TWI336495B - - Google Patents
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- TWI336495B TWI336495B TW96114623A TW96114623A TWI336495B TW I336495 B TWI336495 B TW I336495B TW 96114623 A TW96114623 A TW 96114623A TW 96114623 A TW96114623 A TW 96114623A TW I336495 B TWI336495 B TW I336495B
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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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32366—Localised processing
Description
1336495 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用氟系氣體來對美 蝕刻之方法。 土义面之矽進行 【先前技術】 #例如，於專利文獻卜2中揭示有如下㈣，即 乳而氧化晶圓表面之矽’使上述矽成為氧化矽“曰，、、 用氫氟酸（hydrofWic acid)來進行银刻。藉使 發生器而使氫氟酸蒸發後， 蒸 >飞 B日圓表面上。又， 昌不有如下情形’即’晶圓溫度為抓以 6〇°C以上。 較好的疋 於專利文獻3中揭示有如下情形，即，於⑺等氟 中產生大氣壓附近放電，藉 ’、、體 Γηρ办 精此生成HF、c〇f2等，進而使 混入至⑶等中之水產生反應而生 以上述方式獲得之HF，對氧切進行㈣⑷）。）错由1336495 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of etching a beauty using a fluorine-based gas. [Prior Art] [For example,] Patent Document 2 discloses that (4), that is, milk and oxidizes the surface of the wafer to make the above-mentioned tantalum into yttrium oxide, and hydrofluoric acid ( hydrofWic acid) to carry out silver engraving. After the generator is used to evaporate hydrofluoric acid, steaming > fly B on the surface of the yen. In addition, Chang does not have the following situation 'ie' wafer temperature is above 6 °C In the case of the patent document 3, it is disclosed that the discharge in the vicinity of the atmospheric pressure is generated in the fluorine (7), and the HF, c〇f2, etc. are generated by the ', the body Γηρ, and the mixture is mixed into (3), etc. The water in the reaction is produced by the HF obtained in the above manner, and the oxygen is cut (4) (4)).
Si+203-^Si〇2+2〇2 …、 (式1) C0F2+H20-.C02+2HF (式 2)Si+203-^Si〇2+2〇2 ..., (Formula 1) C0F2+H20-.C02+2HF (Formula 2)
Si〇2+4HF+H20-.SiF4+3H2〇 (式 3) 於專利文獻4中揭示有如 丄， 卜滑形’即’自已加濕之CF4# 由大氣壓電漿放電而獲得H 9 于HP ’向上述HF中添加〇3，對負 化矽進行蝕刻。 乳 於專利文獻5中揭示有如 ^ 頁如下情形，即，使CF4與〇2經大氣 反放电而獲得自由基，將兮ώ 將5亥自由基自電漿空間導引至溫度 為20 C或1 OOt：之基板上，斟。„ 對早晶矽進行蝕刻。 I20365.doc 於專利文獻6中揭示有如下情形，即，使加濕之CF4或乾 燥之CF4經大氣壓放電，於9.0。匸之基板溫度下對晶態矽進 行蝕刻。 [專利文獻1]曰本專利特開2003·264160號公報 [專利文獻2]曰本專利特開2〇〇4_55753號公報 [專利文獻3]曰本專利特開2〇〇〇_585〇8號公報 [專利文獻4]曰本專利特開2〇〇2_27〇575號公報 [專利文獻5]日本專利特開平〇4_358〇76號公報 [專利文獻6]曰本專利特開2〇〇〇_164559號公報 【發明内容】 [發明所欲解決之問題] 於先如之石夕钱刻中，無法使姓刻速度加快。本發明者認 為有如下原因。 例如’於上述所揭示之專利文獻1、2等中，自最初起以 氫氟酸之形態，將作為蝕刻劑之氫氟酸供給至由晶圓構成 之基板上。因此’於基板表面上，除上式1之氧化反應之 外，僅產生上式3之蝕刻反應。於上式3之反應中，氧化矽 成為揮發性之SiF4，隨之新生成水（η2〇)。 此處’於基板溫度較低時，上述新生成之水凝聚，溶入 基板表面上之氫氟酸之凝聚相（液相之氫氟酸）中。因此， 伴隨蝕刻反應之進行，凝聚相成長，且厚度增加。另_方 面’使石夕氧化所必須之臭氧溶解於凝聚相並於凝聚相中擴 散，到達基板表面之後，可有助於使矽氧化，但若凝聚相 之厚度增大’則臭氧到達基板表面之比例減小。因此，於 120365.doc 1336495 凝聚相内發生臭氧之擴散限制， 降。 . 從而導致石夕氧化速度下 又Si〇2+4HF+H20-.SiF4+3H2〇(Formula 3) is disclosed in Patent Document 4 as a sputum, a slip-shaped 'that is, 'self-humidified CF4# is discharged from an atmospheric piezoelectric slurry to obtain H 9 at HP ' 〇3 was added to the above HF, and the negative enthalpy was etched. The milk disclosed in Patent Document 5 discloses that the CF4 and the ruthenium 2 are subjected to reverse discharge in the atmosphere to obtain a radical, and the 亥 5 自由基 radical is guided from the plasma space to a temperature of 20 C or 1 OOt: On the substrate, 斟. Etching of the early enamel. I20365.doc discloses in Patent Document 6 that the humidified CF4 or the dried CF4 is subjected to atmospheric pressure discharge, and the crystalline yttrium is etched at a substrate temperature of 9.0. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-264160 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. 164 559 [Summary of the Invention] [Problems to be Solved by the Invention] In the case of Shi Xia, it is impossible to speed up the surname. The inventors believe that there are the following reasons. For example, the patent document disclosed in the above In the case of hydrofluoric acid, the hydrofluoric acid as an etchant is supplied to the substrate made of the wafer from the beginning. Therefore, on the surface of the substrate, in addition to the oxidation reaction of the above formula 1, Only the etching reaction of the above formula 3 is produced. In the reaction of the above formula 3, cerium oxide For the volatile SiF4, water (η2〇) is newly formed. Here, when the substrate temperature is low, the newly formed water is agglomerated, and the condensed phase of hydrofluoric acid dissolved on the surface of the substrate (hydrogen in the liquid phase) In the case of fluoric acid, the condensed phase grows and the thickness increases as the etching reaction progresses. In addition, the ozone necessary for the oxidation of the sulphur is dissolved in the condensed phase and diffused in the condensed phase, and after reaching the surface of the substrate, It helps to oxidize ruthenium, but if the thickness of the condensed phase increases, the proportion of ozone reaching the surface of the substrate decreases. Therefore, the diffusion of ozone occurs in the condensed phase of 120365.doc 1336495. Speed again
’狹♦邳之氟化氫濃度 咸小亦有可能引起速率下降。 相反，於基板溫度較苒拄 B 、’…、氫氟酸凝聚相之成長之問 4，但另一方面，如圖4所示， 臭氧之氣-液間之分配係數 下降。即，溫度越高，則皇 、臭乳越難以溶解於氫氟酸凝聚 相。因此，發生參惫夕、，六初 、’合解限制，最終導致矽氧化速度下 降。 刖 因此，基板溫度存在使矽氧化 ，60°C左右為較佳之基板溫度 速度達到峰值之值。先 。如圖4所示，於60°C附 近 然 ’刀配係數為0.1左右’僅可溶解整體臭氧之丨成左右。 而因必j抑制氫氟酸凝聚相之成長，故的。◦為最下限The concentration of hydrogen fluoride in the narrow range is also likely to cause a drop in rate. On the contrary, in the case where the substrate temperature is higher than that of B, '..., hydrofluoric acid condensed phase 4, on the other hand, as shown in Fig. 4, the gas-liquid partition coefficient of ozone is lowered. That is, the higher the temperature, the more difficult it is for the emerald and the odor to dissolve in the hydrofluoric acid condensed phase. Therefore, the occurrence of the entanglement, the beginning of the six, and the limitation of the settlement eventually led to a decrease in the rate of enthalpy oxidation.刖 Therefore, the substrate temperature is such that the ruthenium is oxidized, and a temperature of about 60 ° C is a preferable value at which the substrate temperature reaches a peak value. First. As shown in Fig. 4, at around 60 °C, the 'knife ratio is about 0.1', which only dissolves the whole ozone. And because j inhibits the growth of hydrofluoric acid condensed phase, so. ◦ is the lower limit
=溫度4低於6〇。(；，則難以增大分配係數。又，對於高 /辰度之氫氟馱水(液相之氫氟酸)而言，因氟化氫較水更易 蒸發’因此’右為高，則氫氟酸濃度自身亦會減小。 根據上述It形’於先前之矽蝕刻中’矽氧化速度即使於 峰值點亦無法達到充分之值，自衆卜蝕刻速率亦無法達到 充分之大小。 又如專利文獻5等般，於使用由電漿生成之自由基來 進行钱刻時’若電漿空間與基板中間之距離過大，則自由 基到達基板之前將純化，從而導致姓刻速率下降。另一方 面’若電聚空間與基板之間之距離過於靠近，則存在因電 水損傷基板之虞。因此’電漿空間與基板之離開距離之設 定範圍之自由度較小。 J20365.doc 1336495 [解決問題之技術手段] . 然而’由式3之姓刻反應而生成新水，其原因在於，HF 等氟系姓刻氣體具有氫原子。本發明者根據以上之研究而 獲得如下知識見解，即，蝕刻氣體中存在氫原子亦會對矽 蝕刻造成負面影響。 本發明係根據上述知識見解而完成者，且 本發明係對含夕之被處理物進行姓刻之方法，其特徵在 於： 實施將反應性氣體喷至溫度設為1〇t：〜5(rc之被處理物 上之噴吹步驟， 上述反應性氣體包括： (a) 可使矽氧化之氧化性氣體；以及 (b) 氟系反應性氣體，其含有與水反應後成為具氧化矽蝕 刻能力之氟系蝕刻氣體之非自由基氟系中間氣體，且氟原 子數（F)與氫原子數（H)之比為（F)/(H)>1.5。 藉此，可於被處理物之表面上，產生由氟系中間氣體與 水所產生之氟系姓刻氣體之生成反應。於上述氣系银刻氣 體與被處理物氧化後形成之氧化矽進行蝕刻反應時，即使 產生水，亦可將所產生之水消耗於新之氟系中間氣體之蝕 刻氣體化反應中。因此’無須防止氧化矽之蝕刻反應時所 產生之水之凝聚，即使被處理物溫度為10°C〜50。(：之低 H可抑制凝聚相於被處理物之表面上成長。藉由使被 處理物低溫化’可提高氧化性氣體向凝聚相之溶解度。藉 由抑制凝聚相之成長，可確保氧化性氣體於凝聚相中之擴 120365.doc 1336495 散度。而且，將以氟系中間氣體為主成分之氣系反應性氣 體中之氫原子數⑻與氟原子數（F)之比設為（F)/⑻^ 5 , 藉此，可切實地將姓刻反應中所生成之水消耗於氣系中間 氣體，蝕刻氣體化反應中，從而可切實地抑制凝聚相之成 長。藉此，可更充分地確保氧化性氣體於凝聚相十之擴散 度。其結果’可提高石夕之氧化速度，進而可提高録刻速 率。 又’藉由使用非自由基之氣系中間氣體’可根據反應性 氣體之喷出部與被處理物之間之相隔距離，避免產生㈣ 速率之τ降或被處理物之損冑，從而可$高距離設定等之 設計之自由度。 為獲得最初之氟系蝕刻氣體，亦可於反應剛開始時，向 氟系中間氣體中添加水蒸汽。於被處理物為非晶矽之情形 等可藉由該被處理物所含有之氫與上述氧化性氣體而 獲得水，並藉由該水與氟系中間氣體而獲得最初之氟系蝕 刻氣體。或者’可於最初，將與氟系中間氣體不同之氟系 蝕刻氣體供給至被處㈣表面丨，藉由其蝕刻反應中生成 之水而使敗系中間氣體成為蝕刻氣體。 有時可利用被處理物之溫度等來使水蒸發以消除氫氟酸 凝聚相。此時，較好的是，藉由向蝕刻反應或供給氣體中 添加水蒸汽而補充上述已蒸發之水。 "更為理想的是，上述氟系反應性氣體之氟原子數（？）與 氫原子數（H)之比為（f)/(h)>3。藉此，可更切實地消耗水 (H2〇) ’從而可更切實地抑制凝聚相之成長。 120365.doc 1336495 可藉由下述（1)〜（3)而測定上述比（F)/(H)。 ⑴藉由傅立葉轉換紅外線光譜儀（FTIR，以此以= Temperature 4 is below 6〇. (;, it is difficult to increase the partition coefficient. Also, for high/increase hydrofluorinated water (liquid hydrofluoric acid), since hydrogen fluoride is more easily evaporated than water 'so' is right high, then hydrofluoric acid The concentration itself is also reduced. According to the above-mentioned It-shaped 'in the previous etch, the 矽 oxidization rate cannot reach a sufficient value even at the peak point, and the etching rate cannot be sufficiently large. For example, Patent Document 5 In the same way, when using the radical generated by the plasma to carry out the engraving, if the distance between the plasma space and the substrate is too large, the radical will be purified before it reaches the substrate, resulting in a decrease in the surname rate. When the distance between the electro-convergence space and the substrate is too close, there is a possibility that the substrate is damaged by the electro-hydraulic water. Therefore, the degree of freedom of the setting range of the distance between the plasma space and the substrate is small. J20365.doc 1336495 [Technical problem solving] However, the reason for the formation of new water by the reaction of the surname of the formula 3 is that the fluorine-based gas such as HF has a hydrogen atom. The inventors have obtained the following knowledge based on the above research, that is, The presence of a hydrogen atom in the engraved gas also has a negative effect on the enthalpy etching. The present invention has been completed based on the above knowledge, and the present invention is a method for surname engraving of a material containing eve, characterized in that: The gas is sprayed to a blowing step at a temperature of 1 〇 t: 〜5 (rc), and the reactive gas includes: (a) an oxidizing gas capable of oxidizing hydrazine; and (b) a fluorine-based reaction a gas containing a non-radical fluorine-based intermediate gas which reacts with water to form a fluorine-based etching gas having cerium oxide etching ability, and the ratio of the number of fluorine atoms (F) to the number of hydrogen atoms (H) is (F)/ (H) > 1.5 Thereby, a reaction reaction of a fluorine-based gas generated by a fluorine-based intermediate gas and water can be generated on the surface of the object to be treated. When the cerium oxide formed after the oxidation is subjected to an etching reaction, even if water is generated, the generated water can be consumed in the etching gasification reaction of the new fluorine-based intermediate gas. Therefore, it is not necessary to prevent the etching reaction of cerium oxide. Condensation of water, even if The temperature of the chemical is 10 ° C to 50. (The low H can suppress the growth of the condensed phase on the surface of the object to be treated. By lowering the temperature of the object to be treated, the solubility of the oxidizing gas to the condensed phase can be improved. By suppressing the growth of the condensed phase, it is possible to ensure the divergence of the oxidizing gas in the condensed phase. Moreover, the number of hydrogen atoms (8) and the fluorine atom in the gas-based reactive gas containing the fluorine-based intermediate gas as a main component. The ratio of the number (F) is (F)/(8)^5 , whereby the water generated in the surname reaction can be reliably consumed in the gas-based intermediate gas, and the gasification reaction can be etched, whereby the condensation can be reliably suppressed. In this way, the degree of diffusion of the oxidizing gas in the condensed phase can be more fully ensured. As a result, the oxidation rate of the stone can be increased, and the recording rate can be improved. In addition, by using a non-radical gas-based intermediate gas, the distance between the discharge portion of the reactive gas and the object to be treated can be avoided, thereby avoiding the occurrence of a (d) rate of τ drop or damage of the processed object, thereby $ High distance setting and other design freedom. In order to obtain the first fluorine-based etching gas, water vapor may be added to the fluorine-based intermediate gas at the beginning of the reaction. In the case where the object to be treated is amorphous, the water can be obtained by hydrogen contained in the object to be treated and the oxidizing gas, and the first fluorine-based etching gas can be obtained by the water and the fluorine-based intermediate gas. Alternatively, initially, a fluorine-based etching gas different from the fluorine-based intermediate gas may be supplied to the surface of the portion (4), and the generated intermediate gas may be an etching gas by the water generated in the etching reaction. Sometimes, the temperature of the object to be treated or the like can be used to evaporate water to eliminate the hydrofluoric acid condensed phase. At this time, it is preferred to replenish the evaporated water by adding water vapor to the etching reaction or the supply gas. " More preferably, the ratio of the number of fluorine atoms (?) to the number of hydrogen atoms (H) in the fluorine-based reactive gas is (f) / (h) > As a result, water (H2〇) can be more reliably consumed, and the growth of the condensed phase can be more reliably suppressed. 120365.doc 1336495 The above ratio (F)/(H) can be determined by the following (1) to (3). (1) by Fourier transform infrared spectrometer (FTIR)
Tran命m Infrared Spectr〇meter)測定上述氟系反應性氣體 中之氟系中間氣體之濃度，求出氟系中間氣體中之氫原子 數（H)。 (2) —面測定水（鹼性水）之汕值，一面使固定量之上述氟 系反應性氣體通過該水，根據抑值之變化，求出通過上述 氟系反應性氣體之前與通過上述氟系反應性氣體之後之氫 的浪度變化ΔΗ。該濃度變化係因上述氟系反應性氣體與 水之HF生成反應而產生者。根據該濃度變化δη，求出上 述氟系反應性氣體中之氟原子數（F)。 (3) 根據上述（1)與（2)，計算比（f)/(h)。 對於上述氟系中間氣體而言，較好的是不含有氫之氟系 分子，例如，較好的是COL’但並非限定於此，若為與水 反應後生成HF等氟系蝕刻氣體者，則可為〇1^〇只等含有氢 者，亦可為F2。 較好的是，以如下方式生成上述氟系反應性氣體。 於與矽不具反應性之氟系原料中，添加使露點成為 1(TC〜40°c(水蒸汽分壓i.2282 kPa〜7 3844 kpa)之量之水， 獲得低露點I㈣料氣^使該低露點氟料氣體通過 大氣壓附近之電毁空間。 藉此，可獲得以COF2為首之富含氟系中間氣體之氟系反 應性氣體。又，可使處理變得容易。再者，於電漿放電之 輸入電力車乂大時’較好的是，除向氟系原料中添加水之 120365.doc -11 · 1336495 外，亦添加氧氣。 · 此處’所謂之大氣壓附近·，係指〇·5 bar〜2 bar之範圍， 較好的是0.9 bar〜1.1 bar之範圍。 較好的疋貫施.添加水之步驟’其向含有氟且不具有與 矽反應之反應性之氟系原料中，添加露點為1〇〇c〜4(rc^K 洛汽分壓1.2282 kPa〜7.3844 kPa)之量之水，獲得低露點氟 系原料氣體；電漿化步驟，其使上述低露點氟系原料氣體 通過大氣壓附近之電漿空間；以及喷吹步驟，其將含有可 使矽氧化之氧化性氣體與經上述電漿化步驟之氣體的反應 性氣體’噴至溫度设為10 C〜5 01之被處理物上。 藉由上述電漿化步驟，可自氟系原料獲得含有大量氟系 中間氣體之氟系反應性氣體成分。 較好的是，上述氧化性氣體為臭氧。藉此，可切實地使 構成被處理物之石夕氧化。 較好的疋上述氧化性氣體係藉由使氧氣通過臭氧發生 器而獲得者。藉此’可獲得高濃度之臭氧作為氧化性氣 體。 較好的是，臭氧之添加量盡可能多。於氟系中間氣體為 C〇F2，說系钱刻氣體為册時，臭氧之添加流量至少必須 大於或等於c〇F2之體積流量與HF之體積流量之2分之Μ 合計流量，較好的是上述合計流量之2倍左右。 上述氧化性氣體亦可為藉由使氧氣通過大氣壓附近之電 漿空間而獲得者。 上述電槳空間可與用以使上述低露點㈣原料氣體電聚 120365.doc 12 1336495 化之電漿空間相同，亦可與其不同。於前者（相同）之情形 時’可共用1個電漿生成裝置，從而可簡化裝置構成。於 後者（不同）之情形時，可獲得高濃度之臭氧等氧化性氣 體。又’可有效地使低露點氟系原料氣體電漿化。 亦可貫施：混合步驟’其混合含有氟且與矽不具反應性 之說系原料、對上述氟系原料露點成為】❹力〜…它（水蒸汽 分壓1.2282 kPa〜7.3 844 kPa)之量之水、以及氧氣，以獲得 混合氣體； 電漿化步驟，其使上述混合氣體通過大氣壓附近之電漿 空間’以獲得反應性氣體；以及 喷吹步驟’其將上述反應性氣體噴至溫度設為 10 °C〜5 0 °C之被處理物上。 藉此’可於1個電漿空間中，自氟系原料氣體獲得氟系 中間氣體’且自氧氣獲得氧化性氣體。 較理想的是’上述混合氣體中之氧氣之比例相對於上述 敦系原料為5〜20 vol%。藉由將下限設為5 ν〇ι%，即使電 漿放電之輸入電力較高，亦可充分地生成氟系中間氣體。 將上限设為20 vol0/。之原因在於’若超過該上限，則氟系 中間氣體之生成將達到飽和。上述氧氣之比例取決於電漿 放電之輸入電力，但較好的是，上述氧氣之比例相對於上 述氟系原料為7〜13 vol%。 較好的是’上述氟系原料為cf4。 藉此’可於上述電漿空間中’獲得c〇F2、cF3〇h、F2等 作為氟系中間氣體》 120365.doc *13、 1336495 於上述電㈣步驟中’較好的是，通過上述電聚空間之 後之水之濃度為通過前的ur〇以下。 藉此’可使水大部分消耗於氣系中間氣體之蝕刻氣體化 反應中’從而可切實地抑制被處理物表面之凝聚相之成 長，可切實地提高蝕刻速率。