TW201825447A - Substrate treating apparatus and substrate treating method - Google Patents

Substrate treating apparatus and substrate treating method Download PDF

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Publication number
TW201825447A
TW201825447A TW106137740A TW106137740A TW201825447A TW 201825447 A TW201825447 A TW 201825447A TW 106137740 A TW106137740 A TW 106137740A TW 106137740 A TW106137740 A TW 106137740A TW 201825447 A TW201825447 A TW 201825447A
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Taiwan
Prior art keywords
substrate
sublimation
substance
liquid
pattern
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TW106137740A
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Chinese (zh)
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TWI651295B (en
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佐佐木悠太
塙洋祐
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日商斯庫林集團股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus 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
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus 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
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/6715—Apparatus for applying a liquid, a resin, an ink or the like
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus 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
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67242—Apparatus for monitoring, sorting or marking
    • H01L21/67248—Temperature monitoring

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

A substrate processing of the present invention includes a supplying unit which supplies a process liquid containing a sublimable substance in a molten state to the pattern-formed surface of a substrate, a solidifying unit which solidifies the process liquid on the pattern-formed surface so as to form a solidified body and a sublimating unit which sublimes the solidified body so as to remove the solidified body from the pattern-formed surface, and the vapor pressure of the process liquid at a temperature of 20 to 25 DEG C is equal to or more than 5 kPa, and the surface tension thereof at a temperature of 20 to 25 DEG C is equal to or less than 25 mN/m.

Description

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

本發明係關於一種將附著於半導體基板、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(以下簡稱為「基板」)之液體自基板去除的基板處理裝置及基板處理方法。The present invention relates to a substrate for a semiconductor substrate, a glass substrate for a photomask, a glass substrate for a liquid crystal display, a glass substrate for a plasma display, a substrate for a field emission display (FED), a substrate for an optical disk, and a magnetic disk. A substrate processing apparatus and a substrate processing method for removing liquid from various substrates, such as a substrate and a substrate for a magneto-optical disc (hereinafter referred to as "substrate").

於半導體裝置或液晶顯示裝置等之電子零件之製造步驟中，對基板實施使用液體之各種濕式處理後，對基板實施用以去除因濕式處理而附著於基板之液體之乾燥處理。 作為濕式處理，可列舉去除基板表面之污染物質之清洗處理。例如，藉由乾式蝕刻步驟，於形成具有凹凸之微細圖案之基板表面存在反應副產物(蝕刻殘渣)。又，有時除蝕刻殘渣外，於基板表面附著金屬雜質或有機污染物質等，為去除該等物質，進行對基板供給清洗液等之清洗處理。 清洗處理後，實施藉由沖洗液而去除清洗液之沖洗處理與乾燥沖洗液之乾燥處理。作為沖洗處理，可列舉：對附著有清洗液之基板表面供給去離子水(DIW，Deionized Water)等沖洗液，去除基板表面之清洗液的沖洗處理。其後，進行藉由去除沖洗液而使基板乾燥之乾燥處理。 近年來，伴隨形成於基板之圖案之微細化，具有凹凸之圖案之凸部之縱橫比(圖案凸部之高度與寬度之比)變大。故而存在以下問題：乾燥處理時，於進入圖案凹部之清洗液或沖洗液等液體與同液體相接觸之氣體之交界面產生作用之表面張力會牽拉圖案中之鄰接之凸部彼此而使之倒塌，即所謂的圖案倒塌之問題。 作為以防止此種因表面張力引起之圖案倒塌為目的之乾燥技術，例如於日本專利特開2013-16699號公報中揭示有：使形成結構體(圖案)之基板與溶液接觸，使該溶液變化為固體而成為圖案之支撐體(凝固體)，使該支撐體自固相不經過液相而變化為氣相從而去除的方法。又，於該專利文獻中揭示有：作為支撐材，使用甲基丙烯酸系樹脂材料、苯乙烯系樹脂材料及氟碳系材料之至少任一種昇華性物質。 又，於日本專利特開2012-243869號公報及日本專利特開2013-258272號公報中揭示有：對基板上供給昇華性物質之溶液，使溶液中之溶劑乾燥而使基板上充滿昇華性物質之凝固體，使凝固體昇華之乾燥技術。根據該等專利文獻，不會於凝固體與同凝固體相接觸之氣體之交界面產生表面張力之作用，故而可抑制因表面張力引起之圖案之倒塌。 又，於日本專利特開2015-142069號公報中揭示有：對附著有液體之基板供給第三丁醇(昇華性物質)之熔融液，使第三丁醇於基板上凝固而形成凝固體後，使凝固體昇華而去除的乾燥技術。 然而，於日本專利特開2013-16699號公報、日本專利特開2012-243869號公報、日本專利特開2013-258272號公報及日本專利特開2015-142069號公報中揭示之乾燥技術中例如存在如下課題：對具有微細且縱橫比較高(即，相對於凸圖案之寬度，凸圖案之高度更高)之圖案之基板，無法充分防止圖案之倒塌。圖案倒塌之產生原因多種多樣，作為其一，可列舉：包含昇華性物質之凝固體與圖案表面之間作用之力。於圖案表面與凝固體之界面，構成圖案之分子與構成凝固體之昇華性物質之間作用有離子鍵或氫鍵、凡得瓦等之力。 故而，即便凝固體不經過液體狀態而狀態變化為氣體，於昇華不均勻進行之情形時亦對圖案施加應力，產生圖案之倒塌。又，凝固體與圖案表面之間作用之力很大程度上依存於構成凝固體之昇華性物質之物性。故而，為於對微細之圖案面之昇華乾燥中消除圖案倒塌，必須選擇更適合於昇華乾燥之昇華性物質。In the manufacturing steps of the electronic components such as the semiconductor device or the liquid crystal display device, after the substrate is subjected to various wet processes using a liquid, the substrate is subjected to a drying process to remove the liquid adhered to the substrate due to the wet process. Examples of the wet process include a cleaning process to remove contaminants on the substrate surface. For example, by a dry etching step, there are reaction byproducts (etching residues) on the surface of a substrate on which a fine pattern having irregularities is formed. In addition, in addition to the etching residue, metal impurities, organic contamination substances, and the like may be attached to the surface of the substrate. In order to remove these substances, a cleaning treatment such as supplying a cleaning solution to the substrate is performed. After the washing process, a washing process in which the washing solution is removed by a washing solution and a drying process in which the washing solution is dried are performed. Examples of the rinsing treatment include a rinsing treatment in which a rinsing liquid such as deionized water (DIW) is supplied to the substrate surface to which the rinsing liquid is adhered, and the rinsing liquid is removed from the substrate surface. Thereafter, a drying process is performed to dry the substrate by removing the rinse liquid. In recent years, with the miniaturization of the pattern formed on the substrate, the aspect ratio (ratio of the height and width of the pattern convex portion) of the convex portion of the pattern having unevenness has increased. Therefore, there is the following problem: During the drying process, the surface tension that acts on the interface between the liquid such as the cleaning liquid or rinsing liquid entering the concave portion of the pattern and the gas in contact with the liquid will pull the adjacent convex portions in the pattern to cause Collapse, the so-called pattern collapse problem. As a drying technique for the purpose of preventing such a pattern collapse due to surface tension, for example, Japanese Patent Laid-Open No. 2013-16699 discloses that a substrate forming a structure (pattern) is brought into contact with a solution to change the solution. A support (solidified body) that becomes a pattern as a solid, and the support is changed from a solid phase to a gas phase without passing through a liquid phase. Furthermore, it is disclosed in this patent document that as the supporting material, at least one of a methacrylic resin material, a styrene resin material, and a fluorocarbon material is used as a sublimable substance. In addition, Japanese Patent Laid-Open Publication No. 2012-243869 and Japanese Patent Laid-Open Publication No. 2013-258272 disclose that a solution of a sublimable substance is supplied to a substrate, and the solvent in the solution is dried to fill the substrate with a sublimable substance. Drying technology of solidified body and sublimated solidified body. According to these patent documents, the surface tension does not occur at the interface between the solidified body and the gas in contact with the solidified body, so the collapse of the pattern due to the surface tension can be suppressed. Furthermore, Japanese Patent Laid-Open No. 2015-142069 discloses that after supplying a molten liquid of a third butanol (sublimable substance) to a substrate to which a liquid is adhered, the third butanol is solidified on the substrate to form a solidified body. , Drying technology that makes the solidified body sublimate and remove. However, for example, the drying technology disclosed in Japanese Patent Laid-Open No. 2013-16699, Japanese Patent Laid-Open No. 2012-243869, Japanese Patent Laid-Open No. 2013-258272, and Japanese Patent Laid-Open No. 2015-142069 The following problem: For a substrate having a pattern that is fine and has a relatively high aspect ratio (that is, the height of the convex pattern is higher than the width of the convex pattern), the collapse of the pattern cannot be sufficiently prevented. There are various reasons for the pattern collapse. As one of them, the force acting between the solidified body containing a sublimable substance and the surface of the pattern can be cited. At the interface between the surface of the pattern and the solidified body, forces such as ionic bonds or hydrogen bonds, van der Waals, and the like act between the molecules constituting the pattern and the sublimable substances that constitute the solidified body. Therefore, even if the solidified body does not pass through the liquid state and the state changes to gas, when the sublimation progresses unevenly, the pattern is stressed, and the pattern collapses. Moreover, the force acting between the solidified body and the pattern surface largely depends on the physical properties of the sublimable substance constituting the solidified body. Therefore, in order to eliminate the pattern collapse during the sublimation drying of the fine pattern surface, it is necessary to select a sublimation substance more suitable for sublimation drying.

本發明係鑒於上述課題而完成者，其目的在於提供一種可防止於基板之表面形成之圖案之倒塌，並且可去除附著於基板表面之液體的基板處理裝置及基板處理方法。 本發明之基板處理裝置係為解決上述課題，於基板之圖案形成面之乾燥處理中所使用之基板處理裝置，並且其具備對基板之圖案形成面供給含有融解狀態之昇華性物質之處理液的供給機構、使上述處理液於上述圖案形成面上凝固而形成凝固體的凝固機構、使上述凝固體昇華而自上述圖案形成面去除的昇華機構，上述昇華性物質之20℃～25℃下之蒸氣壓為5 kPa以上，20℃～25℃下之表面張力為25 mN/m以下。 根據上述構成，例如於基板之圖案形成面上存在液體之情形時，藉由冷凍乾燥(或昇華乾燥)之原理，可防止圖案之倒塌並去除該液體。具體而言，上述供給機構係藉由對基板之圖案形成面供給處理液，而將上述液體置換為處理液。其次，凝固機構係使處理液凝固而形成凝固體。此處，藉由使用蒸氣壓為5 kPa以上，表面張力為25 mN/m以下者(均為20℃～25℃之溫度範圍內之值)作為昇華性物質，昇華性物質於凝固體中昇華時，可減少昇華進行之程度不均。藉此，與昇華不均勻地進行之情形相比較，可減少對基板圖案施加之應力。其結果為例如與使用有第三丁醇等先前之昇華性物質之基板處理裝置相比較，於具備具有微細之縱橫比之圖案面之基板中亦可減少圖案倒塌之產生。 此處，上述所謂「融解狀態」係指昇華性物質因完全或一部分融解而具有流動性，成為液狀之狀態。又，上述所謂「昇華性」係指單體、化合物或混合物具有不經過液體而自固體相變為氣體或自氣體相變為固體之特性，所謂「昇華性物質」係指具有此種昇華性之物質。又，上述所謂「圖案形成面」係指無論為平面狀、曲面狀或凹凸狀之任一者，於基板中於任意區域形成凹凸圖案之面。上述所謂「凝固體」係指液體狀態之處理液固化而成者，例如，於基板上存在之液體與處理液混合之狀態下，藉由凝固機構而凝固之情形時，為亦可含有該液體者。 於上述構成中，較佳為上述昇華性物質之20℃～25℃下之表面張力為20 mN/m以下。 於上述構成中，較佳為上述昇華性物質為1,1,2,2,3,3,4-七氟環戊烷或十二氟環己烷。 又，於上述構成中，較佳為上述供給機構係於大氣壓下對上述基板之圖案形成面供給上述處理液者，上述凝固機構係於大氣壓下將上述處理液冷卻至上述昇華性物質之凝固點以下者。藉此，至少於供給機構及凝固機構中，無需具有耐壓性之構成，可謀求裝置成本之減少。 又，於上述構成中，較佳為上述昇華性物質於大氣壓下具有昇華性，上述昇華機構係於大氣壓下使上述昇華性物質昇華。藉此，藉由使用於大氣壓下具有昇華性者作為昇華性物質，至少於昇華機構中，無需具有耐壓性之構成，可謀求裝置成本之減少。 又，於上述構成中，較佳為上述凝固機構或昇華機構之至少任一者可為以上述昇華性物質之凝固點以下之溫度向與上述基板之圖案形成面相反側之背面供給冷媒之冷媒供給機構。 根據上述構成，於凝固機構中，藉由向與基板之圖案形成面相反側之背面供給昇華性物質之凝固點以下之冷媒，可冷卻該昇華性物質而使之凝固。又，於昇華機構中，藉由向基板之背面供給上述冷媒，可自基板之背面側防止凝固體之融解並使凝固體自然昇華。進而，於凝固機構及昇華機構之兩者均為可對基板之背面供給冷媒之構成之情形時，可謀求零件數之削減，使裝置成本減少。 又，於上述構成中，上述凝固機構或昇華機構之至少任一者可為以該昇華性物質之凝固點以下之溫度向上述圖案形成面供給至少對上述昇華性物質為惰性之氣體的氣體供給機構。 根據上述構成，對氣體供給機構而言，作為凝固機構，向上述圖案形成面供給昇華性物質之凝固點以下之溫度之惰性氣體，故而可冷卻該昇華性物質而使之凝固。又，氣體供給機構亦對形成於圖案形成面之凝固體供給惰性氣體，藉此可使該凝固體昇華，可作為昇華機構而發揮功能。進而，亦可於凝固機構及昇華機構中併用氣體供給機構，故而可削減零件數，可謀求裝置成本之減少。再者，惰性氣體對昇華性物質為惰性，故而該昇華性物質不會改性。 於上述構成中，上述昇華機構可為以該昇華性物質之凝固點以下之溫度向上述圖案形成面供給至少對上述昇華性物質為惰性之氣體的氣體供給機構與以上述昇華性物質之凝固點以下之溫度向與上述基板之圖案形成面相反側之背面供給冷媒的冷媒供給機構。 根據上述構成，氣體供給機構以昇華性物質之凝固點以下之溫度對於圖案形成面形成之凝固體供給惰性氣體，藉此使該凝固體昇華。又，冷媒供給機構以昇華性物質之凝固點以下之溫度對與基板之圖案形成面相反側之背面供給冷媒，藉此可自基板之背面側防止凝固體之融解。 又，於上述構成中，較佳為上述昇華機構為將形成有上述凝固體之上述圖案形成面減壓至低於大氣壓之環境下的減壓機構。 藉由使用減壓機構作為昇華機構，可使基板之圖案形成面成為低於大氣壓之環境下，從而使凝固體中之昇華性物質昇華。此處，昇華性物質自凝固體昇華而氣化時，該凝固體被奪去作為昇華熱之熱。故而，凝固體冷卻。因此，即便於稍高於昇華性物質之熔點之溫度環境下，亦可不用另外冷卻凝固體，而維持為低於昇華性物質之熔點之溫度之狀態。其結果為，可防止凝固體中之昇華性物質之融解並進行凝固體之昇華。又，無需另外設置冷卻機構，故而可減少裝置成本或處理成本。 又，於上述構成中，較佳為上述凝固機構為將供給上述處理液之上述圖案形成面減壓至低於大氣壓之環境下的減壓機構。 根據該構成，藉由使用減壓機構作為凝固機構，可使基板之圖案形成面成為低於大氣壓之環境下從而使處理液蒸發，藉此藉由其氣化熱而冷卻處理液，從而可形成凝固體。又，無需另外設置冷卻機構，故而可減少裝置成本或處理成本。 又，於上述構成中，較佳為使用上述減壓機構作為上述昇華機構。根據該構成，亦可將用作凝固機構之減壓機構用作昇華機構，故而可削減零件數，可謀求裝置成本之減少。 又，於上述構成中，較佳為上述供給機構具有將上述處理液之溫度調整為上述昇華性物質之熔點以上且低於沸點之溫度的處理液溫度調整部。根據上述構成，藉由使上述供給機構進而具備處理液溫度調整部，可將處理液之溫度調整為昇華性物質之熔點以上且低於沸點之溫度。藉由使處理液之溫度成為昇華性物質之熔點以上，可進一步防止形成於基板上之圖案之倒塌，並且可良好地進行基板上之液體之乾燥處理。 本發明之基板處理方法係為解決上述課題，進行基板之圖案形成面之乾燥處理之基板處理方法，並且其包含對基板之圖案形成面供給含有融解狀態之昇華性物質之處理液的供給方法、使上述處理液於上述圖案形成面上凝固而形成凝固體的凝固方法、及使上述凝固體昇華而自上述圖案形成面去除的昇華方法，上述昇華性物質之20℃～25℃下之蒸氣壓為5 kPa以上，20℃～25℃下之表面張力為25 mN/m以下。 根據上述構成，例如於基板之圖案形成面上存在液體之情形時，藉由冷凍乾燥(或昇華乾燥)之原理，可防止圖案之倒塌並且去除該液體。具體而言，於上述供給步驟中，藉由對基板之圖案形成面供給處理液，而將上述液體置換為處理液。其次，於凝固步驟中，使處理液凝固而形成凝固體。此處，藉由使用蒸氣壓為5 kPa以上，表面張力為25 mN/m以下者(均為20℃～25℃之溫度範圍內之值)作為昇華性物質，於昇華步驟中，凝固體中之昇華性物質昇華時，可使昇華之進行程度均勻化。藉此，與昇華不均勻地進行之情形相比較，可減少對基板圖案施加之應力。其結果為例如與使用有第三丁醇等先前之昇華性物質之基板處理方法相比較，於具備具有微細之縱橫比之圖案面之基板中亦可進一步減少圖案倒塌之產生。 於上述構成中，較佳為上述昇華性物質之20℃～25℃下之表面張力為20 mN/m以下。 於上述構成中，較佳為上述昇華性物質為1,1,2,2,3,3,4-七氟環戊烷或十二氟環己烷。 本發明根據上述說明之機構而發揮以下所述之效果。 即，本發明係例如於基板之圖案形成面上存在液體之情形時，將該液體置換為含有昇華性物質之處理液後，使該處理液凝固而形成凝固體後，使該凝固體中之昇華性物質昇華，從而進行基板上之液體之乾燥處理。此處，於本發明中，藉由使用蒸氣壓(20℃～25℃)為5 kPa以上，表面張力(20℃～25℃)為25 mN/m以下者作為昇華性物質，於該昇華性物質昇華時，可使昇華之進行程度變得均勻。藉此，於本發明中，可減少因昇華之不均勻之進行而導致應力於圖案上之施加。其結果為本發明例如與使用有第三丁醇等先前之昇華性物質之基板處理裝置及基板處理方法相比較，可進一步減少圖案之倒塌，極其適合於基板上之液體之乾燥處理。The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a substrate processing apparatus and a substrate processing method capable of preventing collapse of a pattern formed on a surface of a substrate and removing a liquid adhering to the substrate surface. The substrate processing apparatus of the present invention is a substrate processing apparatus used for drying the pattern forming surface of a substrate in order to solve the above-mentioned problems, and is provided with a method for supplying a processing solution containing a sublimable substance in a molten state to the pattern forming surface of the substrate. A supply mechanism, a coagulation mechanism that solidifies the processing liquid on the pattern forming surface to form a solidified body, a sublimation mechanism that sublimates the solidified body and removes the solidified body from the pattern forming surface, and The vapor pressure is 5 kPa or more, and the surface tension at 20 ° C to 25 ° C is 25 mN / m or less. According to the above configuration, for example, when a liquid is present on the pattern forming surface of the substrate, the liquid can be prevented from being collapsed and removed by the principle of freeze drying (or sublimation drying). Specifically, the supply mechanism is configured to supply the processing liquid to the pattern forming surface of the substrate, and replace the liquid with the processing liquid. Next, the coagulation mechanism coagulates the processing liquid to form a coagulated body. Here, by using a vapor pressure of 5 kPa or more and a surface tension of 25 mN / m or less (both in the temperature range of 20 ° C to 25 ° C) as the sublimable substance, the sublimable substance is sublimated in the solidified body. This can reduce the unevenness in the degree of sublimation. Thereby, compared with the case where the sublimation is performed unevenly, the stress applied to the substrate pattern can be reduced. As a result, compared with a substrate processing apparatus using a conventional sublimable substance such as tertiary butanol, the occurrence of pattern collapse can also be reduced in a substrate having a pattern surface having a fine aspect ratio. Here, the above-mentioned "melted state" refers to a state in which the sublimable substance has fluidity due to complete or partial melting, and is in a liquid state. The above-mentioned "sublimation property" means that the monomer, compound, or mixture has the property of changing from a solid phase to a gas or from a gas phase to a solid without passing through a liquid, and the so-called "sublimable substance" means having such a sublimation property Of matter. The "pattern-forming surface" mentioned above refers to a surface on which an uneven pattern is formed in an arbitrary region on a substrate, regardless of whether it is planar, curved, or uneven. The above-mentioned "solidified body" refers to a solidified processing liquid. For example, when the liquid existing on the substrate is mixed with the processing liquid, the liquid may contain the liquid when it is solidified by a coagulation mechanism. By. In the above configuration, the surface tension at 20 ° C to 25 ° C of the sublimable substance is preferably 20 mN / m or less. In the above configuration, it is preferable that the sublimable substance is 1,1,2,2,3,3,4-heptafluorocyclopentane or dodecafluorocyclohexane. In the above configuration, it is preferable that the supply mechanism supplies the processing solution to the pattern forming surface of the substrate under atmospheric pressure, and the coagulation mechanism cools the processing solution below the freezing point of the sublimable substance under atmospheric pressure. By. Accordingly, at least the supply mechanism and the coagulation mechanism need not have a structure having pressure resistance, and the cost of the device can be reduced. Moreover, in the said structure, it is preferable that the said sublimable substance has sublimability under atmospheric pressure, and the said sublimation mechanism is a sublimation substance which sublimates the said sublimable substance under atmospheric pressure. This makes it possible to reduce the cost of the device by using a sublimable substance at atmospheric pressure as a sublimable substance, at least in a sublimation mechanism, without having a pressure-resistant structure. Further, in the above configuration, it is preferable that at least one of the solidification mechanism or the sublimation mechanism can supply a refrigerant to the rear surface opposite to the pattern forming surface of the substrate at a temperature below the freezing point of the sublimable substance. mechanism. According to the above configuration, in the solidifying mechanism, the sublimating substance can be cooled and solidified by supplying a refrigerant below the freezing point of the sublimable substance to the back surface opposite to the pattern formation surface of the substrate. In the sublimation mechanism, by supplying the refrigerant to the back surface of the substrate, the solidified body can be prevented from melting from the rear surface side of the substrate and the solidified body can be naturally sublimated. Furthermore, when both the solidification mechanism and the sublimation mechanism have a configuration in which a refrigerant can be supplied to the back surface of the substrate, the number of parts can be reduced, and the cost of the device can be reduced. In the above configuration, at least one of the solidification mechanism or the sublimation mechanism may be a gas supply mechanism that supplies the pattern forming surface with a gas at least inert to the sublimation substance at a temperature below the freezing point of the sublimation substance. . According to the above configuration, as the gas supply mechanism, as the solidification mechanism, an inert gas having a temperature below the freezing point of the sublimable substance is supplied to the pattern forming surface, so that the sublimable substance can be cooled and solidified. In addition, the gas supply mechanism also supplies an inert gas to the solidified body formed on the pattern forming surface, so that the solidified body can be sublimated and can function as a sublimation mechanism. Furthermore, since the gas supply mechanism can be used in combination with the solidification mechanism and the sublimation mechanism, the number of parts can be reduced, and the cost of the device can be reduced. Furthermore, since the inert gas is inert to the sublimable substance, the sublimable substance is not modified. In the above configuration, the sublimation mechanism may be a gas supply mechanism that supplies at least a gas inert to the sublimation substance to the pattern forming surface at a temperature below the freezing point of the sublimation substance, and a gas supply mechanism that is at least the freezing point of the sublimation substance. A refrigerant supply mechanism that supplies a refrigerant to a back surface opposite to the pattern formation surface of the substrate at a temperature. According to the above configuration, the gas supply means supplies the inert gas to the solidified body formed on the pattern forming surface at a temperature below the freezing point of the sublimable substance, thereby sublimating the solidified body. In addition, the refrigerant supply mechanism can prevent the melting of the solidified body from the rear surface side of the substrate by supplying the refrigerant to the rear surface opposite to the pattern formation surface of the substrate at a temperature below the freezing point of the sublimable substance. Moreover, in the said structure, it is preferable that the said sublimation mechanism is a pressure reduction mechanism which decompresses the said pattern formation surface in which the said solidified body was formed to the atmosphere lower than atmospheric pressure. By using a decompression mechanism as the sublimation mechanism, the pattern formation surface of the substrate can be brought to an atmosphere lower than atmospheric pressure, and the sublimable substance in the solidified body can be sublimated. Here, when a sublimable substance is sublimated from a solidified body and vaporized, the solidified body is taken away as heat of sublimation heat. Therefore, the solidified body is cooled. Therefore, even in a temperature environment slightly higher than the melting point of the sublimable substance, it is possible to maintain the state lower than the melting point of the sublimable substance without cooling the solidified body separately. As a result, melting of the sublimable substance in the solidified body can be prevented and sublimation of the solidified body can be performed. In addition, there is no need to separately provide a cooling mechanism, so that the equipment cost or the processing cost can be reduced. Moreover, in the said structure, it is preferable that the said coagulation mechanism is a pressure reduction mechanism which decompresses the said pattern formation surface which supplies the said processing liquid to the atmosphere below atmospheric pressure. According to this configuration, by using the decompression mechanism as the coagulation mechanism, the pattern forming surface of the substrate can be made to have an atmosphere lower than atmospheric pressure to evaporate the processing liquid, thereby cooling the processing liquid by the heat of vaporization, thereby forming Solidified body. In addition, there is no need to separately provide a cooling mechanism, so that the equipment cost or the processing cost can be reduced. Moreover, in the said structure, it is preferable to use the said pressure reduction mechanism as the said sublimation mechanism. According to this configuration, the decompression mechanism used as the solidification mechanism can also be used as the sublimation mechanism, so the number of parts can be reduced, and the cost of the device can be reduced. Moreover, in the said structure, it is preferable that the said supply means has a processing-liquid temperature adjustment part which adjusts the temperature of the said processing liquid to the temperature of the melting point of the said sublimable substance which is more than the melting point and below a boiling point. According to the above configuration, by providing the supply mechanism further with a processing liquid temperature adjustment unit, the temperature of the processing liquid can be adjusted to a temperature higher than the melting point of the sublimable substance and lower than the boiling point. By making the temperature of the processing liquid equal to or higher than the melting point of the sublimable substance, the collapse of the pattern formed on the substrate can be further prevented, and the liquid on the substrate can be dried well. The substrate processing method of the present invention is a substrate processing method for drying the pattern forming surface of a substrate in order to solve the above-mentioned problems, and includes a method of supplying a processing solution containing a sublimable substance in a molten state to the pattern forming surface of the substrate, A coagulation method for solidifying the treatment liquid on the pattern forming surface to form a solidified body, and a sublimation method for sublimating the solidified body from the pattern forming surface, and a vapor pressure of the sublimable substance at 20 ° C to 25 ° C It is 5 kPa or more, and the surface tension at 20 ° C to 25 ° C is 25 mN / m or less. According to the above configuration, for example, when a liquid is present on the pattern formation surface of the substrate, the liquid can be prevented from being collapsed and removed by the principle of freeze drying (or sublimation drying). Specifically, in the above-mentioned supplying step, the processing liquid is replaced with the processing liquid by supplying the processing liquid to the pattern forming surface of the substrate. Next, in the solidification step, the treatment liquid is solidified to form a solidified body. Here, by using a vapor pressure of 5 kPa or more and a surface tension of 25 mN / m or less (both in the temperature range of 20 ° C to 25 ° C) as the sublimable substance, in the sublimation step, the solidified body When the sublimation substance is sublimated, the progress of the sublimation can be made uniform. Thereby, compared with the case where the sublimation is performed unevenly, the stress applied to the substrate pattern can be reduced. As a result, compared with a substrate processing method using a conventional sublimable substance such as tertiary butanol, the occurrence of pattern collapse can be further reduced in a substrate having a pattern surface having a fine aspect ratio. In the above configuration, the surface tension at 20 ° C to 25 ° C of the sublimable substance is preferably 20 mN / m or less. In the above configuration, it is preferable that the sublimable substance is 1,1,2,2,3,3,4-heptafluorocyclopentane or dodecafluorocyclohexane. The present invention has the effects described below based on the mechanism described above. That is, in the present invention, for example, when a liquid is present on the pattern forming surface of a substrate, the liquid is replaced with a treatment liquid containing a sublimable substance, and then the treatment liquid is solidified to form a solidified body. The sublimable substance is sublimated to dry the liquid on the substrate. Here, in the present invention, by using a vapor pressure (20 ° C to 25 ° C) of 5 kPa or more and a surface tension (20 ° C to 25 ° C) of 25 mN / m or less as a sublimable substance, the sublimation property is used. Sublimation can make the progress of sublimation uniform. Therefore, in the present invention, the application of stress to the pattern due to the uneven progress of sublimation can be reduced. As a result, compared with a substrate processing apparatus and a substrate processing method using a previously sublimable substance such as tertiary butanol, the present invention can further reduce the collapse of the pattern, and is extremely suitable for drying the liquid on the substrate.

