TWI443190B - Cleaning liquid, cleaning method, cleaning system, and method for manufacturing microstructure - Google Patents
Cleaning liquid, cleaning method, cleaning system, and method for manufacturing microstructure Download PDFInfo
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- TWI443190B TWI443190B TW099130900A TW99130900A TWI443190B TW I443190 B TWI443190 B TW I443190B TW 099130900 A TW099130900 A TW 099130900A TW 99130900 A TW99130900 A TW 99130900A TW I443190 B TWI443190 B TW I443190B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
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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
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
- H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
Description
本文所闡述之實施例大體而言係關於一種清洗液、一種清洗方法、一種清洗系統及一種用於製造微細構造之方法。The embodiments set forth herein are generally directed to a cleaning fluid, a cleaning method, a cleaning system, and a method for making a microstructure.
此申請案係基於2009年9月25日申請之第2009-219890號先前日本專利申請案並主張該申請案之優先權之利益，該申請案之全部內容以引用方式併入本文中。The application is based on the benefit of the priority of the Japanese Patent Application No. 2009- 219 890, filed on
在諸如半導體裝置及MEMS(微機電系統)之領域中，具有細微壁體之微細構造係使用微影技術製造於表面上。在製造製程期間形成且然後變得非必要之抗蝕劑係使用SPM(硫酸過氧化氫混合物)溶液(亦即，濃硫酸與過氧化氫水溶液之混合液)來移除(例如，參見JP-A 2007-123330(Kokai))。In fields such as semiconductor devices and MEMS (Micro Electro Mechanical Systems), fine structures having fine walls are fabricated on the surface using lithography. The resist formed during the manufacturing process and then becoming unnecessary is removed using a SPM (sulfuric acid hydrogen peroxide mixture) solution (ie, a mixture of concentrated sulfuric acid and aqueous hydrogen peroxide solution) (for example, see JP- A 2007-123330 (Kokai)).
在此SPM溶液中包含藉由混合濃硫酸與過氧化氫水溶液產生之氧化物質(例如，過氧單硫酸)。An oxidizing substance (for example, peroxymonosulfuric acid) produced by mixing concentrated sulfuric acid with an aqueous hydrogen peroxide solution is contained in the SPM solution.
此外，已提出使用藉由電解硫酸水溶液產生之氧化物質(例如，過氧單硫酸)來移除黏附至晶圓及類似物之抗蝕劑之技術(參見JP-A 2006-111943(Kokai))。Further, a technique of removing a resist adhered to a wafer and the like by using an oxidizing substance (for example, peroxymonosulfuric acid) produced by electrolyzing an aqueous sulfuric acid solution has been proposed (see JP-A 2006-111943 (Kokai)) .
JP-A 2007-123330(Kokai)及JP-A 2006-111943(Kokai)中所論述之技術使用所產生氧化物質之高氧化分解能力分解並移除抗蝕劑，亦即有機物質。The technique discussed in JP-A 2007-123330 (Kokai) and JP-A 2006-111943 (Kokai) uses the high oxidative decomposition ability of the produced oxidizing substance to decompose and remove the resist, that is, the organic substance.
此處，在藉由以高劑量植入雜質製造高速運作半導體裝置時，藉由以該高劑量植入該雜質在該抗蝕劑之表面中形成經改動層。其中形成有此經改動層之該抗蝕劑不能容易地移除；且遺憾的是，不能僅藉由上文所述氧化物質之氧化分解能力獲得所期望移除邊際。Here, when a high-speed operation semiconductor device is manufactured by implanting impurities at a high dose, a modified layer is formed in the surface of the resist by implanting the impurity at the high dose. The resist in which the modified layer is formed cannot be easily removed; and unfortunately, the desired removal margin cannot be obtained only by the oxidative decomposition ability of the oxidizing substance described above.
大體而言，根據一個實施例，一種清洗液包含氧化物質及氫氟酸且表現酸性。In general, according to one embodiment, a cleaning fluid comprises an oxidizing species and hydrofluoric acid and exhibits acidity.
在另一實施例中，本發明揭示一種清洗方法。該方法包含藉由選自電解硫酸溶液、電解添加至硫酸溶液之氫氟酸及混合硫酸溶液與過氧化氫水溶液中之一者產生包含氧化物質之氧化溶液。該方法包含將氧化溶液及氫氟酸供應至欲清洗之物件之表面。In another embodiment, the invention discloses a method of cleaning. The method comprises producing an oxidizing solution comprising an oxidizing species by one selected from the group consisting of an electrolytic sulfuric acid solution, hydrofluoric acid added to a sulfuric acid solution, and a mixed sulfuric acid solution and an aqueous hydrogen peroxide solution. The method comprises supplying an oxidizing solution and hydrofluoric acid to the surface of the article to be cleaned.
在另一實施例中，清洗系統包含硫酸電解單元、硫酸供應單元、清洗處理單元、第一氫氟酸供應單元及氧化溶液供應單元。硫酸電解單元包含陽極、陰極、提供於該陽極與該陰極之間的隔膜、提供於該陽極與該隔膜之間的陽極室及提供於該陰極與該隔膜之間的陰極室，該硫酸電解單元電解硫酸溶液以在該陽極室中產生氧化物質。該硫酸供應單元將硫酸溶液供應至該陽極室及該陰極室。該清洗處理單元執行對欲清洗之物件之清洗處理。該第一氫氟酸供應單元將氫氟酸供應至該清洗處理單元。另外，該氧化溶液供應單元將包含該氧化物質之氧化溶液供應至該清洗處理單元。In another embodiment, the cleaning system includes a sulfuric acid electrolysis unit, a sulfuric acid supply unit, a cleaning treatment unit, a first hydrofluoric acid supply unit, and an oxidizing solution supply unit. The sulfuric acid electrolysis unit comprises an anode, a cathode, a separator provided between the anode and the cathode, an anode chamber provided between the anode and the separator, and a cathode chamber provided between the cathode and the separator, the sulfuric acid electrolysis unit The sulfuric acid solution is electrolyzed to produce an oxidizing species in the anode compartment. The sulfuric acid supply unit supplies a sulfuric acid solution to the anode chamber and the cathode chamber. The cleaning processing unit performs a cleaning process on the object to be cleaned. The first hydrofluoric acid supply unit supplies hydrofluoric acid to the cleaning processing unit. Further, the oxidizing solution supply unit supplies an oxidizing solution containing the oxidizing substance to the cleaning processing unit.
在另一實施例中，清洗系統包含硫酸電解單元、硫酸供應單元、清洗處理單元、第二氫氟酸供應單元及氧化溶液供應單元。硫酸電解單元包含陽極、陰極、提供於該陽極與該陰極之間的隔膜、提供於該陽極與該隔膜之間的陽極室及提供於該陰極與該隔膜之間的陰極室，該硫酸電解單元電解硫酸溶液以在該陽極室中產生氧化物質。該硫酸供應單元將硫酸溶液供應至該陽極室及該陰極室。該清洗處理單元執行對欲清洗之物件之清洗處理。該第二氫氟酸供應單元將氫氟酸供應至該陽極室。另外，該氧化溶液供應單元將包含該氧化物質之氧化溶液供應至該清洗處理單元。In another embodiment, the cleaning system includes a sulfuric acid electrolysis unit, a sulfuric acid supply unit, a cleaning treatment unit, a second hydrofluoric acid supply unit, and an oxidation solution supply unit. The sulfuric acid electrolysis unit comprises an anode, a cathode, a separator provided between the anode and the cathode, an anode chamber provided between the anode and the separator, and a cathode chamber provided between the cathode and the separator, the sulfuric acid electrolysis unit The sulfuric acid solution is electrolyzed to produce an oxidizing species in the anode compartment. The sulfuric acid supply unit supplies a sulfuric acid solution to the anode chamber and the cathode chamber. The cleaning processing unit performs a cleaning process on the object to be cleaned. The second hydrofluoric acid supply unit supplies hydrofluoric acid to the anode chamber. Further, the oxidizing solution supply unit supplies an oxidizing solution containing the oxidizing substance to the cleaning processing unit.
在另一實施例中，本發明揭示一種用於製造微細構造之方法。該方法包含藉由上述清洗方法清洗欲清洗之物件且形成微細構造。In another embodiment, the present invention discloses a method for making a microstructure. The method includes cleaning the object to be cleaned by the above cleaning method and forming a fine structure.
現在將參照圖式闡述實施例。該等圖式中之類似組件用相同參考編號標記，且酌情省略詳細闡述。Embodiments will now be described with reference to the drawings. Similar components in the drawings are labeled with the same reference numerals, and the detailed description is omitted as appropriate.
圖1係圖解說明根據此實施例之清洗系統之示意圖。Figure 1 is a schematic diagram illustrating a cleaning system in accordance with this embodiment.
如圖1中所圖解說明，清洗系統5包含硫酸電解單元10、氫氟酸供應單元50、清洗處理單元12、溶液循環單元14及硫酸供應單元15。As illustrated in FIG. 1, the cleaning system 5 includes a sulfuric acid electrolysis unit 10, a hydrofluoric acid supply unit 50, a cleaning treatment unit 12, a solution circulation unit 14, and a sulfuric acid supply unit 15.
硫酸電解單元10具有電解硫酸溶液並在陽極室30中產生氧化物質之功能。雖然當包含氧化物質之溶液用於移除黏附至欲清洗之物件之污染物(例如，沈積物，諸如抗蝕劑、金屬雜質、顆粒、幹蝕刻殘渣、二氧化矽、鹵化物等)時，該包含氧化物質之溶液之氧化能力降低，但硫酸電解單元10亦具有恢復降低之氧化能力之功能。The sulfuric acid electrolysis unit 10 has a function of electrolyzing a sulfuric acid solution and generating an oxidizing substance in the anode chamber 30. Although when a solution containing an oxidizing substance is used to remove contaminants (for example, deposits such as resists, metal impurities, particles, dry etching residues, cerium oxide, halides, etc.) adhered to the article to be cleaned, The oxidizing ability of the solution containing the oxidizing substance is lowered, but the sulfuric acid electrolysis unit 10 also has a function of restoring the reduced oxidizing ability.
硫酸電解單元10包含陽極32、陰極42、提供於陽極32與陰極42之間的隔膜20、提供於陽極32與隔膜20之間的陽極室30及提供於陰極42與隔膜20之間的陰極室40。The sulfuric acid electrolysis unit 10 includes an anode 32, a cathode 42, a separator 20 provided between the anode 32 and the cathode 42, an anode chamber 30 provided between the anode 32 and the separator 20, and a cathode chamber provided between the cathode 42 and the separator 20. 40.
上端密封單元22提供於隔膜20、陽極室30及陰極室40之上端處；且下端密封單元23提供於隔膜20、陽極室30及陰極室40之下端處。陽極32與陰極42相對，其之間***有隔膜20。陽極32係由陽極支撐體33支撐；且陰極42係由陰極支撐體43支撐。在陽極32與陰極42之間連接直流電源26。The upper end sealing unit 22 is provided at the upper ends of the diaphragm 20, the anode chamber 30, and the cathode chamber 40; and the lower end sealing unit 23 is provided at the lower ends of the diaphragm 20, the anode chamber 30, and the cathode chamber 40. The anode 32 is opposed to the cathode 42 with a diaphragm 20 interposed therebetween. The anode 32 is supported by the anode support 33; and the cathode 42 is supported by the cathode support 43. A DC power source 26 is connected between the anode 32 and the cathode 42.
陽極32係由導電陽極基底構件34及形成於陽極基底構件34之表面上之陽極導電膜35製成。陽極基底構件34係由陽極支撐體33之內面支撐；且陽極導電膜35面對陽極室30。The anode 32 is made of a conductive anode base member 34 and an anode conductive film 35 formed on the surface of the anode base member 34. The anode base member 34 is supported by the inner surface of the anode support 33; and the anode conductive film 35 faces the anode chamber 30.
