TW201133619A - Method for etching silicon-containing film - Google Patents

Method for etching silicon-containing film Download PDF

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TW201133619A
TW201133619A TW099128944A TW99128944A TW201133619A TW 201133619 A TW201133619 A TW 201133619A TW 099128944 A TW099128944 A TW 099128944A TW 99128944 A TW99128944 A TW 99128944A TW 201133619 A TW201133619 A TW 201133619A
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Taiwan
Prior art keywords
etching
film
raw material
gas
volume
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TW099128944A
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Chinese (zh)
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TWI430367B (en
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Shunsuke Kunugi
Satoshi Mayumi
Takashi Satoh
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • H01L21/31116—Etching inorganic layers by chemical means by dry-etching
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
    • 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
    • H01J37/32357—Generation remote from the workpiece, e.g. down-stream
    • 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
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
    • H01J37/32816—Pressure
    • H01J37/32825—Working under atmospheric pressure or higher

Abstract

Disclosed is a method for etching a silicon-containing film, wherein lifting or separation of an organic film is prevented. Specifically, an etching material gas that does not substantially contain hydrogen atoms is introduced into a plasma space (23) that is at near atmospheric pressure, thereby producing an etching gas. The etching gas is brought into contact with an object to be processed (90) that contains a silicon-containing film (92) and an organic film (93). The silicon-containing film (92) can be oxidized with nitrogen oxide (NOx). The etching material gas contains 7-80% by volume of a fluorine-based material that does not contain hydrogen atoms, 7-80% by volume of nitrogen (N2) and 5-60% by volume of oxygen (O2).

Description

201133619 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種使賴含有U成分之氣體電聚化而 獲得之㈣氣體，對氮化♦等含切之膜進行㈣之方 法。 【先前技術】 於利用大氣壓電漿之含有矽之臈的蝕刻中，已知有藉由 於CF4等氣系原料中添加水（仏〇)而生成hf，欲利用1^進 行触刻之方法（參照下述專利文獻丨〜3)。 例如，於專利文獻丨中，利用臭氧將非晶矽或晶態矽等 矽膜氧化而成為氧化矽（式丨），且藉由於Ch等氟系原料中 添加水，通入至接近大氣壓之電漿空間中而生成hf(式 2)，利用4 HF或其水溶液對氧化^夕進行钮刻（式3)。於上 述電漿空間中’除HF以外亦生成COF2等。COF2與水反應 而生成HF(式4) ’將其提供給氧化矽之蝕刻（式3): Si+203-^Si〇2+202 (式 υ CF4+2H20 —4HF + C02 (式 2)[Technical Field] The present invention relates to a method in which (4) a gas obtained by electropolymerizing a gas containing a U component is obtained, and a film having a cut film such as nitride ♦ is subjected to (d). [Prior Art] In the etching using ruthenium containing a ruthenium in the atmosphere, it is known that hf is formed by adding water (仏〇) to a gas-based raw material such as CF4, and it is known to use a method of etching. The following patent documents 丨~3). For example, in the patent document, ozone is used to oxidize a ruthenium film such as an amorphous ruthenium or a crystalline ruthenium to form ruthenium oxide, and is added to a gas close to atmospheric pressure by adding water to a fluorine-based raw material such as Ch. Hf (Formula 2) is formed in the slurry space, and the oxidation is performed by using 4 HF or an aqueous solution thereof (Formula 3). In the above plasma space, COF2 and the like are also generated in addition to HF. COF2 reacts with water to form HF (Formula 4)' which is supplied to the yttria etching (Formula 3): Si+203-^Si〇2+202 (Formula 4 CF4+2H20-4HF + C02 (Formula 2)

Si02+4HF—>SiF4+2H20 (式 3) COF2+H2O—C〇2+2HF (式 4) [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2007-294642號公報 [專利文獻2]曰本專利特開2000-58508號公報 [專利文獻3]曰本專利特開2002-270575號公報 150469.doc 201133619 【發明内容】 [發明所欲解決之問題] HF氣體或HF水溶液具有於較多有機化合物中浸透、渗 透之性質。因此’於在被處理基材上，除設置蝕刻對象之 含有矽之膜以外’例如亦設置圖案形成用之光阻劑等有機 膜之情形時，若藉由於CF4等氟系原料中添加水而電聚化 之蝕刻氣體進行蝕刻，則HF浸透、滲透至有機膜中。因 此，有機膜之界面密著力下降，有時有機膜會隆起或剝 離。尤其若蝕刻氣體中之水吸附於被處理物之表面，則HF 溶解於該水中，促進浸透、滲透，而有機膜之隆起或剝離 變得顯著。另一方面，若減少水之添加量或抑制HF之生成 量，則飯刻速率降低，並不實用。 [解決問題之技術手段] 氧化石夕、氮化石夕、石夕（非晶石夕、單晶石夕、多晶石夕）等含石夕 物不僅可藉由HF，亦可藉由版化羰基(c〇F2)、氟化氧 (〇F2、o2F2)等含有氧之氟系活性物質而引起蝕刻反應。 關於其反應速度，通常氧切A於其他切物。進而:除 氧化石夕以外之I切或石夕之切物可藉由氧化氮而氧化。示 本發明係基於上述認識而完成者，其係—種含有石夕之膜 之姓刻方法，該含有⑦之膜之_方法係對包含可藉由氧 化氮(NOX)而氧化之含有石夕之膜及有機膜之被處理物中之 含述3有夕之膜進心刻者，該㈣方法之特徵在於包 生成步驟， 其係將實質上不含氫原 子之兹刻原料氣體導 150469.doc 201133619 入至接近大氣壓之電漿空間中，生成蝕刻氣體；及 触刻反應步驟’其係使上述蚀刻氣體接觸上述被處理 物； 上述蝕刻原料氣體含有7〜80體積％之不含氫原子之氟系 原料、7〜80體積°/〇之氮（N2)、5〜60體積。/〇之氧（〇2)。 於上述生成步驟中，藉由將上述組成之蝕刻原料氣體電 漿化（包含分解、激發、活化、離子化），可生成包含含有 氧之氟系活性物質與氧化氮（N0x)，且幾乎或完全不含HF 之蝕刻氣體。 於上述蝕刻反應步驟中，可利用含有氧之氟系活性物質 引起上述含有矽之膜之蝕刻反應。進而，可利用氧化氮將 上述含有矽之膜氧化而轉變為氧化矽，從而提高對含有氧 之氟系活性物質之蝕刻速率。蝕刻氣體中幾乎或完全不含 HF，因此HF於有機膜中之浸透、滲透現象幾乎或完全不 發生。因此，可避免有機膜之界面密著力下降，可抑制或 防止有機膜之隆起或剝離。進而，除上述利用氧化氣之氧 化作用及關速率提冑作用料，亦可藉由使㈣原料氣 體之各成分之流量比處於上述範圍内而確實提高触刻速 率。因此，蚀刻處理時間縮短，藉此可減少❾竟氣體中之 水分吸附於被處理物之機會，故而與_原料氣體不含氣 原子之作用相力口 ’可更確實地抑制或防止有機膜之隆起或 剝離。又，可避免於被處理物之表面之一部分形成水之凝 結層。因A ’可避免氧化反應及蝕刻反應受凝結層妨礙。 進而’可避免於形錢結層之部位與未形成凝結層之部位 150469.doc 201133619 之間產生㈣速率之不均。藉此，可防止被處理物之表面 粗化。 上述3有夕之膜較好的是含有石夕⑻）、氮化石夕（則X)、 碳化石夕（Sic)、t氧化石夕（Si⑽）、碳氧化石夕（si〇c)、碳氮化 矽（SlCN)之任—種。