to start discharging the vertical N2 at the flow rate F1 and opens the valve 68c to start discharging the horizontal N2 at the flow rate F2 from the time of starting the sublimation process (step S9). As a result, vertical N2 is supplied to the central portion of the surface of the substrate W, and the sublimation of the central region SB1 of the solidified body SB is gradually promoted. The gaseous sublimable substance SS generated at this time flows toward the peripheral portion of the surface contained in the nitrogen gas. Therefore, the sublimation substance SS exists in this surface peripheral part. However, in the third embodiment, the horizontal N2 is supplied to the surface peripheral portion of the substrate W at a flow rate F2 greater than the flow rate F1 of the vertical N2 from the time when the sublimation process is started. Therefore, the concentration of the sublimable substance in the nitrogen gas (=vertical N2+horizontal N2 ) on the peripheral portion of the surface is relatively low, and the sublimation of the peripheral region SB2 proceeds in parallel with the sublimation of the central region SB1 by the nitrogen gas.

如上所述,第3實施方式中,控制部4進行使水平N2(第2氣體)之流量F2多於垂直N2(第1氣體)之流量F1之流量控制。結果為,可改善基板W之表面周緣部上之圖案塌陷。As described above, in the third embodiment, the controller 4 performs flow control such that the flow rate F2 of horizontal N2 (second gas) is greater than the flow rate F1 of vertical N2 (first gas). As a result, pattern collapse on the surface peripheral portion of the substrate W can be improved.

此外,上述第1實施方式至第3實施方式中,將本發明應用於藉由使對向構件50之對向板51接近基板W之正面Wf而形成半密閉狀空間SP來進行基板處理之處理單元1A,但本發明之應用對象並不限定於此。例如亦可應用於日本專利特開2020-4948號公報記載之裝置,即於將遮斷板之下表面與基板之上表面平行地接近配置之狀態下進行基板處理之基板處理裝置。此外,亦可將本發明應用於使用較上述對向板51或遮斷板小型、即較基板W之外徑小之氣體噴嘴進行基板處理之處理單元(第4實施方式)、或使掃描噴嘴沿基板W之正面Wf進行掃描而進行基板處理之處理單元(第5實施方式)等。In addition, in the above-mentioned first to third embodiments, the present invention is applied to processing of substrates by forming a semi-closed space SP by bringing the facing plate 51 of the facing member 50 close to the front surface Wf of the substrate W. unit 1A, but the application object of the present invention is not limited thereto. For example, it can also be applied to the device described in Japanese Patent Application Laid-Open No. 2020-4948, that is, a substrate processing device that performs substrate processing in a state where the lower surface of the shielding plate and the upper surface of the substrate are arranged close to each other in parallel. In addition, the present invention can also be applied to a processing unit (fourth embodiment) for substrate processing using gas nozzles that are smaller than the above-mentioned counter plate 51 or the shielding plate, that is, smaller than the outer diameter of the substrate W, or the scanning nozzle A processing unit that performs substrate processing by scanning along the front surface Wf of the substrate W (fifth embodiment) and the like.

圖12係表示相當於本發明之基板處理裝置之第4實施方式之處理單元之構成之圖。圖13係圖12所示之裝置之俯視圖。圖14A係模式性地表示氣體噴嘴之構成之圖。圖14B係從鉛直下方觀察氣體噴嘴之圖。第4實施方式與第1實施方式較大之不同點在於如下構成,即,將藥液、DIW、IPA處理液、乾燥預處理液及氮氣供給至基板W。其他構成與第1實施方式相同。因此,以下以不同點為中心進行說明,對相同構成附上相同符號並省略說明。FIG. 12 is a diagram showing the configuration of a processing unit corresponding to a fourth embodiment of the substrate processing apparatus of the present invention. FIG. 13 is a top view of the device shown in FIG. 12 . Fig. 14A is a diagram schematically showing the configuration of a gas nozzle. Fig. 14B is a view of the gas nozzle viewed from vertically below. The major difference between the fourth embodiment and the first embodiment lies in the configuration in which the chemical solution, DIW, IPA treatment solution, drying pretreatment solution, and nitrogen gas are supplied to the substrate W. Other configurations are the same as those of the first embodiment. Therefore, the following description will focus on different points, and the same components will be given the same symbols and their descriptions will be omitted.

處理單元1B具有氣體噴嘴54,該氣體噴嘴54形成保護旋轉夾頭30上所保持之基板W之正面Wf之氣流。氣體噴嘴54具有外徑小於基板W之直徑之噴嘴主體540。於該噴嘴主體540之外周面設置著2個氣體噴出口541、542。氣體噴出口541、542為遍及氣體噴嘴54之全周於圓周方向上連續之環狀狹縫,分別能夠於基板W之上方呈放射狀噴出氮氣。氣體噴出口541、542配置於較氣體噴嘴54之下表面更靠上方。氣體噴出口542配置於較氣體噴出口541更靠上方。另外,氣體噴出口541、542之直徑可互為相同,亦可互為不同。The processing unit 1B has a gas nozzle 54 that forms a gas flow that protects the front surface Wf of the substrate W held on the spin chuck 30 . The gas nozzle 54 has a nozzle body 540 with an outer diameter smaller than that of the substrate W. As shown in FIG. Two gas ejection ports 541 and 542 are provided on the outer peripheral surface of the nozzle body 540 . The gas ejection ports 541 and 542 are annular slits continuous in the circumferential direction over the entire circumference of the gas nozzle 54 , and can eject nitrogen gas radially above the substrate W, respectively. The gas ejection ports 541 and 542 are arranged above the lower surface of the gas nozzle 54 . The gas ejection port 542 is disposed above the gas ejection port 541 . In addition, the diameters of the gas ejection ports 541 and 542 may be the same as or different from each other.

如圖14A所示,氣體噴出口541與從噴嘴主體540之側面連接至上端面之配管部543連接。配管部543經由配管544b與氮氣供給部(省略圖示)連接。於該配管544b上插裝有閥門544c。因此,當根據來自控制部4之開關指令而打開閥門544c時,氮氣經由配管544b被供給至噴嘴主體540,從氣體噴出口541以旋轉軸線AX1為中心呈放射狀噴出。As shown in FIG. 14A , the gas ejection port 541 is connected to a pipe portion 543 connected from the side surface of the nozzle main body 540 to the upper end surface. The piping unit 543 is connected to a nitrogen gas supply unit (not shown) via a piping 544b. A valve 544c is inserted in the piping 544b. Therefore, when the valve 544c is opened according to the switch command from the control unit 4, nitrogen gas is supplied to the nozzle body 540 through the pipe 544b, and is ejected radially from the gas ejection port 541 around the rotation axis AX1.

氣體噴出口542與從噴嘴主體540之側面連接至上端面之配管部545連接。配管部545如圖14A所示經由配管546b與氮氣供給部(省略圖示)連接。於該配管546b上插裝有閥門546c。因此,當根據來自控制部4之打開指令而打開閥門546c時,氮氣經由配管546b被供給至噴嘴主體540,從氣體噴出口542以旋轉軸線AX1為中心呈放射狀噴出。The gas ejection port 542 is connected to a pipe portion 545 connected from the side surface of the nozzle main body 540 to the upper end surface. The piping unit 545 is connected to a nitrogen gas supply unit (not shown) via a piping 546b as shown in FIG. 14A . A valve 546c is inserted into the piping 546b. Therefore, when the valve 546c is opened in response to an opening command from the control unit 4, nitrogen gas is supplied to the nozzle body 540 through the pipe 546b, and is ejected radially from the gas ejection port 542 around the rotation axis AX1.