Tran Infrared Spectr〇meter) The concentration of the fluorine-based intermediate gas in the fluorine-based reactive gas is measured, and the number of hydrogen atoms (H) in the fluorine-based intermediate gas is determined. (2) measuring the enthalpy of water (alkaline water), and passing a predetermined amount of the fluorine-based reactive gas through the water, and determining the passage of the fluorine-based reactive gas before and after passing through the water The change in the degree of Δ of hydrogen after the fluorine-based reactive gas. This concentration change is caused by the reaction of the fluorine-based reactive gas with water HF. Based on the concentration change δη, the number of fluorine atoms (F) in the fluorine-based reactive gas is determined. (3) Calculate the ratio (f)/(h) based on the above (1) and (2). The fluorine-based intermediate gas is preferably a fluorine-based molecule that does not contain hydrogen. For example, COL' is preferably not limited thereto, and if it is reacted with water, a fluorine-based etching gas such as HF is generated. It can be 〇1^〇 only if it contains hydrogen, or F2. Preferably, the fluorine-based reactive gas is produced in the following manner. In the fluorine-based raw material which is not reactive with hydrazine, water having a dew point of 1 (TC to 40 ° C (water vapor partial pressure i.2282 kPa to 7 3844 kpa) is added to obtain a low dew point I (four) gas; The low dew point fluorine gas passes through an electric destruction space near the atmospheric pressure. Thereby, a fluorine-based reactive gas rich in a fluorine-containing intermediate gas such as COF2 can be obtained. Further, the treatment can be facilitated. When the input power of the slurry discharge is large, it is better to add oxygen to the fluorine-containing raw material, 120365.doc -11 · 1336495. · Here, the so-called atmospheric pressure is nearby. The range of 5 bar to 2 bar, preferably in the range of 0.9 bar to 1.1 bar. The preferred step of adding water is to a fluorine-based raw material containing fluorine and having no reactivity with hydrazine. Medium, adding water having a dew point of 1〇〇c~4 (rc^K Luoqi partial pressure 1.2282 kPa~7.3844 kPa) to obtain a low dew point fluorine-based raw material gas; a plasmaization step for making the above low dew point fluorine system The raw material gas passes through the plasma space near atmospheric pressure; and the blowing step, which will contain oxygen The oxidizing gas and the reactive gas of the gas in the above-described plasmalization step are sprayed onto the object to be treated at a temperature of 10 C to 5 01. By the above-mentioned plasmalizing step, the content can be obtained from the fluorine-based raw material. The fluorine-based reactive gas component of the fluorine-based intermediate gas is preferably ozone. The oxidizing gas is preferably ozone. By obtaining oxygen through the ozone generator, it is possible to obtain a high concentration of ozone as an oxidizing gas. Preferably, the amount of ozone added is as large as possible. The fluorine-based intermediate gas is C〇F2, When the gas is engraved, the ozone addition flow rate must be at least equal to or greater than the volume flow rate of c〇F2 and 2 times the volume flow rate of HF. The total flow rate is preferably about twice the total flow rate. The gas may also be obtained by passing oxygen through the plasma space near atmospheric pressure. The above-mentioned electric pad space may be the same as the plasma space used to make the low dew point (4) material gas electropolymerization 120365.doc 12 1336495 In the case of the former (same), one plasma generating device can be shared, which simplifies the device configuration. In the case of the latter (different), a high concentration of oxidizing gas such as ozone can be obtained. In addition, the low dew point fluorine-based raw material gas can be effectively plasma-treated. It can also be applied: a mixing step of mixing a fluorine-containing material with a non-reactive material and a dew point to the fluorine-based raw material. ...the water (water vapor partial pressure of 1.2282 kPa to 7.3 844 kPa) and oxygen to obtain a mixed gas; a plasmalization step of passing the mixed gas through a plasma space near atmospheric pressure to obtain a reactive gas And a blowing step of spraying the above reactive gas onto the object to be treated at a temperature of 10 ° C to 50 ° C. In this way, a fluorine-based intermediate gas can be obtained from a fluorine-based source gas in one plasma space, and an oxidizing gas can be obtained from oxygen. It is preferable that the ratio of oxygen in the above mixed gas is 5 to 20 vol% with respect to the above-mentioned Dune raw material. By setting the lower limit to 5 ν〇ι%, the fluorine-based intermediate gas can be sufficiently generated even if the input power of the plasma discharge is high. Set the upper limit to 20 vol0/. The reason is that if the upper limit is exceeded, the formation of the fluorine-based intermediate gas is saturated. The ratio of the above oxygen depends on the input power of the plasma discharge, but it is preferable that the ratio of the above oxygen is 7 to 13 vol% with respect to the fluorine-based raw material. Preferably, the fluorine-based raw material is cf4. Therefore, 'c可F2, cF3〇h, F2, etc. can be obtained as the fluorine-based intermediate gas in the above-mentioned plasma space>> 120365.doc *13, 1336495 in the above electric (four) step, preferably, by the above electricity The concentration of water after the gathering space is below ur〇 before passing. In this way, most of the water can be consumed in the etching gasification reaction of the gas-based intermediate gas, whereby the growth of the agglomerated phase on the surface of the workpiece can be reliably suppressed, and the etching rate can be surely increased.
上述露點較好的是1〇r〜3(rc(水蒸汽分壓丨228 1^〜4.24671^)，更好的是1〇。(：〜2〇。(：（水蒸汽分壓1228 让卩卜2.33921^&)’進而更好的是1〇。(：〜17。(：（水蒸汽分壓 1.2282 kPa〜1.9383 kPa卜 藉此’可切貫地提南姓刻速率。 上述被處理物之溫度之上限可低於5〇。。，亦可為贼以 更好的是，將上述被處理物之溫度設為1〇。〇〜3〇它^ 藉此’可易於使臭氧等氧化性氣體溶解於被處理物表面The above dew point is preferably 1〇r~3 (rc (water vapor partial pressure 丨 228 1^~4.24671^), more preferably 1〇. (:~2〇. (: (water vapor partial pressure 1228 let 卩卜2.33921^&)' and further preferably 1〇. (:~17. (: (water vapor partial pressure 1.2282 kPa~1.9383 kPa b) This can be used to extract the south surname rate. The upper limit of the temperature may be less than 5 〇., or the thief may be better, the temperature of the above-mentioned object to be treated is set to 1 〇. 〇 ~ 3 〇 it ^ by this can easily make ozone and other oxidative properties The gas is dissolved on the surface of the treated object
之凝聚相中，從而可提高矽氧化速度。或者 氟化氫等而提高氫氟酸濃度。因此，可進一 率。 ’可易於溶解 步提高钱刻速 因在於， 相對濕度 將上述被處理物之溫度範圍下限設為1〇<t之原 可防止被處理物表面之凝聚（於室溫為25。〇時， 為3 8 %以内即可）。 除將上述被處理物之溫度範圍之下限設為1〇它之外， 可將其設為室内露點。 μ 藉此:可防止室内之水分凝聚於被處理物表面上，從而 可更可靠地防止被處理物表面之凝聚相之成長。 120365.doc ，好的是，將上述被處理物之溫度設為室溫β 藉此，無須對被處理物進杆加熱或冷卻，可省略對被處 理物之溫度進行調節之步驟。 [發明之效果] 、根據本發明，即使於蝕刻反應時產生水，亦可將該水用 於氟系:蝕刻氣體之生成反應中。因此，即使被處理物溫度 ^亦可抑制凝聚相於被處理物之表面上成長。藉 可提同矽氧化速度，進而可提高蝕刻速率。 【實施方式】 以下，對本發明之第1實施形態加以說明。 如圖1所示，於玻璃等基板90之上表面形成有矽之膜 被處理物）。構成膜91之矽可為非晶矽，亦可為微晶Si_ 多晶Si等晶狀矽。ϋ膜91亦彳為以矽為主成分且含有 0〜20%左右之氫的膜。基板9〇由晶圓等矽所構成，且基板 90自身亦可為蝕刻對象（被處理物）。亦可為摻雜有ρ(磷）及 (硼）等之η型或Ρ型之矽。若列舉一例，則於液晶用之TFT (thm film transist〇r，薄膜電晶體）中所使用之基板中，於 玻璃上形成SiN膜，其後，利用電漿CVD (Chemical Vapor Deposition ’化學氣相沈積）來形成作為本實施形態之被處 理物之非晶質矽膜。 於圖中’誇大地表示基板90及矽膜91之厚度。 蝕刻裝置1具備基板溫度調節機構2、搬送機構3以及反 應性氣體供給系統4。 基板/fflL度調節機構2包括加熱器及冷卻器（省略圖示）， 120365.doc 1336495 特定之方式進行調節。基板 更好的是l〇°C〜3〇。(：，進而 更好的是設為室溫。對於溫度範圍之下限而言，除設為 1〇°C之外’亦可設為室内露點。於將基板溫度設為室溫 時’亦可省略基板溫度調節機構2。 搬送機構3使基板90相對於反錢氣體供給系統4而例如 於圖1之左右方向上相對移動。In the condensed phase, the enthalpy oxidation rate can be increased. Or hydrogen fluoride or the like to increase the concentration of hydrofluoric acid. Therefore, it can be increased. 