TWI651295B - Substrate processing apparatus and substrate processing method - Google Patents

Substrate processing apparatus and substrate processing method Download PDF

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Publication number
TWI651295B
TWI651295B TW106137740A TW106137740A TWI651295B TW I651295 B TWI651295 B TW I651295B TW 106137740 A TW106137740 A TW 106137740A TW 106137740 A TW106137740 A TW 106137740A TW I651295 B TWI651295 B TW I651295B
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Taiwan
Prior art keywords
substrate
sublimation
substance
liquid
pattern forming
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TW106137740A
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Chinese (zh)
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TW201825447A (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

本發明之基板處理裝置之特徵在於：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，上述處理液之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。The substrate processing apparatus of the present invention includes a supply mechanism that supplies a treatment liquid containing a sublimation substance in a melted state to a pattern formation surface of the substrate, and a solidification mechanism that solidifies the treatment liquid on the pattern formation surface to form a solidified body. a sublimation mechanism for sublimating the solidified body from the pattern forming surface, wherein the vapor pressure of the treatment liquid at 20 ° C to 25 ° C is 5 kPa or more, and the surface tension at 20 ° C to 25 ° C is 25 mN / m or less. .

Description

基板處理裝置及基板處理方法Substrate processing apparatus 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 semiconductor substrate, a glass substrate for a photomask, a glass substrate for liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for a disk, and a disk. A substrate processing apparatus and a substrate processing method for removing liquids of various substrates (hereinafter simply referred to as "substrates") such as a substrate and a magneto-optical substrate from the 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 process of an electronic component such as a semiconductor device or a liquid crystal display device, after the substrate is subjected to various wet treatments using a liquid, the substrate is subjected to a drying process for removing the liquid adhering to the substrate by the wet process. As the wet treatment, a cleaning treatment for removing contaminants on the surface of the substrate can be cited. For example, by a dry etching step, reaction by-products (etching residue) are present on the surface of the substrate on which the fine pattern having irregularities is formed. Further, in addition to the etching residue, metal impurities, organic contaminants, and the like are attached to the surface of the substrate, and in order to remove the substances, a cleaning treatment such as supplying a cleaning liquid to the substrate is performed. After the cleaning treatment, the rinsing treatment for removing the cleaning liquid by the rinsing liquid and the drying treatment of the drying rinsing liquid are carried out. The rinsing treatment may be a rinsing treatment in which a rinsing liquid such as deionized water (DIW, Deionized Water) is supplied to the surface of the substrate to which the cleaning liquid is attached, and the cleaning liquid on the surface of the substrate is removed. Thereafter, a drying process of drying the substrate by removing the rinse liquid is performed. In recent years, with the miniaturization of the pattern formed on the substrate, the aspect ratio of the convex portion having the pattern of the unevenness (the ratio of the height of the pattern convex portion to the width) is increased. Therefore, there is a problem that the surface tension acting on the interface between the liquid such as the cleaning liquid or the rinsing liquid entering the pattern concave portion and the gas in contact with the liquid during the drying process pulls the adjacent convex portions in the pattern to each other. Collapse, the so-called problem of collapse of the pattern. As a drying technique for preventing the collapse of the pattern due to the surface tension, for example, Japanese Laid-Open Patent Publication No. 2013-16699 discloses that the substrate on which the structure (pattern) is formed is brought into contact with a solution to change the solution. A method of forming a support (solidified body) of a solid as a solid, and changing the support from a solid phase to a gas phase without passing through a liquid phase. Further, in this patent document, at least one of a methacrylic resin material, a styrene resin material, and a fluorocarbon material is used as the support material. Further, Japanese Laid-Open Patent Publication No. 2012-243869 and JP-A-2013-258272 disclose that a solution for supplying a sublimating substance to a substrate is used to dry the solvent in the solution to fill the substrate with a sublimation substance. The solidification body, the drying technique for sublimating the solidified body. According to these patent documents, the surface tension is not generated at the interface between the solidified body and the gas which is in contact with the solidified body, so that the collapse of the pattern due to the surface tension can be suppressed. Further, Japanese Laid-Open Patent Publication No. 2015-142069 discloses that a molten metal of a third butanol (sublimation substance) is supplied to a substrate to which a liquid adheres, and the third butanol is solidified on the substrate to form a solidified body. A drying technique that removes the solidified body and removes it. For example, in the drying technique disclosed in Japanese Laid-Open Patent Publication No. 2013-16699, Japanese Patent Laid-Open No. Hei. No. 2012-243869, Japanese Patent Laid-Open No. Hei. No. Hei. There is a problem that the substrate having a fine pattern and a relatively high aspect ratio (that is, a pattern having a higher height than the width of the convex pattern and having a higher convex pattern) cannot sufficiently prevent the pattern from collapsing. The causes of pattern collapse are various, and as one of them, the force acting between the solidified body containing the sublimating substance and the surface of the pattern can be cited. At the interface between the surface of the pattern and the solidified body, the molecules constituting the pattern interact with the sublimating substance constituting the solidified body to have an ionic bond, a hydrogen bond, a vanadium, and the like. Therefore, even if the solidified body does not pass through the liquid state, the state changes to a gas, and when the sublimation is unevenly performed, stress is applied to the pattern to cause collapse of the pattern. Further, the force acting between the solidified body and the surface of the pattern largely depends on the physical properties of the sublimating substance constituting the solidified body. Therefore, in order to eliminate the pattern collapse in the sublimation drying of the fine pattern surface, it is necessary to select a sublimation substance which is 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 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 liquid adhering to the surface of the substrate. The substrate processing apparatus of the present invention is a substrate processing apparatus used for drying a pattern forming surface of a substrate, and a processing apparatus for supplying a processing liquid containing a sublimating substance in a molten state to a pattern forming surface of a substrate. a supply mechanism, a solidification mechanism for solidifying the treatment liquid on the pattern formation surface to form a solidified body, and a sublimation mechanism for sublimating the solidified body from the pattern formation surface, wherein the sublimation substance is at 20 ° C to 25 ° C 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, by the principle of freeze drying (or sublimation drying), the pattern can be prevented from collapsing and the liquid can be removed. Specifically, the supply mechanism replaces the liquid with the treatment liquid by supplying the treatment liquid to the pattern forming surface of the substrate. Next, the coagulation mechanism solidifies the treatment liquid 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 a sublimation substance, the sublimation substance is sublimated in the solidified body. At the same time, the degree of sublimation can be reduced to an uneven degree. Thereby, the stress applied to the substrate pattern can be reduced as compared with the case where the sublimation is unevenly performed. As a result, for example, compared with a substrate processing apparatus using a conventional sublimation substance such as a third butanol, the occurrence of pattern collapse can be reduced in a substrate having a pattern surface having a fine aspect ratio. Here, the term "melting state" as used herein means a state in which a sublimating substance has fluidity due to complete or partial melting, and is in a liquid state. In addition, the above-mentioned "sublimation property" means that a monomer, a compound or a mixture has a 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 "sublimation substance" means having such sublimation property. Substance. In addition, the above-mentioned "pattern forming surface" means a surface in which a concave-convex pattern is formed in an arbitrary region on a substrate, regardless of whether it is a flat shape, a curved surface, or a concave-convex shape. The above-mentioned "solidified body" refers to a liquid in which the treatment liquid in a liquid state is solidified. For example, when the liquid present on the substrate is mixed with the treatment liquid and solidified by the coagulation mechanism, the liquid may be contained. By. In the above configuration, the surface tension of the sublimable substance at 20 ° C to 25 ° C is preferably 20 mN/m or less. In the above configuration, the sublimable substance is preferably 1,1,2,2,3,3,4-heptafluorocyclopentane or dodecafluorocyclohexane. Further, in the above configuration, preferably, the supply means supplies the treatment liquid to the pattern forming surface of the substrate at atmospheric pressure, and the coagulation mechanism cools the treatment liquid below a freezing point of the sublimable substance under atmospheric pressure. By. Thereby, at least the supply mechanism and the solidification mechanism do not need to have a pressure resistance structure, and the cost of the apparatus can be reduced. Further, in the above configuration, preferably, the sublimation substance has sublimation properties under atmospheric pressure, and the sublimation means sublimes the sublimation substance under atmospheric pressure. Therefore, by using a sublimation substance for sublimation at atmospheric pressure, at least the sublimation mechanism does not require a pressure-resistant structure, and the cost of the apparatus can be reduced. Further, in the above configuration, at least one of the solidification mechanism and the sublimation mechanism may be a refrigerant supply for supplying a refrigerant to a back surface opposite to a pattern forming surface of the substrate at a temperature lower than a freezing point of the sublimable substance. mechanism. According to the above configuration, in the solidification mechanism, the sublimation substance can be cooled and solidified by supplying the refrigerant below the freezing point of the sublimating substance to the back surface on the opposite side to the pattern forming surface of the substrate. Further, 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 back side of the substrate, and the solidified body can be naturally sublimated. Further, in the case where both the solidification mechanism and the sublimation mechanism are configured to supply the refrigerant to the back surface of the substrate, the number of components can be reduced, and the device cost can be reduced. Further, in the above configuration, at least one of the solidification mechanism and 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 equal to or lower than a freezing point of the sublimable substance. . According to the above configuration, the gas supply means supplies the inert gas having a temperature lower than the freezing point of the sublimating substance to the pattern forming surface as the solidifying means, so that the sublimating substance can be cooled and solidified. Further, the gas supply means also supplies an inert gas to the solidified body formed on the pattern forming surface, whereby the solidified body can be sublimated and can function as a sublimation mechanism. Further, since the gas supply mechanism can be used in combination with the solidification mechanism and the sublimation mechanism, the number of components can be reduced, and the cost of the device can be reduced. Furthermore, the inert gas is inert to the sublimating substance, so the sublimation substance is not modified. In the above configuration, the sublimation means may be a gas supply means for supplying at least a gas inert to the sublimation substance to the pattern forming surface at a temperature lower than a freezing point of the sublimable substance, and a solidification point below the sublimation substance. The refrigerant supply mechanism that supplies the refrigerant to the back surface on the opposite side to the pattern forming surface of the substrate. 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 lower than the freezing point of the sublimable substance, thereby sublimating the solidified body. Further, the refrigerant supply means supplies the refrigerant to the back surface opposite to the pattern forming surface of the substrate at a temperature lower than the freezing point of the sublimable substance, whereby the solidified body can be prevented from being melted from the back side of the substrate. Further, in the above configuration, preferably, the sublimation mechanism is a pressure reducing mechanism that decompresses the pattern forming surface on which the solidified body is formed to a temperature lower than atmospheric pressure. By using a pressure reducing mechanism as the sublimation mechanism, the pattern forming surface of the substrate can be made to be subatmospheric, thereby sublimating the sublimating substance in the solidified body. Here, when the sublimating substance is sublimated and vaporized from the solidified body, 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 sublimating substance, it is possible to maintain the temperature lower than the melting point of the sublimating substance without separately cooling the solidified body. As a result, the sublimation of the solidified substance in the solidified body can be prevented and the sublimation of the solidified body can be performed. Moreover, since it is not necessary to separately provide a cooling mechanism, the device cost or the processing cost can be reduced. Further, in the above configuration, preferably, the solidifying means is a pressure reducing mechanism that decompresses the pattern forming surface to which the processing liquid is supplied to an atmosphere lower than atmospheric pressure. According to this configuration, by using the pressure reducing mechanism as the solidifying mechanism, the pattern forming surface of the substrate can be made to be lower than atmospheric pressure, and the processing liquid can be evaporated, whereby the processing liquid can be cooled by the heat of vaporization, thereby forming Solidified body. Moreover, since it is not necessary to separately provide a cooling mechanism, the device cost or the processing cost can be reduced. Further, in the above configuration, it is preferable to use the pressure reducing mechanism as the sublimation mechanism. According to this configuration, the pressure reducing mechanism used as the solidifying mechanism can be used as the sublimation mechanism, so that the number of parts can be reduced, and the cost of the apparatus can be reduced. Further, in the above configuration, preferably, the supply means has a treatment liquid temperature adjustment unit that adjusts the temperature of the treatment liquid to a temperature higher than a melting point of the sublimable substance and lower than a boiling point. According to the above configuration, by providing the processing unit with the processing liquid temperature adjusting unit, the temperature of the processing liquid can be adjusted to a temperature higher than or equal to the melting point of the sublimable substance and lower than the boiling point. By setting the temperature of the treatment liquid to be 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 drying treatment of the liquid on the substrate can be satisfactorily performed. The substrate processing method of the present invention is a substrate processing method for drying a pattern forming surface of a substrate, and a method for supplying a processing liquid for supplying a sublimation substance having a melted state to a pattern forming surface of a substrate, a method for solidifying a solidified body by solidifying the treatment liquid on the pattern forming surface, and a sublimation method for removing 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 forming surface of the substrate, by the principle of freeze drying (or sublimation drying), the pattern can be prevented from collapsing and the liquid can be removed. Specifically, in the supply step, the liquid is replaced with the treatment liquid by supplying the treatment liquid to the pattern formation 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 a sublimation substance, in the sublimation step, in the solidified body When the sublimation material is sublimated, the degree of sublimation can be made uniform. Thereby, the stress applied to the substrate pattern can be reduced as compared with the case where the sublimation is unevenly performed. As a result, for example, in comparison with a substrate processing method using a prior sublimation substance such as a third 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 of the sublimable substance at 20 ° C to 25 ° C is preferably 20 mN/m or less. In the above configuration, the sublimable substance is preferably 1,1,2,2,3,3,4-heptafluorocyclopentane or dodecafluorocyclohexane. The present invention exerts the effects described below in accordance with the mechanism described above. In other words, in the case where a liquid is present on the pattern forming surface of the substrate, for example, after the liquid is replaced with a treatment liquid containing a sublimable substance, the treatment liquid is solidified to form a solidified body, and then the solidified body is formed. The sublimation substance is sublimated to perform drying of the liquid on the substrate. Here, in the present invention, a sublimation property is used as a sublimation substance 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. When the substance is sublimated, the degree of sublimation can be made uniform. Thereby, in the present invention, the application of stress to the pattern due to the progress of sublimation unevenness can be reduced. As a result, the present invention can further reduce the collapse of the pattern, and is extremely suitable for drying the liquid on the substrate, for example, in comparison with a substrate processing apparatus and a substrate processing method using a conventional sublimation substance such as a third butanol.