因此,當打開閥門544c、546c這兩個閥門時,繞氣體噴嘴54形成上下重疊之複數個環狀氣流。即,從氣體噴出口542沿水平方向噴出氮氣而形成環狀之氮氣流。此外,於該氮氣流之下方側,從水平方向朝下方稍傾斜地從氣體噴出口541噴出氮氣而形成圓錐台狀之氮氣流。該呈圓錐台狀噴出之氮氣向基板W之表面周緣部流動,其相當於第1實施方式中之水平N2,作為本發明之「第2氣體」發揮功能。Therefore, when the two valves 544c and 546c are opened, a plurality of annular gas flows overlapping up and down around the gas nozzle 54 are formed. That is, nitrogen gas is ejected from the gas ejection port 542 in the horizontal direction to form an annular nitrogen flow. Further, on the lower side of the nitrogen flow, nitrogen gas is ejected from the gas ejection port 541 at a slight inclination downward from the horizontal direction to form a truncated cone-shaped nitrogen flow. The nitrogen gas ejected in the form of a truncated cone flows toward the surface peripheral portion of the substrate W, which corresponds to the level N2 in the first embodiment, and functions as the "second gas" of the present invention.

如圖14A及圖14B所示,於如此構成之噴嘴主體540之中央部安裝著中心軸噴嘴60。中心軸噴嘴60具有沿旋轉軸線AX1於上下方向延伸設置之噴嘴主體61。於該噴嘴主體61之中央部,從噴嘴主體61之上端面貫通至下端面而設置著5根中央配管部(省略圖示)。此5根中央配管部之下端面側開口分別作為藥液噴出口62a、DIW噴出口63a、IPA噴出口64a、乾燥預處理液噴出口65a及中央氣體噴出口66a發揮功能。與第1實施方式相同,配管62b~66b連接於該些噴出口62a~66a。而且,藉由控制部4對閥門62c~66c進行開關控制而將藥液、DIW、IPA處理液、乾燥預處理液及氮氣選擇性地向基板W之表面中央部噴出。如此從噴出口66a向鉛直下方噴出之氮氣、亦即垂直N2相當於本發明之「第1氣體」之一例。As shown in FIGS. 14A and 14B , the central axis nozzle 60 is attached to the central portion of the nozzle body 540 thus configured. The central axis nozzle 60 has a nozzle body 61 extending in the vertical direction along the rotation axis AX1. In the central portion of the nozzle body 61 , five central piping portions (not shown) are provided penetrating from the upper end surface to the lower end surface of the nozzle body 61 . The openings on the lower end faces of the five central pipes function as the chemical liquid discharge port 62a, the DIW discharge port 63a, the IPA discharge port 64a, the dry pretreatment liquid discharge port 65a, and the central gas discharge port 66a, respectively. Pipes 62b-66b are connected to these discharge ports 62a-66a similarly to 1st Embodiment. Then, the chemical solution, DIW, IPA treatment solution, dry pretreatment solution, and nitrogen gas are selectively sprayed toward the center of the surface of the substrate W by the control unit 4 controlling the opening and closing of the valves 62c to 66c. The nitrogen gas ejected vertically downward from the ejection port 66a in this way, that is, the vertical N2 corresponds to an example of the "first gas" in the present invention.

噴嘴移動機構55連接於一體地安裝有中心軸噴嘴60之氣體噴嘴54。噴嘴移動機構55具有:噴嘴臂551,保持氣體噴嘴54;及噴嘴驅動部552,藉由使噴嘴臂551移動而使氣體噴嘴54於鉛直方向及水平方向移動。噴嘴驅動部552例如為使氣體噴嘴54繞噴嘴旋動軸線AX2水平移動之回轉單元,該噴嘴旋動軸線AX2繞旋轉夾頭30及擋板73鉛直延伸。The nozzle moving mechanism 55 is connected to the gas nozzle 54 integrally mounted with the central axis nozzle 60 . The nozzle moving mechanism 55 has a nozzle arm 551 that holds the gas nozzle 54 , and a nozzle driving unit 552 that moves the gas nozzle 54 vertically and horizontally by moving the nozzle arm 551 . The nozzle driving unit 552 is, for example, a rotary unit that horizontally moves the gas nozzle 54 around the nozzle swivel axis AX2 , and the nozzle swivel axis AX2 extends vertically around the swivel chuck 30 and the baffle 73 .

噴嘴移動機構55使氣體噴嘴54與中心軸噴嘴60一體地於中央上位置(圖13中以二點劃線所示之位置)與待機位置(圖13中以實線所示之位置)之間水平移動。噴嘴移動機構55進而使氣體噴嘴54於中央上位置與中央下位置之間鉛直地移動。待機位置係俯視下氣體噴嘴54位於擋板73周圍之位置。中央上位置及中央下位置係俯視下氣體噴嘴54與基板W之中央部重疊之位置(圖13中以二點劃線所示之位置)。中央上位置係中央下位置之上方之位置。當噴嘴移動機構55接收來自控制部4之下降指令而使氣體噴嘴54從中央上位置下降至中央下位置時,氣體噴嘴54之下表面靠近基板W之表面中央部。The nozzle moving mechanism 55 makes the gas nozzle 54 and the central axis nozzle 60 integrally between the central upper position (the position shown by the two-dot dash line in FIG. 13 ) and the standby position (the position shown by the solid line in FIG. 13 ). Move horizontally. The nozzle moving mechanism 55 further vertically moves the gas nozzle 54 between the upper center position and the lower center position. The standby position is a position where the gas nozzle 54 is located around the baffle plate 73 in a plan view. The central upper position and the central lower position are positions where the gas nozzle 54 overlaps with the central portion of the substrate W in a plan view (positions indicated by two-dot chain lines in FIG. 13 ). The central upper position is the position above the central lower position. When the nozzle moving mechanism 55 receives a lowering command from the control unit 4 to lower the gas nozzle 54 from the upper center position to the lower center position, the lower surface of the gas nozzle 54 is close to the center of the surface of the substrate W.

當氣體噴嘴54配置於中央位置時,氣體噴嘴54於俯視下與基板W之表面中央部重疊。此時,氣體噴嘴54之下表面及中心軸噴嘴60之噴出口62a~66a與基板W之上表面中央部對向。而且,控制部4控制基板旋轉驅動機構34之馬達(省略圖示),一面使基板W與旋轉底座32一起旋轉,一面對閥門62c~66c進行開關控制,而與第1實施方式相同地進行一連串之基板處理。尤其,於昇華處理(步驟S9)中,藉由控制部4打開閥門66c而將垂直N2作為本發明之「第2氣體」供給至基板W之表面中央部。此外,藉由控制部4打開閥門544c、546c而於基板W之上方形成從氣體噴嘴54放射狀擴散之環狀氮氣流。其中,藉由打開閥門544c,而將氮氣作為本發明之「第2氣體」從氣體噴出口541向基板W之表面周緣部供給。When the gas nozzle 54 is arranged at the central position, the gas nozzle 54 overlaps with the central portion of the surface of the substrate W in plan view. At this time, the lower surface of the gas nozzle 54 and the ejection ports 62a to 66a of the central axis nozzle 60 are opposed to the central portion of the upper surface of the substrate W. As shown in FIG. Furthermore, the control unit 4 controls the motor (not shown) of the substrate rotation drive mechanism 34 to rotate the substrate W together with the spin base 32 and to control the opening and closing of the valves 62c to 66c in the same manner as in the first embodiment. A series of substrate processing. In particular, in the sublimation process (step S9 ), the control unit 4 opens the valve 66c to supply vertical N2 as the "second gas" of the present invention to the center of the surface of the substrate W. In addition, when the control unit 4 opens the valves 544c and 546c, an annular nitrogen flow radially diffused from the gas nozzle 54 is formed above the substrate W. Here, by opening the valve 544c, nitrogen gas is supplied to the surface peripheral portion of the substrate W from the gas ejection port 541 as the "second gas" of the present invention.

