置之製造領域中有用的電漿 關於一穆電漿反應用氣體及 含有具有難以產生自身聚合 化物。 步驟中，係進行藉由將形成 預定區威進行電聚#刻，而 之形成中’其窗孔之入口部 生所謂頭縮（necking)。又， 細化，接觸孔洞之徑變更小 、高縱橫比之接觸孔洞以大 形成之技術的開發。 專利文獻1有提案使用式（1) 至6之任一整數；y表示！ 整數’且（y+ z)為2x以下〕 將微小徑、高縱橫比之接觸 的良好形狀，形成接觸孔洞 線構造之一構成構件的層間 更為銅之金屬配線已有進展 減低配線間及層間體積，五 '緣材料。該箅中，，、，„ ~ 201213279 六、發明說明： 【發明所屬之技術領域】 本發明係關於半導體裝 反應用氣體。再詳言之，係 其利用’該電漿反應用氣體 的共扼二烯構造的丁二烯氟 【先前技術】 先前，在半導體之製造 於被處理基板的矽氧化膜之 形成接觸孔洞。在此種窗孔 分成為閉塞之形狀，易於產 近年來伴隨半導體裝置之微 ，其縱橫比傾向於增大。 因而，吾人謀求微小徑 致垂直且無頸縮的良好形狀 為解決本發明之課題， :CxHyFz〔式中，X表示4 至4之任意整數；z表示正 所示之氟化烴（處理氣體）， 孔洞，以大致垂直且無頸縮 之方法。 一方面，在成為多層配 絕緣中，從鋁之金屬配線變 。又，在層間絕緣膜，為了 人研討各種低介電常數之絕 201213279 相成長法〔CVD(Chemical Vapor Deposition)法〕所形成 的氟化非晶形碳膜作為低介電常數材料，已開始受到矚 目。在用以形成氟化非晶形碳膜之成膜用氣體方面，在 專利文獻2有記載使用六氟-丨，3· 丁二烯（全氟-丨，3-丁二 烯）或六氟-2-丁炔的要旨。 [先前技術文獻] [專利文獻] [專利文獻1]國際公開2009/0415 60號要約 [專利文獻2]日本特開平9_237783號公報 【發明内容】 [發明欲解決課題] 本發明之目的係提供一種在半導體裝置之製造領域 中有用的新穎電漿反應用氣體，使用該電漿反應用氣體 之乾餘刻方法及氟碳膜之成膜方法。 [解決課題之手段] 本發明人等研討之結果，已知上述專利文獻1記載 之氣體内，具有共軛二烯構造之全氟-丨，3· 丁二烯，會有 在氣體容器或氣體流通之裝置内部（尤其是配管等之連 接部分）’產生雜質之粒子的問題。而且，並確認該雜質 ，係因電漿反應氣體之自身聚合而產生之物。 貫際上’在 M. Prober, et al.，Journal of the AmericanA plasma useful in the field of manufacturing. It is difficult to produce a self-polymerized product with respect to a gas for plasma reaction. In the step, the so-called necking of the entrance of the window is formed by electroforming the predetermined area. In addition, the development of the technique of forming a small contact hole with a large aspect ratio and a large aspect ratio. Patent Document 1 proposes to use any integer of the formulas (1) to 6; y means! The integer 'and (y+ z) is 2x or less.) The good shape of the contact between the small diameter and the high aspect ratio forms a metal wiring of the copper which is one of the members of the contact hole line structure. The wiring has progressed to reduce the wiring space between the wiring and the interlayer. , five 'edge materials. The present invention relates to a semiconductor-recommended reaction gas. More specifically, it utilizes the symmetry of the gas for plasma reaction. Butadiene Fluorine of Diene Structure [Prior Art] Previously, a contact hole was formed in a tantalum oxide film of a semiconductor to be processed on a substrate to be processed. Such a window hole is in a shape of occlusion, and it is easy to produce a semiconductor device in recent years. Microscopically, the aspect ratio tends to increase. Therefore, a good shape in which the micro-path is vertical and has no necking is to solve the problem of the present invention: CxHyFz (wherein, X represents an arbitrary integer of 4 to 4; z represents positive The fluorinated hydrocarbon (treatment gas) shown, the hole, is substantially vertical and has no necking. On the one hand, in the multi-layered insulation, it changes from the metal wiring of aluminum. Also, in the interlayer insulating film, for the person to discuss Fluorinated amorphous carbon films formed by various low dielectric constants (2012) CVD (Chemical Vapor Deposition) have been used as low dielectric constant materials. In the case of a film forming gas for forming a fluorinated amorphous carbon film, Patent Document 2 describes the use of hexafluoro-antimony, 3·butadiene (perfluoro-fluorene, 3-butadiene) or six. [Prior Art] [Patent Document 1] [Patent Document 1] International Publication No. 2009/0415 No. 60 No. 60 [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei 9-237783 (Invention) [Invention [Problem] An object of the present invention is to provide a novel plasma reaction gas useful in the field of manufacturing a semiconductor device, a dry residual method using the plasma reaction gas, and a film forming method of a fluorocarbon film. In the gas described in Patent Document 1, the perfluoro-indole and the butadiene having a conjugated diene structure are known to exist in a gas container or a gas-flowing device. (especially the connecting portion of pipes, etc.) 'The problem of particles that generate impurities. Moreover, it is confirmed that the impurities are generated by self-polymerization of the plasma reaction gas. "Only in M. Prober, et al. ,Journal of the American