'The easy-to-dissolve step increases the cost because the relative humidity sets the lower limit of the temperature range of the above-mentioned treated object to 1 〇<t to prevent aggregation of the surface of the object to be treated (at room temperature of 25. It can be within 3 8 %). In addition to setting the lower limit of the temperature range of the above-mentioned processed object to 1 〇, it can be set as the indoor dew point. μ: This prevents moisture in the room from condensing on the surface of the object to be treated, thereby more reliably preventing the growth of the condensed phase on the surface of the object to be treated. It is preferable that the temperature of the above-mentioned object to be treated is set to room temperature β, whereby it is not necessary to heat or cool the workpiece, and the step of adjusting the temperature of the workpiece can be omitted. [Effect of the Invention] According to the present invention, even if water is generated during the etching reaction, the water can be used in a fluorine-based: etching gas formation reaction. Therefore, even if the temperature of the object to be treated ^ can suppress the growth of the condensed phase on the surface of the object to be treated. The etch rate can be increased by increasing the oxidizing rate. [Embodiment] Hereinafter, a first embodiment of the present invention will be described. As shown in Fig. 1, a film of a crucible is formed on the upper surface of a substrate 90 such as glass. The crucible constituting the film 91 may be amorphous germanium or a crystalline germanium such as microcrystalline Si_polycrystalline Si. The ruthenium film 91 is also a film containing ruthenium as a main component and containing about 0 to 20% of hydrogen. The substrate 9 is made of a crucible or the like, and the substrate 90 itself may be an object to be etched (object to be processed). It may be an y-type or ytterbium type doped with ρ (phosphorus) and (boron). In an example, a SiN film is formed on a glass used in a TFT for TFT (thin film transistor), and thereafter, by chemical CVD (Chemical Vapor Deposition 'Chemical Vapor The amorphous ruthenium film which is the object to be processed of this embodiment is formed. In the figure, the thickness of the substrate 90 and the ruthenium film 91 is shown exaggeratedly. The etching apparatus 1 includes a substrate temperature adjustment mechanism 2, a transfer mechanism 3, and a reactive gas supply system 4. The substrate/fflL degree adjustment mechanism 2 includes a heater and a cooler (not shown), and is adjusted in a specific manner in 120365.doc 1336495. The substrate is preferably l〇°C~3〇. (:, and further preferably set to room temperature. For the lower limit of the temperature range, in addition to 1 〇 ° C, 'can also be set as indoor dew point. When the substrate temperature is set to room temperature' The substrate temperature adjustment mechanism 2 is omitted. The conveyance mechanism 3 relatively moves the substrate 90 with respect to the anti-money gas supply system 4, for example, in the left-right direction of FIG.
反應性氣體供給系統4具備臭氧供給系統1〇及氣系氣體 供給系統20。 臭氧供給系統H)包括氧氣供給㈣及與該氧氣供給部u 連接之臭氧發生II 12。雖省料細㈣，但氧氣供給料 具有氧氣瓶及質量流量控制器，將特定流量之氧氣（〇2)供 給至臭氧發生器12。臭氧發生器12可自氧氣生成氧化性氣 體、即臭氧（〇3)。較理想的是，臭氧發生器12之出口部之 臭氧濃度，以臭氧對氧氣之比為丨〜丨5 v〇1%。The reactive gas supply system 4 includes an ozone supply system 1A and a gas-based gas supply system 20. The ozone supply system H) includes an oxygen supply (4) and an ozone generation II 12 connected to the oxygen supply unit u. Although the material is fine (4), the oxygen supply has an oxygen cylinder and a mass flow controller to supply a specific flow of oxygen (〇2) to the ozone generator 12. The ozone generator 12 can generate an oxidizing gas, i.e., ozone (〇3), from oxygen. Preferably, the ozone concentration at the outlet of the ozone generator 12 is 臭氧~丨5 v〇1% in terms of ozone to oxygen.
以使欲處理之基板90之溫度為 90之溫度較好的是1 〇°C ~5〇t： 氟系氣體供給系統20具備氟系原料供給部21、與該氟系 原料供給部21連接之加濕器22以及與該加濕器22連接之遠 距電漿喷頭23。雖省略詳細圖示，但氟系原料供給部2丨具 有蓄積有CF4作為氟系原料之貯槽及質量流量控制器，且 將特定流罝之CF4供給至加濕器22。加濕器22向來自氟系 原料供給部21之CF*氣體中添加特定量之水。較好的是， 添加水之置為使添加後之CF#氣體之露點成為丨〜之 I，更好的是使上述露點成為1(rc〜3〇〇c之量，進而更好 的疋使上述露點成為1〇〇c〜2(rc之量。藉此，可生成露點 120365.doc 丄⑽495 低於先前之露點之cf4氣體β 遠距電聚喷頭23配置於基_之上方，上述基板90藉由 上述搬达機構3而相對移動。電漿喷頭23具備一對電極 24、24 〇電源25連接於其中一個電極24上，另一個電極μ 電性接地。於一對電極24、24之間形成有狹縫狀之空間 26。於該電極間空間26之上端部，連結有來自加濕器22之 氣體管路。於電極之對向面上設置有固體電介質層。The temperature at which the temperature of the substrate 90 to be processed is 90 is preferably 1 〇 ° C to 5 〇 :: The fluorine-based gas supply system 20 includes the fluorine-based raw material supply unit 21 and is connected to the fluorine-based raw material supply unit 21 A humidifier 22 and a remote plasma spray head 23 connected to the humidifier 22 are provided. Though not shown in detail, the fluorine-based raw material supply unit 2 has a storage tank and a mass flow controller in which CF4 is stored as a fluorine-based raw material, and CF4 of a specific flow is supplied to the humidifier 22. The humidifier 22 adds a specific amount of water to the CF* gas from the fluorine-based raw material supply unit 21. Preferably, the water is added so that the dew point of the added CF# gas becomes 丨~I, and it is more preferable to make the dew point 1 (rc~3〇〇c), and thus better The dew point is 1〇〇c~2 (the amount of rc. Thereby, a dew point 120365.doc 丄(10)495 can be generated. The cf4 gas β far from the previous dew point is disposed above the base_, the substrate 90 is relatively moved by the above-described transfer mechanism 3. The plasma spray head 23 is provided with a pair of electrodes 24, 24, and the power source 25 is connected to one of the electrodes 24, and the other electrode is electrically grounded to the pair of electrodes 24, 24. A slit-shaped space 26 is formed therebetween. A gas line from the humidifier 22 is connected to an upper end portion of the interelectrode space 26. A solid dielectric layer is provided on the opposite surface of the electrode.
自電源25向其中一個電極24供給電壓，藉此，於電極間 空間26中形成大氣輝光放電。藉此，電極間空間％成為大 氣電漿空間》 較好的是，供給電墨為Vpp=i〇〜i5 kv。 脈衝等間歇波，亦可為正弦波等連續波。 … _自遠距電聚喷頭23之電極間空間26之下端部，延伸出較 之喷出s路27’ 噴出管路27之下端部於電毁喷頭^之 下表面開口。於嗔出管路27之中間部合倂有來自臭氧發生 盗12之魏供給管路13 °於電毁噴頭23下表面之喷出管路 27之下^開口（噴出口）附近，配置有離開基板90之相對移 向之吸引ε路41的端部開口 (吸引口）。吸引管路“與 真空栗專排氣機構42連接。 現說明藉由上述蝕刻裝置1來對基板90之矽膜91進行蝕 基板溫度調節步驟 二=度調節機構2,將欲處理之基板9。調節為 丄u U〜5 0 C之特定、，®庙 ^ „ 度，較好的是，調節為1(TC〜3(TC之特 120365.doc 1336495 疋溫度。於基板90之特定溫度為室溫時，無須特別地進t 溫度調節。 - 丁 將上述基板9〇配置於電漿噴頭23之下側。 臭氧化步驟 其-人，藉由臭氧發生器12而使來自氧氣供給部u之氧氣 臭氧化。藉此，獲得含有臭氧之氧氣。將該含有臭氧之氧 氧導出至臭氧供給管路13中。 添加水之步釋A voltage is supplied from one of the electrodes 24 to the electrode 24, whereby an atmospheric glow discharge is formed in the interelectrode space 26. Thereby, the space between the electrodes becomes the atmospheric plasma space. It is preferable that the supply of the ink is Vpp = i 〇 ~ i5 kv. Intermittent waves such as pulses may also be continuous waves such as sine waves. ... _ from the lower end of the interelectrode space 26 of the remote electro-concentrating nozzle 23, extending from the lower end surface of the ejecting nozzle ^ from the lower end of the ejecting slue 27'. In the middle portion of the outlet pipe 27, there is a Wei supply line 13 from the ozone thief 12, and a discharge port 27 below the discharge pipe 27 on the lower surface of the ejector nozzle 23 is disposed near the opening (the discharge port). The opposite direction of the substrate 90 is toward the end opening (suction port) of the suction ε road 41. The suction line is "connected to the vacuum pump-specific exhaust mechanism 42. It is now described that the substrate 91 of the substrate 90 is subjected to the etching substrate temperature adjustment step 2 = degree adjustment mechanism 2 by the etching device 1, and the substrate 9 to be processed is to be processed. Adjust to 丄u U~5 0 C specific,, ® temple „ degree, preferably, adjust to 1 (TC~3 (TC special 120365.doc 1336495 疋 temperature. The specific temperature of the substrate 90 is room In the case of temperature, it is not necessary to specifically adjust the temperature of t. - The substrate 9 is disposed on the lower side of the plasma nozzle 23. The ozonation step is performed by the ozone generator 12 to oxygen from the oxygen supply unit u. Ozonation. Thereby, ozone-containing oxygen is obtained. The ozone-containing oxygen is led to the ozone supply line 13.