(第1實施形態) 以下對本發明之第1實施形態進行說明。 圖1係表示本實施形態之基板處理裝置1之概略之說明圖。圖2係表示基板處理裝置1之內部構成之概略平面圖。再者，於各圖中，為明確圖示者之方向關係，適宜顯示XYZ正交座標。於圖1及圖2中，XY平面表示水平面，+Z方向表示鉛直向上。 基板處理裝置1例如可用於各種基板之處理。上述所謂「基板」係指半導體基板、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)用基板、光碟用基板、磁碟用基板、磁光碟用基板等各種基板。於本實施形態中，以將基板處理裝置1用於半導體基板(以下稱為「基板W」)之處理之情形為例進行說明。 又，作為基板W，以僅於一個主面形成電路圖案等(以下記為「圖案」)者為例。此處，將形成圖案之圖案形成面(主面)稱為「表面」，將其相反側之未形成圖案之主面稱為「背面」。又，將朝向下方之基板之面稱為「下表面」，將朝向上方之基板之面稱為「上表面」。再者，以下將上表面作為表面而說明。 又，作為上述圖案之形狀，並無特別限定，例如可列舉線狀或筒狀者。又，作為圖案之大小，並無特別限定，可適宜地任意設定。進而，作為圖案之材質，並無特別限定，可列舉金屬或絕緣材料等。 基板處理裝置1係於用以去除附著於基板W之微粒等污染物質之清洗處理(包含沖洗處理)及清洗處理後之乾燥處理中所使用之單片式之基板處理裝置。再者，圖1及圖2中僅顯示用於乾燥處理之部位，未圖示用於清洗處理之清洗用之噴嘴等，但基板處理裝置1可具備該噴嘴等。 ＜1-1 基板處理裝置之構成＞ 首先，基於圖1及圖2說明基板處理裝置1之構成。 基板處理裝置1至少具備：作為收容基板W之容器之腔室11、保持基板W之基板保持機構51、控制基板處理裝置1之各部之控制單元13、對保持於基板保持機構51之基板W供給作為處理液之乾燥輔助液之處理液供給機構(供給機構)21、對保持於基板保持機構51之基板W供給IPA(異丙醇)之IPA供給機構31、對保持於基板保持機構51之基板W供給氣體之氣體供給機構41(凝固機構、昇華機構)、捕集被供給至保持於基板保持機構51之基板W並排出至基板W之周緣部外側之IPA或乾燥輔助液等之飛散防止杯12、使基板處理裝置1之各部之下述支臂分別獨立迴轉驅動之迴轉驅動部14、將腔室11之內部減壓之減壓機構71、對基板W之背面Wb供給冷媒之冷媒供給機構(凝固機構、昇華機構)81。又，基板處理裝置1具備基板搬入搬出機構、夾盤銷開關機構及濕式清洗機構(均未圖示)。以下說明基板處理裝置1之各部。 基板保持機構51具有旋轉驅動部52、旋轉基底53、夾盤銷54。旋轉基底53具有稍許大於基板W之平面尺寸。於旋轉基底53之周緣部附近豎設有固持基板W之周緣部之複數個夾盤銷54。夾盤銷54之設置數並無特別限定，為確實地保持圓形狀之基板W，較佳為設置至少3個以上。於本實施形態中，沿旋轉基底53之周緣部以等間隔配置3個(參照圖2)。各個夾盤銷54具備自下方支撐基板W之周緣部之基板支撐銷、按壓被基板支撐銷支撐之基板W之外周端面而保持基板W之基板保持銷。 各個夾盤銷54可於基板保持銷按壓基板W之外周端面之按壓狀態與基板保持銷自基板W之外周端面離開之解除狀態之間切換，根據來自控制裝置整體之控制單元13之動作指令實行狀態切換。 更詳細而言，於對旋轉基底53搬入搬出基板W時，各個夾盤銷54成為解除狀態，於對基板W進行下述清洗處理至昇華處理為止之基板處理時，各個夾盤銷54成為按壓狀態。若夾盤銷54為按壓狀態，則夾盤銷54固持基板W之周緣部，基板W自旋轉基底53隔開特定間隔而保持為水平狀態(XY面)。藉此，基板W以其表面Wf朝向上方之狀態保持為水平。 如此於本實施形態中，以旋轉基底53與夾盤銷54保持基板W，但基板保持方式並不限定於此。例如，亦可藉由旋轉夾頭等吸附方式保持基板W之背面Wb。 旋轉基底53與旋轉驅動部52連接。旋轉驅動部52藉由控制單元13之動作指令繞沿Z方向之軸Al旋轉。旋轉驅動部52包含公知之皮帶、馬達及旋轉軸。若旋轉驅動部52繞軸Al旋轉，則伴隨於此於旋轉基底53之上方藉由夾盤銷54而保持之基板W與旋轉基底53一同繞軸Al旋轉。 其次，說明處理液供給機構(供給機構)21。 處理液供給機構21係對基板W之圖案形成面供給乾燥輔助液之單元，如圖1所示，至少具備噴嘴22、支臂23、迴轉軸24、配管25、閥門26、處理液貯存部27。 處理液貯存部27如圖3A及圖3B所示，至少具備處理液貯存槽271、攪拌處理液貯存槽271內之乾燥輔助液之攪拌部277、對處理液貯存槽271進行加壓而送出乾燥輔助液之加壓部274、加熱處理液貯存槽271內之乾燥輔助液(處理液)之溫度調整部272。再者，圖3A係表示處理液貯存部27之概略構成之方塊圖，圖3B係表示該處理液貯存部27之具體構成之說明圖。 攪拌部277具備攪拌處理液貯存槽271內之乾燥輔助液之旋轉部279、控制旋轉部279之旋轉之攪拌控制部278。攪拌控制部278與控制單元13電性連接。旋轉部279於旋轉軸之前端(圖4中之旋轉部279之下端)具備螺旋槳狀之攪拌葉，控制單元13對攪拌控制部278進行動作指令，旋轉部279旋轉，藉此攪拌葉攪拌乾燥輔助液，使乾燥輔助液中之乾燥輔助物質等之濃度及溫度均勻化。 又，作為使處理液貯存槽271內之乾燥輔助液之濃度及溫度均勻之方法，並不限定於上述方法，可使用另外設置循環用之泵而使乾燥輔助液循環之方法等公知之方法。 加壓部274包含作為對處理液貯存槽271內進行加壓之氣體之供給源之氮氣槽275、加壓氮氣之泵276及配管273。氮氣槽275藉由配管273而與處理液貯存槽271管路連接，又，於配管273上插介泵276。 溫度調整部272與控制單元13電性連接，藉由控制單元13之動作指令對貯存於處理液貯存槽271之乾燥輔助液加熱從而進行溫度調整。溫度調整係使乾燥輔助液之液溫成為該乾燥輔助液中所含之乾燥輔助物質(昇華性物質；詳細內容下述)之熔點以上即可。藉此，可維持乾燥輔助物質之融解狀態。再者，作為溫度調整之上限，較佳為低於沸點之溫度。又，作為溫度調整部272，並無特別限定，例如可使用電阻加熱器或珀爾帖元件、使溫度調整之水經過之配管等公知之溫度調整機構。再者，於本實施形態中，溫度調整部272為任意構成。例如，於基板處理裝置1之設置環境為高於昇華性物質之熔點之高溫環境之情形時，因可維持該昇華性物質之融解狀態，故而不需要加熱乾燥輔助液。其結果為可省略溫度調整部272。 返回至圖1。處理液貯存部27(更詳細而言，處理液貯存槽271)經由配管25而與噴嘴22管路連接，於配管25之路徑中途插介閥門26。 於處理液貯存槽271內設置有氣壓感測器(未圖示)，與控制單元13電性連接。控制單元13藉由基於氣壓感測器檢測出之值控制泵276之動作，而將處理液貯存槽271內之氣壓維持為高於大氣壓之特定氣壓。另一方面，閥門26亦與控制單元13電性連接，通常為閉閥。又，閥門26之開關亦藉由控制單元13之動作指令而控制。並且，若控制單元13對處理液供給機構21進行動作指令，使閥門26開閥，則乾燥輔助液自加壓之處理液貯存槽271內被壓送，經由配管25自噴嘴22噴出。藉此，可將乾燥輔助液供給至基板W之表面Wf。再者，處理液貯存槽271係如上所述使用藉由氮氣之壓力而壓送乾燥輔助液，故而較佳為氣密之構成。 噴嘴22安裝於水平延伸設置之支臂23之前端部，配置於旋轉基底53之上方。支臂23之後端部藉由於Z方向上延伸設置之迴轉軸24而繞軸J1旋轉自如地被支撐，迴轉軸24固定設置於腔室11內。經由迴轉軸24，支臂23與迴轉驅動部14連接。迴轉驅動部14與控制單元13電性連接，藉由來自控制單元13之動作指令而使支臂23繞軸J1旋動。伴隨支臂23之旋動，噴嘴22亦移動。 噴嘴22如圖2中實線所示，通常為較之基板W之周緣部之更外側，配置於較之飛散防止杯12之更外側之退避位置P1。若支臂23藉由控制單元13之動作指令而旋動，則噴嘴22沿箭頭AR1之路徑移動，配置於基板W之表面Wf之中央部(軸A1或其附近)之上方位置。 返回至圖1。其次，說明IPA供給機構31。IPA供給機構31係對基板W供給IPA之單元，具備噴嘴32、支臂33、迴轉軸34、配管35、閥門36、IPA槽37。 IPA槽37經由配管35而與噴嘴32管路連接，於配管35之路徑中途插介閥門36。於IPA槽37中貯存有IPA，藉由未圖示之加壓機構將IPA槽37內之IPA加壓，將IPA自配管35送至噴嘴32方向。 閥門36與控制單元13電性連接，通常為閉閥。閥門36之開關係藉由控制單元13之動作指令而控制。若藉由控制單元13之動作指令而使閥門36開閥，則IPA經過配管35而自噴嘴32供給至基板W之表面Wf。 噴嘴32安裝於水平延伸設置之支臂33之前端部，配置於旋轉基底53之上方。支臂33之後端部藉由於Z方向上延伸設置之迴轉軸34而繞軸J2旋轉自如地被支撐，迴轉軸34固定設置於腔室11內。支臂33經由迴轉軸34與迴轉驅動部14連接。迴轉驅動部14與控制單元13電性連接，藉由來自控制單元13之動作指令而使支臂33繞軸J2旋動。伴隨支臂33之旋動，噴嘴32亦移動。 如圖2中實線所示，噴嘴32通常為較之基板W之周緣部之更外側，配置於較之飛散防止杯12之更外側之退避位置P2。若支臂33藉由控制單元13之動作指令而旋動，則噴嘴32沿箭頭AR2之路徑移動，配置於基板W之表面Wf之中央部(軸A1或其附近)之上方位置。 再者，於本實施形態中，IPA供給機構31中使用IPA，但本發明中，若為對乾燥輔助物質及去離子水(DIW：Deionized Water)具有溶解性之液體，則不限定於IPA。作為本實施形態之IPA之替代，可列舉：甲醇、乙醇、丙酮、苯、四氯化碳、氯仿、己烷、十氫萘、萘滿、乙酸、環己醇、醚或氫氟醚(Hydro Fluoro Ether)等。 返回至圖1。其次，說明氣體供給機構41。氣體供給機構41係對基板W供給氣體之單元，具備噴嘴42、支臂43、迴轉軸44、配管45、閥門46、貯氣槽47。 圖4係表示貯氣槽47之概略構成之方塊圖。貯氣槽47具備貯存氣體之氣體貯存部471、調整貯存於氣體貯存部471之氣體之溫度之氣體溫度調整部472。氣體溫度調整部472與控制單元13電性連接，藉由控制單元13之動作指令對貯存於氣體貯存部471之氣體加熱或冷卻從而進行溫度調整。溫度調整係使貯存於氣體貯存部471之氣體成為乾燥輔助物質之凝固點以下之較低溫度即可。 作為氣體溫度調整部472，並無特別限定，例如可使用珀爾帖元件、使溫度調整之水經過之配管等公知之溫度調整機構。 返回至圖1。貯氣槽47(更詳細而言，氣體貯存部471)經由配管45而與噴嘴42管路連接，於配管45之路徑中途插介閥門46。藉由未圖示之加壓機構而加壓貯氣槽47內之氣體，送至配管45。再者，加壓機構除藉由泵等之加壓外，亦可藉由將氣體壓縮貯存於貯氣槽47內而實現，故而可使用任一種加壓機構。 閥門46與控制單元13電性連接，通常為閉閥。閥門46之開關係藉由控制單元13之動作指令而控制。若藉由控制單元13之動作指令而使閥門46開閥，則氣體經過配管45，自噴嘴42供給至基板W之表面Wf。 噴嘴42安裝於水平延伸設置之支臂43之前端部，配置於旋轉基底53之上方。支臂43之後端部藉由於Z方向上延伸設置之迴轉軸44而繞軸J3旋轉自如地被支撐，迴轉軸44固定設置於腔室11內。經由迴轉軸44，支臂43與迴轉驅動部14連接。迴轉驅動部14與控制單元13電性連接，藉由來自控制單元13之動作指令而使支臂43繞軸J3旋動。伴隨支臂43之旋動，噴嘴42亦移動。 如圖2中實線所示，噴嘴42通常為較之基板W之周緣部之更外側，配置於較之飛散防止杯12之更外側之退避位置P3。若支臂43藉由控制單元13之動作指令而旋動，則噴嘴42沿箭頭AR3之路徑移動，配置於基板W之表面Wf之中央部(軸A1或其附近)之上方位置。將噴嘴42配置於表面Wf中央部之上方位置之情況於圖2中以虛線表示。 氣體貯存部471中貯存有對乾燥輔助物質至少為惰性之惰性氣體，更具體而言為氮氣。又，貯存之氮氣於氣體溫度調整部472中被調整為乾燥輔助物質之凝固點以下之溫度。若氮氣之溫度為乾燥輔助物質之凝固點以下之溫度，則並無特別限定，通常可設定為0℃以上且15℃以下之範圍內。再者，藉由使氮氣之溫度為0℃以上，可防止腔室11之內部存在之水蒸氣凝固而於基板W之表面Wf附著等，防止對基板W產生不良影響。 又，第1實施形態中使用之氮氣較佳為其露點為0℃以下之乾燥氣體。若將上述氮氣於大氣壓環境下吹附至凝固體，則凝固體中之乾燥輔助物質於氮氣中昇華。因氮氣持續供給至凝固體，故而因昇華而產生之氣體狀態之乾燥輔助物質之於氮氣中之分壓維持為低於氣體狀態之乾燥輔助物質之於該氮氣之溫度下之飽和蒸氣壓之狀態，至少於凝固體表面，氣體狀態之乾燥輔助物質在於其飽和蒸氣壓以下而存在之環境下而充滿。 又，於本實施形態中，使用氮氣作為藉由氣體供給機構41而供給之氣體，但作為本發明之實施，若為對乾燥輔助物質為惰性之氣體，則並不限定於此。於第1實施形態中，作為氮氣之代替氣體，可列舉：氬氣、氦氣或乾燥空氣(氮氣濃度80%、氧氣濃度20%之氣體)。或者，亦可為混合該等複數種氣體而成之混合氣體。 返回至圖1。減壓機構71係將腔室11之內部減壓為低於大氣壓之環境之機構，具備排氣泵72、配管73、閥門74。排氣泵72經由配管73而與腔室11管路連接，係對氣體施加壓力之公知之泵。排氣泵72與控制單元13電性連接，通常為停止狀態。排氣泵72之驅動係藉由控制單元13之動作指令而控制。又，於配管73上插介閥門74。閥門74與控制單元13電性連接，通常為閉閥。閥門74之開關係藉由控制單元13之動作指令而控制。 若排氣泵72藉由控制單元13之動作指令而驅動，閥門74開閥，則藉由排氣泵72，腔室11之內部存在之氣體經由配管73排氣至腔室11之外側。 飛散防止杯12以包圍旋轉基底53之方式設置。飛散防止杯12與圖示省略之升降驅動機構連接，可於Z方向上升降。對基板W供給乾燥輔助液或IPA時，飛散防止杯12藉由升降驅動機構定位至如圖1所示之特定位置，自側方位置包圍藉由夾盤銷54而保持之基板W。藉此，可捕集自基板W或旋轉基底53飛散之乾燥輔助液或IPA等液體。 其次，對冷媒供給機構81加以說明。 冷媒供給機構81係對基板W之背面Wb供給冷媒之單元，如圖1所示，至少具備冷媒貯存部82、配管83、閥門84及冷媒供給管85。 圖5係表示冷媒貯存部82之概略構成之方塊圖。冷媒貯存部82具備貯存冷媒之冷媒槽821、調整貯存於冷媒槽821之冷媒之溫度之冷媒溫度調整部822。 冷媒溫度調整部822係與控制單元13電性連接，藉由控制單元13之動作指令而加熱或冷卻貯存於冷媒槽821之冷媒進行溫度調整者。溫度調整係以貯存於冷媒槽821之冷媒成為乾燥輔助物質之凝固點以下之較低溫度之方式進行即可。再者，作為冷媒溫度調整部822，並無特別限定，例如可使用使用有珀爾帖元件之冷卻器、使溫度調整之水經過之配管等公知之溫度調整機構。 返回至圖1。冷媒貯存部82經由配管83與冷媒供給管85管路連接，於配管83之路徑中途插介閥門84。冷媒供給管85係藉由於旋轉基底53之中央部形成貫通孔而設置者。冷媒貯存部82內之冷媒藉由未圖示之加壓機構而被加壓，送至配管82。加壓機構除藉由泵等之加壓外，亦可藉由將氣體壓縮貯存於冷媒貯存部82內而實現，故而可使用任一種加壓機構。 閥門84與控制單元13電性連接，通常為閉閥。閥門84之開關係藉由控制單元13之動作指令而控制。若藉由控制單元13之動作指令而使閥門84開閥，則冷媒經過配管83及冷媒供給管85，供給至基板W之背面Wb。 作為上述冷媒，可列舉乾燥輔助物質之凝固點以下之液體或氣體。進而，作為上述液體，並無特別限定，例如可列舉7℃之冷水等。又，作為上述氣體，並無特別限定，例如可列舉對乾燥輔助物質為惰性之氣體，更詳細而言可列舉7℃之氮氣等。 圖6係表示控制單元13之構成之模式圖。控制單元13與基板處理裝置1之各部電性連接(參照圖1)，控制各部之動作。控制單元13包含具有運算處理部15、記憶體17之電腦。作為運算處理部15，使用進行各種運算處理之CPU(Central Processing Unit，中央處理單元)。又，記憶體17具備作為記憶基本程式之讀出專用之記憶體之ROM，作為記憶各種資訊之讀寫自如之記憶體之RAM及預先記憶有控制用軟體或資料等之磁碟。根據基板W之基板處理條件(配方(recipe))被預先儲存於磁碟中。CPU將基板處理條件讀出至RAM，依據其內容，CPU控制基板處理裝置1之各部。 ＜1-2 乾燥輔助液＞ 其次，以下說明本實施形態中使用之乾燥輔助液。 本實施形態之乾燥輔助液係含有融解狀態之乾燥輔助物質(昇華性物質)之處理液，於用以去除基板之圖案形成面存在之液體之乾燥處理中，發揮輔助該乾燥處理之功能。又，昇華性物質係具有不經過液體自固體相轉變為氣體或自氣體相轉變為固體之特性者。並且，昇華性物質於融解狀態下含有於乾燥輔助液中，故而可於基板W上形成均勻層厚之膜狀之凝固體。 於本實施形態中，昇華性物質之20℃～25℃之範圍之蒸氣壓為5 kPa以上，較佳為8 kPa以上且100 kPa以下，更佳為15 kPa以上且100 kPa以下。又，昇華性物質之20℃～25℃下之表面張力為25 mN/m以下，較佳為20 mN/m以下，更佳為大於0 mN/m且15 mN/m以下，進而較佳為0 mN/m以上且13 mN/m以下。藉由使用蒸氣壓為5 kPa以上且表面張力為25 mN/m以下之昇華性物質，可抑制凝固體中之昇華性物質之昇華之進行變得不均勻，從而減少圖案之倒塌。例如對於基板上隔開80 nm之間隔排列有直徑30 nm、高480 nm之複數個圓柱(縱橫比16)之圖案，可將圖案之倒塌率抑制在20%以下。再者，所謂圖案之倒塌率係藉由下式而算出之值。 圖案之倒塌率(%)＝(任意之區域中之倒塌之凸部數)÷(該區域中之凸部之總數)×100 於本實施形態中，作為昇華性物質，例如可例示：1,1,2,2,3,3,4-七氟環戊烷(20℃下之蒸氣壓為8.2 kPa，25℃下之表面張力為19.6 mN/m，熔點為20.5℃)、十二氟環己烷(20℃下之蒸氣壓為33.1 kPa，25℃下之表面張力為12.6 mN/m(計算值)，熔點為51℃)等。該等昇華性物質之蒸氣壓高於作為先前之乾燥輔助物質之DIW(20℃下之蒸氣壓為2.3 kPa)或第三丁醇(20℃下之蒸氣壓為4.l kPa，20℃下之表面張力為19.56 mN/m，熔點為25℃)，故而可以高於先前之昇華速度進行昇華步驟。又，該等昇華性物質不具有OH基，與第三丁醇相比較，對水更顯示難溶性，故而不會產生與基板W上殘存之水之混合。其結果為昇華後不會於圖案間殘留水分。 乾燥輔助液可為僅包含處於融解狀態之昇華性物質者，亦可進而含有有機溶劑。於該情形時，昇華性物質之含量相對於乾燥輔助液之總質量較佳為60質量%以上，更佳為95質量%以上。又，作為有機溶劑，若為對融解狀態之昇華性物質顯示相容性者即可，並無特別限定。具體可列舉醇類等。 ＜1-3 基板處理方法＞ 其次，以下基於圖7及圖8對使用有本實施形態之基板處理裝置1之基板處理方法加以說明。圖7係表示第1實施形態之基板處理裝置1之動作之流程圖。圖8係表示圖7之各步驟之基板W之情況之模式圖。再者，藉由前步驟而於基板W上形成有凹凸之圖案Wp。圖案Wp具備凸部Wp1及凹部Wp2。於本實施形態中，凸部Wp1為100～600 nm之範圍之高度，10～50 nm之範圍之寬度。又，鄰接之2個凸部Wp1間之最短距離(凹部Wp2之最短寬度)為10～50 nm之範圍。凸部Wp1之縱橫比，即，將高度除以寬度所得之值(高度/寬度)為10～20。 圖8所示之(a)～(e)為止之各個步驟只要無特別說明，則於大氣壓環境下進行處理。此處，所謂大氣壓環境係指以標準大氣壓(1個大氣壓，1013 hPa)為中心，0.7個大氣壓以上且1.3個大氣壓以下之環境。尤其，於基板處理裝置1配置於成為正壓之無塵室內之情形時，基板W之表面Wf之環境為高於1個大氣壓。 參照圖7。首先，根據特定之基板W之基板處理程式19被操作員指示實行。其後，作為將基板W搬入至基板處理裝置1之準備，控制單元13進行動作指令並進行以下動作。 停止旋轉驅動部52之旋轉，將夾盤銷54定位於適合於基板W之交付之位置。又，使閥門26、36、46、74閉閥，將噴嘴22、32、42分別定位於退避位置Pl、P2、P3。並且，藉由未圖示之開關機構而使夾盤銷54成為開狀態。 若藉由未圖示之基板搬入搬出機構而將未處理之基板W搬入基板處理裝置1內，載置於夾盤銷54上，則藉由未圖示之開關機構而使夾盤銷54成為閉狀態。 未處理之基板W由基板保持機構51保持後，藉由未圖示之濕式清洗機構，對基板進行清洗步驟S11。清洗步驟S11中包含於對基板W之表面Wf供給清洗液進行清洗後，用以去除該清洗液之沖洗處理。清洗液(沖洗處理之情形時為沖洗液)之供給係對藉由利用控制單元13之對旋轉驅動部52之動作指令而繞軸A1以一定速度旋轉之基板W之表面Wf進行。作為清洗液，並無特別限定，例如可列舉：SC-1(含有氨、過氧化氫水及水之液體)或SC-2(含有鹽酸、過氧化氫水及水之液體)等。又，作為沖洗液，並無特別限定，例如可列舉DIW等。清洗液及沖洗液之供給量並無特別限定，可根據清洗範圍等而適宜設定。又，清洗時間亦無特別限定，可適宜根據需要而設定。 再者，於本實施形態中，藉由濕式清洗機構，對基板W之表面Wf供給SC-1而清洗該表面Wf後，進而對表面Wf供給DIW，去除SC-1。 圖8所示之(a)係表示清洗步驟S11之結束時點之基板W之情況。如圖8中所示，於形成有圖案Wp之基板W之表面Wf附著有於清洗步驟S11中供給之DIW(圖中以「60」圖示)。 返回至圖7。其次，進行對附著有DIW60之基板W之表面Wf供給IPA之IPA沖洗步驟S12。首先，控制單元13對旋轉驅動部52進行動作指令，使基板W繞軸A1以一定速度旋轉。 其次，控制單元13對迴轉驅動部14進行動作指令，將噴嘴32定位至基板W之表面Wf中央部。並且，控制單元13對閥門36進行動作指令，使閥門36開閥。藉此，將IPA自IPA槽37經由配管35及噴嘴32供給至基板W之表面Wf。 供給至基板W之表面Wf之IPA由於因基板W旋轉所產生之離心力，而自基板W之表面Wf中央附近向基板W之周緣部流動，擴散至基板W之表面Wf之整個面。藉此，附著於基板W之表面Wf之DIW藉由IPA之供給而被去除，基板W之表面Wf之整個面由IPA覆蓋。基板W之旋轉速度較佳為設定為使包含IPA之膜之膜厚於表面Wf之整個面高於凸部Wp1之高度之程度。又，IPA之供給量並無特別限定，可適宜設定。 IPA沖洗步驟S12結束後，控制單元13對閥門36進行動作指令，使閥門36閉閥。又，控制單元13對迴轉驅動部14進行動作指令，將噴嘴32定位於退避位置P2。 圖8所示之(b)係表示IPA沖洗步驟S12之結束時點之基板W之情況。如圖8所示，於形成有圖案Wp之基板W之表面Wf附著有於IPA沖洗步驟S12中供給之IPA(圖中以「61」圖示)，DIW60被置換為IPA61而自基板W之表面Wf去除。 返回至圖7。其次，進行對附著有IPA61之基板W之表面Wf供給作為含有處於融解狀態之乾燥輔助物質之乾燥輔助液之處理液的處理液供給步驟(供給步驟)S13。首先，控制單元13對旋轉驅動部52進行動作指令，使基板W繞軸Al以一定速度旋轉。此時，基板W之旋轉速度較佳為設定為使包含乾燥輔助液之液膜之膜厚於表面Wf之整個面高於凸部Wp1之高度之程度。 繼而，控制單元13對迴轉驅動部14進行動作指令，將噴嘴22定位至基板W之表面Wf中央部。並且，控制單元13對閥門26進行動作指令，使閥門26開閥。藉此，將乾燥輔助液自處理液貯存槽271經由配管25及噴嘴22供給至基板W之表面Wf。 供給之乾燥輔助液之液溫設定為至少於供給至基板W之表面Wf後為乾燥輔助物質之熔點以上且低於沸點之範圍。例如，於使用上述1,1,2,2,3,3,4-七氟環戊烷(沸點82.5℃)作為乾燥輔助物質之情形時，較佳為設定為35℃以上且82℃以下之範圍。又，乾燥輔助液之供給量並無特別限定，可適宜設定。 如此，將乾燥輔助液於熔點以上之高溫狀態下供給，藉此可於基板W之表面Wf形成乾燥輔助液之液膜後形成凝固體。其結果為，獲得層厚均勻之膜狀之凝固體，可減少乾燥不均之產生。再者，於基板W之溫度及腔室11內之環境溫度為乾燥輔助物質之熔點以下之情形時，若對基板W供給稍稍高於熔點之溫度之乾燥輔助液，則存在乾燥輔助液接觸基板W後於極短時間內凝固之情形。於此種情形時，無法形成均勻層厚之凝固體，難以謀求乾燥不均之減少。因此，於基板W之溫度及腔室11內之環境溫度為乾燥輔助物質之熔點以下之情形時，較佳為將乾燥輔助液之液溫調整為充分高於熔點之溫度。 對基板W之表面Wf供給之乾燥輔助液由於因基板W旋轉所產生之離心力，而自基板W之表面Wf中央附近向基板W之周緣部流動，擴散至基板W之表面Wf之整個面。藉此，附著於基板W之表面Wf之IPA藉由乾燥輔助液之供給而被去除，基板W之表面Wf之整個面由乾燥輔助液覆蓋。處理液供給步驟S13結束後，控制單元13對閥門26進行動作指令，使閥門26閉閥。又，控制單元13對迴轉驅動部14進行動作指令，將噴嘴22定位於退避位置Pl。 圖8所示之(c)係表示處理液供給步驟S13之結束時點之基板W之情況。如圖8所示，於形成有圖案Wp之基板W之表面Wf附著有於處理液供給步驟S13中供給之乾燥輔助液(圖中以「62」圖示)，IPA61被置換為乾燥輔助液62而自基板W之表面Wf去除。 返回至圖7。其次，進行使供給至基板W之表面Wf之乾燥輔助液62凝固，形成乾燥輔助物質之凝固膜之凝固步驟S14。首先，控制單元13對旋轉驅動部52進行動作指令，使基板W繞軸A1以一定速度旋轉。此時，基板W之旋轉速度設定為可使乾燥輔助液62於表面Wf之整個面形成高於凸部Wpl之特定厚度之膜厚之程度之速度。 繼而，控制單元13對閥門84進行動作指令，使閥門84開閥。藉此，自冷媒貯存部82經由配管83及冷媒供給管85向基板W之背面Wb供給冷媒(於本實施形態中為7℃之冷水)。 向基板W之背面Wb供給之冷水由於因基板W旋轉所產生之離心力，而自基板W之背面Wb中央附近向基板W之周緣部方向流動，擴散至基板W之背面Wb之整個面。藉此，形成於基板W之表面Wf之乾燥輔助液62之液膜冷卻至乾燥輔助物質之凝固點以下之低溫而凝固，形成凝固體。 圖8所示之(d)係表示凝固步驟S14之結束時點之基板W之情況。如圖8所示，於處理液供給步驟S13中供給之乾燥輔助液62藉由向基板W之背面Wb之7℃之冷水(圖中以「64」圖示)之供給而冷卻凝固，形成含有乾燥輔助物質之凝固體(圖中以「63」圖示)。 返回至圖7。其次，進行使形成於基板W之表面Wf之凝固體63昇華，而自基板W之表面Wf去除之昇華步驟S15。於昇華步驟S15中，一面持續藉由冷媒供給機構81之向基板W之背面Wb之冷水供給一面進行。藉此，可將凝固體63冷卻至乾燥輔助物質之凝固點以下之溫度，自基板W之背面Wb側防止乾燥輔助物質融解。 於昇華步驟S15中，首先控制單元13對旋轉驅動部52進行動作指令，使基板W繞軸A1以一定速度旋轉。此時，基板W之旋轉速度設定為可使乾燥輔助液62於表面Wf之整個面形成高於凸部Wp1之特定厚度之膜厚之程度之速度。 繼而，控制單元13對迴轉驅動部14進行動作指令，將噴嘴42定位至基板W之表面Wf中央部。並且，控制單元13對閥門46進行動作指令，使閥門46開閥。藉此，將氣體(於本實施形態中，7℃之氮氣)自貯氣槽47經由配管45及噴嘴42向基板W之表面Wf供給。 此處，氮氣中之乾燥輔助物質之蒸氣之分壓設定為低於該氮氣之供給溫度下之乾燥輔助物質之飽和蒸氣壓。因此，若將此種氮氣供給至基板W之表面Wf，與凝固體63接觸，則乾燥輔助物質自該凝固體63於氮氣中昇華。又，氮氣之溫度低於乾燥輔助物質之熔點，故而可防止凝固體63之融解並且進行凝固體63之昇華。 藉此，藉由固體狀態之乾燥輔助物質之昇華而去除於基板W之表面Wf上存在之IPA等物質時，可一面防止對圖案Wp作用表面張力而抑制圖案倒塌之產生，一面良好地乾燥基板W之表面Wf。 圖8所示之(e)係表示昇華步驟S15之結束時點之基板W之情況。如圖8所示，於凝固步驟S14中形成之乾燥輔助物質之凝固體63藉由7℃之氮氣之供給而昇華，從而自表面Wf去除，完成基板W之表面Wf之乾燥。 昇華步驟S15結束後，控制單元13對閥門46進行動作指令，使閥門46閉閥。又，控制單元13對迴轉驅動部14進行動作指令，將噴嘴42定位於退避位置P3。 藉由以上內容，結束一連串之基板乾燥處理。如上述之基板乾燥處理後，利用未圖示之基板搬入搬出機構而將乾燥處理完畢之基板W自腔室11搬出。 如上所述，於本實施形態中，將含有融解狀態之乾燥輔助物質之乾燥輔助液供給至附著有IPA之基板W之表面Wf，使該乾燥輔助液於基板W之表面Wf凝固而形成含有乾燥輔助物質之凝固體後，使該凝固體昇華，自基板W之表面Wf去除，藉此可進行基板W之乾燥處理。 此處，藉由使用20℃～25℃之範圍內之蒸氣壓為5 kPa以上且20℃～25℃之範圍內之表面張力為25 mN/m以下者作為乾燥輔助物質，乾燥輔助物質於凝固體中昇華時，可減少該昇華不均勻地進行。其結果為可防止對圖案施加應力，較之先前之基板乾燥，可更確實地抑制基板上之圖案倒塌。 (第2實施形態) 以下說明本發明之第2實施形態。本實施形態與第1實施形態相比較於以下方面不同：於凝固步驟S14中，藉由氣體供給機構41進行氮氣供給，代替藉由冷媒供給機構81之冷水供給。藉由此種構成，亦可抑制圖案之倒塌並且良好地乾燥基板之表面。 ＜2-1 基板處理裝置之整體構成及乾燥輔助液＞ 第2實施形態之基板處理裝置及控制單元具有與第1實施形態之基板處理裝置1及控制單元13基本相同之構成(參照圖1及圖2)，故而其說明附記同一符號而省略。又，本實施形態中使用之乾燥輔助液亦與第1實施形態之乾燥輔助液相同，故而省略其說明。 ＜2-2 基板處理方法＞ 其次，對使用有與第1實施形態相同之構成之基板處理裝置1之第2實施形態之基板處理方法加以說明。 以下，適宜參照圖1、圖2、圖7及圖9說明基板處理之步驟。圖9係表示圖7之各步驟之基板W之情況之模式圖。再者，於第2實施形態中，圖6與圖9所示之(a)～(c)之清洗步驟S11、IPA沖洗步驟S12及乾燥輔助液供給步驟S13之各步驟與第1實施形態相同，故而省略說明。 此處，圖9所示之(a)係表示第2實施形態之清洗步驟S11之結束時點之表面Wf經DIW60之液膜覆蓋之基板W之情況，圖9所示之(b)係表示第2實施形態之IPA沖洗步驟S12之結束時點之表面Wf經IPA61之液膜覆蓋之基板W之情況，圖9所示之(c)係表示第2實施形態之乾燥輔助液供給步驟S13之結束時點之表面Wf經溶解有乾燥輔助物質之乾燥輔助液62之液膜覆蓋之基板W之情況。 又，圖9所示之(a)～(e)為止之各個步驟若無特別說明，則於大氣壓環境下處理。此處，所謂大氣壓環境係指以標準大氣壓(1個大氣壓，1013 hPa)為中心，0.7個大氣壓以上且1.3個大氣壓以下之環境。尤其，於基板處理裝置1配置於成為正壓之無塵室內之情形時，基板W之表面Wf之環境為高於1個大氣壓。又，圖9所示之(d)及(e)之各處理(下述詳細內容)係於17 Pa(17×10-5 個大氣壓)之減壓環境下進行。 參照圖7。實行清洗步驟S11、IPA沖洗步驟S12及乾燥輔助液供給步驟S13後，進行使供給至基板W之表面Wf之乾燥輔助液62之液膜凝固，形成含有乾燥輔助物質之凝固體的凝固步驟S14。具體而言，首先，控制單元13對旋轉驅動部52進行動作指令，使基板W繞軸A1以一定速度旋轉。此時，基板W之旋轉速度較佳為設定為包含乾燥輔助液之液膜之膜厚於表面Wf之整個面高於凸部Wp1之高度之程度。 繼而，控制單元13對迴轉驅動部14進行動作指令，將噴嘴42定位至基板W之表面Wf中央部。並且，控制單元13對閥門46進行動作指令，使閥門46開閥。藉此，將氣體(於本實施形態中，7℃之氮氣)自貯氣槽47經由配管45及噴嘴42向基板W之表面Wf供給。 向基板W之表面Wf供給之氮氣由於因基板W旋轉所產生之離心力，而自基板W之表面Wf中央附近向基板W之周緣部方向流動，擴散至由乾燥輔助液62覆蓋之基板W之表面Wf之整個面。藉此，形成於基板W之表面Wf之乾燥輔助液62之液膜冷卻至乾燥輔助物質之凝固點以下之低溫而凝固，形成凝固體。 圖9所示之(d)係表示凝固步驟S14之結束時點之基板W之情況。如圖9所示，於處理液供給步驟S13中供給之乾燥輔助液62藉由7℃之氮氣之供給而冷卻凝固，形成含有乾燥輔助物質之凝固體63。 返回至圖7。其次，進行使形成於基板W之表面Wf之凝固體63昇華，自基板W之表面Wf去除的昇華步驟S15。於昇華步驟S15中，亦承接凝固步驟S14繼續自噴嘴42供給氣體(氮氣)。 此處，氮氣中之乾燥輔助物質之蒸氣之分壓設定為低於該氮氣之供給溫度下之乾燥輔助物質之飽和蒸氣壓。因此，若將此種氮氣供給至基板W之表面Wf，與凝固體63接觸，則乾燥輔助物質自該凝固體63於氮氣中昇華。又，氮氣之溫度低於乾燥輔助物質之熔點，故而可防止凝固體63之融解並且進行凝固體63之昇華。 藉此，藉由固體狀態之乾燥輔助物質之昇華而去除於基板W之表面Wf上存在之IPA等物質時，可一面防止對圖案Wp作用表面張力而抑制圖案倒塌之產生，一面良好地乾燥基板W之表面Wf。 圖9所示之(e)係表示昇華步驟S15之結束時點之基板W之情況。如圖9所示，於凝固步驟S14中形成之乾燥輔助物質之凝固體63藉由7℃之氮氣之供給而昇華，從而自表面Wf去除，完成基板W之表面Wf之乾燥。 昇華步驟S15結束後，控制單元13對閥門46進行動作指令，使閥門46閉閥。又，控制單元13對迴轉驅動部14進行動作指令，將噴嘴42定位於退避位置P3。 藉由以上內容，結束一連串之基板乾燥處理。如上述之基板乾燥處理後，利用未圖示之基板搬入搬出機構而將乾燥處理完畢之基板W自腔室11搬出。 於本實施形態中，於凝固步驟S14與昇華步驟S15中，使用共通之氣體供給機構41，以乾燥輔助物質之凝固點以下之溫度，供給作為對乾燥輔助物質為惰性之惰性氣體之氮氣。藉此，凝固步驟S14後，可立即開始昇華步驟S15，可減少伴隨使基板處理裝置1之各部動作之處理時間或使其動作之控制單元13之基板處理程式19之記憶體量，又，亦可減少處理中所使用之零件數，故而存在可減少裝置成本之效果。尤其，於本實施形態中不使用減壓機構71，故而可省略減壓機構71。 (第3實施形態) 以下說明本發明之第3實施形態。本實施形態與第2實施形態相比較於以下方面不同：於凝固步驟S14及昇華步驟S15中，減壓腔室內部而代替氮氣之供給。藉由此種構成，亦可抑制圖案之倒塌，並且良好地乾燥基板W之表面。 ＜3-1 基板處理裝置之整體構成及乾燥輔助液＞ 第3實施形態之基板處理裝置及控制單元具有與第1實施形態之基板處理裝置1及控制單元13基本相同之構成(參照圖1及圖2)，其說明附記同一符號而省略。又，於本實施形態中使用之乾燥輔助液亦與第1實施形態之乾燥輔助液相同，故而省略其說明。 ＜3-2 基板處理方法＞ 其次，對使用有與第1實施形態相同構成之基板處理裝置1之第3實施形態之基板處理方法加以說明。 以下，適宜參照圖1、圖2、圖7及圖10說明基板處理之步驟。圖10係表示圖7之各步驟之基板W之情況之模式圖。再者，於第3實施形態中，圖7與圖10之(a)～(c)為止所示之清洗步驟S11、IPA沖洗步驟S12及處理液供給步驟S13之各步驟與第1實施形態相同，故而省略說明。 此處，圖10所示之(a)係表示第3實施形態之清洗步驟S11之結束時點之表面Wf經DIW60之液膜覆蓋之基板W之情況，圖10所示之(b)係表示第3實施形態之IPA沖洗步驟S12之結束時點之表面Wf經IPA61之液膜覆蓋之基板W之情況，圖10所示之(c)係表示第3實施形態之處理液供給步驟S13之結束時點表面Wf經溶解有乾燥輔助物質(昇華性物質)之乾燥輔助液62之液膜覆蓋之基板W之情況。 又，圖10所示之(a)～(e)為止之各個步驟只要無特別說明，則於大氣壓環境下進行處理。此處，所謂大氣壓環境係指以標準大氣壓(1個大氣壓，1013 hPa)為中心，0.7個大氣壓以上且1.3個大氣壓以下之環境。尤其，於基板處理裝置1配置於成為正壓之無塵室內之情形時，基板W之表面Wf之環境為高於1個大氣壓。又，圖10之(d)及(e)中圖示之處理(下述詳細內容)係於1.7 Pa(1.7×10-5 個大氣壓)之減壓環境下進行。 參照圖7。實行清洗步驟S11、IPA沖洗步驟S12及處理液供給步驟S13後，進行使供給至基板W之表面Wf之乾燥輔助液62之液膜凝固，形成含有乾燥輔助物質之凝固體的凝固步驟S14。具體而言，首先，控制單元13對旋轉驅動部52進行動作指令，使基板W繞軸A1以一定速度旋轉。此時，基板W之旋轉速度較佳為設定為包含乾燥輔助液之液膜之膜厚於表面Wf之整個面高於凸部Wp1之高度之程度。 繼而，控制單元13對排氣泵72進行動作指令，開始排氣泵72之驅動。並且控制單元13對閥門74進行動作指令，使閥門74開閥。藉此，將腔室11內部之氣體經由配管73排氣至腔室11外部。除配管73以外使腔室11內部成為密閉狀態，藉此將腔室11之內部環境自大氣壓減壓。 減壓係自大氣壓(約1個大氣壓，約1013 hPa)進行至1.7×10-5 個大氣壓(1.7 Pa)左右。再者，於本案發明之實施中，並不限定於該氣壓，減壓後之腔室11內之氣壓可根據腔室11等之耐壓性等而適宜設定。若腔室11內減壓，則發生供給至基板W之表面Wf之乾燥輔助液62之蒸發，藉由其氣化熱，乾燥輔助液62冷卻、凝固。 圖10所示之(d)係表示凝固步驟S14之結束時點之基板W之情況。如圖10所示，於處理液供給步驟S13中供給之乾燥輔助液62藉由因腔室11內之減壓而產生之乾燥輔助液62之蒸發而冷卻、凝固，形成乾燥輔助物質之凝固體63。 此時，凝固體63之層厚變薄，其程度相當於乾燥輔助液62蒸發之量。故而，本實施形態之處理液供給步驟S13中，較佳為以考慮凝固步驟S14中之乾燥輔助液62之蒸發量之基礎上，使乾燥輔助液62成為特定以上之厚度之液膜之方式，調整基板W之旋轉速度等。 返回至圖7。其次，進行使形成於基板W之表面Wf之凝固體63昇華，自基板W之表面Wf去除之昇華步驟S15。於昇華步驟S15中，亦承接凝固步驟S14繼續藉由減壓機構71之腔室11內之減壓處理。 藉由減壓處理，使腔室11內之環境成為低於乾燥輔助物質之飽和蒸氣壓之壓力。因此，若維持此種減壓環境，則產生乾燥輔助物質自凝固體63之昇華。 產生乾燥輔助物質自凝固體63之昇華時，亦自凝固體63被奪去作為昇華熱之熱，故而凝固體63冷卻。因此，於第3實施形態中，昇華步驟Sl5中，即便腔室11內之環境為稍高於乾燥輔助物質之熔點之溫度(常溫環境)之情形時，亦可不用另外冷卻凝固體63而將凝固體63維持為低於乾燥輔助物質之熔點之溫度之狀態，可防止凝固體63之融解並進行凝固體63之昇華。