通常該等含石夕物（Si、SiNx、Sic、 SiON SiQC、SiCN)之利用含有氧之敗系活性物質之蚀刻 反應速度小於氧化紗’ ^可藉由氧化氮而氧化。石夕⑶）可 為非晶矽，可為單晶矽，亦可為多晶矽。 上述姓刻原料氣體可含有45體積％以下之氧，較好的是 含有30體積％以下， 、 更好的疋含有20體積。/。以下。此時， 上述姓刻原料氣體之剩餘部分含有氮及氟系、原料，其體積 比可為氮：氟系原料=10:90〜9〇:1〇。藉此，於上述含有矽 之膜尤其包含氮切之情形時，可確保高#刻速率。 上述触刻原料氣體之上述原料及氧之總計與氣之體 積流量比為70:30〜20:80’且上述氟系原料與氧之體積流量 比可為75.25〜4G..6G。於此情形時，上述触刻原料氣體之上 述I系原料及氧之總計與氣之體積流量比較好較6〇4〇〜 扯7〇,更好的是5〇:5()〜4G:6Qe進而於此情形時上述银 刻原料氣體之上述氟系原料與氧之體積流量比較好的是 6〇:40〜4〇:60，更好的是50:50左右。藉此，於上述含有石夕 之膜尤其包含氮化石夕之情形時’可確實提高触刻速率。認 為若上述㈣原料氣體中之氮之含有率過高，職系原料 及氧之含有率變得過低，因此含有氧之氟系活性物質之生 成量變少，>1虫刻速率下降。切、兔u、私、 J疋千r降t為右上述蝕刻原料氣體中之 150469.doc 201133619 氮之含有率過低，則氧化氮之生成量變少，含有石夕之膜之 氧化作用變弱，姓刻速率下降。認為上述钮刻原料氣體中 之上述氟系原料之含有率過低，氧之含有率過低，均導致 含#氧之之生成量減少’因此㈣速率下 降。 上述韻刻原料氣體可含有20〜80體積％之上述氟系原 料、7〜60體積％之氮、5〜6〇體積％之氧，進而可含有4〇〜8〇 體積％之上述亂系原料、7〜4〇體積％之氮、5〜4〇體積％之 氧。藉此，於上述含有矽之膜尤其包含非晶矽等矽之情形 時，可石崔保高钮刻速率。於上述含有石夕之膜包含非晶石夕等 矽之情形時，上述蝕刻原料氣體可含有3〇體積％以上之上 述氟系原#，進而可含有5〇體積％以上，且上述蝕刻原料 氣體之剩餘部分可以n2:〇2=1 〇:9〇〜9〇: 1〇之體積比含有氮及 氧。 較好的是進而實行溫度調節步驟，該溫度調節步驟係將 上述被處理物之溫度設為5〇。(：以上，較好的是5(rc〜12〇t： 左右’更好的是5〇。〇〜100。(3左右。藉此，可防止大氣等環 境氣體中之水分吸附於被處理物。因此，可防止於被處理 物之表面上由水分與蝕刻氣體中之含有氧之氟系活性物質 生成HF。因此，可確實抑制或防止有機膜之隆起或剝離。 於上述含有矽之膜尤其包含氮化矽等之情形時，上述被 處理物之溫度較好的是於不超過構成該被處理物之有機膜 等之耐熱能力之範圍内設為儘量高，可加熱至l〇〇〇c左 右’根據有機膜之耐熱能力亦可加熱至120°c左右。藉 150469.doc 201133619 此，維持較向钱刻迷率，並可確實防止水分吸附於被處理 物，進而可進-步確實抑制或防止有機膜之隆起或剝離。 並且，可防止有機膜之變性（收縮等物性變化）。再者，有 機膜產生變性之、、田痒士 1 义丨之/皿度亦取決於該有機膜之成分，通常為 l〇〇°C〜200。(：以上。 ^上述含有_之膜包含非晶石夕等之情形時，於上述溫度 Ό驟中’較好的是將上述被處理物之溫度設為超過 5〇:〜戰’更好的是設為6〇t〜8〇t。藉此，可提高非晶 石夕專之餘刻速率(參照實施例8及圖7)。藉由將上述被處理 物設為高於常溫，可防止水分吸附於被處理物，可抑制或 防止有機膜之隆起每制離 屹次剝離。並且，可確實防止有機膜之變 性0 =破處理物’例如可列舉液晶顯示裝置等平板顯示器 "體裝置。例如，於應成為用作平板顯示器之各像素 哥70件之TFT(Thln Film 丁⑽化薄膜電晶體）的被 处勿中’包含依序積層之非晶石夕膜、金屬膜及有機膜。 於上述非晶石夕膜之上述金屬膜側之膜部分中摻雜有雜質。 上述有機膜成為餘刻上述金屬膜及上述非晶石夕膜中之上述 換雜有雜質之膜部分(摻雜有雜質之非晶石夕臈)時的遮罩。 β ==上述摻雜有雜質之非晶石夕膜時’可使用上述触刻 孔 34餘刻氣體之原料氣體含有7〜80體積％之不含氫 ^之氣系原料、7〜80體積％之氮㈣、5〜60體積％之氧 (^。較好的是上述_氣體之原料氣體含有2q〜8〇體積％ 氣系原料、7〜60體積％之氮⑽、5〜60體積％之氧 150469.doc 201133619 (〇2)。更好的是上述蝕刻氣體之原料氣體含有4〇〜8〇體積％ 之上述氟系原料、7〜4〇體積％之氮（Nj、5~4〇體積％之氧Si02+4HF—>SiF4+2H20 (Formula 3) COF2+H2O—C〇2+2HF (Formula 4) [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2007-294642 [ [Patent Document 2] 专利 专利 2000 2000 2000 2000 2000 2000 2000 2000 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 HF HF It has the property of being saturated and infiltrated in many organic compounds. Therefore, in the case where an organic film such as a photoresist for pattern formation is provided on the substrate to be treated, except for the film containing the ruthenium to be etched, for example, water is added to the fluorine-based raw material such as CF4. The etching of the electropolymerized etching gas causes the HF to permeate and penetrate into the organic film. Therefore, the adhesion of the interface of the organic film is lowered, and the organic film may be embossed or peeled off. In particular, if water in the etching gas is adsorbed on the surface of the object to be treated, HF is dissolved in the water to promote penetration and penetration, and the bulging or peeling of the organic film becomes remarkable. On the other hand, if the amount of water added is reduced or the amount of HF generated is suppressed, the rice cooking rate is lowered, which is not practical. [Technical means to solve the problem] The inclusions such as oxidized stone eve, nitriding stone eve, Shi Xi (amorphous stone eve, single crystal eve, polycrystalline stone eve) can be used not only by HF but also by plate An oxygen-containing fluorine-based active material such as a carbonyl group (c〇F2) or a fluorinated oxygen (〇F2 or o2F2) causes an etching reaction. Regarding the reaction rate, it is usually oxygen cut A to other cuts. Further, the I cut or the stone cut except for the oxidized stone can be oxidized by nitrogen oxide. The present invention is based on the above-mentioned knowledge, which is a method for engraving a film containing a film of the stone, and the method comprising the film of 7 contains a stone eve which can be oxidized by nitrogen oxides (NOX). The film and the film of the organic film are included in the process of the film, and the method (4) is characterized by a package forming step, which is a material gas guide 150469 which is substantially free of hydrogen atoms. Doc 201133619 enters a plasma space close to atmospheric pressure to generate an etching gas; and a etch reaction step 'contacts the etching gas with the object to be treated; the etching source gas contains 7 to 80% by volume of hydrogen-free atoms A fluorine-based raw material, nitrogen (N2) of 7 to 80 volumes/〇, and a volume of 5 to 60. /〇Oxygen (〇2). In the above-described formation step, by pulverizing (including decomposition, excitation, activation, ionization) of the etching source gas having the above composition, a fluorine-based active material containing oxygen and nitrogen oxide (N0x) can be produced, and almost or It is completely free of HF etching gas. In the etching reaction step, an etching reaction of the above-mentioned film containing ruthenium can be caused by a fluorine-based active material containing oxygen. Further, the film containing ruthenium is oxidized by nitrogen oxide to be converted into ruthenium oxide, thereby increasing the etching rate of the fluorine-containing