Chemistry，Volume 71，Issue 2，598(1 949)，有記載具有 共輒二烯構造之六氟丁二烯在150 °C之溫度下，以高轉 化比，進行二聚物化。 201213279 因此本啦明人等，經戮力探討難以產生自身聚合（ 聚物化）之丁 —晞I化物，結果，首先發ί見1，1,2,4,4- 五氟· 1,3 - 丁二烯，、八$ 邱以王亂_1，3-丁二烯難以產生二聚物， 因而完成本發明。 灰如此根據本發明，可提供了述⑴、⑺之電衆反應用 氣肢，（3) (4)之乾蝕刻方法及（5)之成膜方法。 (1)一種電漿反應用氣體，其特徵為含有1，1，2,4,4-五氟-1，3-丁二烯。 (2)如（1)項之電漿反應用氣體 1，3-丁 一稀之含量為99體積％以上。 ⑺帛乾钮刻方法’其包含將該⑴或⑺項之電梁 應用氣體供給於處理容器内，在該容器内使被 體乾蝕刻之步驟。 垫 (1?如(3)項之乾姓刻方法，其中乾蝕刻係在電毁密度 /cm以上之高密度電漿環境下進行。 之炭膜之成膜方法，其包含將該⑴或⑺項 電名反應用氣體供給於處理容器内，在該容器 處理物之矣C 、锻 物之表面，以CVD法使氟碳膜成膜之步驟。 [發明效果] 致、本發明之電聚反應用氣體，在乾蝕刻法或CVD法所 成膜等中’作為用以電漿反應之氣體可適當使用。 本發明之電聚反應用氣體’在氣體容器或氣體流通 :置内部U其是配管等連接部分），難以產生雜質之 201213279 根據使用本發明之雷婿Θ— β之電桌反應用氣體的乾蝕刻法， 微小徑、高縱橫比之接觸孔洞可以 旯 良好形狀形成 . 八议£夏且無頭縮的 —根據使用本發明之電毅反應用氣體之成膜方法 ’可穩定地再現性良好的使a碳膜成膜。 【實施方式】 該氣體乾 1，1，2，4，4 - 以下茲就本發明之電漿反應用氣體、使用 蝕刻方法及成膜方法，分項加以詳細說明。 1 ·電漿反應用氣體 本發明之電漿反應用氣體，其特徵為含有 五氣-1,3 -丁二稀。 本發明之電漿反應用氣體較佳 -1，3-丁二烯之含量為99體積％以上。，… 在1，1，2,4,4-五氟-1，3_丁二烯，係含有來自該氣體之 原料的有機系之微量化合物、或氮氣、氧氣及水分等之 雜質。1，1,2,4,4-五敗.i，3.丁二稀本身之含量（相當於純度 )’由可良好的顯現本發明效果之觀點觀之，較佳為99 體積％以上，更佳& 99.9體積％以上。雜質多時，在填 充了 1，1，2,4,4-五氟_丨，3_丁二烯的容器内，對^2,4,4- 五氟]，3-丁二烯之純度產生不均衡。其結果，在初期階 段與殘留量變少的階段’在使用各自氣體時之性能產生 極大的不均衡，無法獲得穩定的蝕刻或岣質的膜，在生 產線中’會有招致良率降低之虞。 M，2,4,4-五氟_U3_丁二烯之含量可以使用氫離子 化檢測器（FID)的氣體層析法來測定。 201213279 1，1，2,4,4-五氟_1，3 -丁二烯，通常與先前相同係填 充於圓靖荨之容器’供作姓刻或成膜。 1，1，2,4,4-五氟-1,3-丁二烯可以 D. Lentz，et al., CHEMISTRY AN ASIAN JOURNAL, Volume 3, 7 19(2008) 記載之方法來製造。 本發明之1，1,2,4,4 -五氟-1，3_ 丁二烯（c4f5H)，係難 以產生自身聚合（二聚物化）的物質。相較於屬具有相同 共輥二稀構造的丁二浠氟化物之全氟_1，3_ 丁二浠，該物 質難以產生二聚物。 相較於全氟 1，3-丁二烯（C4F6)，1，1，2,4,4-五氟-1，3- 丁 一烯（C4FSH)難以產生二聚物，這可由下述敘述以理論 加以說明。 亦即，關於各1，1，2,4,4-五氟-1，3-丁二稀（匸4?511)， 與各全氟-1,3 -丁二稀（CJ6)’單體與使F·陰離子反應所 得活性化單體之鍵能量係以下述所述模擬方式進行計算 ，可藉由比較其差而加以說明。 關於上述的模擬方式，詳述如下。 使用根據Accelrys軟體公司製模擬程式、Materials Studio V4.3 中之 DMol3(密度泛函數理論（Density Functional Theory，DFT)的第一原理電子狀態計算程式） ，進行構造最適化計算，關於各^夂扣五^-^-丁二 浠（CUF5H)、及各全氟-1，3 -丁二稀（C4F6)，在最穩定的構 造中計算鍵能量。結果如表1所示。 201213279 [表1] 單體 Ο) 活性化單體 (2) _ 二聚物 (3) (1)-(2) (1)+(2) (3)-((1)+(2)) c4f5h -652.326 -752.247 -1404.611 99.92 -1404.573 0.038 c4f6 -751.561 -851.490 -1603.051 99.93 -1603.051 0.000 由表 1 可知，在 1，1，2,4,4-五氟-1，3-丁二烯（C4F5H) 與全氣-1,3 -丁一烯（c4F6)之間，反映使單體成為活性化 單體時需要的能量之活性化單體之結合能量，與單體及 活性化單體之結合能量之差（表中的「（1)_(2)」）並無差異 。但是，關於反映二聚物化需要的能量之構成二聚物之 單體及活性化單體之結合能量之合計，與二聚物結合能 量之差（表中的「（3)-((1) + (2))」），兩者有極大差異。由 此可說是相較於CJ6，而C4FSH難以產生二聚物。 2.乾餘刻方法 本發明之乾蝕刻法，包含將本發明之電漿反應用氣 體供給於處理容器内，在該容器内將被蝕刻基體進行乾 蝕刻之步驟。 使用本發明之方法之「乾蝕刻（簡稱「蝕刻」）」係 指，在半導體製造裝置之製造步驟等所使用之被處理體 上，將經極高積體化的微細圖案予以蝕刻的技術之意。 通常，在脫氣成真空的處理容器（蝕刻腔室）内’將 本發明之t毁反應用1體依照所期望與其減體成分一 起供給，以使蝕刻腔室内較佳為〇 〇〇13至i3〇〇pa、更佳 為〇·13 1 UPa’ ϋ由使用電毁發生裝置而發生的電聚 ’而進行被處理體之蝕刻。 本發明之敍刻方法中’可在+五氟]，3_丁二 烯併用其他電漿反應性之氣體。 201213279 在將1，1，2,4,4-五氟- ；ι，3_丁二烯使用作為蝕刻用氣 體之情形，為了保持在電漿中發生之蝕刻種類之濃度控 制或離子能量之控制或窗孔形狀之適性，亦可添加選自 由氦 '氩、氖 '氪、氙所組成群組中至少一種之稀有氣 體（第1 8族），使用作為電漿反應用混合氣體亦可。 相對於^。，七‘五氟-丨一-丁二烯之稀有氣體之合 D十里’稀有氣體之添加量較佳為體積比〔惰性氣體 /^2,4,4-五氟_1，3_丁二烯〕成為2至2〇〇、更佳為5至 150。又’稀有氣體可依照需要混合二種、或者三種使用 亦無妨。 又’為了緩和钮刻停止（etching st〇p)，亦可添加〇2 及/或〇3使用。〇2或〇3之添加量，相對於五 氟丨，3-丁二烯之〇2與ο;之合計量，體積比〔（ο〗及/或 〇3)/1’1’2’4,4-五氟-1，3-丁二烯〕，較佳為 〇」至 1〇〇、更 佳為1至5 0。 、隹本七明之蝕刻方法中，蝕刻時之電漿密度方面， 並無特別限定’不過’由欲更良好的顯現本發明效果之 觀點Ή密度較佳為f離子/em、±、更佳為在ι〇ΐ2 至？13離子/cm3之高密度電漿環境下，進行蝕刻為理想 。猎由將電漿密度設為1〇12離子/cm3以上之高密度，： 在先別之含氟化合物，雖有觀察到選擇性降低之現象， 不過在本發明使用之CaHbFc(a = 3至5、b=l至2、c = 3 10)此種現象難以產生，而可—面確保高選擇性，且— 面以高钮刻速度進行麵刻，可有效地形成微細的圖案。 -10- 201213279 使用之電漿發生裝置方面，可例舉在電漿蝕刻採用 的一般裝置。例如螺旋波（helicon wave)方式、高頻感應 方式、平行平板型式、磁控管（magnetron)方式及微波方 式等之裝置。