(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***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。 (First embodiment) Hereinafter, a first embodiment of the present invention will be described. Fig. 1 is an explanatory view showing the outline of the substrate processing apparatus 1 of the embodiment. FIG. 2 is a schematic plan view showing the internal structure of the substrate processing apparatus 1. Furthermore, in each of the figures, the XYZ orthogonal coordinates are appropriately displayed in order to clarify the direction relationship of the figure. In FIGS. 1 and 2, the XY plane represents a horizontal plane, and the +Z direction represents a vertical direction. The substrate processing apparatus 1 can be used, for example, for processing various substrates. The above-mentioned "substrate" refers to a semiconductor substrate, a glass substrate for a photomask, a glass substrate for liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for a disk, a substrate for a disk, and a disk for a magneto-optical disk. Various substrates such as substrates. In the present embodiment, a case where the substrate processing apparatus 1 is used for the processing of a semiconductor substrate (hereinafter referred to as "substrate W") will be described as an example. Further, as the substrate W, a circuit pattern or the like (hereinafter referred to as a "pattern") is formed on only one main surface as an example. Here, the pattern forming surface (main surface) on which the pattern is formed is referred to as "surface", and the main surface on the opposite side where the pattern is not formed is referred to as "back surface". Moreover, the surface of the substrate facing downward is referred to as "lower surface", and the surface of the substrate facing upward is referred to as "upper surface". In addition, the upper surface will be described below as a surface. Moreover, the shape of the above-mentioned pattern is not particularly limited, and examples thereof include a linear shape or a tubular shape. Further, the size of the pattern is not particularly limited, and can be arbitrarily set as appropriate. Further, the material of the pattern is not particularly limited, and examples thereof include a metal or an insulating material. The substrate processing apparatus 1 is a one-piece substrate processing apparatus used for a cleaning process (including a rinsing process) for removing contaminants adhering to particles of the substrate W and a drying process after the cleaning process. In addition, in FIG. 1 and FIG. 2, only the part used for the drying process is shown, and the nozzle for washing|cleaning of the washing|cleaning process is not shown, and the board|substrate processing apparatus 1 can be equipped with this nozzle. <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 as a container for accommodating the substrate W, a substrate holding mechanism 51 for holding the substrate W, a control unit 13 for controlling each unit of the substrate processing apparatus 1, and a substrate W for holding the substrate holding mechanism 51. A processing liquid supply mechanism (supply means) 21 as a drying auxiliary liquid for the treatment liquid, an IPA supply mechanism 31 for supplying IPA (isopropyl alcohol) to the substrate W held by the substrate holding mechanism 51, and a substrate held by the substrate holding mechanism 51 The gas supply mechanism 41 (the solidification mechanism and the sublimation mechanism) that supplies the gas, and the scattering prevention cup that is 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, or the dry auxiliary liquid or the like 12. The rotary drive unit 14 that independently rotates the following arms of the respective sections of the substrate processing apparatus 1 , the pressure reducing mechanism 71 that decompresses the inside of the chamber 11 , and the refrigerant supply mechanism that supplies the refrigerant to the back surface Wb of the substrate W (coagulation mechanism, sublimation mechanism) 81. Further, the substrate processing apparatus 1 includes a substrate loading/unloading mechanism, a chuck pin switching mechanism, and a wet cleaning mechanism (none of which are shown). Each part of the substrate processing apparatus 1 will be described below. The substrate holding mechanism 51 has a rotation driving portion 52, a rotating base 53, and a chuck pin 54. The rotating substrate 53 has a plane size slightly larger than that of the substrate W. A plurality of chuck pins 54 that hold the peripheral edge portion of the substrate W are vertically disposed near the peripheral 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 substrates to reliably hold the circular substrate W. In the present embodiment, three are arranged at equal intervals along the peripheral edge portion of the rotating base 53 (see FIG. 2). Each of the chuck pins 54 includes a substrate supporting pin that supports the peripheral edge portion of the substrate W from the lower side, and a substrate holding pin that presses the outer peripheral end surface of the substrate W supported by the substrate supporting pin to hold the substrate W. Each of the chuck pins 54 is switchable between a pressed state in which the substrate holding pin presses the outer peripheral end surface of the substrate W and a released state in which the substrate holding pin is separated from the outer peripheral end surface of the substrate W, and is executed in accordance with an operation command from the control unit 13 as a whole from the control device. State switching. More specifically, when the substrate W is loaded and unloaded to the rotating base 53, the respective chuck pins 54 are released, and when the substrate W is subjected to the following cleaning process to the sublimation process, the respective chuck pins 54 are pressed. 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) from the rotating base 53 with a predetermined interval therebetween. Thereby, the substrate W is kept horizontal with its surface Wf facing upward. As described above, in the present embodiment, the substrate W is held by the rotating base 53 and the chuck pin 54, but the substrate holding method is not limited thereto. For example, the back surface Wb of the substrate W may be held by an adsorption method such as a rotary chuck. The rotating base 53 is coupled to the rotation driving portion 52. The rotation driving portion 52 is rotated about the axis A1 in the Z direction by the operation command of the control unit 13. The rotation drive unit 52 includes a known belt, a motor, and a rotating shaft. When the rotation driving unit 52 rotates about the axis A1, the substrate W held by the chuck pin 54 above the rotating base 53 rotates around the axis A1 together with the rotating base 53. Next, the processing liquid supply mechanism (supply means) 21 will be described. The processing liquid supply mechanism 21 is a unit that supplies the drying auxiliary liquid to the pattern forming surface of the substrate W, and includes at least the nozzle 22, the arm 23, the rotary shaft 24, the pipe 25, the valve 26, and the processing liquid storage portion 27 as shown in Fig. 1 . . As shown in FIG. 3A and FIG. 3B, the processing liquid storage unit 27 includes at least a stirring unit 277 for the drying auxiliary liquid in the processing liquid storage tank 271 and the stirring treatment liquid storage tank 271, and pressurizes the processing liquid storage tank 271 to be dried. The auxiliary liquid pressurizing unit 274 and the temperature adjusting unit 272 of the drying auxiliary liquid (treatment liquid) in the heat treatment liquid storage tank 271. In addition, FIG. 3A is a block diagram showing a schematic configuration of the processing liquid storage unit 27, and FIG. 3B is an explanatory view showing a specific configuration of the processing liquid storage unit 27. The stirring unit 277 includes a rotating portion 279 that agitates the drying auxiliary liquid in the processing liquid storage tank 271, and a stirring control unit 278 that controls the rotation of the rotating portion 279. The stirring control unit 278 is electrically connected to the control unit 13. The rotating portion 279 includes a propeller-shaped stirring blade at a front end of the rotating shaft (the lower end of the rotating portion 279 in FIG. 4), and the control unit 13 gives an operation command to the stirring control unit 278, and the rotating portion 279 rotates, whereby the stirring blade is stirred and dried. The liquid is used to homogenize the concentration and temperature of the drying auxiliary substance and the like in the drying auxiliary liquid. In addition, the method of uniformizing the concentration and temperature of the drying auxiliary liquid in the processing liquid storage tank 271 is not limited to the above method, and a known method such as a method of separately providing a pump for circulation and circulating the drying auxiliary liquid can be used. The pressurizing unit 274 includes a nitrogen gas tank 275 as a supply source for the gas pressurized in the processing liquid storage tank 271, a pump 276 for pressurizing nitrogen gas, and a pipe 273. The nitrogen gas tank 275 is connected to the treatment liquid storage tank 271 by a pipe 273, and the pump 276 is inserted into the pipe 273. The temperature adjustment unit 272 is electrically connected to the control unit 13, and the drying auxiliary liquid stored in the processing liquid storage tank 271 is heated by the operation command of the control unit 13 to perform temperature adjustment. The temperature adjustment is such that the liquid temperature of the drying auxiliary liquid is equal to or higher than the melting point of the drying auxiliary substance (sublimating substance; details) described in the drying auxiliary liquid. Thereby, the melted state of the drying auxiliary substance can be maintained. Further, as the upper limit of the temperature adjustment, a temperature lower than the boiling point is preferable. Further, the temperature adjustment unit 272 is not particularly limited, and for example, a known temperature adjustment mechanism such as a resistance heater or a Peltier element or a pipe through which temperature-adjusted water passes can be used. Furthermore, in the present embodiment, the temperature adjustment unit 272 has an arbitrary configuration. For example, when the installation environment of the substrate processing apparatus 1 is a high temperature environment higher than the melting point of the sublimation substance, since the melting state of the sublimation 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 treatment liquid storage unit 27 (more specifically, the treatment liquid storage tank 271) is connected to the nozzle 22 through the pipe 25, and the valve 26 is inserted in the middle of the path of the pipe 25. A gas pressure sensor (not shown) is disposed 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 to maintain the air pressure in the processing liquid storage tank 271 at a specific pressure higher than atmospheric pressure. On the other hand, the valve 26 is also electrically connected to the control unit 13, typically a closed valve. Moreover, the switch of the valve 26 is also controlled by the action command of the control unit 13. When the control unit 13 issues an operation command to the processing liquid supply unit 21 to open the valve 26, the drying auxiliary liquid is pressure-fed from the pressurized treatment liquid storage tank 271, and is ejected from the nozzle 22 via the pipe 25. Thereby, the drying auxiliary liquid can be supplied to the surface Wf of the substrate W. Further, since the treatment liquid storage tank 271 is used to pressurize the drying auxiliary liquid by the pressure of nitrogen gas as described above, it is preferably airtight. The nozzle 22 is attached to the front end of the horizontally extending arm 23 and is disposed above the rotating base 53. The rear end portion of the arm 23 is rotatably supported around the axis J1 by a rotary shaft 24 extending in the Z direction, and the rotary shaft 24 is fixedly disposed in the chamber 11. The arm 23 is connected to the turning drive unit 14 via the rotary shaft 24 . The turning drive unit 14 is electrically connected to the control unit 13, and the arm 23 is rotated about the axis J1 by an operation command 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 disposed on the outer side of the peripheral portion of the substrate W, and is disposed at a retracted position P1 that is further 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 center 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 explained. The IPA supply mechanism 31 is a unit that supplies the IPA to the substrate W, and includes a nozzle 32, an arm 33, a rotary shaft 34, a pipe 35, a valve 36, and an IPA groove 37. The IPA tank 37 is connected to the nozzle 32 through a pipe 