active material containing oxygen. The etching gas contains little or no HF, so that the penetration and penetration of HF in the organic film hardly or completely does not occur. Therefore, the adhesion of the interface of the organic film can be prevented from being lowered, and the bulging or peeling of the organic film can be suppressed or prevented. Further, in addition to the above-described oxidation of the oxidizing gas and the shutdown rate, the flow rate ratio of the components of the (IV) raw material gas can be surely increased in the above-mentioned range. Therefore, the etching treatment time is shortened, whereby the opportunity for the moisture in the gas to be adsorbed to the object to be treated can be reduced, so that the action of the organic gas can be more reliably suppressed or prevented. Uplift or peel off. Further, it is possible to avoid formation of a condensation layer of water on a part of the surface of the object to be treated. The oxidation reaction and the etching reaction are prevented by the condensed layer due to A '. Furthermore, it is possible to avoid (4) rate unevenness between the portion where the shape of the money is formed and the portion where the condensation layer is not formed 150469.doc 201133619. Thereby, the surface of the object to be treated can be prevented from being roughened. The above-mentioned three-day film preferably contains Shi Xi (8)), nitrite (then X), carbonized stone (Sic), t-oxidized stone (Si(10)), carbon oxidized stone (si〇c), carbon Any of the types of tantalum nitride (SlCN). In general, the cerium-containing materials (Si, SiNx, Sic, SiON SiQC, SiCN) having an oxygen-containing reactive active material having an etching reaction rate lower than that of the oxidized yarn can be oxidized by nitrogen oxide. Shi Xi (3)) can be amorphous, and can be single crystal germanium or polycrystalline germanium. The above-mentioned raw material gas may contain 45% by volume or less of oxygen, preferably 30% by volume or less, and more preferably 20% by volume. /. the following. In this case, the remainder of the raw material gas of the above-mentioned surname contains nitrogen and a fluorine-based raw material, and the volume ratio thereof may be nitrogen: fluorine-based raw material = 10:90 to 9:1. Thereby, in the case where the film containing ruthenium contains, in particular, nitrogen cut, a high rate can be ensured. The volume ratio of the total amount of the raw material and the oxygen of the above-mentioned etchant material gas to the gas is 70:30 to 20:80', and the volume flow ratio of the fluorine-based raw material to oxygen may be 75.25 to 4 G..6G. In this case, the total amount of the above-mentioned I-based raw materials and oxygen of the above-mentioned contact raw material gas and the volume flow rate of the gas are better than 6〇4〇~ 7〇, more preferably 5〇:5()~4G:6Qe Further, in this case, the volume flow rate of the fluorine-based raw material and oxygen of the silver-cut raw material gas is preferably 6 〇: 40 〜 4 〇: 60, more preferably about 50: 50. Thereby, the etch rate can be surely improved when the film containing the stone cerium contains, in particular, nitrite. When the content of nitrogen in the raw material gas of the above (4) is too high, the content of the raw material of the grade and the oxygen content are too low, so that the amount of the fluorine-containing active material containing oxygen is reduced, and the insecticidal rate is lowered. Cut, rabbit u, private, J疋 thousand r drop t is the right in the above etching raw material gas 150469.doc 201133619 When the nitrogen content is too low, the amount of nitrogen oxides is reduced, and the oxidation of the film containing Shi Xi is weak. The surname rate decreases. It is considered that the content of the fluorine-based raw material in the button-forming material gas is too low, and the oxygen content is too low, resulting in a decrease in the amount of formation of ?-oxygen. Thus, the rate of (IV) is lowered. The rhyme source gas may contain 20 to 80% by volume of the fluorine-based raw material, 7 to 60% by volume of nitrogen, and 5 to 6% by volume of oxygen, and further may contain 4 to 8 % by volume of the above-mentioned disordered raw material. 7 to 4% by volume of nitrogen, and 5 to 4% by volume of oxygen. Thereby, in the case where the film containing ruthenium contains, in particular, an amorphous ruthenium or the like, the stone Cui Baogao button rate can be used. In the case where the film containing the shi shi includes the amorphous iridium, the etching source gas may contain 3% by volume or more of the fluorine-based raw material #, and further may contain 5% by volume or more, and the etching raw material gas The remainder can be n2: 〇 2 = 1 〇: 9 〇 ~ 9 〇: 1 〇 volume ratio contains nitrogen and oxygen. It is preferred to further carry out a temperature adjustment step of setting the temperature of the object to be treated to 5 Torr. (: Above, preferably 5 (rc~12〇t: about 'better' is 5〇.