該等中，由於高密度區域之電漿發生較容 易，故可適當使用螺旋波方式、高頻感應方式及微波方 式之裝置。 被處理體係具有至少一層之矽氧化膜層之物，除此 之外，亦可為含有一層矽氮化膜層的積層膜。被處理體 ，較佳為將設置於其上部的光阻作為光罩予以蝕刻。亦 即，因使用含有CF及CHF基作為構成要素之 五氟-1,3-丁二烯氣體，故 選擇比。 故可提高被處理體之對光阻蝕刻 光阻係指以感光性光阻組成Chemistry, Volume 71, Issue 2, 598 (1 949), it is described that hexafluorobutadiene having a hexadiene structure is dimerized at a high conversion ratio at a temperature of 150 °C. 201213279 Therefore, Benjamin et al., after discussing the difficulty of producing self-polymerization (polymerization), the 丁-晞I compound, the result, first of all, 1,1,2,4,4-pentafluoro- 1,3 - Butadiene, VIII, Qiu Yiwang _1,3-butadiene is difficult to produce dimer, thus completing the present invention. According to the present invention, it is possible to provide the gas limb for electric power reaction of (1) and (7), the dry etching method of (3) (4), and the film forming method of (5). (1) A gas for plasma reaction characterized by containing 1,1,2,4,4-pentafluoro-1,3-butadiene. (2) The gas for plasma reaction as in (1) is 1,3-butyl-diluted at a content of 99% by volume or more. (7) Drying button engraving method </ RTI> The step of supplying the electric beam application gas of the item (1) or (7) to a processing container, and dry etching the body in the container. Pad (1), such as the method of (3), in which the dry etching is performed in a high-density plasma environment having an electric destructive density/cm or more. The carbon film forming method includes the (1) or (7) The electric charge reaction gas is supplied to the processing container, and the fluorocarbon film is formed by a CVD method on the surface of the container treated material C and the forged material. [Effect of the invention] The electropolymerization reaction of the present invention The gas can be suitably used as a gas for plasma reaction by a dry etching method or a film formed by a CVD method. The gas for electropolymerization of the present invention flows in a gas container or a gas: an internal U is a pipe 201213279 According to the dry etching method of the electric table reaction gas using the thunder-β of the present invention, the contact hole of the small diameter and the high aspect ratio can be formed in a good shape. In addition, it is possible to form a film of a carbon film which is stable in reproducibility according to the film forming method of the gas for electric reaction using the present invention. [Embodiment] The gas is dried, and the gas for plasma reaction, the etching method, and the film forming method of the present invention are described in detail below. 1 - Gas for plasma reaction The gas for plasma reaction of the present invention is characterized by containing five gas-1,3-butadiene. The gas for plasma reaction of the present invention preferably has a content of -1,3-butadiene of 99% by volume or more. 1,1,2,4,4-pentafluoro-1,3-butadiene is an organic trace compound containing a raw material derived from the gas, or an impurity such as nitrogen, oxygen or moisture. 1,1,2,4,4-five-failed. i, 3. The content of dibutyl dilute itself (corresponding to purity) is preferably 99% by volume or more from the viewpoint that the effect of the present invention can be favorably exhibited. More preferably & 99.9 vol%. When there are many impurities, the purity of ^2,4,4-pentafluoro],3-butadiene in a container filled with 1,1,2,4,4-pentafluoro-丨,3-butadiene There is an imbalance. As a result, in the initial stage and the stage where the residual amount is small, the performance of the respective gases is extremely unbalanced, and a stable etching or enamel film cannot be obtained, which causes a decrease in yield in the production line. The content of M,2,4,4-pentafluoro-U3_butadiene can be determined by gas chromatography using a hydrogen ionization detector (FID). 