陰極42係由導電陰極基底構件44及形成於陰極基底構件44之表面上之陰極導電膜45製成。陰極基底構件44係由陰極支撐體43之內面支撐；且陰極導電膜45面對陰極室40。The cathode 42 is made of a conductive cathode base member 44 and a cathode conductive film 45 formed on the surface of the cathode base member 44. The cathode base member 44 is supported by the inner surface of the cathode support 43; and the cathode conductive film 45 faces the cathode chamber 40.
陽極入口19形成於陽極室30之下端側上；且陽極出口17形成於上端側上。陽極入口19及陽極出口17與陽極室30連通。陰極入口18形成於陰極室40之下端側上；且陰極出口16形成於上端側上。陰極入口18及陰極出口16與陰極室40連通。An anode inlet 19 is formed on the lower end side of the anode chamber 30; and an anode outlet 17 is formed on the upper end side. The anode inlet 19 and the anode outlet 17 are in communication with the anode chamber 30. A cathode inlet 18 is formed on the lower end side of the cathode chamber 40; and a cathode outlet 16 is formed on the upper end side. Cathode inlet 18 and cathode outlet 16 are in communication with cathode chamber 40.
氫氟酸供應單元50包含保持氟化氫(HF)水溶液(亦即，氫氟酸)之罐51、幫浦52及開/關閥71。罐51、幫浦52及開/關閥71經由管道線路53及管道線路74連接至分配單元61。罐51中所保持之氫氟酸可藉由幫浦52之運作經由管道線路53及管道線路74供應至分配單元61。換言之，氫氟酸供應單元50具有將罐51中所保持之氫氟酸供應至清洗處理單元12之分配單元61之功能；且可將供應至分配單元61之氫氟酸供應至欲清洗之物件W之表面。亦可藉由提供與管道線路74及分配單元61不同之未圖解說明之管道線路及分配單元自與包含氧化物質之溶液(氧化溶液)之彼管道系統不同之管道系統將氫氟酸供應至欲清洗之物件W。The hydrofluoric acid supply unit 50 includes a tank 51 holding a hydrogen fluoride (HF) aqueous solution (i.e., hydrofluoric acid), a pump 52, and an on/off valve 71. The tank 51, the pump 52, and the on/off valve 71 are connected to the distribution unit 61 via a pipe line 53 and a pipe line 74. The hydrofluoric acid held in the tank 51 can be supplied to the distribution unit 61 via the piping line 53 and the piping line 74 by the operation of the pump 52. In other words, the hydrofluoric acid supply unit 50 has a function of supplying the hydrofluoric acid held in the tank 51 to the distribution unit 61 of the cleaning processing unit 12; and the hydrofluoric acid supplied to the distribution unit 61 can be supplied to the object to be cleaned The surface of W. It is also possible to supply hydrofluoric acid to the pipe system which is different from the pipe line 74 and the distribution unit 61 by an unillustrated pipe line and distribution unit from a pipe system different from the pipe system containing the oxidizing substance solution (oxidizing solution). Cleaning object W.
清洗處理單元12具有使用硫酸電解單元10中所獲得之包含氧化物質之溶液(氧化溶液)及由氫氟酸供應單元50供應之氫氟酸清洗欲清洗之物件W之功能。The cleaning processing unit 12 has a function of cleaning the object to be cleaned by using a solution containing an oxidizing substance (oxidizing solution) obtained in the sulfuric acid electrolysis unit 10 and hydrofluoric acid supplied from the hydrofluoric acid supply unit 50.
硫酸電解單元10中所獲得之氧化溶液經由溶液循環單元14供應至提供於清洗處理單元12中之分配單元61。該氫氟酸由氫氟酸供應單元50供應至提供於清洗處理單元12中之分配單元61。可依序供應該氧化溶液及該氫氟酸；且可實質上同時地供應該氧化溶液及該氫氟酸。The oxidizing solution obtained in the sulfuric acid electrolysis unit 10 is supplied to the distribution unit 61 provided in the cleaning processing unit 12 via the solution circulation unit 14. The hydrofluoric acid is supplied from the hydrofluoric acid supply unit 50 to the distribution unit 61 provided in the cleaning processing unit 12. The oxidizing solution and the hydrofluoric acid may be supplied in sequence; and the oxidizing solution and the hydrofluoric acid may be supplied substantially simultaneously.
可混合該氧化溶液與該氫氟酸；且可供應該混合液(清洗液)。在其中將由氫氟酸供應單元50供應之氫氟酸與由硫酸電解單元10供應之氧化溶液實質上同時地供應至管道線路74之情況中，管道線路74形成混合兩種溶液之混合單兀。The oxidizing solution and the hydrofluoric acid may be mixed; and the mixture (cleaning liquid) may be supplied. In the case where the hydrofluoric acid supplied from the hydrofluoric acid supply unit 50 is supplied to the piping line 74 substantially simultaneously with the oxidation solution supplied from the sulfuric acid electrolysis unit 10, the piping line 74 forms a mixed unit in which the two solutions are mixed.
此外，可提供未圖解說明之罐用以混合該氧化溶液與該氫氟酸。在此情況中，該未圖解說明之罐形成混合單元。藉由提供該未圖解說明之罐，可緩衝該混合液(清洗液)之流動速率波動，可調整混合速率等。此外，可使該混合液(清洗液)之混合速率之性質更均勻。Additionally, an unillustrated canister can be provided for mixing the oxidizing solution with the hydrofluoric acid. In this case, the unillustrated can forms a mixing unit. By providing the unillustrated can, the flow rate fluctuation of the mixed liquid (washing liquid) can be buffered, the mixing rate and the like can be adjusted. Further, the nature of the mixing rate of the mixed liquid (washing liquid) can be made more uniform.
分配單元61具有用於將該氧化溶液、該氫氟酸及該氧化溶液與該氫氟酸之混合液(清洗液)分配至欲清洗之物件W上之分配噴嘴。提供旋轉台62，將欲清洗之物件W放置於旋轉臺上以與該分配噴嘴相對。旋轉台62提供於蓋29之內部中。藉由自分配單元61朝向欲清洗之物件W分配該氧化溶液、該氫氟酸及該氧化溶液與該氫氟酸之混合液(清洗液)，可自欲清洗之物件W之頂部移除污染物(例如，沈積物，諸如抗蝕劑、金屬雜質、顆粒、幹蝕刻殘渣、二氧化矽、鹵化物等)。The distribution unit 61 has a dispensing nozzle for distributing the oxidizing solution, the hydrofluoric acid, and the mixed solution (cleaning liquid) of the oxidizing solution and the hydrofluoric acid to the object W to be cleaned. A rotary table 62 is provided to place the object W to be cleaned on the rotary table to oppose the dispensing nozzle. A rotary table 62 is provided in the interior of the cover 29. By displacing the oxidizing solution, the hydrofluoric acid, and the mixed solution of the oxidizing solution and the hydrofluoric acid (cleaning liquid) from the dispensing unit 61 toward the object W to be cleaned, the contamination can be removed from the top of the object W to be cleaned. (eg, deposits such as resists, metal impurities, particles, dry etch residues, cerium oxide, halides, etc.).
雖然在圖1中所圖解說明之清洗處理單元12中使用所謂的單晶圓處理，但亦可使用批量處理。Although so-called single wafer processing is used in the cleaning processing unit 12 illustrated in FIG. 1, batch processing can also be used.
硫酸電解單元10中所產生之氧化溶液經由溶液循環單元14自陽極出口17供應至清洗處理單元12。作為溶液維持單元，陽極出口17經由其中提供開/關閥73a之管道線路73連接至罐28。罐28經由管道線路74連接至分配單元61。罐28中所保持之氧化溶液藉由幫浦81之運作經由管道線路74供應至分配單元61。在管道線路74中幫浦81之分配側上提供開/關閥74a。在此實施例中，罐28、幫浦81等形成將包含氧化物質之氧化溶液供應至清洗處理單元12之氧化溶液供應單元。在此情況中，硫酸電解單元10中所產生之氧化溶液之流動速率波動可藉由將氧化溶液保持及維持於罐28中來得到緩衝。可藉由給罐28提供加熱器來執行對該氧化溶液之溫度控制。The oxidizing solution generated in the sulfuric acid electrolysis unit 10 is supplied from the anode outlet 17 to the cleaning processing unit 12 via the solution circulation unit 14. As the solution maintaining unit, the anode outlet 17 is connected to the tank 28 via a piping line 73 in which the opening/closing valve 73a is provided. Tank 28 is connected to distribution unit 61 via a conduit line 74. The oxidizing solution held in the tank 28 is supplied to the dispensing unit 61 via the piping line 74 by the operation of the pump 81. An on/off valve 74a is provided on the distribution side of the pump 81 in the pipe line 74. In this embodiment, the can 28, the pump 81, and the like form an oxidizing solution supply unit that supplies an oxidizing solution containing an oxidizing substance to the cleaning processing unit 12. In this case, the flow rate fluctuation of the oxidizing solution generated in the sulfuric acid electrolysis unit 10 can be buffered by holding and maintaining the oxidizing solution in the tank 28. Temperature control of the oxidizing solution can be performed by providing a heater to the canister 28.
自清洗處理單元12排放之氧化溶液可藉由溶液循環單元14回收且可再供應至清洗處理單元12。例如，自清洗處理單元12排放之氧化溶液係可藉由依次通過回流罐63、過濾器64、幫浦82及開/關閥76供應至硫酸電解單元10之陽極入口19。換言之，該氧化溶液可在硫酸電解單元10與清洗處理單元12之間循環。在此情況中，視需要，可將該清洗處理期間所使用之氧化溶液供應至硫酸電解單元10；隨後，可使藉由在硫酸電解單元10中執行電解獲得之包含氧化物質之氧化溶液通過罐28等；且可將該氧化溶液供應至清洗處理單元12。The oxidizing solution discharged from the cleaning processing unit 12 can be recovered by the solution recycling unit 14 and can be re-supplied to the cleaning processing unit 12. For example, the oxidizing solution discharged from the cleaning treatment unit 12 can be supplied to the anode inlet 19 of the sulfuric acid electrolysis unit 10 by sequentially passing through the reflux tank 63, the filter 64, the pump 82, and the on/off valve 76. In other words, the oxidizing solution can be circulated between the sulfuric acid electrolysis unit 10 and the cleaning treatment unit 12. In this case, the oxidizing solution used during the cleaning treatment may be supplied to the sulfuric acid electrolysis unit 10 as needed; subsequently, the oxidizing solution containing the oxidizing substance obtained by performing electrolysis in the sulfuric acid electrolysis unit 10 may be passed through the tank 28 and the like; and the oxidizing solution can be supplied to the cleaning treatment unit 12.
此處，視需要，可藉由將經稀釋硫酸自硫酸供應單元15供應至硫酸電解單元10以及將使用過之氧化溶液供應至硫酸電解單元10且然後執行電解來產生該氧化溶液。可使此處所獲得之氧化溶液通過罐28等，且供應至清洗處理單元12。藉由盡可能多地重複該氧化溶液之再利用，可減少產生該氧化溶液所必需之材料(化學溶液等)之量及在欲清洗之物件W之清洗處理期間之廢液之量。Here, the oxidizing solution can be produced by supplying the diluted sulfuric acid from the sulfuric acid supply unit 15 to the sulfuric acid electrolysis unit 10 and supplying the used oxidation solution to the sulfuric acid electrolysis unit 10 and then performing electrolysis, as needed. The oxidizing solution obtained here can be passed through the tank 28 or the like and supplied to the washing treatment unit 12. By repeating the reuse of the oxidizing solution as much as possible, the amount of the material (chemical solution, etc.) necessary for generating the oxidizing solution and the amount of the effluent during the cleaning process of the article W to be cleaned can be reduced.