其結果為，無需另外設置冷卻機構，故而可減少裝置成本或處理成本。 如上所述，藉由固體狀態之乾燥輔助物質之昇華而去除於基板W之表面Wf上存在之IPA等物質時，可一面防止對圖案Wp作用表面張力而抑制圖案倒塌之產生，一面良好地乾燥基板W之表面Wf。 圖10所示之(e)係表示昇華步驟S15之結束時點之基板W之情況。如圖10所示，藉由使腔室11內成為減壓環境，於凝固步驟S14中形成之乾燥輔助物質之凝固體63昇華而自表面Wf去除，完成基板W之表面Wf之乾燥。 昇華步驟S15結束後，控制單元13對閥門74進行動作指令，使閥門74開閥。又，控制單元13對排氣泵72進行動作指令，使排氣泵72之動作停止。並且，控制單元13對閥門46進行動作指令，使閥門46開閥，藉此將氣體(氮氣)自貯氣槽47經由配管45及噴嘴42導入腔室11內，使腔室11內自減壓環境恢復至大氣壓環境。此時，噴嘴42可位於退避位置P3，亦可位於基板W之表面Wf中央部。 再者，昇華步驟S15結束後，作為使腔室11內恢復至大氣壓環境之方法，並不限定於上述，可採用各種公知之方法。 藉由以上內容，結束一連串之基板乾燥處理。如上述之基板乾燥處理後，藉由未圖示之基板搬入搬出機構而將乾燥處理完畢之基板W自腔室11搬出。 如以上所述，於本實施形態中，將融解乾燥輔助物質之乾燥輔助液供給至附著有IPA之基板W之表面Wf而置換IPA。其後，使乾燥輔助液於基板W之表面Wf凝固而形成乾燥輔助物質之凝固膜後，使乾燥輔助物質昇華，從而自基板W之表面Wf去除。藉此進行基板W之乾燥處理。 如本實施形態，藉由減壓而進行乾燥輔助液之凝固及昇華，亦可防止圖案之倒塌並進行基板W之良好之乾燥。關於具體之圖案抑制效果，於下述實施例中說明。 又，於本實施形態中，於凝固步驟S14與昇華步驟S15中，使用共通之減壓機構71減壓腔室11之內部。藉此，可於凝固步驟S14後立即開始昇華步驟S15，可減少伴隨使基板處理裝置1之各部動作之處理時間或使其動作之控制單元13之基板處理程式19之記憶體量。又，亦可減少處理中所使用之零件數，故而存在可減少裝置成本之效果。尤其，於第3實施形態中不使用低溫之氮氣，故而可省略氣體供給機構41中之溫度調整部272。又，於使腔室11內自減壓環境恢復至大氣壓環境時使用氣體供給機構41以外之機構之情形時，可省略氣體供給機構41。 (變化例) 於以上說明中，對本發明之較佳實施態樣進行了說明。然而，本發明並不限定於該等實施態樣，可以其他各種形態實施。以下例示其他之主要形態。 於第1實施形態及第2實施形態中，於1個腔室11內對基板W實行各步驟。然而，關於本發明之實施，並不限定於此，可分別對各步驟準備腔室。 例如，於各實施形態中，可至凝固步驟S14為止於第1腔室內實行，於基板W之表面Wf形成凝固膜後，將基板W自第1腔室搬出，將形成有凝固膜之基板W搬入另外之第2腔室，於第2腔室中進行昇華步驟S15。 又，於第1實施形態中，於昇華步驟S15中，一面持續藉由冷媒供給機構81之冷水供給，一面進行藉由氣體供給機構41之氮氣供給。然而，關於本發明之實施，並不限定於此，亦可停止藉由氣體供給機構41之氮氣供給，一面藉由冷媒供給機構81供給冷水一面使凝固體63之乾燥輔助物質自然昇華。 以下，以例示之方式詳細說明該發明之較佳實施例。其中，該實施例中記載之材料或調配量等，若無特別限定性之記載，則該發明之範圍並非僅限定於該等。 (基板) 作為基板，準備於表面形成有模型圖案之矽基板。圖11中表示顯示矽基板之形成有模型圖案之面之SEM(Scanning Electron Microscope，掃描電子顯微鏡)圖像。作為模型圖案，採用直徑30 nm、高480 nm之圓柱(縱橫比為16)隔開約80 nm之間隔而排列之圖案。圖11中，以白色表示之部分為圓柱部分(即圖案之凸部)之頭部，以黑色表示之部分為圖案之凹部。如圖11所示，確認於圖案形成面規則地排列幾乎相同大小之白圈。 (實施例1) 於本實施例中，依據下述順序進行上述矽基板之乾燥處理，評價圖案倒塌之抑制效果。又，於矽基板之處理中，使用第1實施形態中說明之基板處理裝置。 ＜順序1-1 紫外線光之照射＞ 首先，對矽基板之表面照射紫外線光，使其表面特性成為親水性。藉此，使液體容易進入圖案之凹部，供給該液體後，人工創造出易於產生圖案倒塌之環境。 ＜順序1-2 供給步驟＞ 其次，於處於大氣壓下之腔室11內，對乾燥之矽基板之圖案形成面直接供給昇華性物質融解而成之乾燥輔助液(液溫40℃)。藉此，於矽基板之圖案形成面上形成包含乾燥輔助液之液膜。作為昇華性物質，使用下述化學結構式所表示之1,1,2,2,3,3,4-七氟環戊烷。該化合物之表面張力於25℃之環境下為19.6 mN/m，蒸氣壓於20℃之環境下為8.2 kPa(62.0 mmHg)(均為文獻值，參照下述表1)。又，係熔點及凝固點為20.5℃，比重於25℃之環境下為1.58之物質。進而，作為該化合物，例如氟系聚合物之溶解性優異，因此用作各種塗佈劑之溶劑或油膜污垢之清洗劑。＜順序1-3 凝固步驟＞ 繼而，於大氣壓環境下，將7℃之氮氣供給至包含乾燥輔助液之液膜上，使該乾燥輔助液凝固而形成凝固體。 ＜順序1-4 昇華步驟＞ 進而，於常溫大氣壓環境下，繼續將7℃之氮氣持續供給至凝固體，藉此，防止凝固體之融解並使乾燥輔助物質(昇華性物質)昇華，將凝固體自矽基板之圖案形成面去除。再者，氮氣之溫度為7℃，為低於1,1,2,2,3,3,4-七氟環戊烷之熔點(20.5℃)之溫度，故而不對凝固體另外進行冷卻。 圖12係實行上述順序1-1至順序1-4後之矽基板之SEM圖像。與乾燥處理前之矽基板之圖案形成面(參照圖11)相比較，圖案之倒塌減少，顯示之區域之倒塌率為15.7%。由此表示於使用1,1,2,2,3,3,4-七氟環戊烷作為乾燥輔助物質之情形時，可極好地抑制圖案之倒塌，對昇華乾燥有效。 再者，上述倒塌率係藉由下式而算出之值。 倒塌率(%)＝(任意之區域之倒塌之凸部數)÷(該區域之凸部之總數)×100 (實施例2) 於本實施例中，作為乾燥輔助物質，使用十二氟環己烷(蒸氣壓為33.1 kPa(25℃)，表面張力為12.6 mN/m(25℃)，熔點及凝固點為51℃，均為文獻值)(參照下述表1)代替1,1,2,2,3,3,4-七氟環戊烷。除此以外以與實施例1相同之方式，實行順序1-1至順序1-4，進行矽基板之圖案形成面之冷凍乾燥。 圖13係於本實施例中實行順序1-1至順序1-4後之矽基板之SEM圖像。與乾燥處理前之矽基板之圖案形成面(參照圖11)相比較，圖案之倒塌大幅減少，顯示之區域之倒塌率為2.5%。由此顯示，於使用十二氟環己烷作為乾燥輔助物質之情形時，可極其良好地抑制圖案之倒塌，對昇華乾燥有效。 (比較例1) 於本比較例中，作為乾燥輔助物質，使用第三丁醇(蒸氣壓為4.1 kPa(20℃)，表面張力為19.56 mN/m(20℃)，熔點及凝固點為25℃，均為文獻值)(參照下述表1)代替1,1,2,2,3,3,4-七氟環戊烷。除此以外以與實施例1相同之方式，實行順序1-1至順序1-4，進行矽基板之圖案形成面之冷凍乾燥。 圖14係於本實施例中實行順序1-1至順序1-4後之矽基板之SEM圖像。與乾燥處理前之矽基板之圖案形成面(參照圖11)相比較，圖案之倒塌未減少，顯示之區域之倒塌率為52.3%。由此確認，於使用第三丁醇作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 (比較例2) 於本比較例中，作為乾燥輔助物質，使用乙酸(蒸氣壓為1.50 kPa(20℃)，表面張力為27.7 mN/m(20℃)，熔點及凝固點為17℃，均為文獻值)(參照下述表1)代替1,1,2,2,3,3,4-七氟環戊烷。除此以外以與實施例1相同之方式，實行順序1-1至順序1-4，進行矽基板之圖案形成面之冷凍乾燥。 圖15係於本實施例中實行順序1-1至順序1-4後之矽基板之SEM圖像。與乾燥處理前之矽基板之圖案形成面(參照圖11)相比較，產生大範圍之圖案倒塌，顯示之區域之倒塌率為99.1%。由此確認，於使用第三丁醇作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 (比較例3) 於本比較例中，作為乾燥輔助物質，使用1,4-二㗁烷(蒸氣壓為3.9 kPa(20℃)，表面張力為33.4 mN/m(25℃)，熔點及凝固點為11℃，均為文獻值)(參照下述表1)代替1,1,2,2,3,3,4-七氟環戊烷。除此以外以與實施例1相同之方式，實行順序1-1至順序1-4，進行矽基板之圖案形成面之冷凍乾燥。 圖16係於本實施例中實行順序1-1至順序1-4後之矽基板之SEM圖像。與乾燥處理前之矽基板之圖案形成面(參照圖11)相比較，產生大範圍之圖案倒塌，顯示之區域之倒塌率為99.3%。由此確認，於使用第三丁醇作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 (比較例4) 於本比較例中，作為乾燥輔助物質，使用4,4-二氟環己烷(蒸氣壓為0.37 kPa(25℃)，表面張力為29.2 mN/m(25℃)，熔點及凝固點為35～36℃，均為文獻值)(參照下述表1)代替1,1,2,2,3,3,4-七氟環戊烷。除此以外以與實施例1相同之方式，實行順序1-1至順序1-4，進行矽基板之圖案形成面之冷凍乾燥。 圖17係於本實施例中實行順序1-1至順序1-4後之矽基板之SEM圖像。與乾燥處理前之矽基板之圖案形成面(參照圖11)相比較，產生大範圍之圖案倒塌，顯示之區域之倒塌率為97.0%。由此確認，於使用第三丁醇作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 (比較例5) 於本比較例中，作為乾燥輔助物質，使用氟環己烷(蒸氣壓為5.67 kPa(25℃)，表面張力為21.8 mN/m(25℃)，熔點及凝固點為13℃，均為文獻值)(參照下述表1)代替1,1,2,2,3,3,4-七氟環戊烷。除此以外以與實施例1相同之方式，實行順序1-1至順序1-4，進行矽基板之圖案形成面之冷凍乾燥。 圖18係於本實施例中實行順序1-1至順序1-4後之矽基板之SEM圖像。與乾燥處理前之矽基板之圖案形成面(參照圖11)相比較，圖案之倒塌未減少，顯示之區域之倒塌率為35.8%。由此確認，於使用第三丁醇作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 [表1] (結果) 如圖12～圖18所示，確認於使用1,1,2,2,3,3,4-七氟環戊烷及十二氟環己烷作為乾燥輔助物質之實施例1及2之情形時，例如與使用先前之乾燥輔助物質之比較例1～5之情形相比較，可減少圖案倒塌之產生。 本發明可全面應用於將附著於基板表面之液體去除之乾燥技術、及使用該乾燥技術對基板表面進行處理之基板處理技術。(First Embodiment) A first embodiment of the present invention will be described below. FIG. 1 is an explanatory diagram showing the outline of a substrate processing apparatus 1 according to this embodiment. FIG. 2 is a schematic plan view showing the internal configuration of the substrate processing apparatus 1. In addition, in each figure, in order to clarify the direction relationship of the figure, it is suitable to display the XYZ orthogonal coordinates. In FIGS. 1 and 2, the XY plane indicates a horizontal plane, and the + Z direction indicates a vertical upward direction. The substrate processing apparatus 1 can be used for processing various substrates, for example. The above-mentioned "substrate" refers to a semiconductor substrate, a glass substrate for a photomask, a glass substrate for a liquid crystal display, a glass substrate for a plasma display, a substrate for FED (Field Emission Display), a substrate for an optical disk, a substrate for a magnetic disk, and a magneto-optical disk. Various substrates such as substrates. In this embodiment, a case where the substrate processing apparatus 1 is used for processing a semiconductor substrate (hereinafter referred to as "substrate W") will be described as an example. In addition, as the substrate W, a case where a circuit pattern or the like (hereinafter referred to as a "pattern") is formed on only one main surface is taken as an example. Here, a patterned surface (main surface) on which a pattern is formed is referred to as a "front surface", and a main surface that is not patterned on the opposite side is referred to as a "back surface". The surface of the substrate facing downward is referred to as a "lower surface", and the surface of the substrate facing upward is referred to as an "upper surface". The upper surface will be described below as the surface. The shape of the pattern is not particularly limited, and examples thereof include a linear shape and a cylindrical shape. The size of the pattern is not particularly limited, and can be arbitrarily set as appropriate. Furthermore, the material of the pattern is not particularly limited, and examples thereof include a metal and an insulating material. The substrate processing apparatus 1 is a single-piece substrate processing apparatus used for cleaning processing (including rinsing processing) and drying processing after cleaning to remove particles and other pollutants attached to the substrate W. It should be noted that only the parts used for the drying process are shown in FIGS. 1 and 2, and the nozzles and the like for cleaning processes are not shown. However, the substrate processing apparatus 1 may include the nozzles and the like. <1-1 Configuration of Substrate Processing Apparatus> First, the configuration of the substrate processing apparatus 1 will be described based on FIGS. 1 and 2. The substrate processing apparatus 1 includes at least a chamber 11 serving as a container for accommodating the substrate W, a substrate holding mechanism 51 that holds the substrate W, a control unit 13 that controls each part of the substrate processing apparatus 1, and supply of the substrate W held by the substrate holding mechanism 51. A processing liquid supply mechanism (supply mechanism) 21 as a drying auxiliary liquid for the processing liquid, an IPA supply mechanism 31 that supplies IPA (isopropyl alcohol) to the substrate W held by the substrate holding mechanism 51, and a substrate held by the substrate holding mechanism 51 A gas supply mechanism 41 (solidification mechanism, sublimation mechanism) that supplies gas, and a scattering prevention cup that traps IPA or drying auxiliary liquid supplied to the substrate W held by the substrate holding mechanism 51 and discharged to the outside of the peripheral portion of the substrate W. 12. Rotary drive unit 14 that separately rotates the following arms of each part of substrate processing apparatus 1; a decompression mechanism 71 that decompresses the inside of chamber 11; and a refrigerant supply mechanism that supplies refrigerant to the back surface Wb of substrate W (Coagulation mechanism, sublimation mechanism) 81. The substrate processing apparatus 1 includes a substrate loading and unloading mechanism, a chuck pin switching mechanism, and a wet cleaning mechanism (none of which is shown). Hereinafter, each part of the substrate processing apparatus 1 will be described. The substrate holding mechanism 51 includes a rotation driving section 52, a rotation base 53, and a chuck pin 54. The rotating base 53 has a planar size slightly larger than that of the substrate W. A plurality of chuck pins 54 holding the peripheral edge portion of the substrate W are erected near the peripheral edge portion of the rotating base 53. The number of the chuck pins 54 is not particularly limited, and it is preferable to provide at least three or more in order to reliably maintain the circular substrate W. In this embodiment, three are arranged at regular intervals along the peripheral portion of the rotating base 53 (see FIG. 2). Each chuck pin 54 includes a substrate support pin that supports the peripheral portion of the substrate W from below, and a substrate holding pin that holds the substrate W by pressing the outer peripheral end surface of the substrate W supported by the substrate support pin. Each chuck pin 54 can be switched between a pressing state where the substrate holding pin presses the outer peripheral end surface of the substrate W and a released state where the substrate holding pin is separated from the outer peripheral end surface of the substrate W, and is executed according to an operation instruction from the control unit 13 of the entire control device. State switching. More specifically, each chuck pin 54 is released when the rotary base 53 is carried in and out of the substrate W, and each chuck pin 54 is pressed when the substrate W is subjected to substrate processing from the cleaning process to the sublimation process described below. status. When the chuck pin 54 is in the pressed state, the chuck pin 54 holds the peripheral edge portion of the substrate W, and the substrate W is held in a horizontal state (XY plane) at a predetermined interval from the rotation base 53. Thereby, the substrate W is kept horizontal with the surface Wf thereof facing upward. As described above, in this embodiment, the substrate W is held by the rotating base 53 and the chuck pin 54, but the substrate holding method is not limited to this. For example, the back surface Wb of the substrate W may be held by an adsorption method such as a rotary chuck. The rotation base 53 is connected to a rotation driving portion 52. The rotation driving unit 52 is rotated around the axis A1 in the Z direction by an operation command from the control unit 13. The rotation driving unit 52 includes a known belt, a motor, and a rotation shaft. When the rotation driving part 52 rotates around the axis A1, the substrate W held by the chuck pin 54 above the rotation base 53 is rotated together with the rotation base 53 around the axis A1. Next, a processing liquid supply mechanism (supply mechanism) 21 will be described. The processing liquid supply mechanism 21 is a unit for supplying a drying auxiliary liquid to the pattern forming surface of the substrate W. As shown in FIG. 1, the processing liquid supply mechanism 21 includes at least a nozzle 22, an arm 23, a rotary shaft 24, a pipe 25, a valve 26, and a processing liquid storage unit 27 . As shown in FIG. 3A and FIG. 3B, the processing liquid storage unit 27 includes at least a processing liquid storage tank 271, a stirring unit 277 for agitating the drying auxiliary liquid in the processing liquid storage tank 271, and pressurizes the processing liquid storage tank 271 to be sent out for drying The auxiliary liquid pressurizing section 274 and the temperature of the drying auxiliary liquid (treatment liquid) in the heat treatment liquid storage tank 271 are adjusted by the temperature. 3A is a block diagram showing a schematic configuration of the processing liquid storage unit 27, and FIG. 3B is an explanatory diagram showing a specific configuration of the processing liquid storage unit 27. The stirring unit 277 includes a rotation unit 279 for stirring the drying auxiliary liquid in the processing liquid storage tank 271, and a stirring control unit 278 that controls the rotation of the rotation unit 279. The stirring control unit 278 is electrically connected to the control unit 13. The rotating portion 279 is provided with a propeller-shaped stirring blade at the front end of the rotating shaft (the lower end of the rotating portion 279 in FIG. 4). The control unit 13 instructs the stirring control portion 278 to operate, and the rotating portion 279 rotates, thereby stirring and drying the stirring blade. Liquid to make the concentration and temperature of the drying auxiliary substance in the drying auxiliary liquid uniform. A method for uniformizing the concentration and temperature of the drying auxiliary liquid in the processing liquid storage tank 271 is not limited to the above-mentioned method, and a known method such as a method of circulating a drying auxiliary liquid by separately providing a circulating pump may be used. The pressurizing section 274 includes a nitrogen tank 275 as a supply source of a gas for pressurizing the processing liquid storage tank 271, a pump 276 for pressurizing nitrogen, and a pipe 273. The nitrogen tank 275 is pipe-connected to the processing liquid storage tank 271 through a pipe 273, and a pump 276 is inserted into the pipe 273. The temperature adjustment section 272 is electrically connected to the control unit 13 and heats the drying auxiliary liquid stored in the processing liquid storage tank 271 by the operation instruction of the control unit 13 to perform temperature adjustment. The temperature adjustment may be such that the liquid temperature of the drying auxiliary liquid is equal to or higher than the melting point of the drying auxiliary substance (sublimable substance; details described below) contained in the drying auxiliary liquid. Thereby, the melting state of the drying auxiliary substance can be maintained. The upper limit of the temperature adjustment is preferably a temperature lower than the boiling point. The temperature adjustment unit 272 is not particularly limited, and for example, a known temperature adjustment mechanism such as a resistance heater, a Peltier element, or a pipe through which temperature-adjusted water is passed can be used. In addition, in this embodiment, the temperature adjustment part 272 is arbitrary structure. For example, when the installation environment of the substrate processing apparatus 1 is a high-temperature environment higher than the melting point of the sublimable substance, since the melting state of the sublimable substance can be maintained, it is not necessary to heat and dry the auxiliary liquid. As a result, the temperature adjustment unit 272 can be omitted. Return to Figure 1. The processing liquid storage unit 27 (more specifically, the processing liquid storage tank 271) is pipe-connected to the nozzle 22 via a pipe 25, and a valve 26 is inserted in the middle of the path of the pipe 25. An air pressure sensor (not shown) is provided in the processing liquid storage tank 271 and is electrically connected to the control unit 13. The control unit 13 controls the operation of the pump 276 based on the value detected by the air pressure sensor, and maintains the air pressure in the processing liquid storage tank 271 to a specific air pressure higher than the atmospheric pressure. On the other hand, the valve 26 is also electrically connected