〇~100. (3 or so. This prevents moisture in the atmosphere such as the atmosphere from being adsorbed to the treated object. Therefore, it is possible to prevent HF from being generated from the fluorine-containing active material containing oxygen in the moisture and the etching gas on the surface of the object to be treated. Therefore, it is possible to surely suppress or prevent the bulging or peeling of the organic film. In the case of containing tantalum nitride or the like, the temperature of the object to be treated is preferably as high as possible within a range not exceeding the heat resistance of the organic film or the like constituting the object to be processed, and can be heated to l〇〇〇c. Left and right 'can also be heated to about 120 °c according to the heat resistance of the organic film. By 150469.doc 201133619, it maintains a relatively high rate of money, and can prevent moisture from being adsorbed on the treated object, and can be further inhibited. Or prevent the organic film from being swelled or peeled off. Further, it is possible to prevent denaturation (change in physical properties such as shrinkage) of the organic film. Further, the organic film is denatured, and the dish size is also dependent on the organic film. Ingredients, usually l〇 〇°C~200. (: Above. ^When the film containing _ contains amorphous stone, etc., in the above temperature step, it is preferable to set the temperature of the above-mentioned object to be more than 5 〇: It is better to set it to 6〇t~8〇t. Thereby, the residual rate of the amorphous stone can be increased (refer to Example 8 and FIG. 7). When the temperature is higher than the normal temperature, the moisture can be prevented from being adsorbed on the object to be treated, and the delamination of the organic film can be suppressed or prevented from being peeled off every time. Further, the denaturation of the organic film can be surely prevented. A flat panel display "body device. For example, a TFT (Thln Film butyl (10) film transistor) that should be used as a flat panel display for each of the pixels of the TFT device (including a layered amorphous austenite film) a metal film and an organic film. The film portion on the side of the metal film on the amorphous film is doped with impurities. The organic film is replaced by the metal film and the amorphous film. A mask when the film portion of the impurity (amorphous stone doped with impurities). == When the amorphous phase is doped with impurities, the raw material gas of the gas may be used in the above-mentioned contact hole 34 to contain 7 to 80% by volume of the gas-based raw material containing no hydrogen, and 7 to 80% by volume. Nitrogen (tetra), 5 to 60% by volume of oxygen (^. Preferably, the raw material gas of the above gas contains 2q to 8 vol% of the gas-based raw material, 7 to 60% by volume of nitrogen (10), and 5 to 60% by volume of oxygen. 150469.doc 201133619 (〇2). More preferably, the raw material gas of the etching gas contains 4 〇 to 8 vol% of the fluorine-based raw material, and 7 to 4 vol% of nitrogen (Nj, 5 to 4 vol%) Oxygen

(〇2)。上述被處理物之溫度較好的是設為超過50。(：且l〇(rC 、 更好的疋设為60 C〜8(rc。藉此，可確實姓刻上述 杉雜有雜夤之非晶矽膜，可形成TFT之通道部分。並且， 由於姓刻氣體中幾乎或完全不含HF及H20,故而可避免氣 7 匕而’又透至上述有機膜中。因此，可避免有機膜之 界面密著力下降。因此，可防止有機膜之隆起及剝離，可 維持有機膜與金屬膜之密著狀態。進而，可避免金屬膜藉 而/奋解（蝕刻）。其結果，可形成良好之通道部分。 &此處，所謂「實質上不含氫原子」，並不限於完全不含 風原子之情形’亦包括钮刻原料氣體含有不引起有機膜之 隆起及剝離之程度之微量水分等氫原子含有物之情形。例 蝕刻原料氣體可含有較好的是露點溫度為以 I、更好的是-6(TC以下之水分，該露點溫度之蝕刻原料 ^ 3水里貫質上包含於零之範圍内蝕刻原料氣體實 質上不含氫原子。 人J原料氣體除氟系原料、氧（Ο。'氮（NO以外，亦可 含有1 &等稀釋氣體°作為氧與氮之至少-部分之代 用’亦可使用空氣。 乍為不3氫原子之氟系原料，除a、 等全氟化碳（PFC，perflu〇r〇carb〇n)以外，可列舉F2、(〇2). The temperature of the above-mentioned object to be treated is preferably set to exceed 50. (: and l〇 (rC, better 疋 is set to 60 C~8 (rc. By this, it is possible to form the amorphous ruthenium film of the above-mentioned cedar miscellaneous, which can form the channel portion of the TFT. And, The gas in the last name is almost or completely free of HF and H20, so that the gas can be prevented from passing through to the above organic film. Therefore, the adhesion of the organic film can be prevented from being lowered. Therefore, the swelling of the organic film can be prevented and By peeling, the adhesion between the organic film and the metal film can be maintained. Further, the metal film can be prevented from being borrowed/excited (etched). As a result, a good channel portion can be formed. The hydrogen atom is not limited to the case where the wind atom is not contained at all, and includes a case where the source gas contains a hydrogen atom-containing substance such as a trace amount of moisture which does not cause the organic film to rise and peel. Preferably, the dew point temperature is I, more preferably -6 (the water below TC, the etching source of the dew point temperature is 3, and the etching source gas is substantially free of hydrogen atoms in the range of zero. Human J raw material gas in addition to fluorine raw materials Oxygen (Ο. 'Nitrogen (other than NO, may also contain 1 & diluent gas as a substitute for at least part of oxygen and nitrogen' may also use air. 乍 is a fluorine-based raw material that does not contain 3 hydrogen atoms, except a, Other than perfluorocarbon (PFC, perflu〇r〇carb〇n), F2 can be cited.