201213279 1,1,2,4,4-pentafluoro-1,3-butadiene, usually filled with the same container as the previous one for the surname or film formation. 1,1,2,4,4-pentafluoro-1,3-butadiene can be produced by the method described in D. Lentz, et al., CHEMISTRY AN ASIAN JOURNAL, Volume 3, 7 19 (2008). The 1,1,2,4,4-pentafluoro-1,3-butadiene (c4f5H) of the present invention is a substance which is difficult to produce self-polymerization (dimerization). This material is difficult to produce a dimer compared to perfluoro-1,3-butane which is a fluoride of the same co-rolled dilute structure. Compared with perfluoro1,3-butadiene (C4F6), 1,1,2,4,4-pentafluoro-1,3-butene (C4FSH) is difficult to produce dimers, which can be described below. Explain by theory. That is, with respect to each 1,1,2,4,4-pentafluoro-1,3-butadiene (匸4?511), and each perfluoro-1,3-butadiene (CJ6)' monomer The bond energy of the activated monomer obtained by reacting the F·anion is calculated by the simulation method described below, and can be explained by comparing the difference. The above simulation method will be described in detail below. The structure optimization calculation is performed using the DMol3 (Density Functional Theory (DFT) first state electronic state calculation program) based on the Accelrys software company simulation program and Materials Studio V4.3. Buckle five ^-^-butadiene (CUF5H), and each perfluoro-1,3-butadiene (C4F6), calculate the bond energy in the most stable structure. The results are shown in Table 1. 201213279 [Table 1] Monomer Ο) Activating monomer (2) _ Dimer (3) (1)-(2) (1)+(2) (3)-((1)+(2)) C4f5h -652.326 -752.247 -1404.611 99.92 -1404.573 0.038 c4f6 -751.561 -851.490 -1603.051 99.93 -1603.051 0.000 It can be seen from Table 1 that 1,1,2,4,4-pentafluoro-1,3-butadiene (C4F5H) Between the total gas-1,3-butene-ene (c4F6), the binding energy of the activated monomer reflecting the energy required to make the monomer an activator, and the combination with the monomer and the activated monomer There is no difference in the difference in energy ("(1)_(2)") in the table). However, the difference between the binding energy of the dimer monomer and the activating monomer which reflects the energy required for dimerization, and the difference in the binding energy of the dimer ("(3)-((1) + (2))"), there is a big difference between the two. Therefore, it can be said that C4FS is difficult to produce a dimer compared to CJ6. 2. Dry etching method The dry etching method of the present invention comprises the step of supplying the gas for plasma reaction of the present invention to a processing container, and dry etching the substrate to be etched in the container. The "dry etching" (referred to as "etching") in the method of the present invention is a technique in which a fine pattern which is extremely high in total is etched on a target object used in a manufacturing process of a semiconductor manufacturing apparatus or the like. meaning. Usually, in the degassing vacuum processing vessel (etching chamber), the body of the present invention is supplied with its body as required, so that the etching chamber is preferably 〇〇〇13 to I3〇〇pa, more preferably 〇13 1 UPa' 蚀刻 etching of the object to be processed by electropolymerization generated by the use of the electric destruction generating device. In the characterization method of the present invention, a gas reactive with other plasmas may be used in the form of +pentafluoro, 3-butadiene. 