另一選擇為，自清洗處理單元12排放之氧化溶液係可藉由依次通過回流罐63、過濾器64、幫浦82及開/關閥91供應至罐28，亦即，不通過硫酸電解單元10。此處，接著，可藉由將氧化溶液自罐28供應至清洗處理單元12來執行欲清洗之物件W之清洗處理。在此情況中，可再利用在該清洗處理中使用之後之氧化溶液。藉由盡可能多地重複該氧化溶液之此再利用，可減少產生該氧化溶液所必需之材料(化學溶液等)之量及廢液之量。Alternatively, the oxidizing solution discharged from the cleaning processing unit 12 can be supplied to the tank 28 by sequentially passing through the reflux tank 63, the filter 64, the pump 82, and the on/off valve 91, that is, without passing through the sulfuric acid electrolysis unit. 10. Here, next, the cleaning process of the article W to be cleaned can be performed by supplying the oxidizing solution from the canister 28 to the cleaning processing unit 12. In this case, the oxidizing solution after use in the cleaning process can be reused. By repeating this reuse of the oxidizing solution as much as possible, the amount of the material (chemical solution, etc.) necessary for generating the oxidizing solution and the amount of the effluent can be reduced.
亦可類似地循環及再利用自清洗處理單元12排放之該氫氟酸及該氧化溶液與該氫氟酸之混合液(清洗液)。可針對該氫氟酸將未圖解說明之回流罐、開/關閥等連接至清洗處理單元12以分離並回收該氫氟酸及該氧化溶液。在此情況中，藉由依序供應該氫氟酸及該氧化溶液，可在其各自供應期間執行分離及回收。單獨再利用可藉由單獨再處理等來實現。The hydrofluoric acid discharged from the cleaning processing unit 12 and the mixed solution of the oxidizing solution and the hydrofluoric acid (cleaning liquid) may be similarly recycled and reused. A reflux tank, an on/off valve, and the like, which are not illustrated, may be connected to the cleaning treatment unit 12 for the hydrofluoric acid to separate and recover the hydrofluoric acid and the oxidizing solution. In this case, by sequentially supplying the hydrofluoric acid and the oxidizing solution, separation and recovery can be performed during their respective supply periods. Separate reuse can be achieved by separate reprocessing or the like.
回流罐63提供有具有將在清洗處理單元12中所清洗及所移除之污染物排放至該系統外部之功能之排放管道線路75及排放閥75a。過濾器64具有過濾自清洗處理單元12排放之氧化溶液、氫氟酸及混合液(清洗液)中所包含之污染物之功能。The reflux tank 63 is provided with a discharge line 75 and a discharge valve 75a having a function of discharging the cleaned and removed contaminants in the cleaning processing unit 12 to the outside of the system. The filter 64 has a function of filtering the contaminants contained in the oxidizing solution, the hydrofluoric acid, and the mixed liquid (cleaning liquid) discharged from the cleaning processing unit 12.
硫酸供應單元15具有將稀硫酸溶液供應至硫酸電解單元10(陽極室30及陰極室40)之功能。硫酸供應單元15包含將該稀硫酸溶液供應至陽極室30及陰極室40之幫浦80、保持該稀硫酸之罐60及開/關閥70及72。The sulfuric acid supply unit 15 has a function of supplying a dilute sulfuric acid solution to the sulfuric acid electrolysis unit 10 (the anode chamber 30 and the cathode chamber 40). The sulfuric acid supply unit 15 includes a pump 80 that supplies the dilute sulfuric acid solution to the anode chamber 30 and the cathode chamber 40, a tank 60 that holds the dilute sulfuric acid, and on/off valves 70 and 72.
具有(例如)不低於30重量百分比且不高於70重量百分比之硫酸濃度之稀硫酸溶液保持於罐60中。驅動幫浦80以使得罐60中之稀硫酸溶液通過開/關閥70且經由開/關閥76之下游側上之管道線路及陽極入口19供應至陽極室30。此外，驅動幫浦80以使得罐60中之稀硫酸溶液通過開/關閥72且經由開/關閥72之下游側上之管道線路86及陰極入口18供應至陰極室40。A dilute sulfuric acid solution having, for example, not less than 30% by weight and not more than 70% by weight of sulfuric acid concentration is retained in the canister 60. The pump 80 is driven such that the dilute sulfuric acid solution in the tank 60 is supplied to the anode chamber 30 through the on/off valve 70 and via the piping line on the downstream side of the on/off valve 76 and the anode inlet 19. Further, the pump 80 is driven such that the dilute sulfuric acid solution in the tank 60 is supplied to the cathode chamber 40 through the opening/closing valve 72 and via the piping line 86 and the cathode inlet 18 on the downstream side of the opening/closing valve 72.
在此實施例中，可抑制由於該硫酸之電解所致隔膜20之損壞，此乃因供應至該陰極側之溶液之硫酸濃度係低。換言之，在該硫酸之電解反應期間該陰極側上之水移動至該陽極側；該陰極側上之溶液之硫酸濃度增加；且隔膜20易於劣化。此外，在其中離子交換膜用作隔膜20之情況中，隨著水含量在該濃硫酸溶液中減少，該離子交換膜之電阻增加；且罐電壓不合意地增加。因此，同樣為減輕此等問題，可藉由將稀硫酸供應至陰極側以將水供應至該離子交換膜來抑制該電阻增加。In this embodiment, damage of the separator 20 due to electrolysis of the sulfuric acid can be suppressed because the sulfuric acid concentration of the solution supplied to the cathode side is low. In other words, the water on the cathode side moves to the anode side during the electrolytic reaction of the sulfuric acid; the sulfuric acid concentration of the solution on the cathode side increases; and the separator 20 is liable to deteriorate. Further, in the case where the ion exchange membrane is used as the separator 20, as the water content is reduced in the concentrated sulfuric acid solution, the resistance of the ion exchange membrane increases; and the tank voltage undesirably increases. Therefore, also to alleviate such problems, the increase in resistance can be suppressed by supplying dilute sulfuric acid to the cathode side to supply water to the ion exchange membrane.
藉由減少供應至硫酸電解單元10之硫酸之濃度，可增加該氧化溶液中所包含之氧化物質(例如，過氧單硫酸及過氧二硫酸)之產生效率。下文闡述增加該氧化物質之產生效率。By reducing the concentration of sulfuric acid supplied to the sulfuric acid electrolysis unit 10, the production efficiency of the oxidizing substances (for example, peroxymonosulfuric acid and peroxodisulfuric acid) contained in the oxidizing solution can be increased. The efficiency of increasing the production of the oxidizing species is explained below.
上文所闡述之開/關閥70、71、72、73a、74a、75a、76及91亦具有控制各種溶液之流動速率之功能。幫浦80、81及82亦具有控制各種溶液之流動速度之功能。The on/off valves 70, 71, 72, 73a, 74a, 75a, 76 and 91 described above also have the function of controlling the flow rates of various solutions. Pumps 80, 81 and 82 also have the function of controlling the flow rate of various solutions.
自耐化學性之態樣而言，陽極支撐體33、陰極支撐體43、陰極出口16、陽極出口17、陰極入口18、陽極入口19及清洗處理單元12之蓋29之材料可有利地包含(例如)諸如聚四氟乙烯之氟碳樹脂。The material of the anode support 33, the cathode support 43, the cathode outlet 16, the anode outlet 17, the cathode inlet 18, the anode inlet 19, and the cover 29 of the cleaning treatment unit 12 may advantageously be included in terms of chemical resistance. For example, a fluorocarbon resin such as polytetrafluoroethylene.
將該氧化溶液、該氫氟酸及該氧化溶液與該氫氟酸之混合液(清洗液)供應至清洗處理單元12之管道可包含纏繞有隔熱物等之氟碳樹脂管。此管道亦可提供有由氟碳樹脂製成之內嵌式加熱器。抽送該氧化溶液、該氫氟酸及該氧化溶液與該氫氟酸之混合液(清洗液)之幫浦可包含由具有耐熱性及耐化學性之氟碳樹脂製成之伸縮幫浦。The oxidizing solution, the hydrofluoric acid, and the mixture of the oxidizing solution and the hydrofluoric acid (cleaning liquid) supplied to the cleaning treatment unit 12 may include a fluorocarbon resin tube wound with a heat insulator or the like. The pipe can also be provided with an in-line heater made of fluorocarbon resin. The pump for pumping the oxidizing solution, the hydrofluoric acid, and the mixture of the oxidizing solution and the hydrofluoric acid (cleaning liquid) may comprise a telescopic pump made of a fluorocarbon resin having heat resistance and chemical resistance.
保持該硫酸溶液之罐之材料可包含(例如)石英。保持該氫氟酸及該氧化溶液與該氫氟酸之混合液(清洗液)之罐中之每一者之材料可包含(例如)氟碳樹脂。該等罐中之每一者亦可酌情包含溢流控制裝置、溫度控制裝置等。The material of the tank holding the sulfuric acid solution may comprise, for example, quartz. The material of each of the cans of the hydrofluoric acid and the mixed solution of the oxidizing solution and the hydrofluoric acid (cleaning liquid) may contain, for example, a fluorocarbon resin. Each of the tanks may also include an overflow control device, a temperature control device, etc., as appropriate.
此處，處理時間可藉由增加溶液溫度(處理溫度)(藉由給罐提供溫度控制裝置、給管道提供內嵌式加熱器等)以增加與抗蝕劑等之反應性來縮短。然而，過高增加該溫度可導致關於該清洗系統之組件(例如，每一單元之管道線路、開/關閥、幫浦及罐，清洗處理單元之蓋等)之可容許溫度及強度之問題。該等組件通常係由(例如)氟碳樹脂等形成以增加與該氫氟酸、該硫酸及該氧化溶液接觸之部分之耐化學性。在此情況中，該所需強度在其中溫度係過高之情況中係不可獲得的。Here, the treatment time can be shortened by increasing the solution temperature (treatment temperature) (providing a temperature control device to the tank, providing an in-line heater to the pipe, etc.) to increase reactivity with the resist or the like. However, excessively increasing the temperature can cause problems with the allowable temperature and strength of the components of the cleaning system (eg, the piping lines of each unit, the on/off valves, the pumps and tanks, the lid of the cleaning unit, etc.). . The components are typically formed of, for example, a fluorocarbon resin or the like to increase the chemical resistance of the portion in contact with the hydrofluoric acid, the sulfuric acid, and the oxidizing solution. In this case, the required strength is not available in the case where the temperature is too high.
因此，端視縮短該處理時間及該清洗系統之可容許溫度、強度等，該氫氟酸、該硫酸及該氧化溶液之溫度係不低於100℃且不高於110℃係有利的。Therefore, it is advantageous to shorten the processing time and the allowable temperature, strength, and the like of the cleaning system, and the temperature of the hydrofluoric acid, the sulfuric acid, and the oxidizing solution is not lower than 100 ° C and not higher than 110 ° C.
隔膜20可包含(例如)中性膜(儘管已經歷親水處理)，其包含諸如彼具有產品名Poreflon等之PTFE多孔隔膜及諸如彼等具有產品名Nafion、Aciplex、Flemion等之正離子交換膜。隔膜20之尺寸係(例如)約50平方釐米。上端密封單元22及下端密封單元23包含(例如)塗佈有氟碳樹脂之O環係適合的。The membrane 20 can comprise, for example, a neutral membrane (although having undergone a hydrophilic treatment) comprising a PTFE porous membrane such as the product name Poreflon and the like and positive ion exchange membranes such as those having the product names Nafion, Aciplex, Flemion, and the like. The diaphragm 20 is, for example, about 50 square centimeters in size. The upper end sealing unit 22 and the lower end sealing unit 23 are suitably made of, for example, an O-ring coated with a fluorocarbon resin.
陽極導電基底構件34之材料可包含(例如)p-型矽及諸如鈮之閥用金屬。本文中，「閥用金屬」係指藉由陽極氧化使其金屬表面均勻地覆蓋有氧化物膜且具有優良耐腐蝕性之金屬。陰極導電基底構件44可包含(例如)n-型矽。The material of the anode conductive base member 34 may comprise, for example, a p-type crucible and a valve metal such as tantalum. Herein, the "metal for valve" refers to a metal which is uniformly covered with an oxide film by anodization and which has excellent corrosion resistance. Cathode conductive base member 44 can comprise, for example, an n-type crucible.
陽極導電膜35及陰極導電膜45之材料可包含(例如)玻璃碳。自耐久性之態樣而言，在其中供應具有相對高硫酸濃度之溶液及添加有氫氟酸之溶液之情況中適合使用導電金剛石膜。The material of the anode conductive film 35 and the cathode conductive film 45 may include, for example, glassy carbon. From the standpoint of durability, a conductive diamond film is suitably used in the case where a solution having a relatively high sulfuric acid concentration and a solution to which hydrofluoric acid is added are supplied.