Sh、nf3、\#2等。 為3有氧之氟系活性物質’可列舉⑶h、〇f2、〇仏 '50469.doc 201133619 等。 所謂接近大氣壓’係指1〇1 圍，芒去南η r, 〜5〇.663x1〇4 pa之範 考慮到壓力調整之容易化 較好的是丨^χ1λ4 ιλ ^裝置構成之簡便化，則 疋 1.333x10 ~ι〇·664χ1〇4 l〇.397xi〇4 pa。 ，更好的是 9·331χ104〜 有機獏可為於液晶顯示裝置 φ M m Dt. 干導體裝置等之製造步驟 中經覆膜而最終除去者(例如遮罩…… B% m-f- ^ m ^ ^ 早層），亦可為最終構成液 B日』不裝置或半導體裝置之一 声）。古M时 1刀者（例如絕緣層、保護 亦可槿点人士丨 象之含有矽之膜之表面側， * ,, a乍為積層於含有矽之膜之 =:Γ膜’可列舉遮罩層、絕緣層、保護層等。作 罩層nr膜之正τ層之有機膜，可列舉絕緣層。遮 罩層例如由光阻劑所構成。 乍為構成絕緣層或保護層之有 機膜’例如可列舉：環氧满 氧树月曰、丙烯酸系樹脂、聚醯亞胺 枒月曰、酚醛清漆樹脂等。 [發明之效果] 根據本發明，可一邊永剎 或防止被處理物之有機膜之隆 起或剝離，一邊對含有矽之膜進行蝕刻。 [實施方式】 以下’根據圖式說明本發明之實施形態。 圖1表示本發明之第1實施形態。被處理物90例如為液晶 ,.~員不裝置或半導體裝置，但並不限定於該等。被處理物9〇 之基㈣並無特別限定’可為玻璃，可為半導體晶圓，亦 可為連續狀或單片狀之樹脂膜。於基材91之上表面覆膜有 150469.doc •10· 201133619 蚀刻對象之含有矽之膜92。含有矽之膜92例如由氮化砂所 構成。 於含有矽之膜92上（表面側）積層有有機膜93。有機膜93 例如由經圖案化之光阻劑所構成。含有矽之膜92中之未經 光阻劑93覆膜之部分成為應蝕刻之部分。 有機膜93並不限定於光阻劑等遮罩層，亦可為包含環氧 樹脂、丙烯酸系樹脂、聚醯亞胺樹脂、酚醛清漆樹脂等之 絕緣層或保護層。有機膜93並不限定於積層於含有矽之膜 92之表面側’亦可構成含有矽之膜92之正下層。 大氣壓電漿蝕刻裝置i於接近大氣壓下對被處理物進 行電漿钮刻。電㈣刻裝置i包含支持部2與姓刻氣體供給 系統3。於支持部2上支持有被處理物9〇。支持部2由平台 所構成’但並不限定於此’可為親式輸送機或帶式輸送 機’可為複數個導輥，亦可為操作機（機械臂）。亦可於平 台2上連接搬送機構（未圖示），搬送被處理物。 狀平台2上之被處理物9G藉由溫度調節機構4進行溫度調 即。圖中’溫度調節機構4係組入平台2内，但亦可配置於 平台2之外部。溫度調節機構4可為電熱加熱器，可為輻射 加熱器’亦可為包含使溫度調節液流通之通路之熱交換 蝕刻氣體供給系統3包含敍刻原料氣體供給系統ι〇與電 漿生成部20。敍刻原料氣體供給系㈣包含氟系原料供給 部11、氧供給部丨2及氮供仏卹 次虱供、.，α邛13，將含有氟原料、氧（〇2) 及氮（Ν2)之蝕刻原料氣體供 仏、.〇至電漿生成部20。氟系原料 I50469.doc 201133619 供給部11供給不含氫原子之氟系原料。上述㈣原料例如 為CF4。作為氟系原料，可替代CF4而使用C2F6、C3F6、 等其他全氟化碳（pFC)，亦可使用 等。氧供給部12供給氧（〇2)。氮供給部13供給氮 蝕刻原料氣體供給系統1〇不包含水（Η2〇)之供給部。蝕 刻原料氣體中實質上（幾乎或完全）不含水等氫原子含有物 或含有氫之成分。 電聚生成部20包含相互對向之一對電極21、21。圖中， 電極21、21由平行平板電極所構成，但並不限定於此可 為同軸圓柱電極’可為一對輥式電極，亦可為輥式電極與 平板電極或圓柱凹面電極之組合。於至少一電極。之對向 面設置有固體介電質層（未圖示）。該等電極21、21中之一 者與電源22連接，另-者電性接地。|自電源22之供給電 壓可為脈衝等間歇波狀，亦可為正弦波等連續波。藉由自 電源22供給電壓而電極21、21間之空間23成為接近大氣壓 之電毁空間。於電焚空間23之上游端連接有餘刻原料氣體 供給系統10。亦可於蝕刻原料氣體供給系統1〇與電漿空間 23之連接部，设置用以將氣體均勻導入至電漿空間υ内之 整流部（未圖示）。於電漿空間23之下游端連接有噴出喷嘴 24。於喷出喷嘴24設置有用以將來自電漿空間23之氣體均 句喷出之整流部。噴嘴24面向支持部2上之被處理物9〇。 喷嘴24亦可與電漿生成部2〇成為一體。亦可於噴嘴24上 没置吸入並排出處理完畢之氣體之抽吸部（省略圖示）。 於對被處理物90進行處理時，電漿生成部2〇及喷嘴24可 I50469.doc •12- 201133619 相對於被處理物90而靜止，亦可相對於被處理物90而相對 和動。於電漿生成部2〇及噴嘴24相對於被處理物％而相對 移動之情形時，可於被處理物9G之兩端間往€1次或複數 次，亦可於單程一個方向移動僅丨次。 於上述構成之電漿蝕刻裝置1中，將I系原料供給部u 之CF4、氧供給部12之〇2、及氮供給部13之N2以特定之流 里比相互混合，獲得蝕刻原料氣體。蝕刻原料氣體之各成 分之體積含有率可於CF4為7%〜8〇%，仏為7%〜8〇%，〇2為 5%〜60°/。之範圍内進行設定。 於蚀刻對象膜92尤其為氮化石夕之情形時，1將飯刻原料 氣體之〇2之體積含有率較好的是設為45%以下，更好的是 設為30%以下’進而設為2〇%以下。此時，蚀刻原料氣體 之剩餘部分以N2:CF4 = 10:90〜90:10之體積比含有A及 CF4(氟系原料）。可將蝕刻原料氣體中之CP〆氟系原料\及 〇2之總計與n2之體積流量比設為（CF4+〇2):N2=7q μ 20:80，較好的是設為（〇卩4+〇2):；^2=60:40〜30^ - Μ·70，更好的 疋没為（CF4+〇2):N2=50:50〜40:60。可將触刻原料氣體中 CF4(氣糸原料）與〇2之體積流量比設為__了5 2 40:60，較好的是設為 CF4:〇2=40:60~60:40，争虹 „ 旯好的是設為 CF4:〇2=50:50左右。 統10而導 。藉由電 驟）： 蝕刻原料氣體（CF4+〇2+N2)係藉由氣體供給系 入至電漿生成部20之電漿空間23中，進行電毁化 漿化而例如引起以下之反應物質生成反應（生成步 CF4+O2~~> C OF 2"^F 2 (式 11) \ 50469.doc • 13- 201133619 CF4+02-h.〇2f2+C02 (式 12) N2+〇2—>NOx (式 13) 上式11〜13之各項之係數忽略（後述式21、22、31、 41〜45中亦相同）。 藉此，生成含有氟化羰基（COF2)、氟化氧（〇F2、〇2f2)等 含有氧之氟系活性物質及氧化氮（ΝΟχ)之蝕刻氣體。蝕刻 氣體中幾乎或完全不含HF及水（Η20)。 上述钮刻氣體自噴出部24喷出，而噴附至被處理物9〇 上藉此，钮刻氣體之各成分接觸於包含氮化砍之含有石夕 之膜92中之未覆蓋有機膜93之部分，引起以下之蝕刻反 應： (式 21) S1NX+COF2—>SiF4+CO+N2Sh, nf3, \#2, etc. Examples of the 3 aerobic fluorine-based active material include (3) h, 〇f2, 〇仏 '50469.doc 201133619 and the like. The so-called near-atmospheric pressure refers to the circumference of 1〇1, and the awning to the south ηr, ～5〇.663x1〇4 pa. Considering the ease of pressure adjustment, it is better to simplify the structure of 丨^χ1λ4 ιλ ^疋1.333x10 ~ι〇·664χ1〇4 l〇.397xi〇4 pa. More preferably, it is 9·331χ104~ organic 貘 can be liquid crystal display device φ M m Dt. In the manufacturing steps of dry conductor device, etc., the film is finally removed (for example, mask... B% mf- ^ m ^ ^ Early layer), can also be the final composition of the liquid B day "no device or one of the semiconductor devices"). In the case of the ancient M, there is a knife (for example, the insulating layer, the protective layer can also be used as the surface side of the film containing the enamel, *, , a 乍 is laminated on the film containing 矽 =: Γ film' can be cited as a mask a layer, an insulating layer, a protective layer, etc. An organic film which is a positive layer of the nr film of the cap layer may be an insulating layer. The mask layer is composed of, for example, a photoresist. 