又，將來自氟系原料供給部21之CP#導入至加濕器U 中。於加濕器22中，添加使露點成為1〇£>(：〜4〇它之量之 水’較好的是添加使露點成為1〇t：〜3〇t之量之水。該所 添加水之量較好的是如下之量，即，於下述電漿化：驟Moreover, CP# from the fluorine-based raw material supply unit 21 is introduced into the humidifier U. In the humidifier 22, it is preferable to add water having a dew point of 1 & & ( ( ( 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 较好 。 。 。 。 。 。 The amount of added water is preferably in the following amount, that is, in the following plasma:
中，使通過電漿空間26之後之水的濃度為通過前水的濃度 之1 /1 0以下。 X 電漿化步驟 將添加水之後之CF4導入至電漿噴頭2 电求贾碩23之電極間空間26 中。與此同時’自電源25將電壓供給至電極藉此，於 電極間空間26中產生大氣輝光放電’將電極間空㈣設為 電漿空間。藉此，使CF4電漿化，盘 ，、所添加之水產生反 應，生成COF2 ' CF3OH、F2等氤车中門名μ 軋糸中間氣體、或作為氟系 蝕刻氣體之HF等。而且，對上诚六a u λ 述添加水之量進行設定，藉 此生成較HF多之COF2等中間氣體。拜 猎此’可將富含中間 氣體（例如富含COF2)之氟系反應性氣體 等出至噴出管路27 中 〇 120365.doc 18- 比6495 再者，於電漿放電之輸入電力較大時，較好的是，除向 :(2)°錯此，可更可靠地生成咖2作為氟系中間氣 混合步驟 於上述COF2富氣中，混合來自臭氧供給管㈣之含有臭In the middle, the concentration of water after passing through the plasma space 26 is 1 / 10 or less of the concentration of the water passing through. X Plasma Step The CF4 after the addition of water is introduced into the plasma head 2 to find the interelectrode space 26 of the Jiashuo 23 . At the same time, "the voltage is supplied from the power source 25 to the electrode, thereby generating an atmospheric glow discharge in the inter-electrode space 26", and the inter-electrode space (four) is set as a plasma space. As a result, the CF4 is plasma-formed, and the disk and the added water are reacted to generate a gas such as COF2 'CF3OH or F2, a gate-in-mud intermediate gas, or a fluorine-based etching gas. Further, the amount of water added to the upper six a u λ is set, thereby generating an intermediate gas such as COF2 which is more than HF. By hunting this, a fluorine-based reactive gas rich in intermediate gas (for example, rich in COF2) can be discharged into the discharge line 27 〇120365.doc 18- than 6495. Further, the input power to the plasma discharge is larger. Preferably, in addition to the (2)° error, the coffee 2 can be more reliably produced as a fluorine-based intermediate gas mixing step in the COF2 rich gas, and the mixed stinky from the ozone supply pipe (four)
氧之氧氣。藉由該混合氣體而構成「含有氧化性氣繼 糸中間氣體之反應性氣體J。 喷吹步驟 自噴出管路27喷出上述混合氣體，並將該混合氣體喷至 基板9〇之矽膜91之表面。藉此，於矽膜91之表面上產生反 應，對矽膜91進行蝕刻。因與反應有關之c〇F2、HF、〇3 等係非自由基，故根據電漿噴頭23與基板9〇之間之工作距 離，可避免引起蝕刻速率之下降或基板9〇之損傷，可易於 噴頭向度之設定等’從而可提高設計之自由度。 由吸引管路41吸入處理後之氣體，由排氣機構U排出上 述處理後之氣體。進而，由搬送機構3使基板90相對移 動’對整個基板9 0進行餘刻處理。 該矽蝕刻之詳細機理雖不確定，但認為由如下之反應來 進行蝕刻。可忽視來自電漿空間26之供給氣體中之HF。 [情況1] (氧化過程）Oxygen oxygen. The reactive gas J containing the oxidizing gas and the intermediate gas is formed by the mixed gas. The blowing step ejects the mixed gas from the discharge line 27, and sprays the mixed gas onto the substrate 91. Thereby, a reaction is generated on the surface of the ruthenium film 91, and the ruthenium film 91 is etched. Since the reaction is related to c〇F2, HF, 〇3, etc., it is a non-free radical, so according to the plasma head 23 and the substrate. The working distance between 9〇 can avoid the decrease of the etching rate or the damage of the substrate 9〇, and the setting of the nozzle orientation can be easily performed, thereby improving the degree of freedom of design. The gas after being treated is sucked by the suction line 41, The gas after the treatment is discharged by the exhaust mechanism U. Further, the substrate 90 is relatively moved by the transport mechanism 3, and the entire substrate 90 is subjected to a process. The detailed mechanism of the ruthenium etching is not determined, but it is considered to be the following reaction. The etching is performed. The HF in the supply gas from the plasma space 26 can be ignored. [Case 1] (Oxidation process)
Si+2〇3 —Si〇2+2〇2 (式 11) (HF生成過程） 120365.docSi+2〇3—Si〇2+2〇2 (Formula 11) (HF generation process) 120365.doc
2C0F2+2H20-^2C02 + 4HF (HF溶解過程） 4HF+4HF + 4H20-»4HF2'+4H3〇+ (蝕刻過程）2C0F2+2H20-^2C02 + 4HF (HF dissolution process) 4HF+4HF + 4H20-»4HF2'+4H3〇+ (etching process)
Si02+4HF2.+4H3〇+—SiF4 + 2H2〇+4H2〇+4HF (式 i4) 如式13所示，於矽膜91之表面上，形成有氫氧酸之凝聚Si02+4HF2.+4H3〇+—SiF4 + 2H2〇+4H2〇+4HF (Formula i4) As shown in Formula 13, a condensed form of hydroxy acid is formed on the surface of the ruthenium film 91.
相（液相之氫氟酸）之膜。上述喷出氣體中之各成分與上述 凝聚相之表面接觸。 右噴出氣體中之臭氧與凝聚相表面接觸，則上述臭氧以 如下比例溶解於凝聚相中，該比例與相對於基板溫度之分 配係數（圖4)相對應。因基板溫度設定為1〇t：〜5〇Dc等之低 溫’故分配係數較大，@而可充分增大臭氧向凝聚相中溶 解之溶解度。X ’因處於低溫下，故可防止臭氧分解，從 而可充分延長臭氧壽命。溶解於凝聚相中之臭氧於凝聚相 中擴散後到達矽膜91之表面。藉由該臭氧而使構成矽膜91A membrane of a phase (hydrofluoric acid in the liquid phase). Each component of the above-mentioned gas is in contact with the surface of the agglomerated phase. When the ozone in the right ejected gas comes into contact with the surface of the condensed phase, the ozone is dissolved in the condensed phase in a ratio corresponding to the distribution coefficient with respect to the substrate temperature (Fig. 4). Since the substrate temperature is set to a low temperature of 1 〇 t: 〜5 〇 Dc or the like, the partition coefficient is large, and @ can sufficiently increase the solubility of ozone in the condensed phase. Since X ’ is at a low temperature, ozone can be prevented from decomposing, and the ozone life can be sufficiently prolonged. The ozone dissolved in the condensed phase diffuses in the condensed phase and reaches the surface of the ruthenium film 91. Forming the ruthenium film 91 by the ozone
(式 12) (式 13) 之矽氧化，成為氧化矽（式n)。因臭氧溶解度較大，故可 充分增大矽氧化速度。 構成凝聚相之氫氟酸與以上述方式所獲得之氧化石夕接 觸氧化石夕變成揮發性之SiF4，自吸引口被吸引並除去（式 14卜精此’進行耗刻。时氧化速度較快，故可充分 增大姓刻速率。 、藉由上述钱刻反應而生成水（蒸汽）（式14)。該水之一部 分（式Μ右邊第2項之240)與上述喷出氣體中之〇〇匕反 應’生成HF(式12)。因此，該水（2H2〇)於式ι2及式14之2 120365.doc 1336495 個反應中作為觸媒而發揮作用s + ^ ^ k ^ 用。，再者，由上述蝕刻反應生 成之水之剩餘部分（式14 ,Β^. η 透弟3項之4Η2ο)用於形成氫氟 §九旋聚相（式13左邊第3項）， 消耗（式14)。 $而於氧切之㈣反應中被 藉此，可防止或抑制凝聚 L, ^ 仰％暴材之表面上成長。因 此，可防止發生凝聚相中之 六乳 < 擴散限制，從而可切實 地使臭氧擴散至矽膜9丨之表面。 A > 因此，上述臭氧向凝聚相 中洛解之溶解度提高，隨 J進步加快矽膜91之氧化速 度。 又，亦可防止氫說酸發生擴散限制，從而 蝕刻反應。 丁 進而’抑㈣㈣之成長’藉此可自基㈣表面迅速地 放出於钱刻反應中所產生之响，從而可防止再析出 S"2。其結果，可更進一步提高蝕刻速率。 於式12中’由C〇f2所產生之抑溶解於氫敗酸凝聚相（式 U左邊第叫，可有助於氧切之钱刻（式14)。由韻刻反 應生成之HF(式14右邊第4項）亦同樣地溶解於氣說酸凝聚 相（式13左邊第2項）’可有助於氧化石夕之钱刻（式14)。 式11〜式I4可歸納為以下之反應式。(Formula 12) (Formula 13) is oxidized to form cerium oxide (formula n). Due to the large solubility of ozone, the oxidation rate of ruthenium can be sufficiently increased. The hydrofluoric acid constituting the condensed phase and the oxidized stone obtained in the above manner are in contact with the oxidized stone, and the SiF4 becomes volatile, and is attracted and removed from the suction port. Therefore, the rate of the surname can be sufficiently increased. Water (steam) is generated by the above-mentioned money reaction (formula 14). One part of the water (240 of the second item on the right side of the formula) and the gas in the above-mentioned ejected gas The hydrazine reaction generates HF (Formula 12). Therefore, the water (2H2 〇) acts as a catalyst for the reaction of s + ^ ^ k ^ in the reaction of 2 120365.doc 1336495 of the formula ι2 and the formula 14. The remainder of the water formed by the above etching reaction (Equation 14, Β^. η 透 3 3 4 Η 2 ο) is used to form a hydrofluoric § nine-phase polyphase (3rd item on the left side of Equation 13), consumption (Equation 14) It is used in the reaction of oxygen cut (4) to prevent or inhibit the aggregation of L, ^, and the growth of the surface of the explosive material. Therefore, it is possible to prevent the occurrence of the six emulsions in the condensed phase. The earth diffuses ozone to the surface of the ruthenium film. A > Therefore, the above ozone is dissolved into the condensed phase. The degree of solution is improved, and the oxidation rate of the ruthenium film 91 is accelerated as J progresses. Further, it is also possible to prevent the hydrogen from being said to have a diffusion restriction of the acid, thereby etching the reaction. Ding et al. (4) (4) growth can be quickly released from the surface of the base (4) The sound generated in the reaction of the money can prevent the precipitation of S"2. As a result, the etching rate can be further increased. In the formula 12, the dissolution caused by C〇f2 is dissolved in the hydrogen sulfide acid condensed phase. The first call on the left side of the U can help the oxygen cut (Equation 14). The HF generated by the rhyme reaction (the fourth item on the right side of the formula 14) is also dissolved in the gas condensed phase (the second on the left side of Equation 13) Item ' can contribute to the oxidation of the oxidized stone (Formula 14). Formula 11 to Formula I4 can be summarized as the following reaction formula.