對於該陽極及該陰極二者，該導電膜及該基底構件可由相同材料形成。例如，在其中將玻璃碳用作該陰極基底構件之情況中及在其中將導電金剛石自支撐膜用作該陽極基底構件之情況中，該基底構件本身形成具有可有助於該電解反應之電催化特性之導電膜。For both the anode and the cathode, the conductive film and the base member may be formed of the same material. For example, in the case where glassy carbon is used as the cathode base member and in which the conductive diamond self-supporting film is used as the anode base member, the base member itself is formed to have electricity which can contribute to the electrolytic reaction. A conductive film of catalytic properties.
雖然金剛石具有穩定的化學、機械及熱特性，但由於不良導電性，一直難以在電化學系統中使用金剛石。然而，可藉由使用熱絲化學氣相沈積(HF-CVD)在供應硼氣體及氮氣體的同時形成來獲得導電金剛石膜。該導電金剛石膜具有(例如)3至5伏之寬「電位窗」及(例如)5至100毫-歐姆-釐米之電阻。Although diamond has stable chemical, mechanical, and thermal properties, it has been difficult to use diamond in electrochemical systems due to poor electrical conductivity. However, the conductive diamond film can be obtained by forming a boron gas and a nitrogen gas while using hot wire chemical vapor deposition (HF-CVD). The conductive diamond film has a "potential window" of, for example, 3 to 5 volts and a resistance of, for example, 5 to 100 milli-ohm-cm.
此處，該電位窗係用於電解水所需之最小電位(不低於1.2伏)。該電位窗因材料品質而不同。在其中使用具有寬電位窗之材料且在該電位窗內之電位下執行電解之情況中，可優先於水之電解進行具有在該電位窗內之氧化-還原電位之電解反應；且存在其中可優先進行不易電解之物質之氧化反應或還原反應之情況。因此，對於不能經歷習用電化學反應之物質，可藉由使用此導電金剛石實現分解及合成。Here, the potential window is used for the minimum potential required to electrolyze water (not less than 1.2 volts). This potential window varies depending on the material quality. In the case where a material having a wide potential window is used and electrolysis is performed at a potential within the potential window, an electrolysis reaction having an oxidation-reduction potential in the potential window may be performed in preference to electrolysis of water; The oxidation reaction or the reduction reaction of the substance which is difficult to electrolyze is preferentially carried out. Therefore, for substances that cannot undergo conventional electrochemical reactions, decomposition and synthesis can be achieved by using this conductive diamond.
在HF-CVD中，藉由將源材料氣體供應至處於高溫狀態中之鎢絲來執行分解。形成用於形成該膜所需之自由基。隨後，擴散至該基板表面中之自由基與其他反應性氣體反應以在所需基板上形成該膜。In HF-CVD, decomposition is performed by supplying a source material gas to a tungsten wire in a high temperature state. The free radicals required to form the film are formed. The free radicals diffused into the surface of the substrate then react with other reactive gases to form the film on the desired substrate.
現在將闡述氧化物質在硫酸電解單元10中之產生機制。The mechanism of generation of the oxidizing substance in the sulfuric acid electrolysis unit 10 will now be explained.
圖2A及2B係圖解說明該氧化物質之產生機制之示意圖。圖2A係該硫酸電解單元之示意性側剖視圖。圖2B係圖解說明沿圖2A之線A-A之剖面之示意圖。2A and 2B are schematic views illustrating the mechanism of generation of the oxidized substance. 2A is a schematic side cross-sectional view of the sulfuric acid electrolysis unit. Fig. 2B is a schematic view showing a cross section taken along line A-A of Fig. 2A.
如圖2A及2B中所圖解說明，提供陽極32及陰極42以彼此相對，其之間***有隔膜20。陽極32係由陽極支撐體33支撐，其中陽極32之陽極導電膜35面對陽極室30。陰極42係由陰極支撐體43支撐，其中陰極42之陰極導電膜45面對陰極室40。在隔膜20、陽極支撐體33及陰極支撐體43中之每一者之兩端部分上提供電解單元外殼24。As illustrated in Figures 2A and 2B, an anode 32 and a cathode 42 are provided opposite each other with a membrane 20 interposed therebetween. The anode 32 is supported by the anode support 33, wherein the anode conductive film 35 of the anode 32 faces the anode chamber 30. The cathode 42 is supported by the cathode support 43, wherein the cathode conductive film 45 of the cathode 42 faces the cathode chamber 40. An electrolytic unit outer casing 24 is provided on both end portions of each of the separator 20, the anode support 33, and the cathode support 43.
經由陽極入口19將(例如)70重量百分比之硫酸溶液(稀硫酸溶液)自罐60供應至陽極室30。經由陰極入口18將(例如)該70重量百分比硫酸溶液(該稀硫酸溶液)亦自罐60供應至陰極室40。For example, a 70% by weight sulfuric acid solution (dilute sulfuric acid solution) is supplied from the tank 60 to the anode chamber 30 via the anode inlet 19. The 70 weight percent sulfuric acid solution (the dilute sulfuric acid solution) is also supplied from the canister 60 to the cathode chamber 40 via the cathode inlet 18, for example.
藉由施加正電壓至陽極32及施加負電壓至陰極42，電解反應發生於陽極室30及陰極室40中之每一者中。化學式1、化學式2及化學式3之反應發生於陽極室30中。The electrolytic reaction occurs in each of the anode chamber 30 and the cathode chamber 40 by applying a positive voltage to the anode 32 and applying a negative voltage to the cathode 42. The reactions of Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3 occur in the anode chamber 30.
化學式1Chemical formula 1
2HSO4 - →S2 O8 2- +2H+ +2e- 2HSO 4 - →S 2 O 8 2- +2H + +2e -
化學式2Chemical formula 2
HSO4 - +H2 O→HSO5 - +2H+ +2e- HSO 4 - +H 2 O→HSO 5 - +2H + +2e -
化學式3Chemical formula 3
2H2 O→4H+ +4e- +O2 ↑2H 2 O→4H + +4e - +O 2 ↑
此處，化學式2及化學式3中之水(H2 O)係作為該70重量百分比硫酸溶液之30百分比所包含之水。在陽極室30中，化學式2之反應產生過氧單硫酸離子(HSO5 - )。藉由化學式1及化學式3之基本反應發生化學式4之總反應以產生過氧單硫酸離子(HSO5 - )及硫酸。過氧單硫酸具有比硫酸之彼清洗能力較強之清洗能力。Here, water (H 2 O) in Chemical Formula 2 and Chemical Formula 3 is used as water contained in 30% of the 70% by weight sulfuric acid solution. In the anode chamber 30, the reaction of Chemical Formula 2 produces peroxomonosulfate ions (HSO 5 - ). The total reaction of Chemical Formula 4 is carried out by the basic reaction of Chemical Formula 1 and Chemical Formula 3 to produce peroxomonosulfate ion (HSO 5 - ) and sulfuric acid. Peroxymonosulfuric acid has a higher cleaning ability than sulfuric acid.
化學式4Chemical formula 4
S2 O8 2- +H+ +H2 O→HSO5 - +H2 SO4 S 2 O 8 2- +H + +H 2 O→HSO 5 - +H 2 SO 4
另一選擇為，在某些情況中，化學式4之過氧單硫酸離子(HSO5 - )係在產生過氧化氫(H2 O2 )之後產生，如來自化學式1及化學式3之基本反應之化學式5所圖解說明。在某些情況中，藉由化學式1之反應產生過氧二硫酸(H2 S2 O8 )。化學式4及化學式5係來自化學式1之二級反應。Alternatively, in some cases, the peroxymonosulfate ion (HSO 5 - ) of Chemical Formula 4 is produced after the generation of hydrogen peroxide (H 2 O 2 ), such as the basic reaction from Chemical Formula 1 and Chemical Formula 3. The chemical formula 5 is illustrated. In some cases, peroxydisulfuric acid (H 2 S 2 O 8 ) is produced by the reaction of Chemical Formula 1. Chemical Formula 4 and Chemical Formula 5 are secondary reactions of Chemical Formula 1.
化學式5Chemical formula 5
S2 O8 2- +H+ +H2 O→H2 O2 +H2 SO4 S 2 O 8 2- +H + +H 2 O→H 2 O 2 +H 2 SO 4
在陰極室40中產生氫氣，如由化學式6所圖解說明。此係由於在陽極處產生之氫離子(H+ )經由隔膜20移動至陰極且發生電解反應而發生。該氫氣經由陰極出口16自陰極室40排放。Hydrogen gas is generated in the cathode chamber 40 as illustrated by Chemical Formula 6. This occurs because hydrogen ions (H + ) generated at the anode move to the cathode via the separator 20 and an electrolytic reaction occurs. This hydrogen is discharged from the cathode chamber 40 via the cathode outlet 16.
化學式6Chemical formula 6
2H+ +2e- →H2 ↑2H + +2e - →H 2 ↑
在此實施例中，如由化學式7所圖解說明，藉由電解該硫酸溶液可獲得諸如(例如)過氧單硫酸(H2 SO5 )、過氧二硫酸(H2 S2 O8 )等之氧化物質；且可獲得包含此等氧化物質之氧化溶液。雖然氫氣作為副產物產生，但該氫氣並不影響該抗蝕劑等之移除。In this embodiment, as illustrated by Chemical Formula 7, by, for example, electrolysis of the sulfuric acid solution, for example, peroxymonosulfuric acid (H 2 SO 5 ), peroxydisulfuric acid (H 2 S 2 O 8 ), or the like can be obtained. An oxidizing substance; and an oxidizing solution containing the oxidizing substances can be obtained. Although hydrogen is produced as a by-product, the hydrogen does not affect the removal of the resist or the like.
化學式7Chemical formula 7
H2 SO4 +H2 O→氧化物質+H2 H 2 SO 4 +H 2 O→oxidized species +H 2
在其中使用過氧單硫酸之情況中，過氧單硫酸與諸如抗蝕劑之有機物質之反應速率係高。因此，甚至其中欲移除之量係相對大之抗蝕劑移除亦可在短時間段中完成。此外，在其中使用過氧單硫酸之情況中，亦可在低溫下實現移除。因此，針對溫度斜升及諸如此類之微調時間係非必要的。此外，可穩定地大量產生過氧單硫酸。因此，甚至在低溫下亦可增加該過氧單硫酸與移除之物件之反應速率。In the case where peroxymonosulfuric acid is used, the reaction rate of peroxymonosulfuric acid with an organic substance such as a resist is high. Therefore, even a relatively large amount of resist removal in which the amount to be removed can be completed in a short period of time. Further, in the case where peroxymonosulfuric acid is used, the removal can also be achieved at a low temperature. Therefore, it is not necessary to adjust the temperature for ramping up and the like. Further, peroxymonosulfuric acid can be stably produced in a large amount. Therefore, the reaction rate of the peroxymonosulfuric acid and the removed article can be increased even at a low temperature.
此處，為藉由縮短處理時間來增加生產效率，增加該氧化物質之量係足夠的。在此情況中，可藉由增加設備大小、增加所施加之功率、增加稀硫酸溶液之量等來增加所產生之氧化物質之量。然而，此等行為導致較高生產成本及環境影響。因此，需要藉由增加電解效率來有效地產生該氧化物質。Here, in order to increase the production efficiency by shortening the processing time, it is sufficient to increase the amount of the oxidized substance. In this case, the amount of oxidizing species produced can be increased by increasing the size of the device, increasing the applied power, increasing the amount of dilute sulfuric acid solution, and the like. However, such behavior leads to higher production costs and environmental impact. Therefore, it is necessary to efficiently produce the oxidized substance by increasing the electrolysis efficiency.