於如此構成之處理單元1B中,與第1實施方式相同地,於圖7所示之流程中執行一連串之基板處理(步驟S1~S11),但尤其昇華處理(步驟S9)係以如下方式執行。In the processing unit 1B thus constituted, a series of substrate processing (steps S1 to S11) are executed in the flow shown in FIG. 7 as in the first embodiment, but especially the sublimation processing (step S9) is executed as follows .

圖15係表示本發明之第4實施方式中執行之昇華處理之圖。第4實施方式中,於氣體噴嘴54定位於中央下位置(圖15之下段模式圖中以實線所示之位置)之狀態下執行昇華處理(步驟S9)。於開始該昇華處理之時點,控制部4關閉閥門66c而使垂直N2停止噴出,另一方面,如該圖所示打開閥門544c而開始以流量F2噴出水平N2。由此,於僅供給水平N2之期間,始終對周緣區域SB2供給不含昇華性物質SS之新鮮氮氣。其結果為,例如於時序T41,周緣區域SB2之昇華推進。另一方面,由於不對凝固體SB之中央區域SB1供給氮氣,因此中央區域SB1之昇華被限制。另外,本實施方式中,打開閥門546c而於水平N2之上方形成環狀之氮氣流(該圖中之虛線),但亦可省略該氮氣流。Fig. 15 is a diagram showing sublimation processing performed in the fourth embodiment of the present invention. In the fourth embodiment, the sublimation process is performed with the gas nozzle 54 positioned at the lower center position (the position shown by the solid line in the lower schematic diagram of FIG. 15 ) (step S9 ). At the start of the sublimation process, the controller 4 closes the valve 66c to stop the vertical N2 discharge, while opening the valve 544c as shown in the figure to start the horizontal N2 discharge at the flow rate F2. Thereby, while supplying only level N2, the fresh nitrogen gas which does not contain the sublimable substance SS is always supplied to peripheral area SB2. As a result, for example, at the time sequence T41, the sublimation of the peripheral region SB2 advances. On the other hand, since the nitrogen gas is not supplied to the central region SB1 of the solidified body SB, the sublimation of the central region SB1 is restricted. In addition, in this embodiment, the valve 546c is opened to form an annular nitrogen flow (dotted line in the figure) above the horizontal N2, but this nitrogen flow may also be omitted.

於以此種方式使周緣區域SB2之昇華優先推進、或者昇華完成之時序Tsw,控制部4於保持閥門244c、246c打開之狀態下打開閥門66c,開始以流量F1(<F2)噴出垂直N2。由此,例如時序T42之模式圖(該圖之下段右圖)所示,對中央區域SB1供給新鮮之氮氣,而包含中央區域SB1在內逐漸推進凝固體SB之全面性昇華。此外,對周緣區域SB2持續供給新鮮之水平N2,將昇華性物質SS之濃度抑制得較低。因此,即便於時序Tsw時點周緣區域SB2之昇華未完成之情形時,周緣區域SB2之昇華亦會持續推進。其結果為,藉由昇華處理(步驟S9)而切實地將整個凝固體SB昇華去除。In this way, when the sublimation of the peripheral area SB2 is prioritized or the sublimation is completed, the control unit 4 opens the valve 66c while keeping the valves 244c and 246c open, and starts to spray the vertical N2 at the flow rate F1 (<F2). Thus, for example, as shown in the schematic diagram of timing T42 (lower right diagram of the figure), fresh nitrogen gas is supplied to the central region SB1, and the entire sublimation of the solidified body SB is gradually promoted including the central region SB1. In addition, the concentration of the sublimable substance SS is kept low by continuously supplying fresh level N2 to the peripheral region SB2. Therefore, even when the sublimation of the peripheral region SB2 is not completed at the time sequence Tsw, the sublimation of the peripheral region SB2 will continue to advance. As a result, the entire solidified body SB is surely removed by sublimation by the sublimation treatment (step S9).

如上所述,於使用氣體噴嘴54之處理單元1B中,與第1實施方式相同地,可改善基板W之表面周緣部之圖案塌陷。As described above, in the processing unit 1B using the gas nozzle 54 , similar to the first embodiment, the pattern collapse of the peripheral portion of the surface of the substrate W can be improved.

圖16係表示相當於本發明之基板處理裝置之第5實施方式之處理單元之構成之圖。圖17係圖16所示之裝置之俯視圖。第5實施方式之處理單元1C未設置從上方保護基板W之正面Wf之構成(對向構件50、氣體噴嘴54),且與上述實施方式相同地進行包含昇華處理在內之一連串之基板處理。尤其,第5實施方式與第1實施方式較大之不同點在於噴嘴構成與昇華處理之內容。其他構成與第1實施方式相同。因此,以下以不同點為中心進行說明,對相同構成附上相同符號並省略說明。FIG. 16 is a diagram showing the configuration of a processing unit corresponding to a fifth embodiment of the substrate processing apparatus of the present invention. Fig. 17 is a top view of the device shown in Fig. 16 . The processing unit 1C of the fifth embodiment is not equipped with a configuration (opposed member 50, gas nozzle 54) to protect the front surface Wf of the substrate W from above, and performs a series of substrate processing including sublimation processing similarly to the above-mentioned embodiment. In particular, the major difference between the fifth embodiment and the first embodiment lies in the structure of the nozzle and the content of the sublimation treatment. Other configurations are the same as those of the first embodiment. Therefore, the following description will focus on different points, and the same components will be given the same symbols and their descriptions will be omitted.

處理單元1C具有:掃描噴嘴57,其一體地安裝有中心軸噴嘴60;及噴嘴移動機構55,其使掃描噴嘴57移動。與第4實施方式相同,噴嘴移動機構55具有:噴嘴臂551,其保持掃描噴嘴57;及噴嘴驅動部552,其藉由使噴嘴臂551移動,而使掃描噴嘴57於鉛直方向及水平方向移動。噴嘴驅動部552例如為使掃描噴嘴57繞噴嘴旋動軸線AX2水平移動之回轉單元,該噴嘴旋動軸線AX2繞旋轉夾頭30及擋板73鉛直地延伸。The processing unit 1C has a scanning nozzle 57 integrally attached with the central axis nozzle 60 , and a nozzle moving mechanism 55 that moves the scanning nozzle 57 . Similar to the fourth embodiment, the nozzle moving mechanism 55 has: a nozzle arm 551 that holds the scanning nozzle 57; and a nozzle driving unit 552 that moves the scanning nozzle 57 in the vertical direction and the horizontal direction by moving the nozzle arm 551 . The nozzle driving unit 552 is, for example, a rotary unit that horizontally moves the scanning nozzle 57 around the nozzle swivel axis AX2 that extends vertically around the swivel chuck 30 and the baffle 73 .