Si + 203+2C0F2 —SiF4+202+2C02 (弋 15) 理論上而言，若於處理之最初階段僅供給％〇,則將產 生中間氣體C〇F2之職反應（式12)，並以此為契機而連鎖 地產生式丨卜^之反應，全體而言，式15所表示之反應開 始進行。因此，一旦反應開始，則其後，即使於來自電^ 120365.doc 21 1336495 空間26之富含COF2之供給氣體·中完全不含有HF，只要含 有中間氣體之COF2，則亦可·繼續進行矽蝕刻處理。 此處，若考慮來自電漿空間26之供給氣體所含有之成分 中，氟系蝕刻氣體、氟系中間氣體、及水中之氫原子數 . (H)與氟原子數（F)之比（F)/(H)，則於式15中，氟原子數（F) . 於2COF2中為4個，相對於此，氫原子（H)為零，因此， (F)/(H)=無限大。 φ 另一方面，為產生式14中之蝕刻反應，當考慮到必須於 •矽膜91之表面上存在某程度厚度之凝聚相時，若凝聚相過 薄，則該凝聚相易因水蒸發而蒸發。又，有時蝕刻反應中 所產生之水（式14右邊第2項）於碰到c〇F2而產生HF化反應 (式12)之刖，與S1F4等一倂被自吸引口吸出。因此，實際 上’較好的是持續地進行上述添加水之步驟。 一般而言，於液晶驅動用之打丁（薄膜電晶體）所使用之 藉由電漿CVD而製作之非晶矽之情形時，於膜中含有約 • 1〇%左右之氫。此時，如下式Ua所示，藉由臭氧之氧化反 應而生成水。可利用該水來產生最初之hf化反應（式12)或 於HF化反應之後補給水。Si + 203+2C0F2 —SiF4+202+2C02 (弋15) Theoretically, if only %〇 is supplied in the initial stage of the treatment, the intermediate gas C〇F2 will react (Equation 12) and In response to the trigger, the reaction of the formula is generated in a chain, and the reaction represented by the formula 15 is started as a whole. Therefore, once the reaction is started, even if the COF2-rich supply gas from the space 26 of the electricity source 12026 does not contain HF at all, as long as the COF2 of the intermediate gas is contained, the hydrazine can be continued. Etching treatment. Here, in consideration of the components contained in the supply gas from the plasma space 26, the fluorine-based etching gas, the fluorine-based intermediate gas, and the number of hydrogen atoms in water. (H) and the number of fluorine atoms (F) (F) ) / (H), in the formula 15, the number of fluorine atoms (F) is four in 2COF2, whereas the hydrogen atom (H) is zero, therefore, (F) / (H) = infinity . On the other hand, in order to produce the etching reaction in the formula 14, when it is considered that a certain degree of thickness of the condensed phase exists on the surface of the ruthenium film 91, if the condensed phase is too thin, the condensed phase is liable to evaporate by water. evaporation. Further, the water generated in the etching reaction (the second term on the right side of the formula 14) may be sucked out from the suction port after being subjected to the HF reaction (formula 12) after hitting c〇F2. Therefore, it is actually preferable to carry out the above-described step of adding water continuously. In general, in the case of an amorphous germanium produced by plasma CVD used for a liquid crystal driving doped film (thin film transistor), about 1% by mole of hydrogen is contained in the film. At this time, as shown by the following formula Ua, water is generated by the oxidation reaction of ozone. The water can be utilized to produce an initial hf reaction (Formula 12) or to replenish water after the HF reaction.
SiH2x+(2H-x)〇3->Si02 + (2+x)〇2+xH2〇 (式 11a) 此處’ SiHh表示每個被處理物之矽原子含有2χ個氫原 子，於非晶矽中，2χ与〇.1，於一般之矽中，2χ=〇。 考慮破處理物中所含有之氫時之整個反應式如以所述。 SiH2x+(2+x)〇3+2COF2 —SiF4 + (2 + x)〇2+2C〇2 (式 15a) 上述情況1中，主要著眼於來自電漿空間26之供給氣體 120365.doc •22· 1336495 成刀中之COF2而考慮反應，但亦 ^ ^ , 於供給氣體中含有少蚩 HF。於考慮上述情形時，可·以如 各反應。 < 改寫式11〜式14之 [情況2]SiH2x+(2H-x)〇3->SiO2 + (2+x)〇2+xH2〇(Formula 11a) Here, SiHh indicates that each atom of the object contains 2 hydrogen atoms in the amorphous layer. In the middle, 2χ and 〇.1, in the general 矽, 2χ=〇. The entire reaction formula when considering the hydrogen contained in the treatment is as described. SiH2x+(2+x)〇3+2COF2—SiF4 + (2 + x)〇2+2C〇2 (Formula 15a) In the above case 1, the main focus is on the supply gas from the plasma space 26120365.doc •22· 1336495 Considering the reaction in COF2 in a knife, but also ^ ^, containing less HF in the feed gas. When considering the above situation, it is possible to react as described above. < Rewriting Formula 11 to Formula 14 [Case 2]
(氧化過程） S1+2O3—^Si〇2+2〇2 (HF生成過程） COF2+H20—»C〇2+2HF (HF溶解過程） 2HF+4HF+2HF + 4H20 —4HF2‘+4H3〇+ (蝕刻過程） (式 11 b) (式 12b) (式 1 3 b)(Oxidation process) S1+2O3—^Si〇2+2〇2 (HF generation process) COF2+H20—»C〇2+2HF (HF dissolution process) 2HF+4HF+2HF + 4H20 —4HF2'+4H3〇+ (etching process) (Equation 11 b) (Equation 12b) (Equation 1 3 b)
Si02+4HF2-+4H3〇+-，SiF4+H2〇+4H2〇+H2〇+4HF(^l4b)Si02+4HF2-+4H3〇+-, SiF4+H2〇+4H2〇+H2〇+4HF(^l4b)
式13b左邊第〗項之2HF，與來自電漿空間％之供給氣體 中之HF相對應。該供給氣體中之HF，自矽膜”表面之氫 氟酸凝聚相與空氣層之界面，溶解於氫氟酸凝聚相中。再 者，同式13b左邊第2項之4HF ,與蝕刻反應中所生成者（式 Wb右邊第5項）相對應，式13b左邊第3項之，與供給氣 體中之COF2之HF化反應中所生成者（式12b右邊第2項）相對 應。 又’蝕刻反應（式14b)中所生成之Ηβ中之一部分（式14b 右邊第2項），被用於COF2之HF化反應（式12b左邊第2項）， 另外之一部分（式14b右邊第3項），經HF溶解（式13b左邊第 4項）而被用於新之蝕刻反應（式14b)。 式1 lb〜14b之反應係以H2〇為媒介之由正回.饋起作用之連 ί 20365.doc •23· 1336495 鎖反應6該連鎖反應可以如下方式進行控制，即，於5〇。 以下之範圍内調節基板溫度·，以使矽膜表面之Η"之存= ΐ增減。因上述添加水之步驟中之水之添加量較少故矽 膜表面之Η2〇量亦較少，矽膜表面總是顯現出乾燥之傾 向。因此，藉由將溫度調節為50t以下，可充分控制矽膜 表面之H2〇量，進而可切實地抑制凝聚相之成長。又，石夕 膜表面之H2〇量較少且易蒸發，藉由供給氣體中之HF而額 外地生成H2〇(式14b右邊第4項），藉此，可確保矽膜表面 之H20量以維持反應。 又’因於供給氣體中存在HF，故可於處理開始時，切 實地獲得用以將COF2加以HF化之H20。 歸納式11 b〜14b後如下式所述。The 2HF of the item on the left side of the formula 13b corresponds to HF in the supply gas from the plasma space %. The HF in the supply gas is dissolved in the hydrofluoric acid condensed phase from the interface between the hydrofluoric acid condensed phase and the air layer on the surface of the ruthenium film. Furthermore, the 4HF of the second term on the left side of the same formula 13b, and the etching reaction The generator (the fifth term on the right side of the formula Wb) corresponds to the third term on the left side of the equation 13b, which corresponds to the one generated in the HF reaction of the COF2 in the supply gas (the second term on the right side of the equation 12b). One part of the Ηβ generated in the reaction (formula 14b) (the second term on the right side of the formula 14b) is used for the HF reaction of COF2 (the second term on the left side of the formula 12b), and the other part (the third term on the right side of the formula 14b) It is used for the new etching reaction (Equation 14b) by HF dissolution (the fourth term on the left side of Formula 13b). The reaction of Equation 1 lb~14b is based on H2〇 and is positively fed back. .doc •23· 1336495 Locking reaction 6 The chain reaction can be controlled in the following manner, that is, at 5 〇. The substrate temperature is adjusted within the following range to increase or decrease the enthalpy of the surface of the ruthenium film. The amount of water added in the step of adding water is less, so the amount of ruthenium on the surface of the ruthenium film is also less, and the total surface of the ruthenium film is Therefore, the tendency to dry is exhibited. Therefore, by adjusting the temperature to 50 t or less, the amount of H2 on the surface of the ruthenium film can be sufficiently controlled, and the growth of the condensed phase can be reliably suppressed. And it is easy to evaporate, and H2 〇 (the fourth term on the right side of the formula 14b) is additionally generated by supplying HF in the gas, whereby the amount of H20 on the surface of the ruthenium film can be ensured to maintain the reaction. Further, due to the presence of HF in the supply gas Therefore, H20 for HF-forming COF2 can be obtained at the beginning of the treatment. The general formula 11 b to 14b is as follows.