根據由發明者所獲得之知識，在恒定電解參數(例如，電量、流動速率、溫度等)之情況中，可藉由減少電解期間之該硫酸濃度來產生更多氧化物質。因此，可藉由減少供應至硫酸電解單元10之硫酸濃度來增加該氧化溶液中所包含之氧化物質(例如，過氧單硫酸及過氧二硫酸)之產生效率。According to the knowledge obtained by the inventors, in the case of constant electrolysis parameters (e.g., charge, flow rate, temperature, etc.), more oxidizing species can be produced by reducing the concentration of sulfuric acid during electrolysis. Therefore, the production efficiency of the oxidizing substances (for example, peroxymonosulfuric acid and peroxodisulfuric acid) contained in the oxidizing solution can be increased by reducing the sulfuric acid concentration supplied to the sulfuric acid electrolytic unit 10.
圖3係圖解說明該等氧化物質之濃度及該硫酸之濃度對該剝除時間(移除時間)之影響之圖表。該氧化物質濃度係繪製於水平軸上。該剝除時間(移除時間)係繪製於垂直軸上。在圖3中，B1係其中硫酸濃度係70重量百分比之情況；B2係其中硫酸濃度係80重量百分比之情況；B3係其中硫酸濃度係85重量百分比之情況；B4係其中硫酸濃度係90重量百分比之情況；且B5係其中硫酸濃度係95重量百分比之情況。Figure 3 is a graph illustrating the effect of the concentration of the oxidizing species and the concentration of the sulfuric acid on the stripping time (removal time). The concentration of the oxidizing species is plotted on the horizontal axis. This stripping time (removal time) is plotted on the vertical axis. In Fig. 3, B1 is a case where the concentration of sulfuric acid is 70% by weight; B2 is a case where the concentration of sulfuric acid is 80% by weight; B3 is a case where the concentration of sulfuric acid is 85 weight%; and B4 is a concentration of 90% by weight of sulfuric acid. And B5 is the case where the concentration of sulfuric acid is 95% by weight.
圖3顯示隨著硫酸濃度減少，產生更多氧化物質；且該等氧化物質之濃度因此增加。此外，對於相同硫酸濃度，隨著該等氧化物質之濃度增加(隨著該等氧化物質之量增加)，該剝除時間(移除時間)縮短。Figure 3 shows that as the concentration of sulfuric acid decreases, more oxidizing species are produced; and the concentration of such oxidizing species thus increases. Further, for the same sulfuric acid concentration, as the concentration of the oxidizing substances increases (as the amount of the oxidizing substances increases), the stripping time (removal time) is shortened.
換言之，隨著在氧化物質之產生階段中硫酸濃度減少可產生更多氧化物質。結果，可縮短剝除時間(移除時間)。In other words, more oxidizing species can be produced as the concentration of sulfuric acid decreases during the stage of production of the oxidizing species. As a result, the stripping time (removal time) can be shortened.
因此，在此實施例中，將具有不低於30重量百分比且不高於70重量百分比之硫酸濃度之稀硫酸溶液供應至硫酸電解單元10。Therefore, in this embodiment, a dilute sulfuric acid solution having a sulfuric acid concentration of not less than 30% by weight and not more than 70% by weight is supplied to the sulfuric acid electrolysis unit 10.
因此，可藉由增加硫酸電解單元10之電解效率來產生更多氧化物質。結果，可將包含大量氧化物質之氧化溶液供應至欲清洗之物件W之表面。因此，可縮短該處理時間。Therefore, more oxidizing substances can be produced by increasing the electrolysis efficiency of the sulfuric acid electrolysis unit 10. As a result, an oxidizing solution containing a large amount of oxidizing substance can be supplied to the surface of the article W to be cleaned. Therefore, the processing time can be shortened.
此處，在藉由以高劑量植入雜質製造高速運作半導體裝置時，藉由以該高劑量植入該雜質在該抗蝕劑之表面中形成經改動層。其中形成有此經改動層之抗蝕劑不易移除；且遺憾的是，不可僅藉由上文所述氧化物質之氧化分解能力獲得所期望移除邊際。Here, when a high-speed operation semiconductor device is manufactured by implanting impurities at a high dose, a modified layer is formed in the surface of the resist by implanting the impurity at the high dose. The resist in which the modified layer is formed is not easily removed; and unfortunately, the desired removal margin cannot be obtained only by the oxidative decomposition ability of the oxidizing substance described above.
在此情況中，可感知藉由使用高於氧化物質之彼等分解能力及分移除能力之分解能力及移除能力之物質移除在其表面中形成有經改動層之抗蝕劑。舉例而言，用於移除氧化物膜及天然氧化物膜之氫氟酸具有高分解能力及高移除能力。因此，可想想使用氫氟酸移除在其表面中形成由經改動層之抗蝕劑。In this case, it is perceived that the resist having the modified layer formed in the surface thereof is removed by using a substance having a decomposition ability and a removal ability higher than those of the oxidizing substance. For example, hydrofluoric acid for removing an oxide film and a natural oxide film has high decomposition ability and high removal ability. Therefore, it is conceivable to use hydrofluoric acid to remove a resist formed of a modified layer in its surface.
然而，用於移除氧化物膜及天然氧化物膜之氫氟酸具有分解及移除氧化物(例如，二氧化矽膜等)及氮化物(例如，氮化矽膜等)之能力。因此，可不合意地移除形成於晶圓上之氧化物膜及氮化物膜；且可發生所謂之膜減少。特定而言，在其中氧化物膜、氮化物膜及類似膜曝露於未用抗蝕劑覆蓋之部分處之情況中，可不合意地移除此等部分。However, hydrofluoric acid for removing an oxide film and a natural oxide film has the ability to decompose and remove oxides (for example, a cerium oxide film, etc.) and nitrides (for example, a cerium nitride film, etc.). Therefore, the oxide film and the nitride film formed on the wafer can be undesirably removed; and so-called film reduction can occur. In particular, in the case where an oxide film, a nitride film, and the like are exposed at a portion not covered with a resist, such portions may be undesirably removed.
因此，認為氫氟酸在具有移除諸如抗蝕劑之有機物質之目標之應用中係不用的。Therefore, it is considered that hydrofluoric acid is not used in applications having the objective of removing organic substances such as resists.
作為發明者之調查結果，獲得以下知識：可抑制氫氟酸在包含氧化物質之酸性溶液中對氧化物(例如，二氧化矽膜等)及氮化物(例如，氮化矽膜等)之移除能力。亦獲得以下知識：在此情況中，即使抑制了移除氧化物及氮化物之能力，亦可藉由包含氫氟酸而增加移除抗蝕劑之能力。As a result of investigation by the inventors, the following knowledge has been obtained: the migration of hydrofluoric acid to an oxide (for example, a ruthenium dioxide film, etc.) and a nitride (for example, a ruthenium nitride film, etc.) in an acidic solution containing an oxidizing substance can be suppressed. In addition to ability. The following knowledge is also obtained: in this case, even if the ability to remove oxides and nitrides is suppressed, the ability to remove the resist can be increased by including hydrofluoric acid.
表1比較移除氧化物膜、氮化物膜及其中形成有經改動層之抗蝕劑之能力。Table 1 compares the ability to remove the oxide film, the nitride film, and the resist in which the modified layer is formed.
二氧化矽膜(SiO2 )係藉由形成氧化物膜之熱氧化物膜方法形成於矽基板上。氮化矽膜(SiN)係藉由形成氮化物膜之LP-CVD形成於矽基板上。為形成其中形成有經改動層之抗蝕劑，將抗蝕劑塗佈於矽基板上、曝光、顯影及圖案化；且抗蝕劑表面係藉由1016 原子/cm2 劑量之砷來改動。The cerium oxide film (SiO 2 ) is formed on the ruthenium substrate by a thermal oxide film method of forming an oxide film. A tantalum nitride film (SiN) is formed on the germanium substrate by LP-CVD forming a nitride film. To form a resist in which a modified layer is formed, a resist is applied to the germanium substrate, exposed, developed, and patterned; and the resist surface is modified by arsenic at a dose of 10 16 atoms/cm 2 .
SPM溶液係藉由以3:1之容積比(硫酸溶液：過氧化氫水溶液=3:1)混合具有98重量百分比之硫酸濃度之硫酸溶液與具有35重量百分比之過氧化氫濃度之過氧化氫水溶液來產生。在此情況中，混合硫酸溶液與過氧化氫水溶液產生氧化物質(例如，過氧單硫酸(H2 SO5 )、過氧二硫酸(H2 S2 O8 )等)。因此，SPM溶液亦係包含氧化物質之氧化溶液。The SPM solution is a mixture of a sulfuric acid solution having a sulfuric acid concentration of 98% by weight and a hydrogen peroxide having a hydrogen peroxide concentration of 35 weight percent by a volume ratio of 3:1 (sulfuric acid solution: aqueous hydrogen peroxide solution = 3:1). An aqueous solution is produced. In this case, the mixed sulfuric acid solution and the aqueous hydrogen peroxide solution generate an oxidizing substance (for example, peroxymonosulfuric acid (H 2 SO 5 ), peroxodisulfuric acid (H 2 S 2 O 8 ), or the like). Therefore, the SPM solution is also an oxidizing solution containing an oxidizing substance.
包含氧化物質之氧化溶液係藉由電解具有70重量百分比之硫酸濃度之稀硫酸溶液而產生。The oxidizing solution containing the oxidizing substance is produced by electrolyzing a dilute sulfuric acid solution having a sulfuric acid concentration of 70% by weight.
氫氟酸水溶液係藉由將氫氟酸添加至水以形成具有1000 ppm之氫氟酸濃度之水溶液而製成。The hydrofluoric acid aqueous solution is prepared by adding hydrofluoric acid to water to form an aqueous solution having a hydrofluoric acid concentration of 1000 ppm.
氫氟酸添加至其之硫酸溶液係藉由將氫氟酸添加至具有98重量百分比之硫酸濃度之硫酸溶液以提供1000 ppm之氫氟酸濃度而製成。The sulfuric acid solution to which hydrofluoric acid was added was prepared by adding hydrofluoric acid to a sulfuric acid solution having a sulfuric acid concentration of 98% by weight to provide a hydrofluoric acid concentration of 1000 ppm.
氫氟酸添加至其之氧化溶液係藉由將氫氟酸添加至藉由電解70重量百分比之硫酸濃度之稀硫酸溶液產生之溶液以獲得1000 ppm之氫氟酸濃度而製成。The oxidizing solution to which hydrofluoric acid is added is prepared by adding hydrofluoric acid to a solution produced by electrolyzing a 70 wt% sulfuric acid concentration of a dilute sulfuric acid solution to obtain a hydrofluoric acid concentration of 1000 ppm.
藉由蝕刻速率評估氧化物膜(二氧化矽膜，亦即SiO2 )及氮化物膜(氮化矽膜，亦即SiN)之移除；且在60℃之處理溫度下針對3分鐘之處理時間量測蝕刻量。The removal of the oxide film (cerium oxide film, ie, SiO 2 ) and the nitride film (tantalum nitride film, ie, SiN) is evaluated by the etching rate; and the treatment is performed for 3 minutes at a processing temperature of 60 ° C Time measurement of the amount of etching.
藉由用肉眼觀察來評估其中形成有經改動層之抗蝕劑之移除。移除其中形成有經改動層之抗蝕劑時之處理溫度在其中使用氫氟酸水溶液之情況中係80℃且在其中使用其他溶液之情況中係130℃。The removal of the resist in which the altered layer was formed was evaluated by visual observation. The treatment temperature at which the resist in which the modified layer was formed was removed was 80 ° C in the case where an aqueous solution of hydrofluoric acid was used and 130 ° C in the case where other solutions were used.