201213279 In the case where 1,1,2,4,4-pentafluoro-;ι,3-butadiene is used as an etching gas, concentration control or ion energy control for maintaining the kind of etching occurring in the plasma Alternatively, a rare gas (Group 18) selected from the group consisting of argon, argon, krypton, and neon may be added to the shape of the pores, and may be used as a mixed gas for plasma reaction. Relative to ^. , the addition of the rare gas of the seven-pentafluoro-anthracene-butadiene is preferable to the volume ratio of the rare gas [inert gas / ^ 2,4,4-pentafluoro_1,3_丁二The olefin is 2 to 2 Å, more preferably 5 to 150. In addition, it is also possible to mix two kinds of rare gases or three kinds of them as needed. In addition, 〇2 and/or 〇3 may be added to ease the etching st〇p.添加2 or 〇3 addition amount, relative to pentafluoroindene, 3-butadiene 〇2 and ο; total amount, volume ratio [(ο〗 and / or 〇3) / 1'1'2'4 , 4-pentafluoro-1,3-butadiene], preferably from 〇 to 1〇〇, more preferably from 1 to 50. In the etching method of the present invention, the plasma density at the time of etching is not particularly limited, but the density is preferably f ion/em, ±, more preferably from the viewpoint that the effect of the present invention is better exhibited. At ι〇ΐ2 to? It is desirable to perform etching in a high-density plasma environment of 13 ions/cm3. Hunting is performed by setting the plasma density to a high density of 1 〇 12 ions/cm 3 or more. In the case of the fluorine-containing compound, although the selectivity is lowered, the CaHbFc used in the present invention (a = 3 to 5, b = l to 2, c = 3 10) This phenomenon is difficult to produce, while the surface can ensure high selectivity, and - the surface is engraved at a high button speed, which can effectively form a fine pattern. -10- 201213279 For the plasma generating device to be used, a general device used for plasma etching can be exemplified. For example, a device such as a Helicon wave method, a high frequency induction method, a parallel plate type, a magnetron method, and a microwave method. In these cases, since plasma generation in a high-density region is relatively easy, a device such as a spiral wave method, a high-frequency induction method, and a microwave method can be suitably used. The treated system has at least one layer of the tantalum oxide film layer, and may be a laminated film containing a layer of tantalum nitride film. Preferably, the object to be processed is etched by using a photoresist provided on the upper portion thereof as a mask. That is, since a pentafluoro-1,3-butadiene gas containing CF and a CHF group as a constituent element is used, the ratio is selected. Therefore, it is possible to improve the photoresist of the object to be treated, and the photoresist is composed of photosensitive photoresist.
此外’在本說明書中， 物所 射線 to a resist)，係指（被處理體之平均 均#刻速度）。此對光阻蝕刻選擇比 阻，具有蝕剡選擇性之意。藉由該 壞光阻下可進行被處理體之蝕刻。 在#刻之被處理體為積層膜之 層（ground layer)以電漿反應用氣體Further, in the present specification, the ray to a resist refers to (the average averaging speed of the object to be processed). This pair of photoresist etching selects the specific resistance and has the meaning of etch selectivity. Etching of the object to be processed can be performed by the bad photoresist. In the case where the object to be processed is a ground layer, a gas for plasma reaction