噴嘴移動機構55使掃描噴嘴57與中心軸噴嘴60一體地經由中央上位置(圖17中以二點劃線所示之位置)於第1待機位置(圖17中以實線所示之位置)與第2待機位置(圖17中以二點劃線所示之位置)之間水平移動。此外,噴嘴移動機構55能夠根據來自控制部4之速度指令來變更掃描噴嘴57之移動速度。更具體而言,如圖17所示,噴嘴移動機構55能夠於第1待機位置、第1基板正上方位置P1至第9基板正上方位置P9及第2待機位置之間變更掃描噴嘴57之移動速度。而且,噴嘴移動機構55於進行昇華處理(步驟S9)時使掃描噴嘴57於第1待機位置與第2待機位置之間掃描,另一方面,於進行藥液處理(步驟S3)、沖洗處理(步驟S4)、置換處理(步驟S5)、乾燥預處理液供給處理(步驟S6)、膜厚減少處理(步驟S7)及凝固體形成處理(步驟S8)時將掃描噴嘴57定位於中央上位置(第5基板正上方位置P5)。此處,於凝固體形成處理中,使掃描噴嘴57從中央上位置掃描至第1待機位置或第2待機位置。The nozzle moving mechanism 55 makes the scanning nozzle 57 and the central axis nozzle 60 integrally pass through the upper center position (the position shown by the two-dot dash line in FIG. 17 ) to the first standby position (the position shown by the solid line in FIG. 17 ). Move horizontally between the second standby position (the position shown by the two-dot dash line in Figure 17). In addition, the nozzle moving mechanism 55 can change the moving speed of the scanning nozzle 57 according to the speed command from the control unit 4 . More specifically, as shown in FIG. 17 , the nozzle moving mechanism 55 can change the movement of the scanning nozzle 57 among the first standby position, the first position directly above the substrate P1 to the ninth position directly above the substrate P9, and the second standby position. speed. Furthermore, the nozzle moving mechanism 55 scans the scanning nozzle 57 between the first standby position and the second standby position when performing the sublimation process (step S9), and on the other hand, performs the chemical solution process (step S3) and the rinse process ( During step S4), replacement processing (step S5), dry pretreatment liquid supply processing (step S6), film thickness reduction processing (step S7) and solidified body formation processing (step S8), the scanning nozzle 57 is positioned at the central upper position ( Position P5 directly above the fifth substrate). Here, in the solidified body forming process, the scanning nozzle 57 is scanned from the upper center position to the first standby position or the second standby position.

如圖16所示,於掃描噴嘴57之中央部安裝著中心軸噴嘴60。中心軸噴嘴60具有沿旋轉軸線AX1於上下方向延伸設置之噴嘴主體61。與第1實施方式相同,於該噴嘴主體61之中央部,從噴嘴主體61之上端面貫通至下端面設置著5根中央配管部(省略圖示)。此外,配管62b~66b連接於此5根中央配管部。而且,於掃描噴嘴57定位於中央上位置(第5基板正上方位置P5)之中央定位狀態下,控制部4對閥門62c~66c進行開關控制,由此將藥液、DIW、IPA處理液、乾燥預處理液及氮氣選擇性地向基板W之表面中央部噴出。如此於中央定位狀態下從中心軸噴嘴60噴出之氮氣相當於本發明之「第1氣體」之一例。此外,於掃描噴嘴57位於第1基板正上方位置P1或第9基板正上方位置P9期間從中心軸噴嘴60之中央氣體噴出口66a噴出之氮氣相當於本發明之「第2氣體」之一例。本實施方式中,中央氣體噴出口66a作為本發明之「第1噴出部」及「第2噴出部」發揮功能。As shown in FIG. 16 , a central axis nozzle 60 is attached to the center of the scanning nozzle 57 . The central axis nozzle 60 has a nozzle body 61 extending in the vertical direction along the rotation axis AX1. Similar to the first embodiment, five central piping portions (not shown) are provided in the central portion of the nozzle body 61 to penetrate from the upper end surface to the lower end surface of the nozzle body 61 . In addition, the pipes 62b to 66b are connected to these five central pipe parts. In addition, in the center positioning state where the scanning nozzle 57 is positioned at the upper center position (the position directly above the fifth substrate P5), the control unit 4 controls the opening and closing of the valves 62c to 66c, whereby the chemical liquid, DIW, IPA processing liquid, The dry pretreatment liquid and nitrogen gas are selectively sprayed toward the center of the surface of the substrate W. The nitrogen gas ejected from the central axis nozzle 60 in such a centrally positioned state corresponds to an example of the "first gas" in the present invention. In addition, the nitrogen gas ejected from the central gas ejection port 66a of the center axis nozzle 60 when the scanning nozzle 57 is located at the position P1 immediately above the first substrate or the position P9 directly above the ninth substrate corresponds to an example of the "second gas" of the present invention. In this embodiment, the center gas discharge port 66a functions as the "1st discharge part" and "2nd discharge part" of this invention.

以此種方式構成之處理單元1C與第1實施方式相同,於圖7所示之流程中執行一連串之基板處理(步驟S1~S11),但尤其昇華處理(步驟S9)係以如下方式執行之。控制部4使掃描噴嘴57移動至第1基板正上方位置P1(或第9基板正上方位置P9)、亦即基板W之表面周緣部之上方。此外,藉由掃描噴嘴57於基板W之表面周緣部下降,而使得掃描噴嘴57之下表面接近基板W之表面周緣部。繼而,藉由控制部4打開閥門66c,而將氮氣從保持於掃描噴嘴57上之中心軸噴嘴60供給至基板W之表面周緣部。由此,首先,最初對凝固體SB之周緣區域SB2供給氮氣而開始周緣區域SB2之昇華。然後,於周緣區域SB2之昇華優先推進、或者昇華完成之時序,控制部4於持續從中心軸噴嘴60噴出氮氣之情形時,使掃描噴嘴57依序向基板W之表面中央部之上方移動。而且,藉由使掃描噴嘴57位於中央上位置(第5基板正上方位置P5),而將氮氣從中心軸噴嘴60供給至基板W之表面中央部。由此,最後開始凝固體SB之中央區域SB1之昇華。另外,本實施方式中,控制部4於使掃描噴嘴57位於中央上位置特定時間之後,使掃描噴嘴57經由基板W之表面周緣部之上方返回待機位置。此外,控制部4於上述移動過程中藉由掃描噴嘴57上升而使掃描噴嘴57之下表面離開基板W之正面Wf,並且關閉閥門66c而停止從中心軸噴嘴60噴出氮氣。The processing unit 1C constituted in this way is the same as the first embodiment, and executes a series of substrate processing (steps S1 to S11) in the flow shown in FIG. 7, but especially the sublimation processing (step S9) is executed as follows . The control unit 4 moves the scanning nozzle 57 to the position P1 directly above the first substrate (or the position P9 directly above the ninth substrate), that is, above the peripheral edge of the surface of the substrate W. In addition, since the scanning nozzle 57 descends on the surface peripheral portion of the substrate W, the lower surface of the scanning nozzle 57 is close to the surface peripheral portion of the substrate W. Then, the valve 66 c is opened by the control unit 4 , and nitrogen gas is supplied to the surface peripheral portion of the substrate W from the central axis nozzle 60 held on the scanning nozzle 57 . Thus, first, nitrogen gas is supplied to the peripheral region SB2 of the solidified body SB to start sublimation of the peripheral region SB2. Then, when the sublimation of the peripheral region SB2 advances preferentially or the sublimation is completed, the control unit 4 sequentially moves the scanning nozzle 57 above the central portion of the surface of the substrate W while continuing to spray nitrogen gas from the central axis nozzle 60 . Then, nitrogen gas is supplied from the central axis nozzle 60 to the central portion of the surface of the substrate W by positioning the scanning nozzle 57 at a position above the center (the fifth substrate directly above position P5). Thereby, the sublimation of the central region SB1 of the solidified body SB starts finally. In addition, in the present embodiment, the control unit 4 returns the scanning nozzle 57 to the standby position via above the surface peripheral portion of the substrate W after the scanning nozzle 57 is located at the upper center position for a predetermined time. In addition, the control unit 4 raises the scanning nozzle 57 during the above-mentioned moving process so that the lower surface of the scanning nozzle 57 is separated from the front surface Wf of the substrate W, and closes the valve 66c to stop blowing nitrogen gas from the central axis nozzle 60 .