35, and the 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 normally closed. The open relationship of the valve 36 is controlled by the action 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 attached to the front end of the horizontally extending arm 33 and disposed above the rotating base 53. The rear end portion of the arm 33 is rotatably supported around the axis J2 by a rotary shaft 34 extending in the Z direction, and the rotary shaft 34 is fixedly disposed in the chamber 11. The arm 33 is connected to the turning drive unit 14 via a rotary shaft 34. The turning drive unit 14 is electrically connected to the control unit 13, and the arm 33 is rotated 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 disposed outside the peripheral portion of the substrate W, and is disposed at a retracted position P2 that is further outside the scattering preventing 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 center portion (the axis A1 or its vicinity) of the surface Wf of the substrate W. Further, in the present embodiment, IPA is used in the IPA supply mechanism 31. However, in the present invention, the liquid is soluble in the dry auxiliary material and the deionized water (DIW: Deionized Water), and is not limited to IPA. As an alternative to the IPA of the present embodiment, methanol, ethanol, acetone, benzene, carbon tetrachloride, chloroform, hexane, decalin, tetralin, acetic acid, cyclohexanol, ether or hydrofluoroether (Hydro) Fluoro Ether) and so on. Return to Figure 1. Next, the gas supply mechanism 41 will be described. The gas supply mechanism 41 is a unit that supplies a gas to the substrate W, and includes a nozzle 42, an arm 43, a rotary shaft 44, a pipe 45, a valve 46, and an air reservoir 47. Fig. 4 is a block diagram showing a schematic configuration of the air reservoir 47. The air reservoir 47 includes a gas storage unit 471 that stores a 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 the gas stored in the gas storage unit 471 is heated or cooled by the operation command of the control unit 13 to perform temperature adjustment. The temperature adjustment is such that the gas stored in the gas reservoir 471 becomes a lower temperature below the freezing point of the drying auxiliary material. 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 air reservoir 47 (more specifically, the gas reservoir 471) is connected to the nozzle 42 via a pipe 45, and the valve 46 is inserted in the middle of the path of the pipe 45. The gas in the air reservoir 47 is pressurized by a pressurizing mechanism (not shown) and sent to the pipe 45. Further, the pressurizing mechanism can be realized by compressing and storing the gas in the air reservoir 47 in addition to the pressurization by a pump or the like, and any pressurizing mechanism can be used. The valve 46 is electrically connected to the control unit 13, and is normally closed. The open relationship of the valve 46 is controlled by the action 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 attached to the front end of the horizontally extending arm 43 and is disposed above the rotating base 53. The rear end portion of the arm 43 is rotatably supported around the axis J3 by a rotary shaft 44 extending in the Z direction, and the rotary shaft 44 is fixedly disposed in the chamber 11. The arm 43 is connected to the turning drive unit 14 via the rotary shaft 44. The turning drive unit 14 is electrically connected to the control unit 13, and the arm 43 is rotated about the axis J3 by an operation command from the control unit 13. With the rotation of the arm 43, the nozzle 42 also moves. As shown by the solid line in FIG. 2, the nozzle 42 is generally disposed outside the peripheral portion of the substrate W, and is disposed at a retracted position P3 which is further outside the scattering preventing 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 center portion (the axis A1 or its vicinity) of the surface Wf of the substrate W. The case where the nozzle 42 is disposed above the central portion of the surface Wf is indicated by a broken line in FIG. 2 . The gas storage unit 471 stores an inert gas which is at least inert to the drying auxiliary substance, more specifically nitrogen. Further, the stored nitrogen gas is adjusted to a temperature equal to or lower than the freezing point of the drying auxiliary substance in the gas temperature adjusting unit 472. 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 material, and is usually set to be in the range of 0 ° C or more and 15 ° C or less. In addition, 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. Further, the nitrogen gas used in the first embodiment is preferably a dry gas having a dew point of 0 ° C or less. When the above nitrogen gas is blown to the solidified body under an atmospheric pressure environment, the drying auxiliary substance in the solidified body is sublimed in nitrogen gas. Since the nitrogen gas is continuously supplied to the solidified body, the partial pressure of the drying auxiliary substance in the gaseous state due to sublimation in the nitrogen gas is maintained to be lower than the state of the saturated vapor pressure of the dry auxiliary substance in the gaseous state at the temperature of the nitrogen gas. At least on the surface of the solidified body, the drying auxiliary substance in a gaseous state is filled in an environment in which it exists below the saturated vapor pressure. Further, in the present embodiment, nitrogen gas is used as the gas supplied by the gas supply means 41. However, as a gas inert to the drying auxiliary material, the present invention is not limited thereto. In the first embodiment, examples of the substitute gas for nitrogen include argon gas, helium gas or dry air (a gas having a nitrogen gas concentration of 80% and an oxygen gas concentration of 20%). Alternatively, it may be a mixed gas obtained by mixing the plurality of gases. Return to Figure 1. The pressure reducing mechanism 71 is a mechanism that decompresses the inside of the chamber 11 to an environment lower than atmospheric pressure, and includes an exhaust pump 72, a pipe 73, and a valve 74. The exhaust pump 72 is connected to the chamber 11 through a pipe 73, and is a known pump that applies pressure to the gas. The exhaust pump 72 is electrically connected to the control unit 13, and is normally in a stopped state. The drive of the exhaust pump 72 is controlled by an action command of the control unit 13. Further, a valve 74 is inserted into the pipe 73. The valve 74 is electrically connected to the control unit 13, typically a closed valve. The open relationship of the valve 74 is controlled by the action 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 via the piping 73 by the exhaust pump 72. The scattering prevention cup 12 is provided to surround the rotating base 53. The scattering prevention cup 12 is connected to the lifting drive mechanism (not shown) and can be raised and lowered 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. 1 by the elevation driving mechanism, and the substrate W held by the chuck pin 54 is surrounded by the side position. Thereby, a liquid such as a dry auxiliary liquid or IPA scattered from the substrate W or the rotating substrate 53 can be collected. Next, the refrigerant supply mechanism 81 will be described. The refrigerant supply mechanism 81 is a unit that supplies a refrigerant to the back surface Wb of the substrate W. As shown in FIG. 1, the refrigerant supply unit 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. The refrigerant storage unit 82 includes a refrigerant tank 821 that stores the refrigerant, and a refrigerant temperature adjustment unit 822 that adjusts the temperature of the refrigerant stored in the refrigerant tank 821. The refrigerant temperature adjustment unit 822 is electrically connected to the control unit 13, and the refrigerant stored in the refrigerant tank 821 is heated or cooled by the operation command of the control unit 13 to perform temperature adjustment. The temperature adjustment may be performed such that the refrigerant stored in the refrigerant tank 821 becomes a lower temperature below the freezing point of the drying auxiliary material. In addition, the refrigerant temperature adjustment unit 822 is not particularly limited, and for example, a known temperature adjustment mechanism such as a cooler using a Peltier element or a pipe through which temperature-adjusted water passes may be used. Return to Figure 1. The refrigerant storage unit 82 is connected to the refrigerant supply pipe 85 via a pipe 83, and the valve 84 is inserted in the middle of the path of the pipe 83. The refrigerant supply pipe 85 is provided by forming a through hole in the center 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 portion 82 in addition to the pressurization of the pump or the like. Therefore, any pressurizing mechanism can be used. The valve 84 is electrically connected to the control unit 13, and is normally closed. The open relationship of the valve 84 is controlled by the action command of the control unit 13. When the valve 84 is opened by the operation command of the control unit 13, the refrigerant passes through the pipe 83 and the refrigerant supply pipe 85, and is supplied to the back surface Wb of the substrate W. Examples of the refrigerant include a liquid or a gas below the freezing point of the drying auxiliary material. Further, 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 material, and more specifically, nitrogen gas at 7 ° C is exemplified. Fig. 6 is a schematic view showing the configuration of the control unit 13. The control unit 13 is electrically connected to each unit of the substrate processing apparatus 1 (see FIG. 1), and controls the operation of each unit. The control unit 13 includes a computer having an arithmetic processing unit 15 and a memory 17. As the arithmetic processing unit 15, a CPU (Central Processing Unit) that performs various kinds of arithmetic processing is used. Further, the memory 17 is provided with a ROM which is a memory for reading the memory basic program, a RAM for storing and storing a variety of information, and a disk in which a control software or data is stored in advance. The substrate processing conditions (recipes) of the substrate W are previously stored in the magnetic disk. The CPU reads the substrate processing conditions to the RAM, and the CPU controls each unit of the substrate processing apparatus 1 in accordance with the contents. <1-2 Drying auxiliary liquid> Next, the drying auxiliary liquid used in the present embodiment will be described below. The drying auxiliary liquid of the present embodiment contains a treatment liquid for a drying auxiliary substance (sublimation substance) in a melted state, and functions to assist the drying process in the drying process of the liquid for removing the pattern forming surface of the substrate. Further, the sublimating substance has a property of not converting from a solid phase to a gas or from a gas phase to a solid without a liquid. Further, since the sublimable substance is contained in the drying auxiliary liquid in the melted state, a film-like solidified body having a uniform thickness can be formed on the substrate W. In the present embodiment, the vapor pressure of the sublimable substance in the range of 20 ° C to 25 ° C is 5 kPa or more, preferably 8 kPa or more and 100 kPa or less, more preferably 15 kPa or more and 100 kPa or less. Further, 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 more than 0 mN/m and 15 mN/m or less, and further preferably 0 mN/m or more and 13 mN/m or less. By using a sublimating substance having a vapor pressure of 5 kPa or more and a surface tension of 25 mN/m or less, it is possible to suppress the sublimation of the sublimable substance in the solidified body from becoming uneven, thereby reducing the collapse of the pattern. For example, a pattern of a plurality of cylinders (aspect ratio 16) having a diameter of 30 nm and a height of 480 nm arranged at intervals of 80 nm on the substrate can suppress the collapse rate of the pattern to 20% or less. Further, the collapse rate of the pattern is a value calculated by the following formula. The collapse rate of the pattern (%) = (the number of the convex portions collapsed in an arbitrary region) ÷ (the total number of the convex portions in the region) × 100 In the present embodiment, as the sublimation substance, for example, 1, 1,2,2,3,3,4-heptafluorocyclopentane (vapor pressure at 8.2 kPa at 20 ° C, 19.6 mN/m at 25 ° C, melting point 20.5 ° C), dodecafluorocyclohexane Hexane (vapor pressure at 20 ° C was 33.1 kPa, surface tension at 25 ° C was 12.6 mN/m (calculated value), melting point was 51 ° C), and the like. The vapor pressure of the sublimating substance is higher than the DIW (the vapor pressure at 20 ° C is 2.3 kPa) or the third butanol (the vapor pressure