Si + 203 + C0F2 + 2HF —SiF4 + 202+C02+H20 (式 15b) 於式15b中’有助於反應之氫原子數（H)為左邊第4項之 2HF中之2個，氟原子數（F)，為左邊第3項之c〇F2中之2個 及左邊第4項之2HF中之2個，合計為4個。因此，有助於反 應之氫原子數（H)與氟原子數（F)之比（F)/(H)為（F)/(H)=2。 對於比（F)/(H)而言，較好的是（F)/(H)>1.5。 其次’說明於電漿空間26中生成CF3OH作為氟系中間氣 體之情形。此時，產生如下所述之反應。 [情況3] (氧化過程） (式 11c) S i+2 〇3 —^ Si〇2+2〇2 (COF2生成過程） 120365.doc -24- 1336495 cf3oh+h2o—C0F2+HF+H20， （式 12-lc) (HF生成過程） COF2+H20^CO2+2HF (HF溶解過程） HF+HF+4HF + 2HF+4H20 —4HF2-+4H30+ (式 13c) (蝕刻過程）Si + 203 + C0F2 + 2HF - SiF4 + 202 + C02 + H20 (Formula 15b) In the formula 15b, the number of hydrogen atoms (H) contributing to the reaction is two of the 2HF of the fourth term on the left side, and the number of fluorine atoms (F), which is two of c〇F2 of the third item on the left and two of the 2HF of the fourth item of the left side, and the total is four. Therefore, the ratio (F) / (H) of the number of hydrogen atoms (H) contributing to the reaction to the number of fluorine atoms (F) is (F) / (H) = 2. For the ratio (F) / (H), (F) / (H) > 1.5 is preferred. Next, a case will be described in which CF3OH is formed in the plasma space 26 as a fluorine-based intermediate gas. At this time, a reaction as described below was produced. [Case 3] (Oxidation process) (Equation 11c) S i+2 〇3 —^ Si〇2+2〇2 (COF2 generation process) 120365.doc -24- 1336495 cf3oh+h2o—C0F2+HF+H20, ( Formula 12-lc) (HF generation process) COF2+H20^CO2+2HF (HF dissolution process) HF+HF+4HF + 2HF+4H20 —4HF2-+4H30+ (Formula 13c) (etching process)
Si02 + 4HF2-+4H30+—SiF4+2H20+4H20+4HF (式 14c) (整個反應）Si02 + 4HF2-+4H30+—SiF4+2H20+4H20+4HF (Formula 14c) (entire reaction)
Si + 203 + CF30H+HF — SiF4+202+C02+H20 (式 15c) 如式12-lc所示’ CF3OH不穩定，分解後成為COF2與 HF。因此’於該分解之後，產生與上述情況2相同之反應 (式 1 lc、12-2c、13c、14c)。 於式15c中，有助於反應之氫原子數（H)合計為2個Si + 203 + CF30H + HF - SiF4 + 202 + C02 + H20 (Formula 15c) As shown in Formula 12-lc, CF3OH is unstable and decomposes to become COF2 and HF. Therefore, after the decomposition, the same reaction as in the above case 2 (formula 1 lc, 12-2c, 13c, 14c) was produced. In Formula 15c, the total number of hydrogen atoms (H) contributing to the reaction is two.
(式 12-2c) 即’左邊第3項之CF3〇H中之1個與左邊第4項之HF中之1 個’氧原子數（F)合計為4個，即，.左邊第3項之cf3〇h中之 3個與左邊第4項之HF中之1個。因此，有助於反應之氫原 子數⑻與氟原子數（F)之比（F)/(H)為（F)/(H)=2。 於情況3中，亦可以如下方式對反應進行控制，即，操 作基板溫度以調節矽膜表面之h2〇量。 其次’表示本發明之其他實施形態。 如圖2所示，於本發明之第2實施形態中，省略臭氧發生 叩代之’來自氧氣供給部11之供給管路13，合倂 至加濕S 22與電漿噴頭23之間之氟系氣體管路。 再者，-fr 耶可使供給管路13合倂至加濕器22上游側之氟系 120365.doc -25- 1336495 氣體管路。 . 藉此’可使來自氧氣供給# 11之〇2與來自加濕器22之低 露點CF4混合（混合步驟）。較好的是，〇2與cF4之混合比例 為 5〜20 vol%。 該混合氣體被導入至電漿喷頭23之電漿空間26内而經電 聚化，自CF4生成COF2等氟系反應性氣體，並且自〇2生成 〇3等氧化性氣體（電漿化步驟）。因此，可將氟系反應性氣(Expression 12-2c) That is, the total number of oxygen atoms (F) of one of the CF3〇H of the third term on the left side and the HF of the fourth term of the left side is four, that is, the third term on the left side. One of cf3〇h and one of the HF of the fourth item on the left. Therefore, the ratio (F)/(H) of the number of hydrogen atoms (8) and the number of fluorine atoms (F) contributing to the reaction is (F) / (H) = 2. In case 3, the reaction can also be controlled in such a manner that the substrate temperature is manipulated to adjust the amount of h2 enthalpy on the surface of the ruthenium film. Next, another embodiment of the present invention is shown. As shown in Fig. 2, in the second embodiment of the present invention, the supply line 13 from the oxygen supply unit 11 in which the ozone generation is replaced is omitted, and the fluorine is merged between the humidification S 22 and the plasma discharge head 23. A gas line. Further, -fr yees the supply line 13 to the fluorine system 120365.doc -25 - 1336495 gas line on the upstream side of the humidifier 22. Thereby, the enthalpy 2 from the oxygen supply #11 can be mixed with the low dew point CF4 from the humidifier 22 (mixing step). Preferably, the mixing ratio of 〇2 to cF4 is 5 to 20 vol%. The mixed gas is introduced into the plasma space 26 of the plasma discharge head 23 to be electropolymerized, and a fluorine-based reactive gas such as COF2 is generated from CF4, and an oxidizing gas such as 〇3 is generated from 〇2 (plasma step) ). Therefore, fluorine-based reactive gas
體之生成部通用作氧化性氣體之生成部，從而可簡化構 成0 自噴出管路27噴出該等生成氣體，並將該等 吹至基板90(噴吹步驟），藉由與上述第}實施形態相同之反 應過程，對矽膜92進行蝕刻。The body generating portion is used as a generating portion for the oxidizing gas, and the configuration 0 can be simplified. The generated gas is ejected from the ejecting line 27, and the film is blown onto the substrate 90 (injection step), and the above-described The ruthenium film 92 is etched in the same reaction process.