如上所述,第5實施方式中,亦與第1實施方式相同,可改善基板W之表面周緣部上之圖案塌陷。As described above, also in the fifth embodiment, similar to the first embodiment, it is possible to improve the pattern sinking on the peripheral edge of the surface of the substrate W.

另外,本發明並不限定於上述實施方式,除上述以外,還可於不脫離本發明主旨之限度內進行各種變更。例如上述第1實施方式、第2實施方式、第4實施方式及第5實施方式中,以昇華處理開始後之經過時間來管理周緣區域SB2之昇華優先推進、或者昇華完成之時序Tsw,但亦可根據除此以外之指標來管理。例如亦可根據流量計81~83之檢測值、亦即流量值來決定時序Tsw。即,隨著含有昇華性物質之氣體量變多,黏性有升高之傾向。另一方面,當凝固體SB之周緣區域SB2之昇華完成時,半密閉狀空間SP、被排氣桶70包圍之回收空間或排氣路徑中之氣體狀昇華性物質之濃度降低。即,腔室20之內部空間21及從內部空間21排氣之排氣路徑接近於僅存在氮氣之氛圍,流經內部空間21及排氣路徑之氣體之流量增大。因此,亦可捕捉流量計81~83之測量值變化為特定閾值以上此一情形來決定上述時序Tsw。此外,亦可根據測量值之微分值之變化來決定上述時序Tsw。In addition, this invention is not limited to the said embodiment, Various changes can be added within the limit which does not deviate from the summary of this invention other than the above. For example, in the above-mentioned first embodiment, second embodiment, fourth embodiment, and fifth embodiment, the sublimation priority of the peripheral area SB2 or the timing Tsw of completion of sublimation is managed by the elapsed time after the start of the sublimation process. It can be managed based on indicators other than these. For example, the timing Tsw may be determined based on the detection values of the flow meters 81 to 83 , that is, the flow values. That is, the viscosity tends to increase as the amount of gas containing sublimable substances increases. On the other hand, when the sublimation of the peripheral region SB2 of the solidified body SB is completed, the concentration of the gaseous sublimable substance in the semi-closed space SP, the recovery space surrounded by the exhaust barrel 70 or the exhaust path decreases. That is, the internal space 21 of the chamber 20 and the exhaust path from the internal space 21 are close to the atmosphere where only nitrogen gas exists, and the flow rate of the gas flowing through the internal space 21 and the exhaust path increases. Therefore, the timing Tsw described above may be determined by capturing the fact that the measured values of the flowmeters 81 to 83 have changed to be equal to or greater than a predetermined threshold. In addition, the above-mentioned timing Tsw may also be determined according to the change of the differential value of the measured value.

此外,亦可使用檢測昇華性物質之含量之昇華性物質檢測感測器來代替流量計。此外,第4實施方式、第5實施方式中,亦可將該昇華性物質檢測感測器安裝於氣體噴嘴54或掃描噴嘴57之外周面,來檢測噴嘴之周邊氛圍中之昇華性物質。即,亦可捕捉昇華性物質檢測感測器之檢測值(含量)變化為特定閾值以下此一情形來決定上述時序Tsw。此外,亦可根據複數個流量計或昇華性物質檢測感測器之輸出值中之一個值來決定時序Tsw,亦可綜合性地驗證該些值而決定時序Tsw。In addition, instead of the flow meter, a sublimable substance detection sensor for detecting the content of the sublimable substance may also be used. In addition, in the fourth embodiment and the fifth embodiment, the sublimable substance detection sensor can also be installed on the outer peripheral surface of the gas nozzle 54 or the scanning nozzle 57 to detect the sublimable substance in the surrounding atmosphere of the nozzle. That is, the above-mentioned timing Tsw may be determined by capturing that the detection value (content) of the sublimation substance detection sensor changes below a predetermined threshold value. In addition, the timing Tsw can also be determined based on one of the output values of a plurality of flowmeters or sublimable substance detection sensors, or the timing Tsw can be determined by comprehensively verifying these values.

本發明可應用於對不經過液體即變成氣體之昇華性物質所構成之凝固體供給氣體使凝固體昇華而使基板乾燥之所有基板處理技術。The present invention can be applied to all substrate processing technologies that supply gas to a solidified body composed of a sublimable substance that turns into a gas without passing through a liquid to sublimate the solidified body and dry the substrate.