at 20 ° C is 4. l kPa at 20 ° C). The surface tension is 19.56 mN/m and the melting point is 25 ° C), so that the sublimation step can be carried out higher than the previous sublimation speed. Further, these sublimable substances do not have an OH group, and exhibit poor solubility to water as compared with the third butanol, so that mixing with water remaining on the substrate W does not occur. As a result, there is no residual moisture between the patterns after sublimation. The drying auxiliary liquid may be a sublimation substance containing only a melted state, and may further contain an organic solvent. In this case, the content of the sublimable substance is preferably 60% by mass or more, and more preferably 95% by mass or more based on the total mass of the drying auxiliary liquid. In addition, the organic solvent is not particularly limited as long as it exhibits compatibility with a sublimable substance in a melted state. Specific examples thereof include alcohols and the like. <1-3 Substrate Processing Method> Next, a substrate processing method using the substrate processing apparatus 1 of the present embodiment will be described below with reference to FIGS. 7 and 8. Fig. 7 is a flow chart showing the operation of the substrate processing apparatus 1 of the first embodiment. Fig. 8 is a schematic view showing the state of the substrate W in each step of Fig. 7. Further, a pattern Wp having irregularities is formed on the substrate W by the previous step. The pattern Wp includes a convex portion Wp1 and a concave portion Wp2. In the present embodiment, the convex portion Wp1 has a height in the range of 100 to 600 nm and a width in the range of 10 to 50 nm. Further, 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 treated under an atmospheric pressure atmosphere unless otherwise specified. Here, the atmospheric pressure environment refers to an environment having a standard atmospheric pressure (one atmosphere, 1013 hPa), 0.7 atmospheres or more, and 1.3 atmospheres or less. In particular, when the substrate processing apparatus 1 is disposed in a clean room that is a positive pressure, the environment of the surface Wf of the substrate W is higher than one atmosphere. Refer to Figure 7. First, the substrate processing program 19 according to the specific substrate W is instructed by the operator. Thereafter, as preparation for loading the substrate W into the substrate processing apparatus 1, the control unit 13 performs an operation command and performs the following operations. The rotation of the rotation driving portion 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 retracted positions P1, P2, and P3, respectively. Further, the chuck pin 54 is opened by a switching mechanism (not shown). When the unprocessed substrate W is carried into the substrate processing apparatus 1 by the substrate loading/unloading mechanism (not shown) and placed on the chuck pin 54, the chuck pin 54 is replaced by a switching mechanism (not shown). Closed state. After the unprocessed substrate W is held by the substrate holding mechanism 51, the substrate is subjected to a cleaning 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 supply of the cleaning liquid (the rinsing liquid in the case of the rinsing treatment) is performed on the surface Wf of the substrate W which is rotated at a constant speed about the axis A1 by the operation command of the rotation driving unit 52 of the control unit 13. The washing liquid is not particularly limited, and examples thereof include SC-1 (liquid containing ammonia, hydrogen peroxide water, and water) or SC-2 (liquid containing hydrochloric acid, hydrogen peroxide water, and water). Further, the rinse liquid is not particularly limited, and examples thereof include DIW and the like. The supply amount of the cleaning liquid and the rinsing liquid is not particularly limited, and can be appropriately set depending on the cleaning range and the like. Further, the washing time is not particularly limited, and may be appropriately set as needed. Further, in the present embodiment, SC-1 is supplied to the surface Wf of the substrate W by the wet cleaning mechanism to clean the surface Wf, and then DIW is supplied to the surface Wf to remove the SC-1. (a) shown in Fig. 8 shows the case of the substrate W at the end of the cleaning step S11. As shown in FIG. 8, the DIW supplied in the cleaning step S11 is attached to the surface Wf of the substrate W on which the pattern Wp is formed (indicated by "60" in the drawing). Return to Figure 7. Next, an IPA rinsing step S12 for supplying IPA to the surface Wf of the substrate W to which the DIW 60 is attached is performed. First, the control unit 13 gives an operation command to the rotation driving unit 52 to rotate the substrate W around the axis A1 at a constant speed. Next, the control unit 13 gives an operation command to the turning drive unit 14 to position the nozzle 32 to the center portion of the surface Wf of the substrate W. Further, the control unit 13 issues an operation command to 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 via 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 Wf of the substrate W. Thereby, the DIW attached to the surface Wf of the substrate W is removed by the supply of the IPA, and the entire surface Wf of the substrate W is covered by the IPA. The rotation speed of the substrate W is preferably set such that the film of the film containing IPA is thicker than the entire surface of the surface Wf to a height higher than the height of the convex portion Wp1. Further, the supply amount of the IPA is not particularly limited and can be appropriately set. After the IPA flushing step S12 is completed, the control unit 13 commands the valve 36 to close the valve 36. Further, the control unit 13 issues an operation command to the turning drive unit 14 to position the nozzle 32 at the retracted position P2. (b) shown in Fig. 8 shows the case of the substrate W at the end of the IPA rinsing step S12. As shown in FIG. 8, the surface Wf of the substrate W on which the pattern Wp is formed adheres to the IPA supplied in the IPA rinsing step S12 (indicated by "61" in the drawing), and the DIW 60 is replaced with the IPA 61 from the surface of the substrate W. Wf removed. Return to Figure 7. Then, a treatment liquid supply step (supply step) S13 for supplying a treatment liquid containing a drying auxiliary liquid of a drying auxiliary substance in a melted state to the surface Wf of the substrate W to which the IPA 61 is attached is supplied. First, the control unit 13 gives an operation command to the rotation driving unit 52 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is preferably set such that the film thickness of the liquid film containing the drying auxiliary liquid is thicker than the height of the convex portion Wp1 over the entire surface of the surface Wf. Then, the control unit 13 gives an operation command to the turning drive unit 14 to position the nozzle 22 to the central portion of the surface Wf of the substrate W. Further, the control unit 13 issues an operation command to 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 via the pipe 25 and the nozzle 22. The liquid temperature of the supplied drying auxiliary liquid is set to be 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, when the above 1,1,2,2,3,3,4-heptafluorocyclopentane (boiling point 82.5 ° C) is used as the drying auxiliary substance, it is preferably set to 35 ° C or more and 82 ° C or less. range. Moreover, the supply amount of the drying auxiliary liquid is not particularly limited, and can be appropriately set. In this manner, the drying auxiliary liquid is supplied at a high temperature of a melting point or higher, whereby 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. Further, 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 the substrate A is supplied with a drying auxiliary liquid which is slightly higher than the melting point, the drying auxiliary liquid contacts the substrate. The condition of solidification after W 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 unevenness of 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 preferred to adjust the liquid temperature of the drying auxiliary liquid to a temperature sufficiently higher than the melting point. 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 due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire 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 Wf of the substrate W is covered with the drying auxiliary liquid. After the processing liquid supply step S13 is completed, the control unit 13 gives an operation command to the valve 26 to close the valve 26. Further, the control unit 13 issues an operation command to the turning drive unit 14 to position the nozzle 22 at the retracted position P1. (c) shown in FIG. 8 shows the case of the substrate W at the end of the processing liquid supply step S13. As shown in FIG. 8, the drying auxiliary liquid supplied in the processing liquid supply step S13 is attached to the surface Wf of the substrate W on which the pattern Wp is formed (indicated by "62" in the drawing), and the IPA 61 is replaced with the drying auxiliary liquid 62. It is removed from the surface Wf of the substrate W. Return to Figure 7. Next, a solidification step S14 of solidifying the solidification film of the drying auxiliary material by solidifying the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W is performed. First, the control unit 13 gives an operation command to the rotation driving unit 52 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is set to a speed at which the drying auxiliary liquid 62 is formed to a thickness higher than the film thickness of the specific thickness of the convex portion Wpl over the entire surface Wf. In turn, control unit 13 commands the valve 84 to open valve 84. By this, the refrigerant storage unit 82 supplies the refrigerant (the cold water of 7 ° C in the present embodiment) to the back surface Wb of the substrate W via 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 diffuses to 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 equal to or lower than the freezing point of the drying auxiliary substance, and solidified 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 the supply of cold water (indicated by "64" in the figure) of 7 ° C on the back surface Wb of the substrate W, and is formed to contain The solidified body of the drying auxiliary substance (shown as "63" in the figure). Return to Figure 7. Next, a sublimation step S15 of sublimating the solidified body 63 formed on the surface Wf of the substrate W and removing it from the surface Wf of the substrate W is performed. In the sublimation step S15, the cold water supply to the back surface Wb of the substrate W by the refrigerant supply mechanism 81 is continued while being supplied. Thereby, the solidified body 63 can be cooled to a temperature lower than 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 gives an operation command to the rotation drive unit 52 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is set to a speed at which the drying auxiliary liquid 62 is formed to a thickness higher than the film thickness of the specific thickness of the convex portion Wp1 over the entire surface Wf. Then, the control unit 13 instructs the turning drive unit 14 to position the nozzle 42 to the central portion of the surface Wf of the substrate W. Further, the control unit 13 issues an operation command to the valve 46 to open the valve 46. Thereby, a gas (nitrogen gas at 7 ° C in the present embodiment) is supplied from the air reservoir 47 to the surface Wf of the substrate W via the pipe 45 and the nozzle 42. Here, the partial pressure of the vapor of the drying auxiliary substance in the nitrogen gas is set to be lower than the saturated vapor pressure of the drying auxiliary substance at the supply temperature of the nitrogen gas. 