具有充分蝕刻選擇比的材料 上層完成蝕刻。 腰之情形’只要是其底質 氣體而具有充分蝕刻選擇 為止。又，若為不 則可在積層膜之底質層之 -11- 201213279 触刻時被處理體之達 為0至300。(：、更佳兔μ I，，，、将別限疋，較佳 之範圍為60至250°c、再佳為80至200t 之靶圍。基體之溫度可 ^ 制。蚀刻之時間一般為 丨^ 應用氣體，因可進行％刀鐘’而本發明之電焚反 生產性。 ‘速餘刻，故可在…分鐘提高 1,1,2,4,4 -五氣 _ 】1 鼠丨，3-丁二烯可單獨作為可蝕刻現象 之機構，考慮如下述之過程。 ，五氟丨，3-丁二烯在電漿争分解時，來自i 石炭之CF自由基在氧相φ 在轧相中增加。該CF自由基，因其吸附 特14 @在自孔較淺處’雖可進人’不過在較深處則難 、進#即’ CF自由基雖可蝕刻矽氧化膜，卻無法蝕 刻矽氮化膜。 -方面，來自烴之CH自由基，由於其分子大小較 丨故進人至窗孔之較^處為止，進行碎氮化膜之钱刻 因此接觸孔洞之底面係以來自烴t ch自由基進行 蝕刻，同時，藉由CF自由基之微負載（mier〇1〇ading)效 果（在欠處無蝕刻，而在深處則有蝕刻效果），而可保護 接觸孔洞之側壁或肩部。 藉此，吾人考慮僅窗孔底面之矽氮化膜被選擇地蝕 刻，同時光阻不被蝕刻，而可確保選擇比。 又，丨，1，]，々〆-五氟_1，3-丁二烯氣體係如上述，因自 身聚合極難產生，故在氣體容器或氣體流通之裝置内部 ，亦可獲得難以產生聚合性之雜質的效果。 -12- 201213279 3 ·氟碳膜之成膜方法 本發明之氟碳膜之成膜方、本# 取犋万法係包含：供給本發明之 電漿反應用氣體於處理容器内， ^ ^ 在该容器内於被處理物 之表面，以CVD法使氟碳膜成膜之步驟。 本發明之敦碳膜之成膜方法，更詳言之，包含將 本發明之電毁反應用氣體，依照所期望，與其他之氣體 成分-起供給於處理容器(CVD &置之反應腔室)内在 該容器内於被處理物之表面以CVD、本品难备π摇#时 I ν υ去而使氟碳膜成膜 之步驟。CVD法係指以雷爿§於骨 ^ 电耒放電，將電漿反應用氣體予 以活性化以及聚合，並在各種祐步饰此± 儿你合種被處理物表面予以形成薄 的氟碳膜之技術。 如上述，吾人考量11244?;岛^ ，’，4,4_五鼠_1，3-丁二烯氣體因 有助於電漿反應，故亦可應用於使用到電聚反應用氣體 的CVD法所致氟碳膜之成膜。 將本發明之電敷反應用氣體作為電聚反應CVD用 氣體使用之情形，由於在電聚中發生之活性品類 species)之濃度控制或原料氣體之促進解離，則亦可添加 選自由氦、氖、氬、氙及氪所組成群組中至少一種之惰 性氣體。 惰性氣體之添加量相對於五氟_丨，3_丁二烯 之惰性氣體之合計量，以體積比〔惰性氣體/丨，丨，2,4,4_五 氟-1，3-丁二烯）〕，較佳為2至200、更佳為5至ι5〇。 在使用於電漿CVD的裝置方面，可例舉平行乎板 CVD裝置、微波CVD裝置、ecR-CVD裝置、電威偶合 (inductively coupled)電漿（ICP)CVD裝置及高密度電漿 CVD裝置（螺旋波方式或高頻感應方式）等。 -13- 201213279 電I發生條件方面，並益特別眼— jn ^ m Γνη ^ φ .、，、寺另J限疋，若以使用平行 ^ 裝之情形為例，通常採用外加於平行平板 之上部電極（淋浴噴頭（sh〇Wer headuThe material has a sufficient etching selectivity ratio and the upper layer completes the etching. The case of the waist is sufficient as long as it is a bottom gas. Further, if not, the object to be treated may be 0 to 300 at the time of the -11-201213279 of the underlying layer of the laminated film. (:, better rabbit μ I,,,, and other limits, preferably in the range of 60 to 250 ° C, and preferably 80 to 200 t. The temperature of the substrate can be controlled. The etching time is generally 丨^ Application of gas, because of the % knife knives can be carried out, and the electric combustion of the present invention is reversed. 'Speed residual, so it can be increased by 1, 1, 2, 4, 4 - five gas _ 】 1 groin, 3-butadiene can be used alone as a mechanism for etching. Consider the following process. When pentafluoroindene and 3-butadiene are decomposed in the plasma, the CF radical from i charcoal is in the oxygen phase φ. The increase in phase. The CF radical, because of its adsorption special 14 @ in the shallower from the hole 'can enter the human', but in the deeper it is difficult, enter # ie 'CF radical can etch the oxide film, but It is impossible to etch the tantalum nitride film. - In terms of the CH radical of hydrocarbons, since the molecular size is relatively small, it enters the window of the window, so that the bottom surface of the contact hole is Etching from hydrocarbon tch radicals, at the same time by micro-loading of CF radicals (no etch at the underside, but deep in the etch The etching effect) can protect the sidewall or shoulder of the contact hole. Therefore, it is considered that only the tantalum nitride film on the bottom surface of the window hole is selectively etched, and the photoresist is not etched, and the selection ratio is ensured. , 1,], 々〆-pentafluoro-1,3-butadiene gas system, as described above, is extremely difficult to produce due to self-polymerization, so that it is difficult to produce polymerizable impurities in a gas container or a gas-flowing device. -12-201213279 3 - Film forming method of fluorocarbon film The film forming method of the fluorocarbon film of the present invention, and the method of supplying the plasma reaction gas of the present invention are contained in a processing container, ^ ^ a step of forming a fluorocarbon film by CVD in the surface of the object to be treated in the container. The film forming method of the carbon film of the present invention, more specifically, includes the electrolysis reaction of the present invention. The gas, as desired, is supplied to the processing vessel (CVD & reaction chamber) as required, and is CVD in the container on the surface of the object to be treated, and the