to the control unit 13 and is usually a closed valve. In addition, the switch of the valve 26 is also controlled by the operation command of the control unit 13. In addition, when the control unit 13 instructs the processing liquid supply mechanism 21 to open the valve 26, the drying auxiliary liquid is pressure-fed from the pressured processing liquid storage tank 271, and is discharged from the nozzle 22 through the pipe 25. Thereby, the drying auxiliary liquid can be supplied to the surface Wf of the substrate W. In addition, since the processing liquid storage tank 271 is a pressure-feeding drying auxiliary liquid using the pressure of nitrogen as described above, it is preferably a gas-tight structure. The nozzle 22 is mounted on the front end of the horizontally extending arm 23 and is disposed above the rotating base 53. The rear end of the support arm 23 is rotatably supported around the axis J1 by the rotation shaft 24 extending in the Z direction, and the rotation shaft 24 is fixedly disposed in the chamber 11. The arm 23 is connected to the rotation driving unit 14 via the rotation shaft 24. The swivel driving unit 14 is electrically connected to the control unit 13 and rotates the support arm 23 about the axis J1 by an operation instruction from the control unit 13. With the rotation of the arm 23, the nozzle 22 also moves. As shown by the solid line in FIG. 2, the nozzle 22 is generally located outside the peripheral edge portion of the substrate W, and is disposed at a retreat position P1 outside the scattering prevention cup 12. When the arm 23 is rotated by the operation command of the control unit 13, the nozzle 22 moves along the path of the arrow AR1 and is disposed above the central portion (the axis A1 or its vicinity) of the surface Wf of the substrate W. Return to Figure 1. Next, the IPA supply mechanism 31 will be described. The IPA supply mechanism 31 is a unit for supplying IPA to the substrate W, and includes a nozzle 32, a support arm 33, a rotary shaft 34, a pipe 35, a valve 36, and an IPA tank 37. The IPA tank 37 is pipe-connected to the nozzle 32 via a pipe 35, and a valve 36 is inserted in the middle of the path of the pipe 35. The IPA is stored in the IPA tank 37, and the IPA in the IPA tank 37 is pressurized by a pressurizing mechanism (not shown), and the IPA is sent from the pipe 35 to the direction of the nozzle 32. The valve 36 is electrically connected to the control unit 13 and is usually a closed valve. The opening relationship of the valve 36 is controlled by the operation command of the control unit 13. When the valve 36 is opened by the operation command of the control unit 13, the IPA is supplied from the nozzle 32 to the surface Wf of the substrate W through the pipe 35. The nozzle 32 is mounted on the front end of the horizontally extending arm 33 and is disposed above the rotating base 53. The rear end of the support arm 33 is rotatably supported around the axis J2 by a rotation shaft 34 extending in the Z direction. The rotation shaft 34 is fixedly disposed in the chamber 11. The arm 33 is connected to the rotation driving unit 14 via a rotation shaft 34. The swivel driving unit 14 is electrically connected to the control unit 13 and rotates the support arm 33 about the axis J2 by an operation command from the control unit 13. With the rotation of the arm 33, the nozzle 32 also moves. As shown by the solid line in FIG. 2, the nozzle 32 is generally located outside the peripheral edge portion of the substrate W, and is disposed at a retreat position P2 outside the scattering prevention cup 12. When the arm 33 is rotated by the operation command of the control unit 13, the nozzle 32 moves along the path of the arrow AR2 and is disposed above the central portion (the axis A1 or the vicinity thereof) of the surface Wf of the substrate W. Furthermore, in this embodiment, IPA is used in the IPA supply mechanism 31. However, in the present invention, the liquid is soluble in a drying auxiliary substance and deionized water (DIW: Deionized Water), and is not limited to IPA. As an alternative to the IPA of this embodiment, methanol, ethanol, acetone, benzene, carbon tetrachloride, chloroform, hexane, decahydronaphthalene, naphthalene, acetic acid, cyclohexanol, ether, or hydrofluoroether (Hydro Fluoro Ether). Return to Figure 1. Next, the gas supply mechanism 41 will be described. The gas supply mechanism 41 is a unit that supplies gas to the substrate W, and includes a nozzle 42, a support arm 43, a rotary shaft 44, a pipe 45, a valve 46, and an air storage tank 47. FIG. 4 is a block diagram showing a schematic configuration of the air storage tank 47. The gas storage tank 47 includes a gas storage unit 471 that stores gas, and a gas temperature adjustment unit 472 that adjusts the temperature of the gas stored in the gas storage unit 471. The gas temperature adjustment unit 472 is electrically connected to the control unit 13, and performs temperature adjustment by heating or cooling the gas stored in the gas storage unit 471 by an operation instruction of the control unit 13. The temperature may be adjusted so that the gas stored in the gas storage portion 471 becomes a lower temperature below the freezing point of the drying auxiliary substance. The gas temperature adjustment unit 472 is not particularly limited, and for example, a known temperature adjustment mechanism such as a Peltier element or a pipe through which temperature-adjusted water passes can be used. Return to Figure 1. The gas storage tank 47 (more specifically, the gas storage unit 471) is pipe-connected to the nozzle 42 through a pipe 45, and a valve 46 is inserted in the middle of the path of the pipe 45. The gas in the gas storage tank 47 is pressurized by a pressurizing mechanism (not shown) and sent to the pipe 45. In addition, the pressurizing mechanism can be realized by compressing and storing the gas in the gas storage tank 47 in addition to pressurizing by a pump or the like. Therefore, any pressurizing mechanism can be used. The valve 46 is electrically connected to the control unit 13 and is usually a closed valve. The opening relationship of the valve 46 is controlled by the operation command of the control unit 13. When the valve 46 is opened by the operation command of the control unit 13, the gas is supplied from the nozzle 42 to the surface Wf of the substrate W through the pipe 45. The nozzle 42 is mounted on the front end of the horizontally extending arm 43 and is disposed above the rotating base 53. The rear end of the support arm 43 is rotatably supported around the axis J3 by a rotation shaft 44 extending in the Z direction. The rotation shaft 44 is fixed in the chamber 11. The arm 43 is connected to the rotation driving unit 14 via the rotation shaft 44. The swivel driving unit 14 is electrically connected to the control unit 13 and rotates the support arm 43 about the axis J3 by an operation instruction from the control unit 13. As the arm 43 rotates, the nozzle 42 also moves. As shown by a solid line in FIG. 2, the nozzle 42 is generally located outside the peripheral edge portion of the substrate W, and is disposed at a retreat position P3 further outside than the scattering prevention cup 12. When the arm 43 is rotated by the operation command of the control unit 13, the nozzle 42 moves along the path of the arrow AR3 and is disposed above the central portion (the axis A1 or the vicinity thereof) of the surface Wf of the substrate W. The case where the nozzle 42 is arranged above the center of the surface Wf is shown by a dotted line in FIG. 2. The gas storage section 471 stores an inert gas that is at least inert to the drying auxiliary substance, and more specifically, nitrogen gas. The stored nitrogen gas is adjusted in the gas temperature adjustment unit 472 to a temperature below the freezing point of the drying auxiliary substance. The temperature of the nitrogen gas is not particularly limited as long as it is a temperature lower than the freezing point of the drying auxiliary substance, and it can be generally set within a range of 0 ° C to 15 ° C. Furthermore, by setting the temperature of the nitrogen gas to 0 ° C or higher, it is possible to prevent the water vapor existing inside the chamber 11 from solidifying and adhering to the surface Wf of the substrate W, thereby preventing adverse effects on the substrate W. The nitrogen gas used in the first embodiment is preferably a dry gas having a dew point of 0 ° C or lower. If the nitrogen gas is blown to the solidified body under an atmospheric pressure environment, the drying auxiliary substance in the solidified body is sublimated in the nitrogen gas. Since the nitrogen is continuously supplied to the solidified body, the partial pressure in the nitrogen of the dry auxiliary substance in the gas state generated by sublimation is maintained to be lower than the saturated vapor pressure of the dry auxiliary substance in the gas state at the temperature of the nitrogen gas. At least on the surface of the solidified body, the drying auxiliary substance in a gas state is filled in an environment existing below its saturated vapor pressure. In the present embodiment, nitrogen is used as the gas supplied by the gas supply mechanism 41. However, as an implementation of the present invention, the gas is not limited to this as long as it is inert to the drying auxiliary substance. In the first embodiment, examples of the substitute gas for nitrogen include argon, helium, and dry air (gases having a nitrogen concentration of 80% and an oxygen concentration of 20%). Alternatively, it may be a mixed gas obtained by mixing these plural kinds of gases. Return to Figure 1. The decompression mechanism 71 is a mechanism that decompresses the inside of the chamber 11 to an atmosphere lower than atmospheric pressure, and includes an exhaust pump 72, a pipe 73, and a valve 74. The exhaust pump 72 is pipe-connected to the chamber 11 via a pipe 73 and is a well-known pump that applies pressure to a gas. The exhaust pump 72 is electrically connected to the control unit 13 and is normally in a stopped state. The driving of the exhaust pump 72 is controlled by an operation command from the control unit 13. A valve 74 is inserted into the pipe 73. The valve 74 is electrically connected to the control unit 13 and is usually a closed valve. The opening relationship of the valve 74 is controlled by the operation command of the control unit 13. When the exhaust pump 72 is driven by the operation command of the control unit 13 and the valve 74 is opened, the gas existing inside the chamber 11 is exhausted to the outside of the chamber 11 through the pipe 73 by the exhaust pump 72. The scattering prevention cup 12 is provided so as to surround the rotation base 53. The scattering prevention cup 12 is connected to an elevation driving mechanism (not shown), and can be elevated in the Z direction. When the drying auxiliary liquid or IPA is supplied to the substrate W, the scattering prevention cup 12 is positioned to a specific position as shown in FIG. Thereby, a liquid such as a drying auxiliary liquid or IPA scattered from the substrate W or the rotating base 53 can be captured. Next, the refrigerant supply mechanism 81 will be described. The refrigerant supply mechanism 81 is a unit that supplies refrigerant to the back surface Wb of the substrate W. As shown in FIG. 1, the refrigerant supply mechanism 81 includes at least a refrigerant storage unit 82, a pipe 83, a valve 84, and a refrigerant supply pipe 85. FIG. 5 is a block diagram showing a schematic configuration of the refrigerant storage unit 82. As shown in FIG. The refrigerant storage unit 82 includes a refrigerant tank 821 that stores a refrigerant, and a refrigerant temperature adjustment unit 822 that adjusts the temperature of the refrigerant stored in the refrigerant tank 821. The refrigerant temperature adjusting section 822 is electrically connected to the control unit 13 and is a person who heats or cools the refrigerant stored in the refrigerant tank 821 to perform temperature adjustment according to the operation command of the control unit 13. The temperature adjustment may be performed so that the refrigerant stored in the refrigerant tank 821 becomes a lower temperature below the freezing point of the drying auxiliary substance. The refrigerant temperature adjustment unit 822 is not particularly limited. For example, a known temperature adjustment mechanism such as a cooler using a Peltier element or a pipe through which temperature-adjusted water passes can be used. Return to Figure 1. The refrigerant storage unit 82 is connected to the refrigerant supply pipe 85 via a pipe 83 in a pipeline, and a valve 84 is inserted in the middle of the route of the pipe 83. The refrigerant supply pipe 85 is provided by forming a through hole in the central portion of the rotating base 53. The refrigerant in the refrigerant storage unit 82 is pressurized by a pressurizing mechanism (not shown) and sent to the pipe 82. The pressurizing mechanism can be realized by compressing and storing the gas in the refrigerant storage unit 82 in addition to pressurization by a pump or the like, and thus any type of pressurizing mechanism can be used. The valve 84 is electrically connected to the control unit 13 and is usually a closed valve. The opening relationship of the valve 84 is controlled by the operation command of the control unit 13. When the valve 84 is opened by the operation command of the control unit 13, the refrigerant is supplied to the back surface Wb of the substrate W through the pipe 83 and the refrigerant supply pipe 85. Examples of the refrigerant include liquids or gases below the freezing point of the drying auxiliary substance. Furthermore, the liquid is not particularly limited, and examples thereof include cold water at 7 ° C. In addition, the gas is not particularly limited, and examples thereof include a gas inert to the drying auxiliary substance, and more specifically, nitrogen at 7 ° C. FIG. 6 is a schematic diagram showing the configuration of the control unit 13. The control unit 13 is electrically connected to each part of the substrate processing apparatus 1 (see FIG. 1), and controls operations of each part. The control unit 13 includes a computer including an arithmetic processing unit 15 and a memory 17. As the arithmetic processing unit 15, a CPU (Central Processing Unit) that performs various arithmetic processes is used. In addition, the memory 17 includes a ROM that is a dedicated memory for reading the basic program, a RAM that is a read-write memory that stores various kinds of information, and a magnetic disk that stores control software or data in advance. According to the substrate processing conditions (recipe) of the substrate W, it is stored in a magnetic disk in advance. The CPU reads the substrate processing conditions into the RAM, and according to the contents, the CPU controls each part of the substrate processing apparatus 1. <1-2 Drying auxiliary liquid> Next, the drying auxiliary liquid used in this embodiment will be described below. The drying auxiliary liquid in this embodiment is a processing liquid containing a drying auxiliary substance (sublimable substance) in a molten state, and performs a function of assisting the drying process in a drying process for removing a liquid existing on a pattern forming surface of a substrate. In addition, the sublimable substance has a characteristic that it does not change from a solid phase to a gas or from a gas phase to a solid without passing through a liquid. In addition, since the sublimable substance is contained in the drying auxiliary liquid in a molten state, a film-like solidified body having a uniform layer thickness can be formed on the substrate W. In this embodiment, the vapor pressure in the range of 20 ° C to 25 ° C of the sublimable substance is 5 kPa or more, preferably 8 kPa or more and 100 kPa or less, and more preferably 15 kPa or more and 100 kPa or less. The surface tension of the sublimable substance at 20 ° C to 25 ° C is 25 mN / m or less, preferably 20 mN / m or less, more preferably 0 mN / m to 15 mN / m or less, and further preferably 0 mN / m or more and 13 mN / m or less. By using a sublimable substance having a vapor pressure of 5 kPa or more and a surface tension of 25 mN / m or less, the sublimation progress of the sublimable substance in the solidified body can be suppressed from becoming uneven, thereby reducing pattern collapse. For example, for a pattern in which a plurality of cylinders (aspect ratio 16) with a diameter of 30 nm and a height of 480 nm are arranged on the substrate at an interval of 80 nm, the collapse rate of the pattern can be suppressed below 20%. The collapse rate of the pattern is a value calculated by the following formula. Pattern collapse rate (%) = (Number of collapsed convex parts in an arbitrary area) ÷ (Total number of convex parts in the area) × 100 In this embodiment, as a sublimable substance, for example, 1, 1,2,2,3,3,4-Heptafluorocyclopentane (Vapor pressure at 20 ° C is 8. 