如表1中所圖解說明，在其中僅使用SPM溶液(藉由混合硫酸溶液及過氧化氫水溶液產生之包含氧化物質之氧化溶液)之情況中及其中僅使用藉由電解稀硫酸溶液產生之包含氧化物質之氧化溶液之情況中未移除二氧化矽膜(SiO2 )及氮化矽膜(SiN)。換言之，在其中僅使用包含氧化物質之氧化溶液來移除諸如抗蝕劑之有機物質之情況中，未損壞二氧化矽膜(SiO2 )及氮化矽膜(SiN)。然而，當移除其表面中形成有經改動層之抗蝕劑時，未完全移除該抗蝕劑且留下所謂的剝除殘餘(殘渣)。As illustrated in Table 1, in the case where only the SPM solution (the oxidizing solution containing the oxidizing substance produced by mixing the sulfuric acid solution and the aqueous hydrogen peroxide solution) is used, and only the inclusion by the electrolytic dilute sulfuric acid solution is used. The ruthenium dioxide film (SiO 2 ) and the tantalum nitride film (SiN) were not removed in the case of the oxidizing solution of the oxidizing substance. In other words, in the case where only an oxidizing solution containing an oxidizing substance is used to remove an organic substance such as a resist, the ruthenium dioxide film (SiO 2 ) and the tantalum nitride film (SiN) are not damaged. However, when the resist in which the modified layer is formed in the surface is removed, the resist is not completely removed and a so-called strip residue (residue) is left.
在其中透過下一製程之處理仍然存在此剝除殘餘(殘渣)之情況中，存在良率可顯著降低之風險。雖然可想像藉由在先前製程中使用更嚴格之幹蝕刻條件及執行其他化學溶液處理來解決此等問題，但成本會增加且可發生新的問題，例如晶圓之氧化。In the case where the stripping residue (residue) still exists through the processing of the next process, there is a risk that the yield can be significantly lowered. While it is conceivable to solve these problems by using more stringent dry etching conditions and performing other chemical solution processes in previous processes, the cost increases and new problems can occur, such as oxidation of the wafer.
在其中使用具有1000 ppm之氫氟酸濃度之水溶液之情況中，蝕刻且不合意地移除二氧化矽膜(SiO2 )及氮化矽膜(SiN)。換言之，在其中僅使用氫氟酸水溶液移除諸如抗蝕劑之有機物質之情況中，存在對二氧化矽膜(SiO2 )及氮化矽膜(SiN)之損壞之風險。In the case where an aqueous solution of hydrofluoric acid concentrations of 1000 ppm, the etching does not remove the silicon dioxide film desirably (SiO 2) and silicon nitride film (SiN). In other words, in the case where an organic substance such as a resist is removed using only a hydrofluoric acid aqueous solution, there is a risk of damage to the ceria film (SiO 2 ) and the tantalum nitride film (SiN).
根據由發明者執行之實驗，斷定在其中使用氫氟酸水溶液之情況中不能移除其表面中形成有經改動層之抗蝕劑。換言之，斷定氫氟酸水溶液不適合移除該抗蝕劑。According to the experiment performed by the inventors, it was judged that the resist having the modified layer formed on the surface thereof could not be removed in the case where the hydrofluoric acid aqueous solution was used. In other words, it is concluded that the hydrofluoric acid aqueous solution is not suitable for removing the resist.
在其中將氫氟酸添加至硫酸溶液且使用具有1000 ppm之氫氟酸濃度之硫酸溶液之情況中，不合意地蝕刻及移除二氧化矽膜(SiO2 )及氮化矽膜(SiN)。換言之，在其中僅使用氫氟酸添加至其之硫酸溶液釋出諸如抗蝕劑之有機物質之情況中，存在對二氧化矽膜(SiO2 )及氮化矽膜(SiN)之損壞之風險。In the case where hydrofluoric acid is added to a sulfuric acid solution and a sulfuric acid solution having a hydrofluoric acid concentration of 1000 ppm is used, the hafnium oxide film (SiO 2 ) and the tantalum nitride film (SiN) are undesirably etched and removed. . In other words, in the case where only a sulfuric acid solution to which hydrofluoric acid is added is used to release an organic substance such as a resist, there is a risk of damage to the cerium oxide film (SiO 2 ) and the tantalum nitride film (SiN). .
此外，根據由發明者執行之實驗，斷定在其中使用氫氟酸添加至其之硫酸溶液之情況中，不能移除其表面中形成有經改動層之抗蝕劑。換言之，斷定氫氟酸添加至其之硫酸溶液不適合移除該抗蝕劑。Further, according to the experiment performed by the inventors, it was judged that in the case where the sulfuric acid solution to which hydrofluoric acid was added was used, the resist having the modified layer formed on the surface thereof could not be removed. In other words, it is concluded that the sulfuric acid solution to which hydrofluoric acid is added is not suitable for removing the resist.
相反，在其中使用氫氟酸添加至其之氧化溶液(在此實驗中，該氧化溶液具有1000 ppm之氫氟酸濃度)之情況中，輕微地蝕刻及移除氮化矽膜(SiN)，但抑制二氧化矽膜(SiO2 )之蝕刻及移除。此外，可移除其表面中形成有經改動層之抗蝕劑而不具有剝除殘餘(殘渣)。In contrast, in the case where an oxidizing solution to which hydrogen fluoride is added (in this experiment, the oxidizing solution has a hydrofluoric acid concentration of 1000 ppm), the tantalum nitride film (SiN) is slightly etched and removed, However, the etching and removal of the ruthenium dioxide film (SiO 2 ) is suppressed. Further, the resist having the modified layer formed on its surface can be removed without stripping residue (residue).
因此，藉由使用氫氟酸添加至其之氧化溶液作為清洗液，可移除其表面中形成有經改動層之抗蝕劑(其傳統上係難以移除)而不留下剝除殘餘(殘渣)且不損壞二氧化矽膜(SiO2 )及氮化矽膜(SiN)。Therefore, by using an oxidizing solution to which hydrofluoric acid is added as a cleaning liquid, a resist having a modified layer formed on the surface thereof (which is conventionally difficult to remove) can be removed without leaving a peeling residue ( Residue) does not damage the hafnium oxide film (SiO 2 ) and the tantalum nitride film (SiN).
傳統上，需要藉由藉助幹蝕刻進行灰化移除抗蝕劑表面之經改動層且隨後藉由執行使用SPM溶液之處理移除剩餘抗蝕劑。因此，此導致更多處理製程、更多處理設備類型、更長處理時間等。相反，藉由使用氫氟酸添加至其之氧化溶液作為清洗液，可藉由一種類型處理來移除其表面中形成有經改動層之抗蝕劑。因此，可增加生產率，可減少生產成本等。Conventionally, it is necessary to remove the altered layer of the resist surface by ashing by dry etching and then remove the remaining resist by performing a process using the SPM solution. Therefore, this leads to more processing processes, more processing device types, longer processing times, and the like. On the contrary, by using an oxidizing solution to which hydrofluoric acid is added as a cleaning liquid, a resist having a modified layer formed on the surface thereof can be removed by one type of treatment. Therefore, productivity can be increased, production cost can be reduced, and the like.
雖然在此實施例中預先圖解說明其中將氫氟酸添加至氧化溶液之情況，但亦可藉由(例如)將該氧化溶液及該氫氟酸依序或實質上同時地供應至欲清洗之物件W之表面來執行抗蝕劑等之移除。該移除可不僅在其表面中形成有經改動層之抗蝕劑上而且在其表面中未形成有經改動層之抗蝕劑上執行。然而，其可尤其用於移除其表面中形成有經改動層之抗蝕劑，該抗蝕劑傳統上係難以移除。Although the case where hydrofluoric acid is added to the oxidizing solution is previously illustrated in this embodiment, the oxidizing solution and the hydrofluoric acid may be supplied to the liquid to be cleaned, for example, sequentially or substantially simultaneously. The surface of the object W is used to perform removal of a resist or the like. This removal can be performed not only on the resist having the modified layer formed on its surface but also on the resist in which the modified layer is not formed. However, it can be used in particular to remove a resist having a modified layer formed in its surface which is conventionally difficult to remove.
現在將闡述根據此實施例之一種清洗方法。A cleaning method according to this embodiment will now be explained.
圖4係圖解說明該清洗方法之流程圖。Figure 4 is a flow chart illustrating the cleaning method.
首先，藉由電解硫酸溶液產生包含氧化物質(例如，過氧單硫酸及過氧二硫酸)之氧化溶液(步驟S1-1)。在此情況中，可藉由使該硫酸溶液之硫酸濃度不低於30重量百分比且不高於70重量百分比來有效地產生該等氧化物質。First, an oxidizing solution containing an oxidizing substance (for example, peroxymonosulfuric acid and peroxodisulfuric acid) is produced by electrolytic sulfuric acid solution (step S1-1). In this case, the oxidizing substances can be efficiently produced by making the sulfuric acid solution having a sulfuric acid concentration of not less than 30% by weight and not more than 70% by weight.
然後，調整所產生氧化溶液之溫度(步驟S1-2)。雖然此溫度調整並非總是必需的，但端視處理時間之縮短、清洗系統之可允許溫度及強度等，將該氧化溶液之溫度調整為不低於100℃且不高於110℃係有利的。可對所產生氧化溶液、產生期間(電解期間)之氧化溶液、及為該電解供應之硫酸溶液中之任何溶液執行該溫度調整。Then, the temperature of the generated oxidation solution is adjusted (step S1-2). Although this temperature adjustment is not always necessary, it is advantageous to adjust the temperature of the oxidizing solution to not lower than 100 ° C and not higher than 110 ° C because the processing time is shortened, the allowable temperature and strength of the cleaning system, and the like. . This temperature adjustment can be performed on the generated oxidizing solution, the oxidizing solution during the production period (during electrolysis), and any solution in the sulfuric acid solution supplied for the electrolysis.
調整氫氟酸之溫度(步驟S2)。雖然此溫度調整並非總是必需的，但端視處理時間之縮短、清洗系統之可允許溫度及強度等，將氫氟酸之溫度調整為不低於100℃且不高於110℃係有利的。The temperature of the hydrofluoric acid is adjusted (step S2). Although this temperature adjustment is not always necessary, it is advantageous to adjust the temperature of the hydrofluoric acid to not lower than 100 ° C and not higher than 110 ° C, such as shortening of the treatment time, the allowable temperature and strength of the cleaning system, and the like. .
然後，將氫氟酸與氧化溶液依序地或實質上同時地供應至欲清洗之物件W之表面(步驟S3)。可針對欲清洗且將依序浸入於該氫氟酸及該氧化溶液中之物件W中之每一者而自分配單元等執行該供應。此外，例如，可自針對該氫氟酸及該氧化溶液之單獨管道系統依序地或實質上同時地來執行該供應。可使用所謂的單晶圓處理、批量處理及諸如此類。Then, hydrofluoric acid and the oxidizing solution are supplied to the surface of the article W to be cleaned sequentially or substantially simultaneously (step S3). The supply may be performed from a dispensing unit or the like for each of the articles W to be cleaned and immersed in the hydrofluoric acid and the oxidizing solution in sequence. Further, for example, the supply can be performed sequentially or substantially simultaneously from a separate piping system for the hydrofluoric acid and the oxidizing solution. So-called single wafer processing, batch processing, and the like can be used.
圖5係圖解說明根據另一實施例之清洗方法之流程圖。Figure 5 is a flow chart illustrating a cleaning method in accordance with another embodiment.
在此實施例中，混合該氧化溶液及該氫氟酸，且將該混合物供應至欲清洗之物件W之表面。In this embodiment, the oxidizing solution and the hydrofluoric acid are mixed, and the mixture is supplied to the surface of the article W to be cleaned.
首先，藉由電解硫酸溶液來產生包含氧化物質(例如，過氧單硫酸及過氧二硫酸)之氧化溶液(步驟S10)。在此情況中，可藉由使該硫酸溶液之硫酸濃度不低於30重量百分比且不高於70重量百分比來有效地產生該等氧化物質。First, an oxidizing solution containing an oxidizing substance (for example, peroxymonosulfuric acid and peroxodisulfuric acid) is produced by electrolyzing a sulfuric acid solution (step S10). In this case, the oxidizing substances can be efficiently produced by making the sulfuric acid solution having a sulfuric acid concentration of not less than 30% by weight and not more than 70% by weight.
然後，將該氧化溶液及該氫氟酸混合以產生清洗液(步驟S11)。此時，適當地調整該清洗液中之該無機酸濃度及該等氧化物質之量。Then, the oxidizing solution and the hydrofluoric acid are mixed to produce a cleaning liquid (step S11). At this time, the concentration of the inorganic acid in the cleaning liquid and the amount of the oxidizing substances are appropriately adjusted.