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. Further, since the temperature of the nitrogen gas is lower than the melting point of the drying auxiliary substance, the melting of the solidified body 63 can be prevented and the sublimation of the solidified body 63 can be performed. By removing the substance such as IPA present on the surface Wf of the substrate W by sublimation of the drying auxiliary material in a solid state, it is possible to prevent the surface tension from being applied to the pattern Wp while suppressing the occurrence of pattern collapse, and to dry the substrate well. W surface Wf. (e) shown in Fig. 8 shows the case 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 solidifying step S14 is sublimated by the supply of nitrogen gas at 7 ° C to be removed from the surface Wf to complete the drying of the surface Wf of the substrate W. After the sublimation step S15 is completed, the control unit 13 issues an operation command to the valve 46 to close the valve 46. Further, the control unit 13 gives an operation command to the turning drive unit 14 to position the nozzle 42 at the retracted position P3. With the above, a series of substrate drying processes are ended. After the substrate drying process as described above, the substrate W that has been dried and processed is carried out from the chamber 11 by a substrate loading/unloading mechanism (not shown). As described above, in the present embodiment, the drying auxiliary liquid containing the drying auxiliary material in the 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 After the solidified body of the auxiliary substance is sublimated, the solidified body is sublimated and removed from the surface Wf of the substrate W, whereby the drying process of the substrate W can be performed. Here, by using a vapor pressure in the range of 20 ° C to 25 ° C of 5 kPa or more and a surface tension of 25 mN / m or less in the range of 20 ° C to 25 ° C as a drying auxiliary substance, the drying auxiliary substance is solidified. When the body is sublimated, the sublimation can be reduced unevenly. As a result, it is possible to prevent stress from being applied to the pattern, and it is possible to more reliably suppress pattern collapse on the substrate than the previous substrate drying. (Second embodiment) A second embodiment of the present invention will be described below. This embodiment differs from the first embodiment in that, in the solidifying step S14, nitrogen gas is supplied by the gas supply means 41 instead of the cold water supply by the refrigerant supply means 81. With such a configuration, it is also possible to suppress the collapse of the pattern and to dry the surface of the substrate well. <2-1 Overall configuration of the substrate processing apparatus and the drying auxiliary liquid> The substrate processing apparatus and the control unit of the second embodiment have substantially the same configuration as the substrate processing apparatus 1 and the control unit 13 of the first embodiment (see FIG. 1 and 2), the description of the same reference numerals will be omitted. Further, the drying auxiliary liquid used in the present embodiment is also the same as the drying auxiliary liquid of the first embodiment, and thus the description thereof will be omitted. <2-2 Substrate Processing Method> Next, a substrate processing method according to a second embodiment of the substrate processing apparatus 1 having the same configuration as that of the first embodiment will be described. Hereinafter, the steps of substrate processing will be described with reference to FIGS. 1, 2, 7, and 9. Fig. 9 is a schematic view showing the state of the substrate W in each step of Fig. 7. Further, in the second embodiment, the steps of the cleaning step S11, the IPA rinsing step S12, and the drying auxiliary liquid supply step S13 shown in Figs. 6 and 9 (a) to (c) are the same as in the first embodiment. Therefore, the description is omitted. Here, (a) of FIG. 9 shows a case where the surface Wf at the end of the cleaning step S11 of the second embodiment is covered with the liquid film of the DIW 60, and (b) of FIG. (2) In the case where the surface Wf at the end of the IPA rinsing step S12 of the embodiment is covered by the liquid film of the IPA 61, the (c) shown in Fig. 9 indicates the end of the drying auxiliary liquid supply step S13 of the second embodiment. The surface Wf is filled with the substrate W covered with the liquid film of the drying auxiliary liquid 62 of the drying auxiliary substance. Further, each step (a) to (e) shown in Fig. 9 is treated under an atmospheric pressure unless otherwise specified. Here, the atmospheric pressure environment refers to an environment having a standard atmospheric pressure (one atmosphere, 1013 hPa), 0.7 atmospheres or more, and 1.3 atmospheres or less. In particular, when the substrate processing apparatus 1 is disposed in a clean room that is a positive pressure, the environment of the surface Wf of the substrate W is higher than one atmosphere. Further, each of the processes (d) and (e) shown in FIG. 9 (details below) is at 17 Pa (17×10). -5 Under atmospheric pressure) 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 liquid film of the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W is solidified to form a solidifying step S14 of the solidified body containing the drying auxiliary material. Specifically, first, the control unit 13 gives an operation command to the rotation driving unit 52 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is preferably set such that the film thickness of the liquid film containing the drying auxiliary liquid is such that the entire surface of the surface Wf is higher than the height of the convex portion Wp1. Then, the control unit 13 instructs the turning drive unit 14 to position the nozzle 42 to the central portion of the surface Wf of the substrate W. Further, the control unit 13 issues an operation command to the valve 46 to open the valve 46. Thereby, a gas (nitrogen gas at 7 ° C in the present embodiment) is supplied from the air reservoir 47 to the surface Wf of the substrate W via 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 portion 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 equal to or lower than the freezing point of the drying auxiliary substance, and solidified 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 supply of nitrogen gas at 7 ° C to form a solidified body 63 containing a drying auxiliary material. Return to Figure 7. Next, a sublimation step S15 of sublimating the solidified body 63 formed on the surface Wf of the substrate W and removing it from the surface Wf of the substrate W is performed. In the sublimation step S15, the solidification step S14 is also continued to supply the gas (nitrogen gas) from the nozzle 42. Here, the partial pressure of the vapor of the drying auxiliary substance in the nitrogen gas is set to be lower than the saturated vapor pressure of the drying auxiliary substance at the supply temperature of the nitrogen gas. 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. Further, since the temperature of the nitrogen gas is lower than the melting point of the drying auxiliary substance, the melting of the solidified body 63 can be prevented and the sublimation of the solidified body 63 can be performed. By removing the substance such as IPA present on the surface Wf of the substrate W by sublimation of the drying auxiliary material in a solid state, it is possible to prevent the surface tension from being applied to the pattern Wp while suppressing the occurrence of pattern collapse, and to dry the substrate well. W surface Wf. (e) shown in FIG. 9 indicates the case 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 to be removed from the surface Wf to complete the drying of the surface Wf of the substrate W. After the sublimation step S15 is completed, the control unit 13 issues an operation command to the valve 46 to close the valve 46. Further, the control unit 13 gives an operation command to the turning drive unit 14 to position the nozzle 42 at the retracted position P3. With the above, a series of substrate drying processes are ended. After the substrate drying process as described above, the substrate W that has been dried and processed is carried out from the chamber 11 by a substrate loading/unloading mechanism (not shown). In the present embodiment, in the solidifying step S14 and the sublimation step S15, the common gas supply means 41 is used to supply nitrogen gas which is an inert gas inert to the drying auxiliary substance at a temperature lower than the freezing point of the drying auxiliary substance. Thereby, after the solidification step S14, the sublimation step S15 can be started immediately, and the amount of memory of the substrate processing program 19 of the control unit 13 that causes the processing time of each unit of the substrate processing apparatus 1 to be operated can be reduced, and Since the number of parts used in the process can be reduced, there is an effect of reducing the cost of the device. In particular, in the present embodiment, the pressure reducing mechanism 71 is not used, so that the pressure reducing mechanism 71 can be omitted. (Third embodiment) A third embodiment of the present invention will be described below. This embodiment differs from the second embodiment in that, in the solidification step S14 and the sublimation step S15, the inside of the chamber is decompressed instead of supplying nitrogen. With such a configuration, it is also possible to suppress the collapse of the pattern and to dry the surface of the substrate W well. <3-1 Overall configuration of the substrate processing apparatus and the drying auxiliary liquid> The substrate processing apparatus and the control unit of the third embodiment have substantially the same configuration as the substrate processing apparatus 1 and the control unit 13 of the first embodiment (see FIG. 1 and Fig. 2), the description of which is attached with the same reference numerals and is omitted. Further, the drying auxiliary liquid used in the present embodiment is also the same as the drying auxiliary liquid of the first embodiment, and thus the description thereof will be omitted. <3-2 Substrate Processing Method> Next, a substrate processing method using the third embodiment of the substrate processing apparatus 1 having the same configuration as that of the first embodiment will be described. Hereinafter, the steps of substrate processing will be described with reference to FIGS. 1, 2, 7, and 10. Fig. 10 is a schematic view showing the state of the substrate W in each step of Fig. 7. Further, in the third embodiment, the steps of the cleaning step S11, the IPA rinsing step S12, and the processing liquid supply step S13 shown in Figs. 7 and 10(a) to (c) are the same as in the first embodiment. Therefore, the description is omitted. Here, (a) of FIG. 10 shows a case where the surface Wf at the end of the cleaning step S11 of the third embodiment is covered with the liquid film of the DIW 60, and (b) of FIG. (3) In the case where the surface Wf at the end of the IPA rinsing step S12 of the embodiment is covered by the liquid film of the liquid film of the IPA 61, the (c) shown in Fig. 10 indicates the surface at the end of the processing liquid supply step S13 of the third embodiment. Wf is a case where the substrate W covered with the liquid film of the drying auxiliary liquid 62 in which the drying auxiliary substance (sublimation substance) is dissolved is dissolved. Further, each step up to (a) to (e) shown in FIG. 10 is treated in an atmospheric pressure atmosphere unless otherwise specified. Here, the atmospheric pressure environment refers to an environment having a standard atmospheric pressure (one atmosphere, 1013 hPa), 0.7 atmospheres or more, and 1.3 atmospheres or less. In particular, when the substrate processing apparatus 1 is disposed in a clean room that is a positive pressure, the environment of the surface Wf of the substrate W is higher than one atmosphere. Further, the processing shown in (d) and (e) of FIG. 10 (details of the following) is 1.7 Pa (1.7×10). -5 Under atmospheric pressure) 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, the liquid film of the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W is solidified to form a solidifying step S14 of the solidified body containing the drying auxiliary material. Specifically, first, the control unit 13 gives an operation command to the rotation driving unit 52 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is preferably set such that the film thickness of the liquid film containing the drying auxiliary liquid is such that the entire surface of the surface Wf is higher than the height of the convex portion Wp1. Then, the control unit 13 issues an operation command to the exhaust pump 72 to start driving of the exhaust pump 72. And the control unit 13 gives an action command to the valve 74 to open the valve 74. Thereby, the gas inside the chamber 11 is exhausted to the outside of the chamber 11 via the piping 73. The inside of the chamber 11 is sealed except for the piping 73, whereby the internal environment of the chamber 11 is depressurized from atmospheric pressure. The decompression system is carried out from atmospheric pressure (about 1 atmosphere, about 1013 hPa) to 1.7×10. -5 About atmospheric pressure (1.7 Pa). In addition, in the practice of the present invention, the air pressure is not limited to the air pressure, and the air pressure in the chamber 11 after the pressure reduction can be appropriately set according to the pressure resistance of the chamber 11 or the like. When the inside of the chamber 11 is depressurized, 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 pressure reduction in the chamber 11, thereby forming a solidified body of the drying auxiliary substance. 