1:處理單元 1A:處理單元(基板處理裝置) 1B:處理單元(基板處理裝置) 1C:處理單元(基板處理裝置) 4:控制部 20:腔室 21:內部空間 22:擋閘開關機構 23:擋閘 30:旋轉夾頭 31:夾頭銷 32:旋轉底座 32b:外周面(外周端) 33:旋轉軸 34:基板旋轉驅動機構 35:第1卡合構件 50:對向構件 51:對向板 52:卡合構件 53:支撐部 54:氣體噴嘴 55:噴嘴移動機構 56:對向板升降驅動機構 57:掃描噴嘴 60:中心軸噴嘴 61:噴嘴主體 61a:下端面 61b:下端部 62a:藥液噴出口 62b:配管 62c:閥門 63a:DIW噴出口 63b:配管 63c:閥門 64a:IPA噴出口 64b:配管 64c:閥門 65a:乾燥預處理液噴出口 65b:配管 65c:閥門 66a:中央氣體噴出口(第1噴出部、第2噴出部) 66b:配管 66c:閥門 67:周緣氣體噴出口(第2噴出部) 68:周緣配管部 68b:配管 68c:閥門 70:排氣桶 71:擋板升降驅動機構 72:承杯 73:擋板 74:排氣機構 75:配管 81:流量計 82:流量計 83:流量計 100:基板處理系統 110:基板處理部 111:基板搬送機械手 112:載置台 120:分度器部 121:容器保持部 122:分度機械手 122a:底座部 122b:多關節臂 122c:手部 511:圓板部 512:圓筒部 513:內表面 513a:基板對向面 513b:中央傾斜面 513c:內周面 514:第2卡合構件 515:貫通孔 521:圓筒部 522:凸緣部 540:噴嘴主體 541:氣體噴出口(第2噴出部) 542:氣體噴出口(第2噴出部) 543:配管部 544b:配管 544c:閥門 545:配管部 546b:配管 546c:閥門 551:噴嘴臂 552:噴嘴驅動部 AX1:(凝固體之)旋轉軸線 AX2:噴嘴旋動軸線 C:容器 F1:流量 F2:流量 GP:間隙 P1:第1基板正上方位置 P2:第2基板正上方位置 P3:第3基板正上方位置 P4:第4基板正上方位置 P5:第5基板正上方位置 P6:第6基板正上方位置 P7:第7基板正上方位置 P8:第8基板正上方位置 P9:第9基板正上方位置 PT:圖案 S9:昇華處理 SB:凝固體 SB1:(凝固體之)中央區域 SB2:周緣區域 SP:半密閉狀空間 SS:昇華性物質 T01:時序 T02:時序 T11:時序 T12:時序 T21:時序 T22:時序 T31:時序 T32:時序 T41:時序 T42:時序 Tsw:時序 W:基板 Wf:(基板之)正面1: Processing unit 1A: Processing unit (substrate processing device) 1B: Processing unit (substrate processing device) 1C: processing unit (substrate processing device) 4: Control Department 20: chamber 21: Internal space 22: Shutter switch mechanism 23: gate 30: Swivel Chuck 31: Collet pin 32: Rotating base 32b: Outer peripheral surface (outer peripheral end) 33: axis of rotation 34: Substrate rotation drive mechanism 35: The first engaging member 50: opposite component 51: opposite board 52: Fastening member 53: support part 54: Gas nozzle 55: Nozzle moving mechanism 56: Opposite plate lifting drive mechanism 57:Scan nozzle 60: Central axis nozzle 61: Nozzle body 61a: lower end face 61b: lower end 62a: liquid medicine ejection port 62b: Piping 62c: valve 63a: DIW outlet 63b: Piping 63c: valve 64a: IPA outlet 64b: Piping 64c: valve 65a: Drying pretreatment liquid outlet 65b: Piping 65c: Valve 66a: Central gas ejection port (1st ejection part, 2nd ejection part) 66b: Piping 66c: valve 67: Peripheral gas ejection port (second ejection part) 68: Peripheral piping part 68b: Piping 68c: valve 70: exhaust barrel 71: Baffle lift drive mechanism 72: Cheng Cup 73: Baffle 74: exhaust mechanism 75: Piping 81: flow meter 82: Flow meter 83: flow meter 100: Substrate processing system 110: Substrate processing department 111:Substrate transfer manipulator 112: loading table 120: Indexer Department 121: container holding part 122: Indexing manipulator 122a: base part 122b: multi-joint arm 122c: hand 511: Circular plate part 512: Cylindrical part 513: inner surface 513a: Substrate facing surface 513b: central inclined surface 513c: inner peripheral surface 514: The second engaging member 515: through hole 521: cylindrical part 522: Flange 540: nozzle body 541: Gas ejection port (second ejection part) 542: Gas ejection port (2nd ejection part) 543: Piping department 544b: Piping 544c: valve 545: Piping department 546b: Piping 546c: valve 551: nozzle arm 552:Nozzle drive unit AX1: (solidified body) axis of rotation AX2: nozzle rotation axis C: container F1: Flow F2: Flow GP: gap P1: The position directly above the first substrate P2: The position directly above the second substrate P3: Right above the third substrate P4: Position directly above the 4th substrate P5: Position directly above the 5th substrate P6: Position directly above the 6th substrate P7: Position directly above the 7th substrate P8: Position directly above the 8th substrate P9: Position directly above the 9th substrate PT: pattern S9: sublimation treatment SB: solidified body SB1: (of the solidified body) central area SB2: Peripheral area SP: semi-closed space SS: sublimation substance T01: Timing T02: Timing T11: timing T12: Timing T21: Timing T22: Timing T31: Timing T32: Timing T41: Timing T42: Timing Tsw: timing W: Substrate Wf: (substrate) front

圖1係表示裝備本發明之基板處理裝置之第1實施方式之基板處理系統之概略構成之俯視圖。 圖2係圖1所示之基板處理系統之側視圖。 圖3係表示相當於本發明之基板處理裝置之第1實施方式之處理單元之構成之局部剖視圖。 圖4係表示控制處理單元之控制系統之電氣構成之框圖。 圖5係模式性地表示對向構件位於對向位置時之旋轉底座、基板及對向構件之位置關係之圖。 圖6A係對向構件及中心軸噴嘴之局部剖視圖。 圖6B係從下方觀察中心軸噴嘴之下端部附近之模式圖。 圖7係表示處理單元中執行之基板處理之內容之流程圖。 圖8係表示以往技術中執行之昇華處理之圖。 圖9係表示本發明之第1實施方式中執行之昇華處理之圖。 圖10係表示本發明之第2實施方式中執行之昇華處理之圖。 圖11係表示本發明之第3實施方式中執行之昇華處理之圖。 圖12係表示相當於本發明之基板處理裝置之第4實施方式之處理單元之構成之圖。 圖13係圖12所示之裝置之俯視圖。 圖14A係模式性地表示氣體噴嘴之構成之圖。 圖14B係從鉛直下方觀察氣體噴嘴之圖。 圖15係表示本發明之第4實施方式中執行之昇華處理之圖。 圖16係表示相當於本發明之基板處理裝置之第5實施方式之處理單元之構成之圖。 圖17係圖16所示之裝置之俯視圖。FIG. 1 is a plan view showing a schematic configuration of a substrate processing system equipped with a substrate processing apparatus according to a first embodiment of the present invention. FIG. 2 is a side view of the substrate processing system shown in FIG. 1 . 3 is a partial cross-sectional view showing the configuration of a processing unit corresponding to the first embodiment of the substrate processing apparatus of the present invention. Fig. 4 is a block diagram showing the electrical configuration of the control system of the control processing unit. FIG. 5 is a diagram schematically showing the positional relationship among the rotating base, the base plate, and the opposing member when the opposing member is at the opposing position. Fig. 6A is a partial sectional view of the opposing member and the central axis nozzle. Fig. 6B is a schematic view of the vicinity of the lower end of the central axis nozzle viewed from below. FIG. 7 is a flowchart showing the contents of substrate processing performed in the processing unit. Fig. 8 is a diagram showing a sublimation process performed in the prior art. Fig. 9 is a diagram showing a sublimation process performed in the first embodiment of the present invention. Fig. 10 is a diagram showing sublimation processing performed in the second embodiment of the present invention. Fig. 11 is a diagram showing sublimation processing performed in the third embodiment of the present invention. FIG. 12 is a diagram showing the configuration of a processing unit corresponding to a fourth embodiment of the substrate processing apparatus of the present invention. FIG. 13 is a top view of the device shown in FIG. 12 . Fig. 14A is a diagram schematically showing the configuration of a gas nozzle. Fig. 14B is a view of the gas nozzle viewed from vertically below. Fig. 15 is a diagram showing sublimation processing performed in the fourth embodiment of the present invention. FIG. 16 is a diagram showing the configuration of a processing unit corresponding to a fifth embodiment of the substrate processing apparatus of the present invention. Fig. 17 is a top view of the device shown in Fig. 16 .