2 kPa, the surface tension at 25 ℃ is 19. 6 mN / m, melting point is 20. 5 ℃), dodecafluorocyclohexane (vapor pressure at 20 ℃ is 33. 1 kPa, the surface tension at 25 ℃ is 12. 6 mN / m (calculated value), melting point is 51 ° C) and the like. The vapor pressure of these sublimable substances is higher than the DIW as the previous drying auxiliary substance (the vapor pressure at 20 ° C is 2. 3 kPa) or tertiary butanol (vapor pressure at 20 ° C is 4. l kPa, the surface tension at 20 ℃ is 19. 56 mN / m, melting point is 25 ° C), so the sublimation step can be performed faster than the previous sublimation speed. In addition, these sublimable substances do not have OH groups, and because they are less soluble in water than third-butanol, they do not mix with the water remaining on the substrate W. As a result, moisture does not remain between the patterns after sublimation. The drying auxiliary liquid may include only a sublimable substance in a molten state, and may further contain an organic solvent. In this case, the content of the sublimable substance relative to the total mass of the drying auxiliary liquid is preferably 60% by mass or more, and more preferably 95% by mass or more. The organic solvent is not particularly limited as long as it is compatible with a sublimable substance in a molten state. Specific examples include alcohols. <1-3 Substrate Processing Method> Next, a substrate processing method using the substrate processing apparatus 1 according to this embodiment will be described below based on FIGS. 7 and 8. Fig. 7 is a flowchart showing the operation of the substrate processing apparatus 1 according to the first embodiment. FIG. 8 is a schematic view showing a state of the substrate W in each step of FIG. 7. In addition, the uneven pattern Wp is formed on the substrate W in the previous step. The pattern Wp includes a convex portion Wp1 and a concave portion Wp2. In this embodiment, the convex portion Wp1 has a height in a range of 100 to 600 nm, and a width in a range of 10 to 50 nm. The shortest distance between the two adjacent convex portions Wp1 (the shortest width of the concave portion Wp2) is in the range of 10 to 50 nm. The aspect ratio of the convex portion Wp1, that is, the value obtained by dividing the height by the width (height / width) is 10 to 20. Each step up to (a) to (e) shown in FIG. 8 is processed under an atmospheric pressure environment unless otherwise specified. Here, the so-called atmospheric pressure environment refers to a standard atmospheric pressure (1 atmosphere, 1013 hPa) as the center, 0. Above 7 atmospheres and 1. Under 3 atmospheres. In particular, when the substrate processing apparatus 1 is placed in a clean room under a positive pressure, the environment of the surface Wf of the substrate W is higher than 1 atmosphere. Refer to Figure 7. First, the substrate processing program 19 according to the specific substrate W is instructed to be executed by the operator. Thereafter, in preparation for carrying the substrate W into the substrate processing apparatus 1, the control unit 13 issues an operation command and performs the following operations. The rotation of the rotation driving section 52 is stopped, and the chuck pin 54 is positioned at a position suitable for the delivery of the substrate W. Further, the valves 26, 36, 46, and 74 are closed, and the nozzles 22, 32, and 42 are positioned at the retraction positions P1, P2, and P3, respectively. The chuck pin 54 is turned on by a switch mechanism (not shown). When the unprocessed substrate W is carried into the substrate processing apparatus 1 by a substrate carrying-in and carrying-out mechanism (not shown) and placed on the chuck pin 54, the chuck pin 54 becomes a switching mechanism (not shown). Closed state. After the unprocessed substrate W is held by the substrate holding mechanism 51, the substrate is cleaned in step S11 by a wet cleaning mechanism (not shown). The cleaning step S11 includes a rinsing process for removing the cleaning liquid after the cleaning liquid is supplied to the surface Wf of the substrate W for cleaning. The cleaning liquid (in the case of a rinsing process, the rinsing liquid) is supplied to the surface Wf of the substrate W that is rotated at a constant speed about the axis A1 by using the operation command of the control unit 13 to the rotation driving unit 52. The cleaning liquid is not particularly limited, and examples thereof include SC-1 (a liquid containing ammonia, hydrogen peroxide water, and water) or SC-2 (a liquid containing hydrochloric acid, hydrogen peroxide water, and water). The rinse solution is not particularly limited, and examples thereof include DIW. The supply amounts of the cleaning liquid and the rinsing liquid are not particularly limited, and can be appropriately set depending on the cleaning range and the like. The washing time is not particularly limited, and can be appropriately set as needed. Furthermore, in this embodiment, SC-1 is supplied to the surface Wf of the substrate W by a wet cleaning mechanism, and the surface Wf is cleaned. Then, DIW is supplied to the surface Wf to remove SC-1. (A) shown in FIG. 8 shows the state of the substrate W at the end of the cleaning step S11. As shown in FIG. 8, on the surface Wf of the substrate W on which the pattern Wp is formed, the DIW supplied in the cleaning step S11 is attached (illustrated by “60” in the figure). Return to FIG. 7. Next, an IPA rinsing step S12 in which IPA is supplied to the surface Wf of the substrate W to which the DIW 60 is attached is performed. First, the control unit 13 instructs the rotation driving unit 52 to rotate the substrate W at a constant speed around the axis A1. Next, the control unit 13 instructs the rotation drive unit 14 to position the nozzle 32 to the center portion of the surface Wf of the substrate W. In addition, the control unit 13 instructs the operation of the valve 36 to open the valve 36. Thereby, the IPA is supplied from the IPA tank 37 to the surface Wf of the substrate W through the pipe 35 and the nozzle 32. The IPA supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W to the peripheral portion of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the surface Wf of the substrate W. Thereby, the DIW attached to the surface Wf of the substrate W is removed by the supply of IPA, and the entire surface of the surface Wf of the substrate W is covered by the IPA. The rotation speed of the substrate W is preferably set so that the thickness of the film including the IPA is larger than the height of the convex portion Wp1 over the entire surface of the surface Wf. The supply amount of IPA is not particularly limited, and can be appropriately set. After the IPA flushing step S12 is completed, the control unit 13 instructs the operation of the valve 36 to close the valve 36. In addition, the control unit 13 instructs the rotation drive unit 14 to position the nozzle 32 at the retreat position P2. (B) shown in FIG. 8 shows the state of the substrate W at the end of the IPA washing step S12. As shown in FIG. 8, on the surface Wf of the substrate W on which the pattern Wp is formed, the IPA (illustrated by "61" in the figure) supplied in the IPA washing step S12 is attached. Wf removed. Return to FIG. 7. Next, a processing liquid supply step (supplying step) S13 of supplying a processing liquid containing a drying auxiliary liquid of a drying auxiliary substance in a melting state to the surface Wf of the substrate W to which the IPA61 is attached is performed. First, the control unit 13 instructs the rotation driving unit 52 to rotate the substrate W at a constant speed around the axis A1. At this time, the rotation speed of the substrate W is preferably set so that the film thickness of the liquid film containing the drying auxiliary liquid is larger than the height of the convex portion Wp1 over the entire surface of the surface Wf. Then, the control unit 13 instructs the rotation driving unit 14 to position the nozzle 22 to the center portion of the surface Wf of the substrate W. In addition, the control unit 13 instructs the operation of the valve 26 to open the valve 26. Thereby, the drying auxiliary liquid is supplied from the processing liquid storage tank 271 to the surface Wf of the substrate W through the pipe 25 and the nozzle 22. The liquid temperature of the supplied drying auxiliary liquid is set to a range that is at least the melting point of the drying auxiliary substance and lower than the boiling point after being supplied to the surface Wf of the substrate W. For example, the above 1,1,2,2,3,3,4-heptafluorocyclopentane (boiling point 82. 5 ° C) In the case of a drying auxiliary substance, it is preferably set to a range of 35 ° C or higher and 82 ° C or lower. The supply amount of the drying auxiliary liquid is not particularly limited, and can be appropriately set. In this way, by supplying the drying auxiliary liquid at a high temperature state above the melting point, a liquid film of the drying auxiliary liquid can be formed on the surface Wf of the substrate W to form a solidified body. As a result, a film-like solidified body having a uniform layer thickness can be obtained, and the occurrence of uneven drying can be reduced. In addition, when the temperature of the substrate W and the ambient temperature in the chamber 11 are below the melting point of the drying auxiliary substance, if a drying auxiliary liquid having a temperature slightly higher than the melting point is supplied to the substrate W, the drying auxiliary liquid contacts the substrate. After W solidifies in a very short time. In such a case, a solidified body having a uniform layer thickness cannot be formed, and it is difficult to reduce the uneven drying. Therefore, when the temperature of the substrate W and the ambient temperature in the chamber 11 are below the melting point of the drying auxiliary substance, it is preferable to adjust the liquid temperature of the drying auxiliary liquid to a temperature sufficiently higher than the melting point. Due to the centrifugal force generated by the rotation of the substrate W, the drying auxiliary liquid supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W to the peripheral portion of the substrate W and diffuses to the entire surface of the surface Wf of the substrate W. Thereby, the IPA adhering to the surface Wf of the substrate W is removed by the supply of the drying auxiliary liquid, and the entire surface of the surface Wf of the substrate W is covered with the drying auxiliary liquid. After the processing liquid supply step S13 ends, the control unit 13 instructs the operation of the valve 26 to close the valve 26. In addition, the control unit 13 instructs the rotation driving unit 14 to position the nozzle 22 at the retreat position P1. (C) shown in FIG. 8 shows the state of the substrate W at the end of the processing liquid supply step S13. As shown in FIG. 8, on the surface Wf of the substrate W on which the pattern Wp is formed, the drying auxiliary liquid (illustrated by “62” in the figure) supplied in the processing liquid supply step S13 is attached, and the IPA 61 is replaced with the drying auxiliary liquid 62. And it is removed from the surface Wf of the substrate W. Return to FIG. 7. Next, a coagulation step S14 is performed in which the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W is solidified to form a solidified film of the drying auxiliary substance. First, the control unit 13 instructs the rotation driving unit 52 to rotate the substrate W at a constant speed around the axis A1. At this time, the rotation speed of the substrate W is set to a speed at which the drying auxiliary liquid 62 can form a film thickness higher than a specific thickness of the convex portion Wpl on the entire surface of the surface Wf. Then, the control unit 13 instructs the operation of the valve 84 to open the valve 84. As a result, a refrigerant (in this embodiment, 7 ° C. cold water) is supplied from the refrigerant storage unit 82 to the back surface Wb of the substrate W through the pipe 83 and the refrigerant supply pipe 85. The cold water supplied to the back surface Wb of the substrate W flows from the vicinity of the center of the back surface Wb of the substrate W toward the peripheral portion of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and spreads over the entire surface of the back surface Wb of the substrate W. Thereby, the liquid film of the drying auxiliary liquid 62 formed on the surface Wf of the substrate W is cooled to a low temperature below the freezing point of the drying auxiliary substance and solidifies to form a solidified body. (D) shown in FIG. 8 shows the state of the substrate W at the end of the solidification step S14. As shown in FIG. 8, the drying auxiliary liquid 62 supplied in the processing liquid supply step S13 is cooled and solidified by supplying cold water (shown as “64” in the figure) at 7 ° C. on the back surface Wb of the substrate W to form a liquid containing Dry solidified solids ("63" in the figure). Return to FIG. 7. Next, a sublimation step S15 is performed in which the solidified body 63 formed on the surface Wf of the substrate W is sublimated and removed from the surface Wf of the substrate W. In the sublimation step S15, the cooling water is continuously supplied to the back surface Wb of the substrate W by the refrigerant supply mechanism 81. Thereby, the solidified body 63 can be cooled to a temperature below the freezing point of the drying auxiliary substance, and the drying auxiliary substance can be prevented from melting from the back surface Wb side of the substrate W. In the sublimation step S15, first, the control unit 13 instructs the rotation driving unit 52 to make the substrate W rotate at a constant speed around the axis A1. At this time, the rotation speed of the substrate W is set to a speed at which the drying auxiliary liquid 62 can form a film thickness higher than a specific thickness of the convex portion Wp1 on the entire surface of the surface Wf. Then, the control unit 13 instructs the rotation driving unit 14 to position the nozzle 42 to the center portion of the surface Wf of the substrate W. In addition, the control unit 13 instructs the operation of the valve 46 to open the valve 46. Thereby, a gas (in this embodiment, nitrogen at 7 ° C.) is supplied from the gas storage tank 47 to the surface Wf of the substrate W through the pipe 45 and the nozzle 42. Here, the partial pressure of the vapor of the drying auxiliary substance in nitrogen is set to be lower than the saturated vapor pressure of the drying auxiliary substance at the nitrogen supply temperature. Therefore, when such nitrogen gas is supplied to the surface Wf of the substrate W and comes into contact with the solidified body 63, the drying auxiliary substance is sublimated from the solidified body 63 in nitrogen gas. In addition, since the temperature of the nitrogen is lower than the melting point of the drying auxiliary substance, the solidified body 63 can be prevented from melting and the solidified body 63 can be sublimated. With this, when sublimation of the solid auxiliary drying substance removes IPA and other substances existing on the surface Wf of the substrate W, it is possible to prevent the pattern from collapsing while preventing the surface tension from acting on the pattern Wp, and to dry the substrate well The surface W of W. (E) shown in FIG. 8 shows the state of the substrate W at the end of the