product is difficult to prepare. a step of forming a film of a fluorocarbon film by smashing. ^ Electron discharge, the plasma reaction gas is activated and polymerized, and in various ways, you can form a thin fluorocarbon film on the surface of the treated object. As mentioned above, we consider 11244? The island ^ , ', 4, 4_ five rat _ 1,3-butadiene gas can also be applied to the fluorocarbon film caused by the CVD method using the gas for electropolymerization because it contributes to the plasma reaction. When the gas for electroforming reaction of the present invention is used as a gas for electropolymerization CVD, the concentration control of the active species generated during electropolymerization or the promotion of dissociation of the material gas may be selected from An inert gas of at least one of the group consisting of ruthenium, osmium, argon, krypton and xenon. The amount of inert gas added relative to the total amount of inert gas of pentafluoro-hydrazine, 3-butadiene, in volume ratio [inert gas / hydrazine, hydrazine, 2, 4, 4 - pentafluoro-1,3-butyl Alkene) is preferably 2 to 200, more preferably 5 to ι 5 Å. In the apparatus for plasma CVD, a parallel plate CVD apparatus, a microwave CVD apparatus, an ecR-CVD apparatus, an inductively coupled plasma (ICP) CVD apparatus, and a high density plasma CVD apparatus ( Spiral wave method or high frequency induction method). -13- 201213279 In terms of the condition of electric I, it is beneficial to the special eye - jn ^ m Γνη ^ φ ., ,, and the temple is limited to J. If the case of parallel mounting is used as an example, it is usually applied to the upper part of the parallel plate. Electrode (shower head (sh〇Wer headu
$ 1Λ, w 、+ + ftead))之尚頻電力為10W 至_、破處理物溫度為〇·5〇。。。、反應室壓力為 U⑽UU.3kPa。堆積之膜厚度，通常在⑽至 之範圍。 被處理物並無特別限定’其係半導體製造領域、電 子電氣領域、精密機械領域、其他領域要求絕緣性、拒 水性、抗腐㈣、抗酸性、潤滑性、光之抗反射性等功 能或性質的物品或構件，較佳為在半導體製造領域及電 子電氣領域中要求絕緣性的物品或構件，特別佳為在該 等領域所使用之基板。 適當基板之具體例方面，可例舉單結晶矽膜、多結 晶矽膜及非晶形矽膜等之矽膜；由鎢、鉬、鈦及钽等所 組成矽化（silicide)膜；SiN、SiON、Si02、BSG(硼矽酸 鹽玻璃）、PSG(磷矽酸鹽玻璃）、BPSG(硼磷矽酸鹽玻璃） 、AsSG(砷矽酸鹽玻璃）、SbSG(銻矽酸鹽玻璃）、NSG(氮 一矽酸鹽玻璃）、PbSG(鉛一矽酸鹽玻璃）及S0G(旋塗式 玻璃）等之含矽絕緣膜；TiN及TaN等之導電性膜；鎵_ 石申基板；金剛石狀碳膜或鋁板；鹼石灰玻璃；氧化鋁膜 ;氧化锆膜以及由氮化鋁及氧化鋁所組成陶瓷等。 [實施例] 茲以實施例進一步詳細說明本發明，不過本發明並非 受以下實施例而受到任何限定。此外，只要無特別說明， 則「份」及「％」各自表示「重量份」及「重量％」。 -14- 201213279 [製造例] 依照 D· Lentz，et al., CHEMISTRY AN ASIAN JOURNAL, Volume 3，7 19(2008)記載之方法來製造 1，1，2,4,4-五氟-1，3_ 丁 二烯。$ 1Λ, w , + + ftead)) The frequency of the power is 10W to _, and the temperature of the treated material is 〇·5〇. . . The reaction chamber pressure is U(10)UU.3kPa. The thickness of the deposited film is usually in the range of (10) to. The object to be treated is not particularly limited. It is a function or property that requires insulation, water repellency, corrosion resistance (IV), acid resistance, lubricity, and anti-reflection of light in the field of semiconductor manufacturing, electrical and electronic, precision machinery, and other fields. The article or member is preferably an article or member that requires insulation in the field of semiconductor manufacturing and electrical and electronic fields, and is particularly preferably a substrate used in such fields. Specific examples of the appropriate substrate include a ruthenium film such as a single crystal ruthenium film, a polycrystalline ruthenium film, and an amorphous ruthenium film; a silicide film composed of tungsten, molybdenum, titanium, tantalum, or the like; SiN, SiON, Si02, BSG (boron silicate glass), PSG (phosphorite glass), BPSG (borophosphonate glass), AsSG (arsenate glass), SbSG (silicate glass), NSG ( Niobium monosilicate glass), PbSG (lead monosilicate glass) and S0G (spin-coated glass), etc.; conductive film