F1:流量F1: Flow

F2:流量F2: Flow

PT:圖案PT: pattern

SB:凝固體SB: solidified body

SB1:(凝固體之)中央區域SB1: (of the solidified body) central area

SB2:周緣區域SB2: Peripheral area

SS:昇華性物質SS: sublimation substance

T11:時序T11: timing

T12:時序T12: Timing

Tsw:時序Tsw: timing

W:基板W: Substrate

Claims (10)

一種基板處理方法,其特徵在於:其係使包含不經過液體即變成氣體之昇華性物質的凝固體從基板昇華而使上述基板乾燥者,上述基板於整個表面上形成有上述凝固體;且上述基板處理方法具備:第1昇華工序,其向上述基板之表面中央部噴出第1氣體,使上述第1氣體經由整個上述凝固體流通至上述基板之周邊而使整個上述凝固體昇華;第2昇華工序,其向上述基板之表面周緣部噴出第2氣體,使上述第2氣體經由上述凝固體中之上述表面周緣部上之周緣區域流通至上述基板之周邊而使上述周緣區域昇華;且上述第2昇華工序之開始早於上述第1昇華工序之開始,或上述第2氣體之流量多於上述第1氣體之流量;其中於上述第2昇華工序開始後,於持續噴出上述第2氣體之狀態下開始上述第1昇華工序。 A method for treating a substrate, wherein the substrate is dried by sublimating a solidified body containing a sublimable substance that turns into a gas without passing through a liquid, wherein the solidified body is formed on the entire surface of the substrate; and The substrate processing method includes: a first sublimation step of spraying a first gas to the central portion of the surface of the substrate, causing the first gas to flow through the entire solidified body to the periphery of the substrate to sublimate the entire solidified body; A step of spraying a second gas toward the surface peripheral portion of the substrate, allowing the second gas to flow through the peripheral region on the surface peripheral portion of the solidified body to the periphery of the substrate to sublimate the peripheral region; 2 The start of the sublimation process is earlier than the start of the first sublimation process, or the flow rate of the second gas is greater than the flow rate of the first gas; after the start of the second sublimation process, the second gas is continuously sprayed Next, the above-mentioned first sublimation step is started. 如請求項1之基板處理方法,其中上述第1昇華工序開始後之上述第1氣體之流量為第1流量,上述第2氣體之流量為較上述第1流量多之第2流量。 The substrate processing method according to claim 1, wherein the flow rate of the first gas after the start of the first sublimation step is a first flow rate, and the flow rate of the second gas is a second flow rate greater than the first flow rate. 如請求項1之基板處理方法,其中從上述第1昇華工序開始之時點起,上述第1氣體之流量隨著時間經過而增大,另一方面,上述第2氣體 之流量隨著時間經過而減少。 The substrate processing method according to claim 1, wherein the flow rate of the first gas increases with time from the start of the first sublimation step, and on the other hand, the second gas The flow rate decreases over time. 如請求項1之基板處理方法,其具備以下工序:對要執行上述第1昇華工序及上述第2昇華工序之腔室之內部空間進行排氣;及對存在於上述內部空間之氣體成分及從上述內部空間排出之氣體成分中之至少一者之流量值進行測量;且根據上述流量值而決定開始上述第1昇華工序之時序。 The substrate processing method according to claim 1, which includes the following steps: exhausting the internal space of the chamber where the first sublimation process and the second sublimation process are to be performed; The flow value of at least one of the gas components discharged from the internal space is measured; and the timing of starting the first sublimation process is determined according to the flow value. 如請求項1之基板處理方法,其具備以下工序:對要執行上述第1昇華工序及上述第2昇華工序之腔室之內部空間進行排氣;及以昇華性物質檢測感測器,對存在於上述內部空間之氣體狀昇華性物質及從上述內部空間排出之氣體狀昇華性物質中之至少一者進行檢測;且根據上述昇華性物質檢測感測器之檢測值而決定開始上述第1昇華工序之時序。 Such as the substrate processing method of claim 1, which has the following steps: exhausting the internal space of the chamber where the first sublimation step and the second sublimation step are to be performed; Detect at least one of the gaseous sublimation substance in the internal space and the gaseous sublimation substance discharged from the internal space; and decide to start the first sublimation based on the detection value of the sublimation substance detection sensor The timing of the process. 一種基板處理方法,其特徵在於:其係使包含不經過液體即變成氣體之昇華性物質的凝固體從基板昇華而使上述基板乾燥者,上述基板於整個表面上形成有上述凝固體;且上述基板處理方法具備:第1昇華工序,其向上述基板之表面中央部噴出第1氣體,使上述第1氣體經由整個上述凝固體流通至上述基板之周邊而使整個上述凝固體昇 華;第2昇華工序,其向上述基板之表面周緣部噴出第2氣體,使上述第2氣體經由上述凝固體中之上述表面周緣部上之周緣區域流通至上述基板之周邊而使上述周緣區域昇華;且上述第2昇華工序之開始早於上述第1昇華工序之開始,或上述第2氣體之流量多於上述第1氣體之流量;其中於進行上述第2昇華工序後執行上述第1昇華工序。 A method for treating a substrate, wherein the substrate is dried by sublimating a solidified body containing a sublimable substance that turns into a gas without passing through a liquid, wherein the solidified body is formed on the entire surface of the substrate; and The substrate processing method includes: a first sublimation step, which sprays a first gas toward the central portion of the surface of the substrate, makes the first gas flow through the entire solidified body to the periphery of the substrate, and raises the entire solidified body. Hua; the second sublimation process, which sprays the second gas to the surface peripheral part of the above-mentioned substrate, and makes the above-mentioned second gas circulate to the periphery of the above-mentioned substrate through the peripheral area on the above-mentioned surface peripheral part of the above-mentioned solidified body to make the above-mentioned peripheral area Sublimation; and the start of the above-mentioned second sublimation process is earlier than the start of the above-mentioned first sublimation process, or the flow rate of the above-mentioned second gas is greater than the flow rate of the above-mentioned first gas; wherein the above-mentioned first sublimation process is performed after the above-mentioned second sublimation process process. 一種基板處理方法,其特徵在於:其係使包含不經過液體即變成氣體之昇華性物質的凝固體從基板昇華而使上述基板乾燥者,上述基板於整個表面上形成有上述凝固體;且上述基板處理方法具備:第1昇華工序,其向上述基板之表面中央部噴出第1氣體,使上述第1氣體經由整個上述凝固體流通至上述基板之周邊而使整個上述凝固體昇華;第2昇華工序,其向上述基板之表面周緣部噴出第2氣體,使上述第2氣體經由上述凝固體中之上述表面周緣部上之周緣區域流通至上述基板之周邊而使上述周緣區域昇華;且上述第2昇華工序之開始早於上述第1昇華工序之開始,或上述第2氣體之流量多於上述第1氣體之流量,藉此上述周緣區域之氣體狀之上述昇華性物質之濃度低於經由上述表面中央部流入至上述周緣區域之上述第1氣體中所包含的氣體狀之上述昇華性物質之濃度。 