乍 is an organic film constituting an insulating layer or a protective layer. For example, an epoxy resin, an acrylic resin, an acrylic resin, a polyamidamine, a novolac resin, etc. [Effects of the Invention] According to the present invention, an organic film capable of preventing or preventing a processed object can be used. The embodiment of the present invention is described below with reference to the drawings. Fig. 1 shows a first embodiment of the present invention. The object to be processed 90 is, for example, a liquid crystal. The member is not a device or a semiconductor device, but is not limited thereto. The substrate (4) of the object to be processed is not particularly limited. It may be glass, may be a semiconductor wafer, or may be a continuous or monolithic resin. Membrane. The surface of the substrate 91 is covered with 150469.doc •10 201133619 A film 92 containing germanium to be etched. The film 92 containing germanium is composed of, for example, silicon nitride. The organic film 93 is laminated on the film 92 (surface side) containing the germanium. The organic film 93 is patterned, for example. The photoresist is formed of a portion of the film 92 containing germanium which is not coated with the photoresist 93. The organic film 93 is not limited to a mask layer such as a photoresist, and may be epoxy. An insulating layer or a protective layer of a resin, an acrylic resin, a polyimide resin, a novolak resin, etc. The organic film 93 is not limited to being laminated on the surface side of the film 92 containing germanium, and may also constitute a film 92 containing germanium. The atmospheric piezoelectric slurry etching apparatus i performs plasma padding on the object to be processed under atmospheric pressure. The electric (four) etching apparatus i includes the support part 2 and the surname gas supply system 3. The object to be processed is supported on the support part 2. 9. The support portion 2 is constituted by a platform, but is not limited thereto. The parent conveyor or the belt conveyor may be a plurality of guide rollers or an operation machine (mechanical arm). The platform 2 is connected to a transport mechanism (not shown) and transported The workpiece 9G on the platform 2 is temperature-adjusted by the temperature adjustment mechanism 4. In the figure, the temperature adjustment mechanism 4 is incorporated into the platform 2, but may be disposed outside the platform 2. The temperature adjustment mechanism 4 may be an electrothermal heater, which may be a radiant heater, or may include a heat exchange etching gas supply system 3 including a passage for circulating a temperature regulating liquid, including a quotation material gas supply system ι and a plasma generating portion 20. The raw material gas supply system (4) includes a fluorine-based raw material supply unit 11, an oxygen supply unit 及2, a nitrogen supply, and an α 邛13, which are etched containing a fluorine raw material, oxygen (〇2), and nitrogen (Ν2). The raw material gas is supplied to the plasma generating unit 20. The fluorine-based raw material I50469.doc 201133619 The supply unit 11 supplies a fluorine-based raw material containing no hydrogen atoms. The above (4) raw material is, for example, CF4. As the fluorine-based raw material, other perfluorocarbons (pFC) such as C2F6 or C3F6 may be used instead of CF4, and the like may be used. The oxygen supply unit 12 supplies oxygen (〇2). The nitrogen supply unit 13 supplies a supply unit for the nitrogen etching raw material gas supply system 1 that does not include water. The material gas is substantially (almost or completely) free of hydrogen atomic substances such as water or components containing hydrogen. The electropolymerization unit 20 includes a pair of counter electrodes 21 and 21 facing each other. In the figure, the electrodes 21 and 21 are composed of parallel plate electrodes, but the present invention is not limited thereto. The coaxial cylindrical electrodes may be a pair of roller electrodes, or may be a combination of a roller electrode and a plate electrode or a cylindrical concave electrode. At least one electrode. A solid dielectric layer (not shown) is provided on the opposite side. One of the electrodes 21, 21 is connected to the power source 22, and the other is electrically grounded. The supply voltage from the power source 22 may be an intermittent wave such as a pulse, or may be a continuous wave such as a sine wave. By supplying a voltage from the power source 22, the space 23 between the electrodes 21, 21 becomes an electrical destruction space close to atmospheric pressure. A residual material gas supply system 10 is connected to the upstream end of the electric combustion space 23. Further, a rectifying portion (not shown) for uniformly introducing the gas into the plasma space can be provided at the connection portion between the etching source gas supply system 1 and the plasma space 23. A discharge nozzle 24 is connected to the downstream end of the plasma space 23. A rectifying portion for discharging the gas from the