本發明並非限定於上述實施形態，可進行各種改變。 例如，於第1實施形態中，亦可不混合來自電漿喷頭23 之c〇f2等敦系氣體與來自臭氧發生器12之臭氧，而自互不 相同之喷出口:將上述氣體供給至矽膜表面。 '、可取代臭氧發生器i 2 ’使用與氟系氣體用之電漿喷頭 23不同之氧€電漿放電裝置生成氧化性氣體。 亦可於噴吹，氧化性氣體之後’嘴吹⑺^系反應性氣 體。 [實施例1 ] 現對實施例丨加以說明。 蓋於玻璃基板表面之 ’藉由加濕器22添加 使用圖1中所示之蝕刻裝置丨，對覆 非晶矽進行蝕刻。向〇·8 slm之CF4中 120365.doc -26- 1336495 使露點達到13.5°c (水蒸汽分壓1:55 kpa)之量之H2〇作為氟 系原料。該添加之出〇相對於CF4之流量比為丨55 ν〇ι%。 將該低露點CF4導入至電漿噴頭23之電極間空間26中，於 大氣壓下使之電漿化。電漿化之條件如下所述。 供給電力：0.165 kW 供給電壓：Vpp =】3 k V 電極面積：35 cm2 當藉由傅立葉轉換紅外線光譜儀（FTIR)而分析電漿化後 之氣體成分時，可確認：每i slmtCF4，生成〇 〇〇57 dm 之 HF，且生成 0 0149 slm 之 COF2。 此處，0.0057 mol之HF與0.0149 mol之COF2中所含有之 氟原子數（F)與氫原子數（H)之比（F)/(H)為 (F)/(H)=(0.0149x2 + 0.0057)/0.0057 = 6.2，且滿足（F)/(h)> 1.5之條件。 又’可確認：幾乎並未觀測到電漿化後之Η2〇，電聚化 後之Η2〇為電漿化前之1/1〇以下。 此外’將0.4 slm之〇2作為氧化性氣體之原料而供給至 臭氧發生器12中，獲得8 vol%(與〇2之比）即〇.〇32 sim之 〇3。〇3之量至少必須大於或等於COL之體積流量 (0.0149 slm)及HF之體積流量（0.0057 slm)之一半之合計 值（〇·〇1 775 slm)，且當上述〇3之量為上述合計值之2倍左 右時’由上述臭氧發生器12獲得之Ο;之流量達到大致最 佳之大小。 將基板溫度設為20 °C，混合來自上述電梁喷頭23之氣體 120365.doc -27· 1336495 與來自臭氧發生器12之氣體 面0 將該兩種氣體喷至基板表 繼而’當測定钱刻速率時，該私 干町忑蝕刻迷率為45000 A/min ’可獲得充分大之蝕刻速率。 [實施例2]The present invention is not limited to the above embodiment, and various modifications can be made. For example, in the first embodiment, the refrigerant gas such as c〇f2 from the plasma discharge head 23 and the ozone from the ozone generator 12 may not be mixed, and the discharge ports may be different from each other: the gas is supplied to the crucible. Membrane surface. ', the ozone generator i 2 ' can be used to generate an oxidizing gas using an oxygen plasma discharge device different from the plasma nozzle 23 for a fluorine-based gas. It is also possible to spray, after the oxidizing gas, the nozzle is blown (7) into a reactive gas. [Embodiment 1] Embodiment 丨 will now be described. Covering the surface of the glass substrate by adding the humidifier 22, the amorphous germanium is etched using the etching apparatus 图 shown in Fig. 1. CF4 in 〇·8 slm 120365.doc -26- 1336495 H2〇 having a dew point of 13.5°c (water vapor partial pressure 1:55 kpa) is used as a fluorine-based raw material. The flow ratio of the added effluent to CF4 was 丨55 ν〇ι%. The low dew point CF4 is introduced into the interelectrode space 26 of the plasma jet head 23, and is plasmad at atmospheric pressure. The conditions of the plasma formation are as follows. Power supply: 0.165 kW Supply voltage: Vpp =] 3 k V Electrode area: 35 cm2 When the plasma component of the plasma is analyzed by Fourier transform infrared spectroscopy (FTIR), it can be confirmed that 每 is generated every i slmtCF4 HF57 dm HF and generate COF2 of 0 0149 slm. Here, the ratio (F)/(H) of the number of fluorine atoms (F) to the number of hydrogen atoms (H) contained in 0.0057 mol of HF and 0.0149 mol of COF2 is (F) / (H) = (0.0149 x 2 + 0.0057) / 0.0057 = 6.2, and the conditions of (F) / (h) > 1.5 are satisfied. Further, it was confirmed that almost no 电 2 电 after the plasma formation was observed, and Η 2 电 after the electropolymerization was 1/1 〇 or less before the plasma formation. Further, 0.42 of 0.4 slm is supplied as a raw material of the oxidizing gas to the ozone generator 12, and 8 vol% (ratio to 〇2) is obtained, that is, 〇3 sim32 sim. The amount of 〇3 must be at least greater than or equal to the total flow of COL volume flow (0.0149 slm) and HF volume flow rate (0.0057 slm) (〇·〇1 775 slm), and when the above 〇3 amount is the above total When the value is about 2 times, 'the enthalpy obtained by the ozone generator 12 described above; the flow rate reaches a substantially optimal size. The substrate temperature is set to 20 ° C, and the gas 120365.doc -27· 1336495 from the above-mentioned electric beam nozzle 23 is mixed with the gas surface 0 from the ozone generator 12 to spray the two gases onto the substrate table, and then At the engraving rate, the etching rate of the private shovel is 45000 A/min', and a sufficiently large etching rate can be obtained. [Embodiment 2]
於實施例2中’研究基板溫度、向氟系原料氣體中添加 之水之添加量、及蝕刻速率之間之關係。針對〇 $ 之 CF4，於藉由加濕器22而調節HA之添加量之後，藉f電 漿喷頭23而進行電漿化。電漿化之條件如下所述。曰 供給電力：0.165 kW 供給電壓：Vpp=13 kV 電極面積：35 cm2 又，使用0.5 slm之〇2，藉由臭氧發生器n而製作8 v〇l%(與A之比）之A，將該A與上述電漿化後之氣體混合In the second embodiment, the relationship between the substrate temperature, the amount of water added to the fluorine-based source gas, and the etching rate was examined. For CF4 of 〇$, after the addition amount of HA is adjusted by the humidifier 22, it is plasmaized by the f plasma head 23. The conditions of the plasma formation are as follows.曰Power supply: 0.165 kW Supply voltage: Vpp=13 kV Electrode area: 35 cm2 Also, using 0.5 slm ,2, 8 v〇l% (ratio to A) A is produced by the ozone generator n, The A is mixed with the above plasma gas
後供給至玻璃基板上，以對該玻璃基板表面上之非晶矽膜 進行钱刻。 將基板溫度設為以下3種溫度 '即2 〇。〇、4 0 °C、6 0 °C，並 測定各溫度條件下之蝕刻速率（再者，6〇1為先前之普通 之基板溫度，係比較例）。 圖3表示結果。 根據圖3可知’於基板溫度為與先前相同之60°C時，即 使增加向氟系原料氣體中添加之水之添加量，蝕刻速率亦 幾乎不改變。 相對於此’明確的是：於基板溫度為20。(：時，自使露點 120365.doc • 28· 1336495 達到10 °c之水之添加量附近’餘刻速率大幅上升，於使露 點達到20°c之水之添加量附ii，蝕刻速率達到峰值，直至 使露點達到4〇t：之水之添加量附近，仍可獲得充分超過先 前蝕刻速率（基板蕰度為60°c時）之蝕刻速率。 明確的是：即使基板溫度為40 C時，於使露點達到 10eC〜4〇°C之水之添加範圍内，可獲得充分超過先前（基板 温度為6 0 °C時）之姓刻速率之姓刻速率。 [產業上之可利用性] 本發明可應用於例如於半導體晶圓或液晶等平板玻璃等 製造中，對表面之矽膜進行蝕刻。 【圖式簡單說明】 圖1係本發明之第1實施形態之姓刻裝置的概略構成圖。 圖2係本發明之第2實施形態之蝕刻裝置的概略構成圖。 圖3係表示以改變基板溫度之方式來測定相對於向氟系 原料CF4添加水之量.（露點顯示）之蝕刻速率之實施例1的結 杲之圖表。 圖4係表示相對於溫度之臭氧之氣_液分配係數的圖表。 【主要元件符號說明】 1 蝕刻裝置 2 基板溫度調節機構 3 搬送機構 4 反應性氣體供給系統 10 臭氧供給系統 11 氧氣供給部 120365.doc -29- 1336495 12 臭氧發生器 13 臭氧供給管路 20 氟系氣體供給系統 21 氟系原料供給部 22 加濕器 23 電漿噴頭 24 電極 25 電源 26 電漿空間 27 噴出管路 41 吸引管路 42 排氣機構 90 基板 91 矽膜（被處理物） 120365.doc -30-Thereafter, it is supplied onto a glass substrate to carry out an engraving of the amorphous germanium film on the surface of the glass substrate. The substrate temperature was set to the following three temperatures 'ie 2 〇. 〇, 40 ° C, 60 ° C, and the etching rate under various temperature conditions was measured (further, 6 〇 1 is the previous common substrate temperature, which is a comparative example). Figure 3 shows the results. According to Fig. 3, when the substrate temperature is 60 ° C which is the same as before, the etching rate is hardly changed even if the amount of water added to the fluorine-based source gas is increased. Relative to this, it is clear that the substrate temperature is 20. (: When the dew point 120365.doc • 28· 1336495 reaches 10 °c, the amount of water increases sharply, and the amount of water added to the dew point reaches 20 °c, ii, the etch rate peaks Until the dew point reaches the vicinity of the addition amount of 4 〇t: water, an etch rate sufficiently higher than the previous etching rate (when the substrate twist is 60 ° C) can be obtained. It is clear that even when the substrate temperature is 40 C, In the addition range of the water having a dew point of 10 eC to 4 〇 ° C, a surpass rate sufficiently higher than the previous (the substrate temperature is 60 ° C) can be obtained. [Industrial Applicability] The invention can be applied to, for example, the production of a flat glass such as a semiconductor wafer or a liquid crystal, and the ruthenium film on the surface is etched. [Fig. 1] Fig. 1 is a schematic configuration diagram of a surname apparatus according to the first embodiment of the present invention. Fig. 2 is a schematic configuration diagram of an etching apparatus according to a second embodiment of the present invention. Fig. 3 is a view showing an etching rate with respect to the amount of water added to the fluorine-based raw material CF4 (dew point display) so as to change the temperature of the substrate. Embodiment 1 Fig. 4 is a graph showing the gas-liquid partition coefficient of ozone with respect to temperature. [Description of main components] 1 etching apparatus 2 substrate temperature adjusting mechanism 3 conveying mechanism 4 reactive gas supply system 10 ozone supply system 11 Oxygen supply unit 120365.doc -29- 1336495 12 Ozone generator 13 Ozone supply line 20 Fluorine-based gas supply system 21 Fluorine-based raw material supply unit 22 Humidifier 23 Plasma spray head 24 Electrode 25 Power supply 26 Plasma space 27 Discharge Line 41 suction line 42 exhaust mechanism 90 substrate 91 diaphragm (processed object) 120365.doc -30-
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| US10453986B2 (en) * | 2008-01-23 | 2019-10-22 | Solvay Fluor Gmbh | Process for the manufacture of solar cells |
| JP4540729B2 (en) * | 2008-03-13 | 2010-09-08 | 積水化学工業株式会社 | Method and apparatus for etching silicon-containing film |
| JP2009224366A (en) * | 2008-03-13 | 2009-10-01 | Sekisui Chem Co Ltd | Etching apparatus |
| JP4596287B2 (en) | 2008-09-19 | 2010-12-08 | カシオ計算機株式会社 | Method for dry etching of a film containing silicon |
| JP5310409B2 (en) * | 2009-09-04 | 2013-10-09 | 東京エレクトロン株式会社 | Plasma etching method |
| WO2011032983A2 (en) * | 2009-09-18 | 2011-03-24 | Solvay Fluor Gmbh | Process for the manufacture of wafers for solar cells at ambient pressure |
| CN102754201A (en) * | 2009-10-26 | 2012-10-24 | 苏威氟有限公司 | Etching process for producing a tft matrix |
| CN102770944B (en) * | 2010-02-25 | 2013-11-06 | 积水化学工业株式会社 | Etching method and etching apparatus |
| WO2011108382A1 (en) * | 2010-03-05 | 2011-09-09 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing semiconductor device |
| JP5645157B2 (en) * | 2010-06-03 | 2014-12-24 | 国立大学法人東京工業大学 | Plasma device |
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