接著，調整所產生清洗液之溫度(步驟S12)。雖然此溫度調整並非總是必需的，但端視處理時間之縮短及清洗系統之可允許溫度及強度等，將清洗液之溫度調整為不低於100℃且不高於110℃係有利的。可在混合之前對該氧化溶液及該氫氟酸執行該溫度調整。Next, the temperature of the generated cleaning liquid is adjusted (step S12). Although this temperature adjustment is not always necessary, it is advantageous to adjust the temperature of the cleaning liquid to not lower than 100 ° C and not higher than 110 ° C, such as shortening of the treatment time and the allowable temperature and strength of the cleaning system. This temperature adjustment can be performed on the oxidizing solution and the hydrofluoric acid prior to mixing.
然後，將該清洗液(該氫氟酸與該氧化溶液之混合液)供應至欲清洗之物件W之表面(步驟S13)。可針對欲清洗且將浸入於該清洗液中之物件W中之每一者而自分配單元等執行該供應。可使用所謂的單晶圓處理、批量處理及諸如此類。Then, the cleaning liquid (the mixture of the hydrofluoric acid and the oxidizing solution) is supplied to the surface of the article W to be cleaned (step S13). The supply can be performed from the dispensing unit or the like for each of the articles W to be cleaned and to be immersed in the cleaning liquid. So-called single wafer processing, batch processing, and the like can be used.
雖然在圖5中圖解說明其中在產生包含氧化物質之氧化溶液之後將氫氟酸添加至該氧化溶液之情況，但可將該氫氟酸添加至硫酸溶液，該硫酸溶液係氧化溶液之源材料；且然後可電解此溶液來產生包含氧化物質且氫氟酸添加至其之清洗液(參照圖6)。Although the case where hydrofluoric acid is added to the oxidizing solution after the generation of the oxidizing solution containing the oxidizing substance is illustrated in FIG. 5, the hydrofluoric acid may be added to the sulfuric acid solution, which is the source material of the oxidizing solution. And then this solution can be electrolyzed to produce a cleaning solution containing an oxidizing substance and hydrofluoric acid added thereto (refer to FIG. 6).
此外，可藉由透過混合硫酸溶液與過氧化氫水溶液產生包含氧化物質之氧化溶液(SPM溶液)且將氫氟酸添加至其來產生清洗液。此外，可藉由混合硫酸溶液、過氧化氫水溶液及氫氟酸來產生包含氧化物質及具有添加至其之氫氟酸之清洗液。Further, a cleaning liquid can be produced by generating an oxidizing solution (SPM solution) containing an oxidizing substance by mixing a sulfuric acid solution with an aqueous hydrogen peroxide solution and adding hydrofluoric acid thereto. Further, a cleaning liquid containing an oxidizing substance and having hydrofluoric acid added thereto can be produced by mixing a sulfuric acid solution, an aqueous hydrogen peroxide solution, and hydrofluoric acid.
換言之，清洗液係表現酸性且包含氧化物質及氫氟酸之溶液係足夠的。其製造方法可包含在產生包含氧化物質之酸性溶液(氧化溶液)之後添加氫氟酸或自具有添加至其之氫氟酸之硫酸溶液產生氧化物質。In other words, the cleaning liquid is acidic and the solution containing the oxidizing substance and hydrofluoric acid is sufficient. The manufacturing method may include adding an hydrofluoric acid or generating a oxidizing substance from a sulfuric acid solution having hydrofluoric acid added thereto after generating an acidic solution (oxidizing solution) containing an oxidizing substance.
圖6係圖解說明其中電解具有添加至其之氫氟酸之硫酸溶液之清洗系統之示意圖。Figure 6 is a schematic diagram illustrating a cleaning system in which a sulfuric acid solution having hydrofluoric acid added thereto is electrolyzed.
如圖6中所圖解說明，氫氟酸供應單元50包含保持氫氟酸之罐51、幫浦52及開/關閥71。罐51、幫浦52及開/關閥71經由管道線路53a連接至硫酸供應單元15側上之管道線路。換言之，管道線路53a連接至開/關閥70之下游側上之管道線路。保持在罐51中之氫氟酸可藉由幫浦52之運作經由管道線路53a供應至硫酸電解單元10之陽極室30。換言之，氫氟酸供應單元50具有將保持在罐51中之氫氟酸供應至硫酸電解單元10之陽極室30之功能；且可藉由電解具有添加至其之氫氟酸之硫酸溶液來產生包含氧化物質及具有添加至其之氫氟酸之清洗液。As illustrated in FIG. 6, the hydrofluoric acid supply unit 50 includes a tank 51 holding a hydrofluoric acid, a pump 52, and an on/off valve 71. The tank 51, the pump 52, and the on/off valve 71 are connected to the piping line on the side of the sulfuric acid supply unit 15 via the piping line 53a. In other words, the pipe line 53a is connected to the pipe line on the downstream side of the opening/closing valve 70. The hydrofluoric acid held in the tank 51 can be supplied to the anode chamber 30 of the sulfuric acid electrolysis unit 10 via the piping line 53a by the operation of the pump 52. In other words, the hydrofluoric acid supply unit 50 has a function of supplying the hydrofluoric acid held in the tank 51 to the anode chamber 30 of the sulfuric acid electrolysis unit 10; and can be produced by electrolyzing a sulfuric acid solution having hydrofluoric acid added thereto An oxidizing substance and a cleaning liquid having hydrofluoric acid added thereto.
端視氫氟酸之添加，至少陽極導電膜35係由導電金剛石膜製成係有利的。The addition of hydrofluoric acid is advantageous, and at least the anode conductive film 35 is advantageously made of a conductive diamond film.
現在將闡述根據此實施例之一種用於製造微細構造之方法。A method for manufacturing a fine structure according to this embodiment will now be explained.
一種用於製造微細構造之方法之實例包含(例如)一種用於製造半導體裝置之方法。此處，該半導體裝置之製造製程包含所謂的前端製程，諸如藉由膜形成、抗蝕劑塗佈、曝光、顯影、蝕刻、抗蝕劑移除等在基板(晶圓)上形成圖案之製程、檢查製程、清洗製程、熱處理製程、雜質引入製程、擴散製程、平坦化製程等。所謂的後端製程包含切割、安裝、接合、囊封等之組裝製程，功能性及可靠性檢查製程等。An example of a method for fabricating a fine structure includes, for example, a method for fabricating a semiconductor device. Here, the manufacturing process of the semiconductor device includes a so-called front-end process, such as a process of forming a pattern on a substrate (wafer) by film formation, resist coating, exposure, development, etching, resist removal, and the like. , inspection process, cleaning process, heat treatment process, impurity introduction process, diffusion process, flattening process, etc. The so-called back-end process includes assembly processes such as cutting, mounting, joining, encapsulation, etc., and functional and reliability inspection processes.
在此情況中，可藉由在抗蝕劑移除過程期間使用上文所述(例如)該等清洗液、該等清洗方法及該等清洗系統來增加該抗蝕劑之可移除性。特定而言，可移除其表面中形成有經改動層之抗蝕劑(其傳統上係難以移除)而不留下剝除殘餘(殘渣)且不損壞二氧化矽膜(SiO2 )及氮化矽膜(SiN)。In this case, the removability of the resist can be increased by using the above-described cleaning liquids, such cleaning methods, and the cleaning systems during the resist removal process. In particular, a resist having a modified layer formed on its surface (which is conventionally difficult to remove) may be removed without leaving a residue (residue) and not damaging the cerium oxide film (SiO 2 ) and Tantalum nitride film (SiN).
傳統上，需要藉由藉助幹蝕刻進行灰化移除抗蝕劑表面之經改動層且隨後藉由執行使用SPM溶液之處理移除剩餘抗蝕劑。因此，此導致更多處理製程、更多處理設備類型、更長處理時間等。相反，藉由使用上文所述該等清洗液、該等清洗方法及該等清洗系統，可藉由一種類型處理來移除其表面中形成有經改動層之抗蝕劑。因此，可增加生產率，可減少生產成本等。Conventionally, it is necessary to remove the altered layer of the resist surface by ashing by dry etching and then remove the remaining resist by performing a process using the SPM solution. Therefore, this leads to more processing processes, more processing device types, longer processing times, and the like. In contrast, by using the cleaning liquids, the cleaning methods, and the cleaning systems described above, the resist having the modified layer formed on the surface thereof can be removed by one type of treatment. Therefore, productivity can be increased, production cost can be reduced, and the like.
習知技術可應用於除根據上文所闡述此實施例之清洗方法及清洗系統之彼等製程以外之製程，且因此省略其詳細闡述。The prior art is applicable to processes other than those of the cleaning method and cleaning system of the embodiment described above, and thus detailed description thereof is omitted.
雖然將用於製造半導體裝置之方法圖解說明為用於製造該微細構造之該方法之一個實例，但用於製造該微細構造之方法並不限於此。例如，在諸如液晶顯示裝置、相位移遮罩、MEMS領域中之微機械、精密光學組件等之領域中，可實現應用。Although the method for manufacturing a semiconductor device is illustrated as an example of the method for manufacturing the fine structure, the method for manufacturing the fine structure is not limited thereto. For example, applications can be realized in fields such as liquid crystal display devices, phase shift masks, micromachines in the field of MEMS, precision optical components, and the like.
在上文所闡述之清洗系統中，並非總是需要提供循環該溶液之組態。如圖7中所圖解說明，清洗處理單元12中所使用之溶液可與污染物及諸如此類一起回收至回流罐63中且然後經由排放管道線路75排放至該系統外部。In the cleaning system described above, it is not always necessary to provide a configuration for circulating the solution. As illustrated in Figure 7, the solution used in the cleaning process unit 12 can be recycled to the reflux tank 63 along with contaminants and the like and then discharged to the exterior of the system via the discharge conduit line 75.
此處理可不僅用於移除由有機物質製成之抗蝕劑，亦可用於類似地移除金屬雜質、顆粒及幹蝕刻殘渣等。This treatment can be used not only for removing a resist made of an organic substance, but also for similarly removing metal impurities, particles, dry etching residues, and the like.
例如，在圖案化具有大的縱橫比之金屬互連件期間，沈積眾多互連金屬、該等互連金屬之氧化物及鹵化物、障壁金屬及該等障壁金屬之氧化物及鹵化物等。此外，在圖案化具有大的縱橫比之矽系統期間，沈積眾多二氧化矽及鹵化物。在眾多情況中，此等物質不能僅藉由SPM溶液之氧化物質之氧化能力來移除。For example, during patterning of metal interconnects having a large aspect ratio, a plurality of interconnect metals, oxides and halides of the interconnect metals, barrier metals, oxides and halides of the barrier metals, and the like are deposited. In addition, numerous cerium oxides and halides are deposited during the patterning of a germanium system having a large aspect ratio. In many cases, such materials cannot be removed solely by the oxidizing ability of the oxidizing species of the SPM solution.
然而，可藉由氫氟酸分解及移除此等沈積物中之眾多沈積物。藉由使用上文所述該等清洗液、該等清洗方法及該等清洗系統，可在不損壞二氧化矽膜(SiO2 )及氮化矽膜(SiN)之情形下實現此移除。However, it is possible to decompose and remove numerous deposits in such deposits by hydrofluoric acid. This removal can be achieved without damaging the ruthenium dioxide film (SiO 2 ) and the tantalum nitride film (SiN) by using the cleaning liquids described above, the cleaning methods, and the cleaning systems.
換言之，當移除黏附至微細構造之污染物時可實現眾多應用。在此情況中，當氧化物及氮化物位於該表面上時其係尤其有用，此乃因可在抑制該等氧化物及該等氮化物之移除之同時移除該等污染物。In other words, numerous applications can be realized when removing contaminants adhered to the fine structure. In this case, oxides and nitrides are particularly useful when they are on the surface because the contaminants can be removed while inhibiting the removal of the oxides and the nitrides.