plasma space 23 uniformly is provided in the discharge nozzle 24. The nozzle 24 faces the workpiece 9 on the support portion 2. The nozzle 24 may be integrated with the plasma generating unit 2''. A suction portion (not shown) for sucking and discharging the processed gas may be omitted from the nozzle 24. When the workpiece 90 is processed, the plasma generating unit 2 and the nozzle 24 may be stationary with respect to the workpiece 90 or may be relatively moved with respect to the workpiece 90. When the plasma generating unit 2 and the nozzle 24 are relatively moved with respect to the object to be processed, it is possible to move to the first or second time between the two ends of the workpiece 9G, or to move only one direction in one direction. Times. In the plasma etching apparatus 1 of the above-described configuration, CF4 of the I-type raw material supply unit u, 〇2 of the oxygen supply unit 12, and N2 of the nitrogen supply unit 13 are mixed with each other at a specific flow ratio to obtain an etching source gas. The volume fraction of each component of the etching source gas may be 7% to 8 % by weight of CF4, 7% to 8% by weight of 仏, and 5% to 60 °% of 〇2. Set within the range. In the case where the etching target film 92 is particularly nitrided, the volume content of the crucible 2 of the rice cooking material gas is preferably 45% or less, more preferably 30% or less. 2〇% or less. At this time, the remaining portion of the etching source gas contains A and CF4 (fluorine-based raw materials) in a volume ratio of N2:CF4 = 10:90 to 90:10. The volume flow ratio of the total of CP 〆 fluorine-based raw materials \ and 〇 2 in the etching source gas to n 2 may be set to (CF4 + 〇 2): N2 = 7q μ 20: 80, preferably set to (〇卩4) +〇2):;^2=60:40~30^ - Μ·70, better 疋 is not (CF4+〇2): N2=50:50~40:60. The volume flow ratio of CF4 (gas enthalpy material) to 〇2 in the etchant material gas can be set to __ 5 2 40:60, preferably CF4: 〇 2 = 40: 60 to 60: 40, It is better to set it to CF4: 〇2=50:50. The system is guided by electricity.) In the plasma space 23 of the generating portion 20, electro-destructive slurrying is performed to cause, for example, the following reaction substance formation reaction (generating step CF4+O2~~> C OF 2"^F 2 (Formula 11) \ 50469.doc • 13- 201133619 CF4+02-h.〇2f2+C02 (Formula 12) N2+〇2—> NOx (Formula 13) The coefficients of the above formulas 11 to 13 are ignored (the following equations 21, 22, 31, 41) In the same manner as in the case of -45, an etching gas containing an oxygen-containing fluorine-based active material such as a fluorinated carbonyl group (COF2) or a fluorinated oxygen (〇F2, 〇2f2) and nitrogen oxide (ΝΟχ) is formed. Almost or completely free of HF and water (Η20). The above-mentioned button gas is ejected from the ejecting portion 24, and is sprayed onto the workpiece 9 to thereby cause the components of the button gas to be in contact with the nitrile-containing inclusion. Uncovered in the film of Shi Xizhi 92 The portion of the organic film 93 causes the following etching reaction: (Formula 21) S1NX+COF2—> SiF4+CO+N2

SiNx + 〇2F2—>SiF4+NOx (式 22) 如此，可對含有矽之膜92進行蝕刻。蝕刻氣體中幾乎或 完全不含HF及ΗζΟ ,因此HF於有機膜93中之浸透、滲透幾 乎或完全不發生《因此，可避免有機膜93之界面密著力下 降，可抑制或防止有機膜93隆起或剝離。因此，可僅對含 有矽之膜92之應蝕刻之部分澈底地進行蝕刻。 較好的是於喷附上述蝕刻氣體之同時，藉由溫度調節機 構4將被處理物90加熱至50。〇以上。藉此，可防止大氣中 之水分吸附於被處理物90之表面。因此，可防止大氣中之 水分與蝕刻氣體中之含有氧之氟系活性物質（氟化幾基、 氟化氧）反應而生成HF。進而，可進一步確實防止有機膜 93之隆起或剝離》被處理物9〇之設定溫度之上限設為 150469.doc -14- 201133619 可防止有機膜93由於 120°C ’較好的是設為l〇〇t：。藉此， 熱而變性。 構成含有矽之膜92之氮化矽之一 —部分藉由與由式13生成SiNx + 〇 2F2 - > SiF4 + NOx (Formula 22) Thus, the film 92 containing ruthenium can be etched. The etching gas contains almost no or completely HF and yttrium, so that the penetration and penetration of HF into the organic film 93 hardly or completely do not occur. Therefore, the interface adhesion of the organic film 93 can be prevented from being lowered, and the organic film 93 can be suppressed or prevented from rising. Or peel off. Therefore, only the portion of the film 92 containing germanium to be etched can be etched. It is preferable that the object to be treated 90 is heated to 50 by the temperature adjusting mechanism 4 while the etching gas is sprayed. 〇 Above. Thereby, moisture in the atmosphere can be prevented from being adsorbed on the surface of the workpiece 90. Therefore, it is possible to prevent the moisture in the atmosphere from reacting with the fluorine-containing active material (fluorinated group or fluorinated oxygen) containing oxygen in the etching gas to generate HF. Further, the upper limit of the set temperature of the material to be treated 9 〇 can be surely prevented from being set to 150469.doc -14 - 201133619. The organic film 93 can be prevented from being set at 120 ° C. 〇〇t:. Thereby, heat and denaturation. One of the tantalum nitrides constituting the film 92 containing germanium - in part by being generated by Equation 13