sublimation step S15. As shown in FIG. 8, the solidified body 63 of the drying auxiliary substance formed in the solidification step S14 is sublimated by the supply of nitrogen gas at 7 ° C., so as to be removed from the surface Wf, and the surface Wf of the substrate W is dried. After the sublimation step S15 is completed, the control unit 13 instructs the operation of the valve 46 to close the valve 46. In addition, the control unit 13 instructs the rotation driving unit 14 to position the nozzle 42 at the retreat position P3. With the above, a series of substrate drying processes are ended. After the substrate drying process is performed as described above, the substrate W after the drying process is carried out from the chamber 11 by a substrate carrying-in and carrying-out mechanism (not shown). As described above, in this embodiment, a drying auxiliary liquid containing a drying auxiliary substance in a melted state is supplied to the surface Wf of the substrate W to which the IPA is attached, and the drying auxiliary liquid is solidified on the surface Wf of the substrate W to form a dry solution. After the solidified body of the auxiliary substance is sublimated, the solidified body is removed from the surface Wf of the substrate W, so that the substrate W can be dried. Here, by using a vapor pressure in a range of 20 ° C to 25 ° C of 5 kPa or more and a surface tension in a range of 20 ° C to 25 ° C of 25 mN / m or less as a drying auxiliary substance, the drying auxiliary substance is allowed to solidify. During sublimation in the body, the unevenness of the sublimation can be reduced. As a result, stress can be prevented from being applied to the pattern, and the pattern on the substrate can be more reliably prevented from collapsing as compared with the case where the substrate is dried. (Second Embodiment) A second embodiment of the present invention will be described below. This embodiment is different from the first embodiment in the following points: In the solidification step S14, nitrogen gas is supplied by the gas supply mechanism 41 instead of the cold water supply by the refrigerant supply mechanism 81. With this configuration, it is possible to suppress the collapse of the pattern and dry the surface of the substrate well. <2-1 Overall configuration of substrate processing apparatus and drying auxiliary liquid> The substrate processing apparatus and control unit of the second embodiment have basically the same configuration as the substrate processing apparatus 1 and control unit 13 of the first embodiment (see FIG. 1 and FIG. FIG. 2), and therefore, the same symbols are attached to the descriptions and omitted. The drying auxiliary liquid used in this embodiment is also the same as the drying auxiliary liquid in the first embodiment, so its description is omitted. <2-2 Substrate Processing Method> Next, a substrate processing method of the second embodiment using the substrate processing apparatus 1 having the same configuration as the first embodiment will be described. Hereinafter, the steps of substrate processing will be described with reference to FIGS. 1, 2, 7 and 9 as appropriate. FIG. 9 is a schematic view showing a state of the substrate W in each step of FIG. 7. Moreover, in the second embodiment, the steps of the washing step S11, the IPA washing step S12, and the drying auxiliary liquid supply step S13 shown in (a) to (c) in Figs. 6 and 9 are the same as those in the first embodiment. , So the description is omitted. Here, (a) shown in FIG. 9 shows the case where the surface Wf at the end of the cleaning step S11 of the second embodiment is covered with the substrate W of the DIW60 liquid film, and (b) shown in FIG. 9 shows the first 2 In the case where the surface Wf at the end of the IPA washing step S12 of the embodiment is covered with the substrate W of the IPA61 liquid film, (c) in FIG. 9 shows the end of the drying auxiliary liquid supply step S13 in the second embodiment In the case where the surface Wf is covered by the substrate W with the liquid film of the drying auxiliary liquid 62 in which the drying auxiliary substance is dissolved. In addition, each step up to (a) to (e) shown in FIG. 9 is processed under an atmospheric pressure environment unless otherwise specified. Here, the so-called atmospheric pressure environment refers to a standard atmospheric pressure (1 atmosphere, 1013 hPa) as the center, 0. Above 7 atmospheres and 1. Under 3 atmospheres. In particular, when the substrate processing apparatus 1 is placed in a clean room under a positive pressure, the environment of the surface Wf of the substrate W is higher than 1 atmosphere. In addition, each of the processes (d) and (e) shown in FIG. 9 (the details below) is 17 Pa (17 × 10 -5 Atmospheres) under reduced pressure. Refer to Figure 7. After the cleaning step S11, the IPA rinsing step S12, and the drying auxiliary liquid supply step S13 are performed, the solidifying step S14 of solidifying the liquid containing the drying auxiliary substance to form a liquid film of the drying auxiliary liquid 62 supplied to the substrate W surface Wf is performed. Specifically, first, the control unit 13 instructs the rotation driving unit 52 to rotate the substrate W at a constant speed around the axis A1. At this time, the rotation speed of the substrate W is preferably set such that the thickness of the liquid film containing the drying auxiliary liquid is larger than the height of the convex portion Wp1 on the entire surface of the surface Wf. Then, the control unit 13 instructs the rotation driving unit 14 to position the nozzle 42 to the center portion of the surface Wf of the substrate W. In addition, the control unit 13 instructs the operation of the valve 46 to open the valve 46. Thereby, a gas (in this embodiment, nitrogen at 7 ° C.) is supplied from the gas storage tank 47 to the surface Wf of the substrate W through the pipe 45 and the nozzle 42. The nitrogen gas supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the surface of the substrate W covered by the drying auxiliary liquid 62. The whole face of Wf. Thereby, the liquid film of the drying auxiliary liquid 62 formed on the surface Wf of the substrate W is cooled to a low temperature below the freezing point of the drying auxiliary substance and solidifies to form a solidified body. (D) shown in FIG. 9 shows the state of the substrate W at the end of the solidification step S14. As shown in FIG. 9, the drying auxiliary liquid 62 supplied in the processing liquid supply step S13 is cooled and solidified by supplying a nitrogen gas at 7 ° C. to form a solidified body 63 containing a drying auxiliary substance. Return to FIG. 7. Next, a sublimation step S15 is performed in which the solidified body 63 formed on the surface Wf of the substrate W is sublimated and removed from the surface Wf of the substrate W. In the sublimation step S15, the coagulation step S14 is also continued to supply gas (nitrogen) from the nozzle 42. Here, the partial pressure of the vapor of the drying auxiliary substance in nitrogen is set to be lower than the saturated vapor pressure of the drying auxiliary substance at the nitrogen supply temperature. Therefore, when such nitrogen gas is supplied to the surface Wf of the substrate W and comes into contact with the solidified body 63, the drying auxiliary substance is sublimated from the solidified body 63 in nitrogen gas. In addition, since the temperature of the nitrogen is lower than the melting point of the drying auxiliary substance, the solidified body 63 can be prevented from melting and the solidified body 63 can be sublimated. With this, when sublimation of the solid auxiliary drying substance removes IPA and other substances existing on the surface Wf of the substrate W, it is possible to prevent the pattern from collapsing while preventing the surface tension from acting on the pattern Wp, and to dry the substrate well The surface W of W. (E) shown in FIG. 9 shows the state of the substrate W at the end of the sublimation step S15. As shown in FIG. 9, the solidified body 63 of the drying auxiliary substance formed in the solidifying step S14 is sublimated by the supply of nitrogen gas at 7 ° C., so as to be removed from the surface Wf, and the surface Wf of the substrate W is dried. After the sublimation step S15 is completed, the control unit 13 instructs the operation of the valve 46 to close the valve 46. In addition, the control unit 13 instructs the rotation driving unit 14 to position the nozzle 42 at the retreat position P3. With the above, a series of substrate drying processes are ended. After the substrate drying process is performed as described above, the substrate W after the drying process is carried out from the chamber 11 by a substrate carrying-in and carrying-out mechanism (not shown). In this embodiment, in the solidification step S14 and the sublimation step S15, a common gas supply mechanism 41 is used to supply nitrogen, which is an inert gas inert to the drying auxiliary substance, at a temperature below the freezing point of the drying auxiliary substance. Thereby, the sublimation step S15 can be started immediately after the coagulation step S14, which can reduce the processing time accompanying the operation of the various parts of the substrate processing apparatus 1 or the memory amount of the substrate processing program 19 of the control unit 13 that makes it operate. Since the number of parts used in processing can be reduced, there is an effect that the cost of the device can be reduced. In particular, since the pressure reducing mechanism 71 is not used in this embodiment, the pressure reducing mechanism 71 can be omitted. (Third Embodiment) A third embodiment of the present invention will be described below. This embodiment is different from the second embodiment in the following points: In the solidification step S14 and the sublimation step S15, the inside of the chamber is decompressed instead of supplying nitrogen. With this configuration, it is also possible to suppress the collapse of the pattern and dry the surface of the substrate W satisfactorily. <3-1 Overall structure of substrate processing apparatus and drying auxiliary liquid> The substrate processing apparatus and control unit of the third embodiment have basically the same configuration as the substrate processing apparatus 1 and control unit 13 of the first embodiment (see FIG. 1 and FIG. FIG. 2), the description is omitted by attaching the same reference numerals. The drying auxiliary liquid used in this embodiment is also the same as the drying auxiliary liquid in the first embodiment, and therefore description thereof is omitted. <3-2 Substrate Processing Method> Next, a substrate processing method of a third embodiment using a substrate processing apparatus 1 having the same configuration as the first embodiment will be described. Hereinafter, the steps of substrate processing will be described with reference to FIGS. 1, 2, 7 and 10 as appropriate. FIG. 10 is a schematic diagram showing a state of the substrate W in each step of FIG. 7. In the third embodiment, the steps of the cleaning step S11, the IPA rinse step S12, and the processing liquid supply step S13 shown in FIGS. 7 and 10 (a) to (c) are the same as those in the first embodiment. , So the description is omitted. Here, (a) shown in FIG. 10 shows the case where the surface Wf at the end of the cleaning step S11 of the third embodiment is covered with the substrate W of the liquid film of DIW60, and (b) shown in FIG. 10 shows the first 3 In the case where the surface Wf at the end of the IPA washing step S12 of the embodiment is covered by the liquid film of the IPA61 substrate W, (c) shown in FIG. 10 shows the surface at the end of the processing liquid supply step S13 of the third embodiment Wf In the case where the substrate W is covered by the liquid film of the drying auxiliary liquid 62 in which the drying auxiliary substance (sublimable substance) is dissolved. In addition, each step up to (a) to (e) shown in FIG. 10 is processed under an atmospheric pressure environment unless otherwise specified. Here, the atmospheric pressure environment refers to an environment with a standard atmospheric pressure (1 atmosphere, 1013 hPa) as the center, 0.7 atmospheres or more and 1.3 atmospheres or less. In particular, when the substrate processing apparatus 1 is placed in a clean room under a positive pressure, the environment of the surface Wf of the substrate W is higher than 1 atmosphere. The processing shown in (d) and (e) of Fig. 10 (the details below) is 1.7 Pa (1.7 × 10 -5 Atmospheres) under reduced pressure. Refer to Figure 7. After the cleaning step S11, the IPA rinsing step S12, and the processing liquid supply step S13 are performed, a coagulation step S14 is performed to solidify the liquid film of the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W to form a solidified body containing a drying auxiliary substance. Specifically, first, the control unit 13 instructs the rotation driving unit 52 to rotate the substrate W at a constant speed around the axis A1. At this time, the rotation speed of the substrate W is preferably set such that the thickness of the liquid film containing the drying auxiliary liquid is larger than the height of the convex portion Wp1 on the entire surface of the surface Wf. Then, the control unit 13 issues an operation command to the exhaust pump 72 and starts driving the exhaust pump 72. In addition, the control unit 13 instructs the operation of the valve 74 to open the valve 74. Thereby, the gas inside the chamber 11 is exhausted to the outside of the chamber 11 through the pipe 73. With the exception of the piping 73, the inside of the chamber 11 is hermetically closed, whereby the internal environment of the chamber 11 is decompressed from atmospheric pressure. Decompression is from atmospheric pressure (about 1 atmosphere, about 1013 hPa) to 1.7 × 10 -5 Around atmospheric pressure (1.7 Pa). Furthermore, in the implementation of the present invention, the pressure is not limited to this pressure, and the pressure in the chamber 11 after the decompression can be appropriately set according to the pressure resistance of the chamber 11 and the like. When the pressure in the chamber 11 is reduced, evaporation of the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W occurs, and the drying auxiliary liquid 62 is cooled and solidified by the heat of vaporization. (D) shown in FIG. 10 shows the state of the substrate W at the end of the solidification step S14. As shown in FIG. 10, the drying auxiliary liquid 62 supplied in the processing liquid supply step S13 is cooled and solidified by evaporation of the drying auxiliary liquid 62 generated by the decompression in the chamber 11 to form a solidified body of the drying auxiliary material. 