可提供機器人以傳送欲清洗之物件。保持該硫酸溶液之罐60及保持該氫氟酸之罐51中之每一者可連接至工廠之線路以自動地補充該溶液。可提供沖洗槽以用於在移除該等污染物之後沖洗欲清洗之物件。此沖洗槽可包含溢流控制裝置及使用內嵌式加熱器之溫度控制裝置。適合將石英用作該沖洗槽之材料。A robot can be provided to transport the item to be cleaned. Each of the tank 60 holding the sulfuric acid solution and the tank 51 holding the hydrofluoric acid can be connected to the line of the factory to automatically replenish the solution. A rinsing tank may be provided for rinsing the item to be cleaned after removing the contaminants. The rinsing tank may include an overflow control device and a temperature control device using an in-line heater. It is suitable to use quartz as the material of the rinsing tank.
在上文，對實施例進行圖解說明。然而，本發明並不限於其闡述。In the above, the embodiments are illustrated. However, the invention is not limited to the description thereof.
關於上文所闡述之實施例熟習此項技術者所適當做出之設計修改就包含本發明之特徵而言亦系包含於本發明之範疇內。The design modifications that are appropriately made by those skilled in the art in light of the above-described embodiments are also included in the scope of the present invention.
例如，上文所闡述之該等清洗系統之該等組件之組態、尺寸、材料品質、佈置等並不限於本文所圖解說明之彼等且可適當地修改。For example, the configuration, dimensions, material qualities, arrangements, etc. of such components of the cleaning systems set forth above are not limited to those illustrated herein and may be modified as appropriate.
此外，上文所闡述之實施例之組件可在可行性範圍內進行組合；且此等組合就包含本發明之特徵而言亦系包含於本發明之範疇內。Furthermore, the components of the embodiments set forth above may be combined within the scope of the invention; and such combinations are also included within the scope of the invention, including the features of the invention.
雖然已闡述某些實施例，但此等實施例已僅以實例之方式來呈現，且並不意欲限制本發明之範疇。實際上，本文所闡述之新穎液體、清洗方法、清洗系統及製造方法可以多種其他形式來體現；此外，可在不背離本發明之精神的條件下做出本文所闡述之液體、清洗方法、清洗系統及製造方法之形式之各種省略、替代及改變。隨附申請專利範圍及其等效物意欲涵蓋將屬於本發明之範疇及精神之此等形式或修改。Although certain embodiments have been set forth, these embodiments have been shown by way of example only and are not intended to limit the scope of the invention. In fact, the novel liquids, cleaning methods, cleaning systems, and manufacturing methods described herein can be embodied in a variety of other forms; furthermore, the liquids, cleaning methods, and cleanings described herein can be made without departing from the spirit of the invention. Various omissions, substitutions and changes in the form of the system and method of manufacture. The scope of the claims and the equivalents thereof are intended to cover such forms or modifications that are within the scope and spirit of the invention.
5．．．清洗系統5. . . Cleaning system
10．．．硫酸電解單元10. . . Sulfuric acid electrolysis unit
12．．．清洗處理單元12. . . Cleaning unit
14．．．溶液循環單元14. . . Solution circulation unit
15．．．硫酸供應單元15. . . Sulfuric acid supply unit
16．．．陰極出口16. . . Cathode outlet
17．．．陽極出口17. . . Anode outlet
18．．．陰極入口18. . . Cathode inlet
19．．．陽極入口19. . . Anode inlet
20．．．隔膜20. . . Diaphragm
22．．．上端密封單元twenty two. . . Upper sealing unit
23．．．下端密封單元twenty three. . . Lower sealing unit
24．．．電解單元外殼twenty four. . . Electrolytic unit housing
26．．．直流電源26. . . DC power supply
28．．．罐28. . . tank
29．．．蓋29. . . cover
30．．．陽極室30. . . Anode chamber
32．．．陽極32. . . anode
33．．．陽極支撐體33. . . Anode support
34．．．陽極基底構件34. . . Anode base member
35．．．陽極導電膜35. . . Anode conductive film
40．．．陰極室40. . . Cathode chamber
42．．．陰極42. . . cathode
43．．．陰極支撐體43. . . Cathode support
44．．．陰極基底構件44. . . Cathode base member
45．．．陰極導電膜45. . . Cathode conductive film
50．．．氫氟酸單元50. . . Hydrofluoric acid unit
51．．．罐51. . . tank
52．．．幫浦52. . . Pump
53．．．管道線路53. . . Pipeline
53a．．．管道線路53a. . . Pipeline
60．．．罐60. . . tank
61．．．分配單元61. . . Distribution unit
62．．．旋轉台62. . . Rotary table
63．．．回流罐63. . . Reflux tank
64．．．過濾器64. . . filter
70．．．開/關閥70. . . On/off valve
71．．．開/關閥71. . . On/off valve
72．．．開/關閥72. . . On/off valve
73．．．管道線路73. . . Pipeline
73a．．．開/關閥73a. . . On/off valve
74,85．．．管道線路74,85. . . Pipeline
74a．．．開/關閥74a. . . On/off valve
75．．．管道線路75. . . Pipeline
75a．．．開/關閥75a. . . On/off valve
76．．．開/關閥76. . . On/off valve
80．．．幫浦80. . . Pump
81．．．幫浦81. . . Pump
82．．．幫浦82. . . Pump
86．．．管道線路86. . . Pipeline
91．．．開/關閥91. . . On/off valve
圖1係圖解說明根據此實施例之清洗系統之示意圖；Figure 1 is a schematic view illustrating a cleaning system according to this embodiment;
圖2A及2B係圖解說明氧化物質之產生機制之示意圖；2A and 2B are schematic views illustrating a mechanism of generating an oxidized substance;
圖3係圖解說明該等氧化物質之濃度及硫酸之濃度對該移除時間之影響之圖表；Figure 3 is a graph illustrating the effect of the concentration of the oxidizing species and the concentration of sulfuric acid on the removal time;
圖4係圖解說明該清洗方法之流程圖；Figure 4 is a flow chart illustrating the cleaning method;
圖5係圖解說明根據另一實施例之清洗方法之流程圖；Figure 5 is a flow chart illustrating a cleaning method in accordance with another embodiment;
圖6係圖解說明其中電解具有添加至其之氫氟酸之硫酸之清洗系統之示意圖；及Figure 6 is a schematic view showing a cleaning system in which sulfuric acid having hydrofluoric acid added thereto is electrolyzed;
圖7係圖解說明不提供有循環溶液之組態之清洗系統之示意圖。Figure 7 is a schematic diagram illustrating a cleaning system that is not provided with a configuration of a circulating solution.
5．．．清洗系統5. . . Cleaning system
10．．．硫酸電解單元10. . . Sulfuric acid electrolysis unit
12．．．清洗處理單元12. . . Cleaning unit
14．．．溶液循環單元14. . . Solution circulation unit
15．．．硫酸供應單元15. . . Sulfuric acid supply unit
16．．．陰極出口16. . . Cathode outlet
17．．．陽極出口17. . . Anode outlet
18．．．陰極入口18. . . Cathode inlet
19．．．陽極入口19. . . Anode inlet
20．．．隔膜20. . . Diaphragm
22．．．上端密封單元twenty two. . . Upper sealing unit
23．．．下端密封單元twenty three. . . Lower sealing unit
26．．．直流電源26. . . DC power supply
28．．．罐28. . . tank
29．．．蓋29. . . cover
30．．．陽極室30. . . Anode chamber
32．．．陽極32. . . anode
33．．．陽極支撐體33. . . Anode support
34．．．陽極基底構件34. . . Anode base member
35．．．陽極導電膜35. . . Anode conductive film
40．．．陰極室40. . . Cathode chamber
42．．．陰極42. . . cathode
43．．．陰極支撐體43. . . Cathode support
44．．．陰極基底構件44. . . Cathode base member
45．．．陰極導電膜45. . . Cathode conductive film
50．．．氫氟酸單元50. . . Hydrofluoric acid unit
51．．．罐51. . . tank
52．．．幫浦52. . . Pump
53．．．管道線路53. . . Pipeline
60．．．罐60. . . tank
61．．．分配單元61. . . Distribution unit
62．．．旋轉台62. . . Rotary table
63．．．回流罐63. . . Reflux tank
64．．．過濾器64. . . filter
70．．．開/關閥70. . . On/off valve
71．．．開/關閥71. . . On/off valve
72．．．開/關閥72. . . On/off valve
73．．．管道線路73. . . Pipeline
73a．．．開/關閥73a. . . On/off valve
74,85．．．管道線路74,85. . . Pipeline
74a．．．開/關閥74a. . . On/off valve
75．．．管道線路75. . . Pipeline
75a．．．開/關閥75a. . . On/off valve
76．．．開/關閥76. . . On/off valve
80．．．幫浦80. . . Pump
81．．．幫浦81. . . Pump
82．．．幫浦82. . . Pump
86．．．管道線路86. . . Pipeline
91．．．開/關閥91. . . On/off valve
Claims (18)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2009219890A JP5066152B2 (en) | 2009-09-25 | 2009-09-25 | Cleaning system |
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| TW201127950A TW201127950A (en) | 2011-08-16 |
| TWI443190B true TWI443190B (en) | 2014-07-01 |
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| JP (1) | JP5066152B2 (en) |
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| WO2016152371A1 (en) * | 2015-03-24 | 2016-09-29 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method and substrate processing device |
| JP6493839B2 (en) * | 2015-03-24 | 2019-04-03 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method and substrate processing apparatus |
| US10780461B2 (en) * | 2015-05-15 | 2020-09-22 | Taiwan Semiconductor Manufacturing Co., Ltd | Methods for processing substrate in semiconductor fabrication |
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| CA1059943A (en) * | 1976-07-20 | 1979-08-07 | Pierre L. Claessens | Electrolytically forming peroxosulfuric acid to oxidize organic material in sulfuric acid |
| JP2787788B2 (en) * | 1990-09-26 | 1998-08-20 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Residue removal method |
| JPH0750281A (en) * | 1993-08-05 | 1995-02-21 | Sumitomo Chem Co Ltd | Cleaning method for silicon wafer |
| US6827814B2 (en) * | 2000-05-08 | 2004-12-07 | Tokyo Electron Limited | Processing apparatus, processing system and processing method |
| KR100684064B1 (en) * | 2002-04-02 | 2007-02-16 | 페르메렉덴꾜꾸가부시끼가이샤 | Functional water, and the process and the apparatus for preparing the same |
| JP2004247416A (en) * | 2003-02-12 | 2004-09-02 | Toshiba Corp | Cleaning liquid and method for manufacturing electronic device |
| US20050139487A1 (en) * | 2003-05-02 | 2005-06-30 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Method for the oxidative treatment of components comprised of or containing elementary silicon and/or substantially inorganic silicon compounds |
| JP4462146B2 (en) * | 2004-09-17 | 2010-05-12 | 栗田工業株式会社 | Sulfuric acid recycling type cleaning system and sulfuric acid recycling type persulfuric acid supply device |
| KR100685738B1 (en) * | 2005-08-08 | 2007-02-26 | 삼성전자주식회사 | Removing composition for an insulation material, method of removing an insulation layer and method of recycling a substrate using the same |
| JP4816888B2 (en) * | 2005-08-18 | 2011-11-16 | 栗田工業株式会社 | Sulfuric acid recycling cleaning system |
| JP2007194351A (en) * | 2006-01-18 | 2007-08-02 | Shibaura Mechatronics Corp | Method and device for processing substrate |
| JP2007266497A (en) * | 2006-03-29 | 2007-10-11 | Kurita Water Ind Ltd | Semiconductor substrate cleaning system |
| JP5087325B2 (en) * | 2006-06-16 | 2012-12-05 | 株式会社東芝 | Cleaning system and cleaning method |
| TWI351446B (en) * | 2006-06-16 | 2011-11-01 | Toshiba Kk | Cleaning system and cleaning method |
| GB0622482D0 (en) * | 2006-11-10 | 2006-12-20 | Element Six Ltd | Diamond electrode |
| CN102623328B (en) * | 2007-05-18 | 2014-11-26 | Fsi国际公司 | Process for treatment of substrates with water vapor or steam |
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