A method for treating a substrate, wherein the substrate is dried by sublimating a solidified body containing a sublimable substance that turns into a gas without passing through a liquid, wherein the solidified body is formed on the entire surface of the substrate; and The substrate processing method includes: a first sublimation step of spraying a first gas to the central portion of the surface of the substrate, causing the first gas to flow through the entire solidified body to the periphery of the substrate to sublimate the entire solidified body; A step of spraying a second gas toward the surface peripheral portion of the substrate, allowing the second gas to flow through the peripheral region on the surface peripheral portion of the solidified body to the periphery of the substrate to sublimate the peripheral region; 2. The start of the sublimation process is earlier than the start of the first sublimation process, or the flow rate of the second gas is greater than the flow rate of the first gas, so that the concentration of the gaseous sublimable substance in the peripheral region is lower than that through the above-mentioned The concentration of the gaseous sublimable substance contained in the first gas flowing into the peripheral region from the center of the surface. 一種基板處理裝置,其特徵在於:其係使包含不經過液體即變成氣 體之昇華性物質的凝固體從基板昇華而使上述基板乾燥者,上述基板於整個表面上形成有上述凝固體;且上述基板處理裝置具備:第1噴出部,其向上述基板之表面中央部噴出第1氣體;第2噴出部,其向上述基板之表面周緣部噴出第2氣體;及控制部,其使上述第1氣體從上述第1噴出部噴出,使上述第1氣體經由整個上述凝固體流通至上述基板之周邊而使整個上述凝固體昇華,且使上述第2氣體從上述第2噴出部噴出,使上述第2氣體經由上述凝固體中之上述表面周緣部上之周緣區域流通至上述基板之周邊而使上述周緣區域昇華;且上述控制部係:進行使上述第2氣體之噴出開始早於上述第1氣體之噴出開始的噴出時序控制、及使上述第2氣體之流量多於上述第1氣體之流量的流量控制中之至少一者,且於上述第2昇華工序開始後,於持續噴出上述第2氣體之狀態下開始上述第1昇華工序。 A substrate processing device, characterized in that: it is made to make the contained liquid into gas without passing through If the solidified substance of the sublimable substance is sublimated from the substrate to dry the substrate, the solidified substance is formed on the entire surface of the substrate; The first gas is ejected; the second ejection unit ejects the second gas toward the surface peripheral portion of the substrate; and the control unit ejects the first gas from the first ejection portion so that the first gas passes through the entire solidification The fluid flows to the periphery of the above-mentioned substrate to sublimate the entire solidified body, and the second gas is ejected from the second ejection part, so that the second gas flows through the peripheral region on the peripheral edge of the surface of the solidified body to The surrounding area of the substrate is sublimated; and the control unit is: performing the ejection timing control so that the ejection start of the second gas is earlier than the ejection start of the first gas, and the flow rate of the second gas is greater than that of the first gas. At least one of the flow control of the flow rate of the first gas, and after the start of the second sublimation step, the first sublimation step is started while the second gas is continuously sprayed. 一種基板處理裝置,其特徵在於:其係使包含不經過液體即變成氣體之昇華性物質的凝固體從基板昇華而使上述基板乾燥者,上述基板於整個表面上形成有上述凝固體;且上述基板處理裝置具備:第1噴出部,其向上述基板之表面中央部噴出第1氣體;第2噴出部,其向上述基板之表面周緣部噴出第2氣體;及控制部,其使上述第1氣體從上述第1噴出部噴出,使上述第1氣體經由整個上述凝固體流通至上述基板之周邊而使整個上述凝固體昇華,且使上述第2氣體從上述第2噴出部噴出,使上述第2氣體經由上述凝固體中之上述表面周緣部上之周緣區域流通至上述基板之周邊而使上述周緣區域昇 華;且上述控制部係:進行使上述第2氣體之噴出開始早於上述第1氣體之噴出開始的噴出時序控制、及使上述第2氣體之流量多於上述第1氣體之流量的流量控制中之至少一者,且於進行了上述第2昇華工序後,執行上述第1昇華工序。 A substrate processing apparatus characterized in that it dries the substrate by sublimating a solidified body containing a sublimable substance that turns into a gas without passing through a liquid, wherein the solidified body is formed on the entire surface of the substrate; and The substrate processing apparatus includes: a first ejection unit that ejects the first gas toward the central portion of the surface of the substrate; a second ejection portion that ejects the second gas toward the peripheral portion of the surface of the substrate; and a control unit that causes the first gas to The gas is ejected from the first ejection part, the first gas flows through the entire solidified body to the periphery of the substrate to sublimate the entire solidified body, and the second gas is ejected from the second ejection part to make the second gas 2. The gas flows through the peripheral region on the peripheral portion of the surface of the solidified body to the periphery of the substrate to raise the peripheral region. Hua; and the above-mentioned control unit is to: perform the ejection timing control that makes the ejection start of the second gas earlier than the ejection start of the first gas, and the flow rate control that makes the flow rate of the second gas more than the flow rate of the first gas At least one of them, and after performing the above-mentioned second sublimation process, perform the above-mentioned first sublimation process. 一種基板處理裝置,其特徵在於:其係使包含不經過液體即變成氣體之昇華性物質的凝固體從基板昇華而使上述基板乾燥者,上述基板於整個表面上形成有上述凝固體;且上述基板處理裝置具備:第1噴出部,其向上述基板之表面中央部噴出第1氣體;第2噴出部,其向上述基板之表面周緣部噴出第2氣體;及控制部,其使上述第1氣體從上述第1噴出部噴出,使上述第1氣體經由整個上述凝固體流通至上述基板之周邊而使整個上述凝固體昇華,且使上述第2氣體從上述第2噴出部噴出,使上述第2氣體經由上述凝固體中之上述表面周緣部上之周緣區域流通至上述基板之周邊而使上述周緣區域昇華;且上述控制部係:進行使上述第2氣體之噴出開始早於上述第1氣體之噴出開始的噴出時序控制、及使上述第2氣體之流量多於上述第1氣體之流量,藉此使上述周緣區域之氣體狀之上述昇華性物質之濃度低於經由上述表面中央部流入至上述周緣區域之上述第1氣體中所含的氣體狀之上述昇華性物質之濃度的流量控制中之至少一者。 A substrate processing apparatus characterized in that it dries the substrate by sublimating a solidified body containing a sublimable substance that turns into a gas without passing through a liquid, wherein the solidified body is formed on the entire surface of the substrate; and The substrate processing apparatus includes: a first ejection unit that ejects the first gas toward the central portion of the surface of the substrate; a second ejection portion that ejects the second gas toward the peripheral portion of the surface of the substrate; and a control unit that causes the first gas to The gas is ejected from the first ejection part, the first gas flows through the entire solidified body to the periphery of the substrate to sublimate the entire solidified body, and the second gas is ejected from the second ejection part to make the second gas 2. The gas flows through the peripheral region on the peripheral portion of the surface of the solidified body to the peripheral region of the substrate to sublimate the peripheral region; The discharge sequence control of the discharge start, and the flow rate of the above-mentioned second gas is greater than the flow rate of the above-mentioned first gas, so that the concentration of the gaseous sublimable substance in the peripheral region is lower than that flowing into the At least one of flow control of the concentration of the gaseous sublimable substance contained in the first gas in the peripheral region.
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