63. At this time, the layer thickness of the solidified body 63 becomes thinner to the extent that the drying auxiliary liquid 62 is evaporated. Therefore, in the processing liquid supply step S13 of this embodiment, it is preferable to take the evaporation amount of the drying auxiliary liquid 62 in the coagulation step S14 into consideration, so that the drying auxiliary liquid 62 becomes a liquid film having a specific thickness or more. The rotation speed of the substrate W is adjusted. Return to FIG. 7. Next, a sublimation step S15 is performed in which the solidified body 63 formed on the surface Wf of the substrate W is sublimated and removed from the surface Wf of the substrate W. In the sublimation step S15, the solidification step S14 is also performed to continue the pressure reduction treatment in the chamber 11 of the pressure reduction mechanism 71. By the decompression treatment, the environment in the chamber 11 becomes a pressure lower than the saturated vapor pressure of the drying auxiliary substance. Therefore, if such a reduced pressure environment is maintained, sublimation of the drying auxiliary substance from the solidified body 63 occurs. When the sublimation of the drying auxiliary substance from the solidified body 63 occurs, the solidified body 63 is also taken away as heat of the sublimation heat, so the solidified body 63 is cooled. Therefore, in the third embodiment, in the sublimation step S15, even when the environment in the chamber 11 is a temperature slightly higher than the melting point of the drying auxiliary substance (normal temperature environment), the solidified body 63 can be cooled without separately cooling. The solidified body 63 is maintained at a temperature lower than the melting point of the drying auxiliary substance, and it is possible to prevent the solidified body 63 from melting and sublimation of the solidified body 63. As a result, it is not necessary to provide a separate cooling mechanism, so that it is possible to reduce the equipment cost or the processing cost. As described above, when a substance such as IPA existing on the surface Wf of the substrate W is removed by sublimation of the drying auxiliary substance in a solid state, the surface can be prevented from acting on the pattern Wp and the pattern collapse can be prevented, and the pattern can be dried well. The surface Wf of the substrate W. (E) shown in FIG. 10 shows the state of the substrate W at the end of the sublimation step S15. As shown in FIG. 10, by making the inside of the chamber 11 into a reduced pressure environment, the solidified body 63 of the drying auxiliary substance formed in the solidification step S14 is sublimated and removed from the surface Wf, thereby completing the drying of the surface Wf of the substrate W. After the sublimation step S15 is ended, the control unit 13 instructs the operation of the valve 74 to open the valve 74. In addition, the control unit 13 instructs an operation of the exhaust pump 72 to stop the operation of the exhaust pump 72. In addition, the control unit 13 instructs the operation of the valve 46 to open the valve 46, thereby introducing gas (nitrogen) from the gas storage tank 47 into the chamber 11 through the piping 45 and the nozzle 42, and the pressure in the chamber 11 is reduced. The environment returns to atmospheric pressure. At this time, the nozzle 42 may be located at the retreat position P3, or may be located at the center portion of the surface Wf of the substrate W. In addition, after the sublimation step S15 is completed, the method for returning the atmosphere in the chamber 11 to the atmospheric pressure environment is not limited to the above, and various known methods may be adopted. With the above, a series of substrate drying processes are ended. After the substrate drying process as described above, the substrate W after the drying process is carried out from the chamber 11 by a substrate carrying-in and carrying-out mechanism (not shown). As described above, in this embodiment, a drying auxiliary liquid that melts the drying auxiliary substance is supplied to the surface Wf of the substrate W to which the IPA is attached to replace the IPA. Thereafter, the drying auxiliary liquid is solidified on the surface Wf of the substrate W to form a solidified film of the drying auxiliary material, and the drying auxiliary material is sublimated to be removed from the surface Wf of the substrate W. Thereby, the substrate W is dried. As in the present embodiment, coagulation and sublimation of the drying auxiliary liquid can be performed under reduced pressure, and it is also possible to prevent the pattern from collapsing and perform good drying of the substrate W. The specific pattern suppressing effect will be described in the following examples. In the present embodiment, in the solidification step S14 and the sublimation step S15, the inside of the chamber 11 is decompressed by using a common decompression mechanism 71. Thereby, the sublimation step S15 can be started immediately after the solidification step S14, and the processing time accompanying the operation of each part of the substrate processing apparatus 1 or the memory amount of the substrate processing program 19 of the control unit 13 that operates can be reduced. In addition, the number of parts used in the process can be reduced, so there is an effect that the cost of the device can be reduced. In particular, since the low-temperature nitrogen is not used in the third embodiment, the temperature adjustment section 272 in the gas supply mechanism 41 can be omitted. Further, when a mechanism other than the gas supply mechanism 41 is used when the chamber 11 is restored from the reduced-pressure environment to the atmospheric pressure environment, the gas supply mechanism 41 may be omitted. (Modifications) In the above description, preferred embodiments of the present invention have been described. However, the present invention is not limited to these embodiments, and can be implemented in various other forms. The other main forms are exemplified below. In the first embodiment and the second embodiment, each step is performed on the substrate W in one chamber 11. However, the implementation of the present invention is not limited to this, and a chamber may be prepared for each step. For example, in each embodiment, it can be performed in the first chamber until the solidification step S14. After forming a solidified film on the surface Wf of the substrate W, the substrate W is carried out from the first chamber, and the substrate W on which the solidified film is formed The second chamber is carried into another sublimation step S15 in the second chamber. Further, in the first embodiment, in the sublimation step S15, the supply of nitrogen gas by the gas supply mechanism 41 is performed while the cold water supply by the refrigerant supply mechanism 81 is continued. However, the implementation of the present invention is not limited to this. The nitrogen supply by the gas supply mechanism 41 may be stopped, and the cold auxiliary water of the solidified body 63 may be sublimated while the cold water is supplied by the refrigerant supply mechanism 81. Hereinafter, preferred embodiments of the present invention will be described in detail by way of illustration. It should be noted that the scope of the invention is not limited to the materials or the blending amounts described in this embodiment unless there is any particular limitation. (Substrate) As a substrate, a silicon substrate having a pattern formed on the surface was prepared. FIG. 11 shows a SEM (Scanning Electron Microscope) image of a surface of a silicon substrate on which a pattern is formed. As a model pattern, a cylinder having a diameter of 30 nm and a height of 480 nm (aspect ratio of 16) was arranged at intervals of about 80 nm. In FIG. 11, the part shown in white is the head of the cylindrical part (ie, the convex part of the pattern), and the part shown in black is the concave part of the pattern. As shown in FIG. 11, it is confirmed that white circles having almost the same size are regularly arranged on the pattern forming surface. (Example 1) In this example, the above-mentioned drying process of the silicon substrate was performed in the following order to evaluate the effect of suppressing pattern collapse. In the processing of the silicon substrate, the substrate processing apparatus described in the first embodiment is used. <Procedure 1-1 Irradiation of Ultraviolet Light> First, the surface of the silicon substrate is irradiated with ultraviolet light to make its surface characteristics hydrophilic. Thereby, the liquid can easily enter the concave portion of the pattern, and after the liquid is supplied, an environment prone to collapse of the pattern is manually created. <Procedure 1-2 Supply Step> Next, in the chamber 11 at atmospheric pressure, a drying auxiliary liquid (liquid temperature 40 ° C.) obtained by melting a sublimable substance is directly supplied to the pattern forming surface of the dried silicon substrate. Thereby, a liquid film containing a drying auxiliary liquid is formed on the pattern forming surface of the silicon substrate. As a sublimable substance, 1,1,2,2,3,3,4-heptafluorocyclopentane represented by the following chemical structural formula was used. The surface tension of this compound is 19.6 mN / m under the environment of 25 ° C, and 8.2 kPa (62.0 mmHg) under the environment of vapor pressure of 20 ° C (both literature values, see Table 1 below). In addition, it is a substance having a melting point and a freezing point of 20.5 ° C and a specific gravity of 1.58 under an environment of 25 ° C. Furthermore, since this compound has excellent solubility, for example, a fluorine-based polymer, it is used as a solvent for various coating agents or as a cleaning agent for oil film stains. <Sequence 1-3 coagulation step> Next, a nitrogen gas at 7 ° C. was supplied to a liquid film containing a drying auxiliary liquid under an atmospheric pressure environment, and the drying auxiliary liquid was solidified to form a solidified body. <Sequence 1-4 Sublimation Step> Further, under normal temperature and atmospheric pressure environment, continuously supplying nitrogen at 7 ° C to the solidified body, thereby preventing the solidified body from melting and sublimating the drying auxiliary substance (sublimable substance), and solidifying. The body is removed from the patterning surface of the silicon substrate. Furthermore, the temperature of the nitrogen gas was 7 ° C, which was lower than the melting point (20.5 ° C) of 1,1,2,2,3,3,4-heptafluorocyclopentane. Therefore, the solidified body was not cooled separately. FIG. 12 is a SEM image of the silicon substrate after performing the above-mentioned procedures 1-1 to 1-4. Compared with the pattern formation surface (see FIG. 11) of the silicon substrate before the drying process, the collapse of the pattern is reduced, and the collapse rate of the displayed area is 15.7%. This shows that when 1,1,2,2,3,3,4-heptafluorocyclopentane is used as a drying auxiliary substance, the collapse of the pattern can be suppressed extremely well, and it is effective for sublimation drying. The collapse rate is a value calculated by the following formula. Collapse rate (%) = (Number of collapsed protrusions in an arbitrary area) ÷ (Total number of protrusions in the area) × 100 (Example 2) In this example, a twelve fluorine ring was used as a drying auxiliary substance. Hexane (vapor pressure is 33.1 kPa (25 ° C), surface tension is 12.6 mN / m (25 ° C), melting point and freezing point are 51 ° C, both of which are literature values) (see Table 1 below) instead of 1,1,2 , 2,3,3,4-Heptafluorocyclopentane. Except for this, in the same manner as in Example 1, the procedures 1-1 to 1-4 were performed, and the pattern forming surface of the silicon substrate was freeze-dried. FIG. 13 is an SEM image of the silicon substrate after performing the order 1-1 to 1-4 in this embodiment. Compared with the pattern formation surface (see FIG. 11) of the silicon substrate before the drying process, the collapse of the pattern is greatly reduced, and the collapse rate of the displayed area is 2.5%. This shows that when dodecafluorocyclohexane is used as the drying auxiliary substance, the collapse of the pattern can be suppressed very well, and it is effective for sublimation drying. (Comparative example 1) In this comparative example, as a drying auxiliary substance, a third butanol (a vapor pressure of 4.1 kPa (20 ° C), a surface tension of 19.56 mN / m (20 ° C), and a melting point and a freezing point of 25 ° C were used. (Both are literature values) (see Table 1 below) instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Except for this, in the same manner as in Example 1, the procedures 1-1 to 1-4 were performed, and the pattern forming surface of the silicon substrate was freeze-dried. FIG. 14 is a SEM image of the silicon substrate after performing the order 1-1 to 1-4 in this embodiment. Compared with the pattern formation surface (see FIG. 11) of the silicon substrate before the drying process, the pattern collapse did not decrease, and the collapse rate of the displayed area was 52.3%. From this, it was confirmed that when tertiary butanol was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient. (Comparative example 2) In this comparative example, acetic acid (a vapor pressure of 1.50 kPa (20 ° C), a surface tension of 27.7 mN / m (20 ° C), and a melting point and a freezing point of 17 ° C were used as a drying auxiliary substance. Literature value) (refer to Table 1 below) instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Except for this, in the same manner as in Example 1, the procedures 1-1 to 1-4 were performed, and the pattern forming surface of the silicon substrate was freeze-dried. FIG. 15 is a SEM image of the silicon substrate after performing the order 1-1 to 1-4 in this embodiment. Compared with the pattern formation surface (see FIG. 11) of the silicon substrate before the drying process, a large range of pattern collapse occurred, and the collapse rate of the displayed area was 99.1%. From this, it was confirmed that when tertiary butanol was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient. (Comparative example 3) In this comparative example, 1,4-dioxane (a vapor pressure of 3.9 kPa (20 ° C), a surface tension of 33.4 mN / m (25 ° C), a melting point and a freezing point were used as a drying auxiliary substance. (At 11 ° C, all literature values) (see Table 1 below) instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Except for this, in the same manner as in Example 1, the procedures 1-1 to 1-4 were performed, and the pattern forming surface of the silicon substrate was freeze-dried. FIG. 16 is an SEM image of the silicon substrate after performing the order 1-1 to 1-4 in this embodiment. Compared with the pattern formation surface (see FIG. 11) of the silicon substrate before the drying process, a large range of pattern collapse occurred, and the collapse rate of the displayed area was 99.3%. From this, it was confirmed that when tertiary butanol was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient. (Comparative example 4) In this comparative example, 4,4-difluorocyclohexane (a vapor pressure of 0.37 kPa (25 ° C), a surface tension of 29.2 mN / m (25 ° C), and a melting point were used as a drying auxiliary substance. And the freezing point is 35 to 36 ° C, both of which are literature values) (see Table 1 below) instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Except for this, in the same manner as in Example 1, the procedures 1-1 to 1-4 were performed, and the pattern forming surface of the silicon substrate was freeze-dried. FIG. 17 is a SEM image of the silicon substrate after performing the order 1-1 to 1-4 in this embodiment. Compared with the pattern formation surface (see FIG. 11) of the silicon substrate before the drying process, the pattern collapse occurred in a wide range, and the collapse rate of the displayed area was 97.0%. From this, it was confirmed that when tertiary butanol was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient. (Comparative example 5) In this comparative example, fluorocyclohexane (a vapor pressure of 5.67 kPa (25 ° C), a surface tension of 21.8 mN / m (25 ° C), and a melting point and a freezing point of 13 ° C) were used as a drying auxiliary substance. (Both are literature values) (see Table 1 below) instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Except for this, in the same manner as in Example 1, the procedures 1-1 to 1-4 were performed, and the pattern forming surface of the silicon substrate was freeze-dried. FIG. 18 is a SEM image of the silicon substrate after performing the order 1-1 to 1-4 in this embodiment. Compared with the pattern formation surface (see FIG. 11) of the silicon substrate before the drying process, the collapse of the pattern was not reduced, and the collapse rate of the displayed area was 35.8%. From this, it was confirmed that when tertiary butanol was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient. [Table 1] (Results) As shown in FIG. 12 to FIG. 18, it was confirmed that Examples 1 and 1 using 1,1,2,2,3,3,4-heptafluorocyclopentane and dodecafluorocyclohexane as drying aid In the case of 2, it is possible to reduce the occurrence of pattern collapse compared to the case of Comparative Examples 1 to 5 using the previous drying auxiliary substance. The present invention can be comprehensively applied to a drying technology for removing a liquid adhered to a substrate surface, and a substrate processing technology for processing a substrate surface using the drying technology.