63. At this time, the layer thickness of the solidified body 63 is reduced to a degree equivalent to the amount of evaporation of the drying auxiliary liquid 62. Therefore, in the treatment liquid supply step S13 of the present embodiment, it is preferable to make the drying auxiliary liquid 62 a liquid film having a specific thickness or more in consideration of the evaporation amount of the drying auxiliary liquid 62 in the solidifying step S14. The rotation speed of the substrate W and the like are adjusted. Return to Figure 7. Next, a sublimation step S15 of sublimating the solidified body 63 formed on the surface Wf of the substrate W and removing it from the surface Wf of the substrate W is performed. In the sublimation step S15, the solidification step S14 is also continued to be subjected to the pressure reduction treatment in the chamber 11 of the pressure reducing mechanism 71. By the reduced pressure 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 material from the solidified body 63 occurs, the solidified body 63 is also taken away as heat of sublimation heat, so that the solidified body 63 is cooled. Therefore, in the third embodiment, in the sublimation step S15, even if the environment in the chamber 11 is slightly higher than the melting point of the drying auxiliary substance (normal temperature environment), the solidified body 63 may not be separately cooled. The solidified body 63 is maintained at a temperature lower than the melting point of the drying auxiliary substance, and the solidification body 63 is prevented from being melted and the sublimation of the solidified body 63 is performed. As a result, there is no need to separately provide a cooling mechanism, so that the device cost or the processing cost can be reduced. As described above, when the substance such as IPA present on the surface Wf of the substrate W is removed by sublimation of the drying auxiliary substance in a solid state, the surface tension can be prevented from acting on the pattern Wp, and the occurrence of pattern collapse can be prevented, and the film can be dried well. The surface Wf of the substrate W. (e) shown in FIG. 10 indicates the state of the substrate W at the end of the sublimation step S15. As shown in FIG. 10, the solidified body 63 of the drying auxiliary substance formed in the solidifying step S14 is sublimated and removed from the surface Wf by the inside of the chamber 11 as a reduced pressure environment, thereby completing the drying of the surface Wf of the substrate W. After the sublimation step S15 is completed, the control unit 13 commands the valve 74 to open the valve 74. Further, the control unit 13 issues an operation command to the exhaust pump 72 to stop the operation of the exhaust pump 72. Further, the control unit 13 issues an operation command to the valve 46 to open the valve 46, thereby introducing a gas (nitrogen gas) from the air reservoir 47 into the chamber 11 through the pipe 45 and the nozzle 42, thereby decompressing the inside of the chamber 11. The environment is restored to an atmospheric environment. At this time, the nozzle 42 may be located at the retracted position P3 or at the central portion of the surface Wf of the substrate W. Further, after the completion of the sublimation step S15, the method of returning the inside of the chamber 11 to the atmospheric pressure environment is not limited to the above, and various known methods can be employed. With the above, a series of substrate drying processes are ended. After the substrate drying process as described above, the substrate W that has been dried and processed is carried out from the chamber 11 by a substrate loading/unloading mechanism (not shown). As described above, in the present embodiment, the drying auxiliary liquid for melting the drying auxiliary material is supplied to the surface Wf of the substrate W to which the IPA is attached, and the IPA is replaced. 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 then the drying auxiliary material is sublimated to be removed from the surface Wf of the substrate W. Thereby, the drying process of the substrate W is performed. According to the present embodiment, solidification and sublimation of the drying auxiliary liquid are performed by decompression, and the pattern can be prevented from collapsing and the substrate W can be dried well. The specific pattern suppressing effect is explained in the following examples. Further, in the present embodiment, in the solidifying step S14 and the sublimation step S15, the inside of the chamber 11 is decompressed by using the common pressure reducing mechanism 71. Thereby, the sublimation step S15 can be started immediately after the solidification step S14, and the amount of memory of the substrate processing program 19 of the control unit 13 that causes the processing time of each unit of the substrate processing apparatus 1 to operate or can be reduced can be reduced. Moreover, the number of parts used in the process can also be reduced, so that the effect of reducing the cost of the device can be reduced. In particular, in the third embodiment, since low-temperature nitrogen gas is not used, the temperature adjustment unit 272 in the gas supply mechanism 41 can be omitted. Further, when the mechanism other than the gas supply mechanism 41 is used to restore the pressure reduction environment to the atmospheric pressure in the chamber 11, the gas supply mechanism 41 can be omitted. (Variation) In the above description, a preferred embodiment of the present invention has been described. However, the present invention is not limited to the embodiments and can be implemented in other various 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 thereto, and the chambers may be prepared for each step. For example, in each embodiment, it is possible to perform the solidification film on the surface Wf of the substrate W after the solidification step S14, and then the substrate W is carried out from the first chamber, and the substrate W on which the solidified film is formed is formed. The second chamber is moved into the second chamber, and the sublimation step S15 is performed in the second chamber. Further, in the first embodiment, in the sublimation step S15, the supply of nitrogen gas by the gas supply means 41 is continued while the cold water supply by the refrigerant supply means 81 continues. However, the implementation of the present invention is not limited thereto, and the supply of nitrogen gas by the gas supply mechanism 41 may be stopped, and the cooling auxiliary material of the solidified body 63 may be naturally sublimated while the cold water is supplied by the refrigerant supply mechanism 81. Hereinafter, preferred embodiments of the invention will be described in detail by way of illustration. However, the materials, the blending amounts, and the like described in the examples are not limited to those described above unless otherwise specified. (Substrate) As a substrate, a germanium substrate having a model pattern formed on its surface is prepared. Fig. 11 shows an SEM (Scanning Electron Microscope) image showing the surface on which the pattern of the ruthenium substrate is formed. As a model pattern, a pattern in which a cylinder having a diameter of 30 nm and a height of 480 nm (an aspect ratio of 16) is arranged at intervals of about 80 nm is used. In Fig. 11, the portion indicated by white is the head portion of the cylindrical portion (i.e., the convex portion of the pattern), and the portion indicated by black is the concave portion of the pattern. As shown in FIG. 11, it was confirmed that the pattern forming surface regularly arranged white circles of almost the same size. (Example 1) In the present example, the drying process of the above-mentioned ruthenium substrate was carried out in the following order, and the effect of suppressing the collapse of the pattern was evaluated. Further, in the processing of the substrate, the substrate processing apparatus described in the first embodiment is used. <Sequence 1-1 Irradiation of Ultraviolet Light> First, the surface of the ruthenium substrate is irradiated with ultraviolet light to make the surface characteristics hydrophilic. Thereby, the liquid is easily allowed to enter the concave portion of the pattern, and after the liquid is supplied, an environment in which the pattern collapse is easily created is artificially created. <Sequence 1-2 Supply Step> Next, in the chamber 11 under atmospheric pressure, a drying auxiliary liquid (liquid temperature: 40 ° C) obtained by melting a sublimating substance is directly supplied to the pattern forming surface of the dried crucible substrate. Thereby, a liquid film containing a drying auxiliary liquid is formed on the pattern forming surface of the tantalum substrate. As the sublimable substance, 1,1,2,2,3,3,4-heptafluorocyclopentane represented by the following chemical structural formula is used. The surface tension of the compound was 19.6 mN/m in an environment of 25 ° C, and the vapor pressure was 8.2 kPa (62.0 mmHg) in an environment of 20 ° C (both literature values, see Table 1 below). Further, it is a substance having a melting point and a freezing point of 20.5 ° C and a specific gravity of 1.58 in an environment of 25 ° C. Further, since the compound is excellent in 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 fouling. <Sequence 1-3 Solidification Step> Next, nitrogen gas at 7 ° C is supplied to a liquid film containing a drying auxiliary liquid under atmospheric pressure, and the drying auxiliary liquid is solidified to form a solidified body. <Sequence 1-4 Sublimation Step> Further, under a normal temperature and atmospheric pressure environment, nitrogen gas at 7 ° C is continuously supplied to the solidified body, thereby preventing the solidification body from melting and sublimating the drying auxiliary substance (sublimating substance), and solidifying The body is removed from the pattern forming surface of the substrate. Further, the temperature of the nitrogen gas was 7 ° C, which was lower than the melting point of the 1,1,2,2,3,3,4-heptafluorocyclopentane (20.5 ° C), so that the solidified body was not additionally cooled. Figure 12 is an SEM image of a ruthenium substrate after the above sequence 1-1 to 1-4. The collapse of the pattern was reduced as compared with the pattern forming surface of the substrate (see FIG. 11) before the drying process, and the collapse rate of the displayed region was 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 excellently suppressed, and it is effective for sublimation drying. Furthermore, the above collapse rate is a value calculated by the following formula. Collapse rate (%) = (number of convex portions of collapse in an arbitrary region) ÷ (total number of convex portions in the region) × 100 (Example 2) In the present embodiment, as a drying auxiliary substance, a dodecafluorocyclo ring was used. Hexane (vapor pressure of 33.1 kPa (25 ° C), surface tension of 12.6 mN / m (25 ° C), melting point and freezing point of 51 ° C, all literature values) (refer to Table 1 below) instead of 1,1,2 , 2,3,3,4-heptafluorocyclopentane. Otherwise, in the same manner as in the first embodiment, the order 1-1 to the order 1-4 were carried out, and freeze-drying of the pattern forming surface of the ruthenium substrate was performed. Fig. 13 is an SEM image of the ruthenium substrate after the execution of the sequence 1-1 to the order 1-4 in the present embodiment. The collapse of the pattern was greatly reduced as compared with the pattern forming surface of the substrate (see FIG. 11) before the drying process, and the collapse rate of the displayed region was 2.5%. This shows that when dihydrofluorocyclohexane is used as the drying auxiliary substance, the collapse of the pattern can be suppressed extremely well, and it is effective for sublimation drying. (Comparative Example 1) In the comparative example, third butanol was used as the drying auxiliary material (vapor pressure was 4.1 kPa (20 ° C), surface tension was 19.56 mN/m (20 ° C), and melting point and freezing point were 25 ° C. , which are literature values) (refer to Table 1 below) instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Otherwise, in the same manner as in the first embodiment, the order 1-1 to the order 1-4 were carried out, and freeze-drying of the pattern forming surface of the ruthenium substrate was performed. Fig. 14 is an SEM image of the ruthenium substrate after the execution of the sequence 1-1 to the order 1-4 in the present embodiment. The collapse of the pattern was not reduced as compared with the pattern forming surface of the substrate (see FIG. 11) before the drying treatment, and the collapse ratio of the displayed region was 52.3%. From this, it was confirmed that when the third butanol was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient.