of TiN and TaN; gallium_Shishen substrate; diamond-like carbon Film or aluminum plate; soda lime glass; aluminum oxide film; zirconia film and ceramic composed of aluminum nitride and aluminum oxide. [Examples] The present invention is further illustrated by the following examples, but the present invention is not limited by the following examples. In addition, "parts" and "%" mean "parts by weight" and "% by weight", unless otherwise stated. -14- 201213279 [Production Example] 1,1,2,4,4-pentafluoro-1 was produced according to the method described in D. Lentz, et al., CHEMISTRY AN ASIAN JOURNAL, Volume 3, 7 19 (2008). 3_ Butadiene.
使用乾冰丙酮浴，將3升之3 口反應器冷卻至-1 1 〇 °C 。自圓筒（cylinder)輸送1-氯ι，ΐ-二氟乙烷25g。裝入無 水四氫呋喃500ml予以溶解。將二級丁基鋰、環己烷、 正己烧溶液（lmol/升）滴下5〇〇ml。在照樣保持溫度為 -1 l〇°C，滴下氯化三丁基錫（IV)68ml，攪拌2小時。藉 由自粗原料進行減壓蒸餾，而獲得三丁基氟乙炔基錫烷 78g。 在1升之熱壓器，裝入二環己基-2-(2，，4，，6，-三異丙 基聯苯基）膦1.2g、乙酸鈀（juo.lg，實施三次以旋轉泵 所致減壓與灸氣所致取代。接著，裝入二曱基曱酿胺 20 0ml、三丁基氟乙炔基錫烷78g、溴三氟乙烯32g。使 用油浴’將熱壓器加溫至6 0 °C，並攪拌4 0小時。藉由 精餾粗產物，而獲得1，1,2,4,4-五氟丁二烯26g。 重複上述操作’以使1，1，2,4,4-五氟丁二烯成為所期 望量。 [實施例]The 3-liter 3-port reactor was cooled to -1 1 〇 °C using a dry ice acetone bath. From the cylinder, 1-chloroum, hydrazine-difluoroethane 25 g was supplied. It was dissolved in 500 ml of anhydrous tetrahydrofuran. A solution of 2 butyl chloride, cyclohexane, and a hexane solution (1 mol/liter) was dropped 5 liters. While maintaining the temperature at -1 l ° ° C, 68 ml of tributyltin (IV) chloride was dropped and stirred for 2 hours. By vacuum distillation from a crude material, 78 g of tributylfluoroethynylstannane was obtained. In a 1 liter autoclave, 1.2 g of dicyclohexyl-2-(2,4,6,3-triisopropylbiphenyl)phosphine, palladium acetate (juo.lg, three times for rotary pump) The resulting decompression was replaced by moxibustion. Next, 20 ml of dimercaptocarnitine, 78 g of tributylfluoroethynylstannane, and 32 g of bromotrifluoroethylene were charged. The oil bath was used to warm the autoclave. To 60 ° C, and stirred for 40 hours. By rectifying the crude product, 26 g of 1,1,2,4,4-pentafluorobutadiene was obtained. The above operation was repeated 'to make 1, 1, 2, 4,4-pentafluorobutadiene is the desired amount. [Examples]
It由重複填充氣體於容器，而進行比較發生之粒子 個數的實驗。 將 150ml 之 SUS 製容器以渦輪分子策 (turbomolecular pump)減壓，同時在i〇〇°c經1小時乾燥 。冷卻SUS容器’並輸送全氟_ι，3· 丁二烯i〇〇g。 -15- 201213279 回至常溫，並釋出容器中内容物。目前 進行1次，而相同乾燥與填充之操作則進行 21次，釋出前，使用Lion股份有限公司製 K S - 9 3，測定氣體中大於0.1 μ m粒子之個數 其次，上述測定係藉由輸送1，1,2,4，4-五 烯89g以替代全氟-1，3-丁二烯100g來實施< 其結果，相較於全氟-1,3 - 丁二烯，使月 五氟-1,3 - 丁二烯時粒子之個數為0.6倍。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 為止之操作 20次。在第 粒子感應器 氟-1,3-丁二 I 1,1,2,4,4- -16 -It is an experiment in which the number of particles occurring is compared by repeating the filling of the gas into the container. A 150 ml SUS container was depressurized with a turbomolecular pump while drying at i ° ° C for 1 hour. The SUS container was cooled and transported with perfluoro_3,butadiene i〇〇g. -15- 201213279 Return to normal temperature and release the contents of the container. At present, the operation is carried out 21 times, and the same drying and filling operation is carried out 21 times. Before release, the number of particles larger than 0.1 μm in the gas is measured by using KS - 9 3 manufactured by Lion Co., Ltd., and the above measurement is carried out by transport. 89 g of 1,1,2,4,4-pentene was used in place of 100 g of perfluoro-1,3-butadiene. As a result, compared with perfluoro-1,3-butadiene, the fifth month The number of particles of fluorine-1,3-butadiene was 0.6 times. [Simple description of the diagram] None. [Main component symbol description] None. The operation has been 20 times. In the particle sensor fluoro-1,3-butane I 1,1,2,4,4- -16 -