1‧‧‧基板處理裝置1‧‧‧ substrate processing device

11‧‧‧腔室11‧‧‧ chamber

12‧‧‧飛散防止杯12‧‧‧Scatter Prevention Cup

13‧‧‧控制單元13‧‧‧Control unit

14‧‧‧迴轉驅動部14‧‧‧Slewing drive unit

15‧‧‧運算處理部15‧‧‧ Operation Processing Department

17‧‧‧記憶體17‧‧‧Memory

19‧‧‧基板處理程式19‧‧‧ substrate processing program

21‧‧‧處理液供給機構21‧‧‧ treatment liquid supply mechanism

22‧‧‧噴嘴22‧‧‧Nozzle

23‧‧‧支臂23‧‧‧arm

24‧‧‧迴轉軸24‧‧‧Rotary shaft

25‧‧‧配管25‧‧‧Piping

26‧‧‧閥門26‧‧‧ Valve

27‧‧‧處理液貯存部27‧‧‧Treatment liquid storage section

31‧‧‧IPA供給機構31‧‧‧IPA supply agency

32‧‧‧噴嘴32‧‧‧ Nozzle

33‧‧‧支臂33‧‧‧arm

34‧‧‧迴轉軸34‧‧‧Rotary shaft

35‧‧‧配管35‧‧‧Piping

36‧‧‧閥門36‧‧‧ Valve

37‧‧‧IPA槽37‧‧‧IPA slot

41‧‧‧氣體供給機構41‧‧‧Gas supply mechanism

42‧‧‧噴嘴42‧‧‧Nozzle

43‧‧‧支臂43‧‧‧arm

44‧‧‧迴轉軸44‧‧‧Rotary shaft

45‧‧‧配管45‧‧‧Piping

46‧‧‧閥門46‧‧‧ Valve

47‧‧‧貯氣槽47‧‧‧air tank

51‧‧‧基板保持機構51‧‧‧ substrate holding mechanism

52‧‧‧旋轉驅動部52‧‧‧Rotary drive unit

53‧‧‧旋轉基底53‧‧‧ rotating base

54‧‧‧夾盤銷54‧‧‧ chuck pin

60‧‧‧DIW60‧‧‧DIW

61‧‧‧IPA61‧‧‧IPA

62‧‧‧乾燥輔助液62‧‧‧Drying auxiliary liquid

63‧‧‧凝固體63‧‧‧solidified body

64‧‧‧冷水64‧‧‧ cold water

71‧‧‧減壓機構71‧‧‧ Decompression mechanism

72‧‧‧排氣泵72‧‧‧Exhaust Pump

73‧‧‧配管73‧‧‧Piping

74‧‧‧閥門74‧‧‧ Valve

81‧‧‧冷媒供給機構81‧‧‧Refrigerant Supply Agency

82‧‧‧冷媒貯存部82‧‧‧Refrigerant Storage Department

83‧‧‧配管83‧‧‧Piping

84‧‧‧閥門84‧‧‧ Valve

85‧‧‧冷媒供給管85‧‧‧Refrigerant supply pipe

271‧‧‧處理液貯存槽271‧‧‧Treatment liquid storage tank

272‧‧‧溫度調整部272‧‧‧Temperature Adjustment Department

273‧‧‧配管273‧‧‧Piping

274‧‧‧加壓部274‧‧‧Pressure section

275‧‧‧氮氣槽275‧‧‧nitrogen tank

276‧‧‧泵276‧‧‧Pump

277‧‧‧攪拌部277‧‧‧mixing section

278‧‧‧攪拌控制部278‧‧‧Mixing Control Department

279‧‧‧旋轉部279‧‧‧Rotating part

471‧‧‧氣體貯存部471‧‧‧Gas storage department

472‧‧‧氣體溫度調整部472‧‧‧Gas temperature adjustment section

821‧‧‧冷媒槽821‧‧‧Refrigerant tank

822‧‧‧冷媒溫度調整部822‧‧‧Refrigerant temperature adjustment section

A1‧‧‧軸A1‧‧‧axis

AR1‧‧‧箭頭AR1‧‧‧Arrow

AR2‧‧‧箭頭AR2‧‧‧Arrow

AR3‧‧‧箭頭AR3‧‧‧Arrow

J1‧‧‧軸J1‧‧‧axis

J2‧‧‧軸J2‧‧‧axis

J3‧‧‧軸J3‧‧‧axis

P1‧‧‧退避位置P1‧‧‧Retreat position

P2‧‧‧退避位置P2‧‧‧Retreat position

P3‧‧‧退避位置P3‧‧‧Retreat position

W‧‧‧基板W‧‧‧ substrate

Wb‧‧‧背面Wb‧‧‧ back

Wf‧‧‧表面Wf‧‧‧ surface

Wp‧‧‧圖案Wp‧‧‧ pattern

Wp1‧‧‧凸部Wp1‧‧‧ convex

Wp2‧‧‧凹部Wp2‧‧‧ Recess

X‧‧‧方向X‧‧‧ direction

Y‧‧‧方向Y‧‧‧ direction

Z‧‧‧方向Z‧‧‧ direction

圖1係表示本發明之第1實施形態之基板處理裝置之概略之說明圖。 圖2係表示上述基板處理裝置之概略平面圖。 圖3A係表示上述基板處理裝置之乾燥輔助液貯存部之概略構成之方塊圖。 圖3B係表示該乾燥輔助液貯存部之具體構成之說明圖。 圖4係表示上述基板處理裝置之貯氣槽之概略構成之方塊圖。 圖5係表示上述基板處理裝置之冷媒貯存部之概略構成之方塊圖。 圖6係表示上述基板處理裝置之控制單元之概略構成之說明圖。 圖7係表示使用上述基板處理裝置之基板處理方法之流程圖。 圖8(a)～(e)係表示上述基板處理方法之各步驟之基板之情況之圖。 圖9(a)～(e)係表示本發明之第2實施形態之基板處理方法之流程圖。 圖10(a)～(e)係表示本發明之第3實施形態之基板處理方法之流程圖。 圖11係表示本發明之實施例及比較例中使用之未處理之矽基板之圖案形成面之SEM圖像。 圖12係表示實施有本發明之實施例1之基板處理之矽基板之圖案形成面之SEM圖像。 圖13係表示實施有本發明之實施例2之基板處理之矽基板之圖案形成面之SEM圖像。 圖14係表示實施有比較例1之基板處理之矽基板之圖案形成面之SEM圖像。 圖15係表示實施有比較例2之基板處理之矽基板之圖案形成面之SEM圖像。 圖16係表示實施有比較例3之基板處理之矽基板之圖案形成面之SEM圖像。 圖17係表示實施有比較例4之基板處理之矽基板之圖案形成面之SEM圖像。 圖18係表示實施有比較例5之基板處理之矽基板之圖案形成面之SEM圖像。FIG. 1 is an explanatory diagram showing the outline of a substrate processing apparatus according to a first embodiment of the present invention. FIG. 2 is a schematic plan view showing the substrate processing apparatus. 3A is a block diagram showing a schematic configuration of a drying auxiliary liquid storage section of the substrate processing apparatus. FIG. 3B is an explanatory diagram showing a specific configuration of the drying auxiliary liquid storage section. FIG. 4 is a block diagram showing a schematic configuration of an air storage tank of the substrate processing apparatus. Fig. 5 is a block diagram showing a schematic configuration of a refrigerant storage section of the substrate processing apparatus. FIG. 6 is an explanatory diagram showing a schematic configuration of a control unit of the substrate processing apparatus. FIG. 7 is a flowchart showing a substrate processing method using the substrate processing apparatus. 8 (a) to 8 (e) are diagrams showing the state of a substrate in each step of the substrate processing method. 9 (a) to (e) are flowcharts showing a substrate processing method according to a second embodiment of the present invention. 10 (a) to (e) are flowcharts showing a substrate processing method according to a third embodiment of the present invention. FIG. 11 is a SEM image showing a pattern formation surface of an untreated silicon substrate used in Examples and Comparative Examples of the present invention. FIG. 12 is a SEM image showing a pattern formation surface of a silicon substrate on which the substrate processing of Example 1 of the present invention has been performed. FIG. 13 is a SEM image showing a pattern formation surface of a silicon substrate on which the substrate treatment of Example 2 of the present invention is performed. 14 is a SEM image showing a pattern formation surface of a silicon substrate subjected to the substrate treatment of Comparative Example 1. FIG. 15 is a SEM image showing a pattern formation surface of a silicon substrate subjected to the substrate treatment of Comparative Example 2. FIG. 16 is a SEM image showing a pattern formation surface of a silicon substrate subjected to the substrate treatment of Comparative Example 3. FIG. FIG. 17 is a SEM image showing a pattern formation surface of a silicon substrate subjected to the substrate treatment of Comparative Example 4. FIG. FIG. 18 is a SEM image showing a pattern formation surface of a silicon substrate subjected to the substrate treatment of Comparative Example 5. FIG.

Claims (15)

一種基板處理裝置，其係用於基板之圖案形成面之乾燥處理者，其具備 對基板之圖案形成面供給含有融解狀態之昇華性物質之處理液的供給機構、 使上述處理液於上述圖案形成面上凝固而形成凝固體之凝固機構、及 使上述凝固體昇華而自上述圖案形成面去除的昇華機構，並且 上述昇華性物質之20℃～25℃下之蒸氣壓為5 kPa以上，20℃～25℃下之表面張力為25 mN/m以下。A substrate processing device is used for drying a pattern forming surface of a substrate. The substrate processing device includes a supply mechanism for supplying a processing solution containing a sublimable substance in a molten state to the pattern forming surface of the substrate, and forming the processing solution on the pattern. A solidification mechanism that solidifies on a surface to form a solidified body, and a sublimation mechanism that sublimates the solidified body from the pattern forming surface, and the vapor pressure of the sublimable substance at 20 ° C to 25 ° C is 5 kPa or more and 20 ° C The surface tension at -25 ° C is 25 mN / m or less. 如請求項1之基板處理裝置，其中 上述昇華性物質之20℃～25℃下之表面張力為20 mN/m以下。The substrate processing apparatus according to claim 1, wherein the surface tension of the sublimable substance at 20 ° C to 25 ° C is 20 mN / m or less. 如請求項2之基板處理裝置，其中 上述昇華性物質為1,1,2,2,3,3,4-七氟環戊烷或十二氟環己烷。The substrate processing apparatus according to claim 2, wherein the sublimable substance is 1,1,2,2,3,3,4-heptafluorocyclopentane or dodecafluorocyclohexane. 如請求項2之基板處理裝置，其中 上述供給機構係於大氣壓下對上述基板之圖案形成面供給上述處理液者， 上述凝固機構係於大氣壓下將上述處理液冷卻至上述昇華性物質之凝固點以下者。For example, the substrate processing apparatus of claim 2, wherein the supply mechanism supplies the processing solution to the pattern forming surface of the substrate under atmospheric pressure, and the coagulation mechanism cools the processing solution below the freezing point of the sublimable substance at atmospheric pressure. By. 如請求項2之基板處理裝置，其中 上述昇華性物質於大氣壓下具有昇華性， 上述昇華機構係於大氣壓下使上述昇華性物質昇華。For example, the substrate processing apparatus of claim 2, wherein the sublimable substance has sublimability under atmospheric pressure, and the sublimation mechanism sublimates the sublimable substance under atmospheric pressure. 如請求項4之基板處理裝置，其中 上述凝固機構或昇華機構之至少任一者係以上述昇華性物質之凝固點以下之溫度向與上述基板之圖案形成面相反側之背面供給冷媒的冷媒供給機構。For example, the substrate processing apparatus of claim 4, wherein at least one of the solidification mechanism or the sublimation mechanism is a refrigerant supply mechanism that supplies a refrigerant to a back surface opposite to the pattern formation surface of the substrate at a temperature below the freezing point of the sublimable substance. . 如請求項4之基板處理裝置，其中 上述凝固機構或昇華機構之至少任一者係以該昇華性物質之凝固點以下之溫度向上述圖案形成面供給至少對上述昇華性物質為惰性之氣體的氣體供給機構。If the substrate processing apparatus of claim 4, wherein at least one of the solidification mechanism or the sublimation mechanism is a gas that is at least a gas inert to the sublimation substance to the pattern forming surface at a temperature below the freezing point of the sublimation substance. Supply agency. 如請求項4之基板處理裝置，其中 上述昇華機構係以該昇華性物質之凝固點以下之溫度向上述圖案形成面供給至少對上述昇華性物質為惰性之氣體的氣體供給機構與以上述昇華性物質之凝固點以下之溫度向與上述基板之圖案形成面相反側之背面供給冷媒的冷媒供給機構。For example, the substrate processing apparatus of claim 4, wherein the sublimation mechanism is a gas supply mechanism that supplies a gas at least inert to the sublimation substance to the pattern forming surface at a temperature below the freezing point of the sublimation substance and the sublimation substance A refrigerant supply mechanism that supplies a refrigerant to a rear surface opposite to the pattern forming surface of the substrate at a temperature below the freezing point. 如請求項2之基板處理裝置，其中 上述昇華機構係將形成有上述凝固體之上述圖案形成面減壓至低於大氣壓之環境下的減壓機構。The substrate processing apparatus according to claim 2, wherein the sublimation mechanism is a decompression mechanism that decompresses the pattern forming surface on which the solidified body is formed to an atmosphere lower than atmospheric pressure. 如請求項1之基板處理裝置，其中 上述凝固機構係將供給上述處理液之上述圖案形成面減壓至低於大氣壓之環境下的減壓機構。The substrate processing apparatus according to claim 1, wherein the coagulation mechanism is a pressure reduction mechanism that decompresses the pattern forming surface to which the processing liquid is supplied to an atmosphere lower than atmospheric pressure. 如請求項10之基板處理裝置，其中 使用上述減壓機構作為上述昇華機構。The substrate processing apparatus according to claim 10, wherein the decompression mechanism is used as the sublimation mechanism. 如請求項2之基板處理裝置，其中 上述供給機構具有將上述處理液之溫度調整為上述昇華性物質之熔點以上且低於沸點之溫度的處理液溫度調整部。The substrate processing apparatus according to claim 2, wherein the supply mechanism includes a processing liquid temperature adjustment unit that adjusts the temperature of the processing liquid to a temperature higher than the melting point of the sublimable substance and lower than the boiling point. 一種基板處理方法，其係進行基板之圖案形成面之乾燥處理者，其包含 對基板之圖案形成面供給含有融解狀態之昇華性物質之處理液的供給方法、 使上述處理液於上述圖案形成面上凝固而形成凝固體的凝固方法、及 使上述凝固體昇華而自上述圖案形成面去除的昇華方法，並且 上述昇華性物質之20℃～25℃下之蒸氣壓為5 kPa以上，20℃～25℃下之表面張力為25 mN/m以下。A substrate processing method is a method for drying a pattern forming surface of a substrate. The method includes a method for supplying a processing solution containing a sublimable substance in a molten state to the pattern forming surface of the substrate, and the processing solution is provided on the pattern forming surface. Solidification method for solidification to form a solidified body, and sublimation method for sublimating the solidified body from the pattern forming surface, and the vapor pressure of the sublimable substance at 20 ° C to 25 ° C is 5 kPa or more and 20 ° C to The surface tension at 25 ° C is 25 mN / m or less. 如請求項13之基板處理方法，其中 上述昇華性物質之20℃～25℃下之表面張力為20 mN/m以下。The substrate processing method according to claim 13, wherein the surface tension of the sublimable substance at 20 ° C to 25 ° C is 20 mN / m or less. 如請求項13之基板處理方法，其中 上述昇華性物質為1,1,2,2,3,3,4-七氟環戊烷或十二氟環己烷。The substrate processing method according to claim 13, wherein the sublimable substance is 1,1,2,2,3,3,4-heptafluorocyclopentane or dodecafluorocyclohexane.
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