(比較例2) (Comparative Example 2)

於本比較例中，作為乾燥輔助物質，使用乙酸(蒸氣壓為1.50kPa(20℃)，表面張力為27.7mN/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。 In the comparative example, acetic acid was used as the drying auxiliary material (vapor pressure was 1.50 kPa (20 ° C), surface tension was 27.7 mN/m (20 ° C), melting point and freezing point were 17 ° C, both are literature values) (Refer to Table 1) below replaces 1,1,2,2,3,3,4-heptafluorocyclopentane. Otherwise, in the same manner as in the first embodiment, the order 1-1 to the order 1-4 were carried out, and freeze-drying of the pattern forming surface of the ruthenium substrate was performed.

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，於使用乙酸作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 Fig. 15 is an SEM image of the ruthenium substrate after the execution of the sequence 1-1 to the order 1-4 in the present embodiment. Compared with the pattern forming surface of the substrate before the drying process (see FIG. 11), a large-scale pattern collapse occurred, and the collapse rate of the displayed region was 99.1%. From this, it was confirmed that when acetic acid was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient.

(比較例3) (Comparative Example 3)

於本比較例中，作為乾燥輔助物質，使用1,4-二烷(蒸氣壓為3.9kPa(20℃)，表面張力為33.4mN/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。 In this comparative example, as a drying auxiliary substance, 1,4-two is used. Alkane (vapor pressure 3.9 kPa (20 ° C), surface tension 33.4 mN / m (25 ° C), melting point and freezing point of 11 ° C, are literature values) (refer to Table 1 below) instead of 1,1,2, 2,3,3,4-heptafluorocyclopentane. Otherwise, in the same manner as in the first embodiment, the order 1-1 to the order 1-4 were carried out, and freeze-drying of the pattern forming surface of the ruthenium substrate was performed.

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1,4-二烷作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 Fig. 16 is an SEM image of the ruthenium substrate after the execution of the sequence 1-1 to the order 1-4 in the present embodiment. Compared with the pattern forming surface of the substrate (see FIG. 11) before the drying process, a large-scale pattern collapse occurred, and the collapse rate of the displayed region was 99.3%. It is confirmed that the use of 1,4-two When the alkane is used as a drying auxiliary substance, the reduction in pattern collapse is insufficient.

(比較例4) (Comparative Example 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 0.37kPa(25℃)，表面張力為29.2mN/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。 In this comparative example, as a drying auxiliary substance, 4,4-difluorocyclohexane was used (vapor pressure was 0.37 kPa (25 ° C), surface tension of 29.2 mN / m (25 ° C), melting point and freezing point of 35 ~ 36 ° C, are literature values) (refer to Table 1 below) instead of 1,1,2,2,3 , 3,4-heptafluorocyclopentane. Otherwise, in the same manner as in the first embodiment, the order 1-1 to the order 1-4 were carried out, and freeze-drying of the pattern forming surface of the ruthenium substrate was performed.

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4,4-二氟環己烷作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 Fig. 17 is an SEM image of the ruthenium substrate after the execution of the sequence 1-1 to the order 1-4 in the present embodiment. Compared with the pattern forming surface of the ruthenium substrate before the drying treatment (see Fig. 11), a large-scale pattern collapse occurred, and the collapse ratio of the displayed region was 97.0%. From this, it was confirmed that when 4,4-difluorocyclohexane was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient.

(比較例5) (Comparative Example 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5.67kPa(25℃)，表面張力為21.8mN/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。 In the comparative example, as a drying auxiliary substance, fluorocyclohexane (vapor pressure: 5.67 kPa (25 ° C), surface tension of 21.8 mN/m (25 ° C), melting point and freezing point of 13 ° C, all of which are literature values. (Refer to Table 1 below) instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Otherwise, in the same manner as in the first embodiment, the order 1-1 to the order 1-4 were carried out, and freeze-drying of the pattern forming surface of the ruthenium substrate was performed.

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，於使用氟環己烷作為乾燥輔助物質之情形時，圖案倒塌之減少不充分。 Fig. 18 is an SEM image of the ruthenium substrate after the execution of the sequence 1-1 to the order 1-4 in the present embodiment. The collapse of the pattern was not reduced as compared with the pattern forming surface of the substrate (see FIG. 11) before the drying treatment, and the collapse rate of the displayed region was 35.8%. From this, it was confirmed that when fluorocyclohexane was used as the drying auxiliary substance, the reduction in pattern collapse was insufficient.

(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。(Result) As shown in FIG. 12 to FIG. 18, Example 1 in which 1,1,2,2,3,3,4-heptafluorocyclopentane and dodecafluorocyclohexane were used as drying auxiliary substances was confirmed. In the case of 2, for example, the occurrence of pattern collapse can be reduced as compared with the case of Comparative Examples 1 to 5 using the previous drying auxiliary substance. The present invention can be applied to a drying technique for removing a liquid adhering to a surface of a substrate, and a substrate processing technique for treating the surface of the substrate using the drying technique.

1‧‧‧基板處理裝置1‧‧‧Substrate processing unit

11‧‧‧腔室11‧‧‧ chamber

12‧‧‧飛散防止杯12‧‧‧scattering prevention cup

13‧‧‧控制單元13‧‧‧Control unit

14‧‧‧迴轉驅動部14‧‧‧Slewing drive department

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‧‧‧Processing liquid supply mechanism

22‧‧‧噴嘴22‧‧‧Nozzles

23‧‧‧支臂23‧‧‧ Arms

24‧‧‧迴轉軸24‧‧‧Rotary axis

25‧‧‧配管25‧‧‧Pipe

26‧‧‧閥門26‧‧‧ Valve

27‧‧‧處理液貯存部27‧‧‧Processing liquid storage department

31‧‧‧IPA供給機構31‧‧‧IPA supply agency

32‧‧‧噴嘴32‧‧‧Nozzles

33‧‧‧支臂33‧‧‧ Arms

34‧‧‧迴轉軸34‧‧‧Rotary axis

35‧‧‧配管35‧‧‧Pipe

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‧‧‧Nozzles

43‧‧‧支臂43‧‧‧ Arm

44‧‧‧迴轉軸44‧‧‧Rotary axis

45‧‧‧配管45‧‧‧Pipe

46‧‧‧閥門46‧‧‧ Valve

47‧‧‧貯氣槽47‧‧‧ gas storage tank

51‧‧‧基板保持機構51‧‧‧Substrate retention mechanism

52‧‧‧旋轉驅動部52‧‧‧Rotary drive department

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‧‧‧Dry auxiliary liquid

63‧‧‧凝固體63‧‧‧ solidified body

64‧‧‧冷水64‧‧‧ cold water

71‧‧‧減壓機構71‧‧‧Relief mechanism

72‧‧‧排氣泵72‧‧‧Exhaust pump

73‧‧‧配管73‧‧‧Pipe

74‧‧‧閥門74‧‧‧ Valve

81‧‧‧冷媒供給機構81‧‧‧Refrigerant supply agency

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

83‧‧‧配管83‧‧‧Pipe

84‧‧‧閥門84‧‧‧ Valve

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

271‧‧‧處理液貯存槽271‧‧‧Processing fluid storage tank

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

273‧‧‧配管273‧‧‧Pipe

274‧‧‧加壓部274‧‧‧ Pressurization

275‧‧‧氮氣槽275‧‧‧nitrogen tank

276‧‧‧泵276‧‧‧ pump

277‧‧‧攪拌部277‧‧‧Stirring Department

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

279‧‧‧旋轉部279‧‧‧Rotating Department

471‧‧‧氣體貯存部471‧‧‧ Gas Storage Department

472‧‧‧氣體溫度調整部472‧‧‧ Gas Temperature Adjustment Department

821‧‧‧冷媒槽821‧‧‧ refrigerant tank

822‧‧‧冷媒溫度調整部822‧‧‧Refrigerant Temperature Adjustment Department

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‧‧‧Retraction position

P2‧‧‧退避位置P2‧‧‧Retraction position

P3‧‧‧退避位置P3‧‧‧Retraction 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 view 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 above substrate processing apparatus. 3A is a block diagram showing a schematic configuration of a drying auxiliary liquid storage unit of the substrate processing apparatus. Fig. 3B is an explanatory view showing a specific configuration of the drying auxiliary liquid storage unit. Fig. 4 is a block diagram showing a schematic configuration of a gas storage tank of the substrate processing apparatus. Fig. 5 is a block diagram showing a schematic configuration of a refrigerant storage unit of the substrate processing apparatus. Fig. 6 is an explanatory view showing a schematic configuration of a control unit of the substrate processing apparatus. Fig. 7 is a flow chart showing a substrate processing method using the above substrate processing apparatus. 8(a) to 8(e) are views showing a state of a substrate in each step of the substrate processing method. 9(a) to 9(e) are flowcharts showing a substrate processing method according to a second embodiment of the present invention. 10(a) to 10(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 forming surface of an untreated ruthenium substrate used in Examples and Comparative Examples of the present invention. Fig. 12 is a view showing an SEM image of a pattern forming surface of a ruthenium substrate on which substrate processing according to the first embodiment of the present invention is carried out. Fig. 13 is a view showing an SEM image of a pattern forming surface of a substrate on which a substrate of Example 2 of the present invention is applied. Fig. 14 is a SEM image showing the pattern forming surface of the ruthenium substrate on which the substrate treatment of Comparative Example 1 was carried out. Fig. 15 is a SEM image showing the pattern forming surface of the ruthenium substrate on which the substrate treatment of Comparative Example 2 was carried out. Fig. 16 is a SEM image showing the pattern forming surface of the ruthenium substrate on which the substrate treatment of Comparative Example 3 was carried out. Fig. 17 is a SEM image showing the pattern forming surface of the ruthenium substrate on which the substrate treatment of Comparative Example 4 was carried out. Fig. 18 is a SEM image showing the pattern forming surface of the ruthenium substrate on which the substrate treatment of Comparative Example 5 was carried out.

Claims (13)

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5kPa以上，20℃~25℃下之表面張力為20mN/m以下。 A substrate processing apparatus for drying a pattern forming surface of a substrate, comprising: a supply mechanism for supplying a processing liquid containing a sublimable substance in a melted state to a pattern forming surface of the substrate; and forming the processing liquid in the pattern a solidification mechanism that solidifies to form a solidified body, and a sublimation mechanism that removes the solidified body and is removed from the pattern forming surface, and the vapor pressure of the sublimation substance at 20 ° C to 25 ° C is 5 kPa or more, 20 ° C ~ The surface tension at 25 ° C is 20 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為1,1,2,2,3,3,4-七氟環戊烷或十二氟環己烷。 The substrate processing apparatus of claim 1, wherein the sublimation substance is 1,1,2,2,3,3,4-heptafluorocyclopentane or dodecafluorocyclohexane. 如請求項1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。 The substrate processing apparatus according to claim 1, wherein the supply mechanism supplies the treatment liquid to a pattern forming surface of the substrate at atmospheric pressure, and the solidification mechanism cools the treatment liquid to a freezing point of the sublimable substance under atmospheric pressure. By. 如請求項1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。 The substrate processing apparatus of claim 1, wherein the sublimation substance has sublimation at atmospheric pressure, The sublimation mechanism is such that the sublimation substance is sublimated under atmospheric pressure. 如請求項1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。 The substrate processing apparatus according to claim 1, wherein at least one of the solidification mechanism and the sublimation mechanism is a refrigerant supply mechanism that supplies a refrigerant to a back surface opposite to a pattern forming surface of the substrate at a temperature lower than a freezing point of the sublimable substance. . 如請求項3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。 The substrate processing apparatus according to claim 3, wherein at least one of the solidification mechanism or the sublimation mechanism supplies a gas which is at least inert to the sublimation substance to the pattern forming surface at a temperature lower than a freezing point of the sublimable substance. Supply agency. 如請求項3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。 The substrate processing apparatus according to claim 3, wherein the sublimation mechanism supplies a gas supply mechanism that supplies at least a gas inert to the sublimation substance to the pattern forming surface at a temperature lower than a freezing point of the sublimable substance, and the sublimation substance The refrigerant supply mechanism that supplies the refrigerant to the back surface opposite to the pattern forming surface of the substrate at a temperature lower than the freezing point. 如請求項1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 1, wherein the sublimation mechanism is a pressure reducing mechanism in which the pattern forming surface of the solidified body is depressurized 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 of claim 1, wherein The coagulation mechanism is a decompression mechanism that decompresses the pattern forming surface of the treatment liquid to an atmosphere lower than atmospheric pressure. 如請求項9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 of claim 9, wherein the above-described pressure reducing mechanism is used as the sublimation mechanism. 如請求項1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 1, wherein the supply mechanism has a processing liquid temperature adjusting unit that adjusts a temperature of the processing liquid to a temperature higher than a melting point of the sublimable substance and lower than a 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5kPa以上，20℃~25℃下之表面張力為20mN/m以下。 A substrate processing method for drying a pattern forming surface of a substrate, comprising: supplying a processing liquid containing a sublimating substance in a melted state to a pattern forming surface of the substrate; and applying the processing liquid to the pattern forming surface a method of solidification which solidifies to form a solidified body, and a sublimation method for removing 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, 20 ° C to 25 The surface tension at ° C is 20 mN/m or less. 如請求項12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 of claim 12, wherein the sublimation substance is 1,1,2,2,3,3,4-heptafluorocyclopentane or dodecafluorocyclohexane.
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