有氧之氟系活性物質（氟化羰基、氟化氧）反應而進行蝕刻 (式32及式33): (式 3 .1) (式 32)The aerobic fluorine-based active material (fluorinated carbonyl, fluorinated oxygen) is etched by reaction (Formula 32 and Formula 33): (Formula 3.1) (Formula 32)

SiNx+NOx-»Si02+N2 Si02+2C0F2—SiF4+2CO S1O2+2O2F2—^SiF4+3〇2 (式 33) 式32及式33所示之氧化矽之蝕刻反應速度大於上述式21 及式22所示之氮化矽之蝕刻反應速度。因此，藉由經由利 用NOx之氧化反應（式31)，可提高含有矽之膜92之蝕刻速 率°氮化矽之利用NOx之上述氧化反應（式3丨）之速度較 快’故而蝕刻速率提昇之效果較大。藉此，可縮短蝕刻之 處理時間。因此，可於蝕刻中減少環境氣體之水分吸附於 被處理物90之機會，可進一步確實抑制或防止有機膜之隆 起或剥離。 蚀刻氣體中幾乎或完全不含HF及HaO，因此可避免於被處 理物90之表面之一部分形成水之凝結層。因此，可避免氧 化反應及蝕刻反應受凝結層妨礙。進而，可避免於形成凝 結層之部位與未形成凝結層之部位之間產生蝕刻速率之不 均。因此，可防止被處理物90之表面粗化。 至此為止之實施形態中，對蝕刻對象之含有矽之膜92為 氮化矽進行了說明，但含有矽之膜92並不限定於氮化矽， 150469.doc 201133619 只要為可藉由氧化氮（ΝΟχ)氧化之切物即可可為非晶 石夕或多晶Μ⑦’ φ可為碳切、氮氧切、碳氧化石夕曰、曰 碳氮切等。無論㈣對象之膜質，均將_原料氣體之 各成分之體積含有率於氟系原料（CF4等）為7〜8〇%，Ν2為 7〜80%，〇2為5〜60%之範圍内進行設定即可。 於银刻對象膜92尤其為非晶石夕（a_Si)等石夕之情形時，將 蝕刻原料氣體之各成分之體積含有率較好的是設 20〇/。〜80%，>^2為7%〜60%，〇2為5%〜6〇%，更好的·是設為 理物90之設定溫度較好的是設為超過5〇。〇且丄〇〇它以下， 更好的是設為60°C〜80。(：。 於3有石夕之膜92包含非晶石夕（a_si)等;g夕之情形時，藉由 與姓刻氣體之接觸而引起以下之姓刻反應： S1+2COF2~^S1F4+2CΟ (式 23) S1+2O2F2—>SiF4+2〇2 (式 24) 關於上述式21及式22所示之氮化矽之蝕刻反應速度、與 式23及式24所示之石夕之钱刻反應速度，根據處理條件不同 而前者大於或小於後者。例如處理溫度為1 〇〇它左右時， 氮化矽之蝕刻反應速度大於矽之蝕刻反應速度。處理溫度 為60°C左右時’矽之#刻反應速度大於氮化矽之触刻反應 速度。 又’非晶石夕等石夕如下式所示般與NOx反應而氧化，成為 氧化矽：SiNx+NOx-»Si02+N2 Si02+2C0F2—SiF4+2CO S1O2+2O2F2—^SiF4+3〇2 (Formula 33) The etch rate of yttrium oxide represented by Formula 32 and Formula 33 is greater than that of Equations 21 and 22 above. The etching reaction rate of the tantalum nitride shown. Therefore, by using the oxidation reaction of NOx (Formula 31), the etching rate of the film 92 containing germanium can be increased. The above-mentioned oxidation reaction using NOx (Formula 3) is faster, and thus the etching rate is increased. The effect is greater. Thereby, the processing time of etching can be shortened. Therefore, it is possible to reduce the chance that the moisture of the ambient gas is adsorbed to the object to be treated 90 during the etching, and it is possible to further surely suppress or prevent the bulging or peeling of the organic film. The etching gas contains little or no HF and HaO, so that a condensation layer of water is formed on a part of the surface of the substrate 90. Therefore, the oxidation reaction and the etching reaction can be prevented from being hindered by the condensation layer. Further, unevenness in etching rate between the portion where the condensation layer is formed and the portion where the condensation layer is not formed can be avoided. Therefore, the surface of the workpiece 90 can be prevented from being roughened. In the embodiment of the present invention, the film 92 containing germanium for etching is described as tantalum nitride. However, the film 92 containing germanium is not limited to tantalum nitride, and 150469.doc 201133619 may be made by nitrogen oxide ( ΝΟχ) The oxidized cut material may be amorphous or polycrystalline Μ 7' φ may be carbon cut, oxynitride, carbon oxidized stone 曰, 曰 carbon nitrogen cut, and the like. Regardless of the film quality of the (IV) object, the volume content of each component of the raw material gas is 7 to 8 % by weight of the fluorine-based raw material (CF4 or the like), 7 to 80% of Ν 2, and 5 to 60% of 〇 2 Make settings. In the case where the silver engraved target film 92 is, in particular, austenite (a_Si) or the like, the volume content of each component of the etching source gas is preferably set to 20 Å/. ~80%, >^2 is 7%~60%, 〇2 is 5%~6〇%, and it is better to set the temperature of the physical object 90 to be better than 5 〇.丄〇〇 and 丄〇〇 it below, it is better to set it to 60 ° C ~ 80. (:. In the case of 3, the film 92 of Shi Xi includes amorphous stone eve (a_si); etc.; in the case of g eve, the following surname reaction is caused by contact with the gas of the surname: S1+2COF2~^S1F4+ 2CΟ (Formula 23) S1+2O2F2—>SiF4+2〇2 (Expression 24) The etching reaction rate of the tantalum nitride shown in the above formulas 21 and 22, and the Shi Xizhi of the formula 23 and the formula 24 The reaction speed of the money is different according to the processing conditions, and the former is larger or smaller than the latter. For example, when the treatment temperature is about 1 〇〇, the etching reaction speed of the tantalum nitride is greater than the etching reaction speed of the crucible. When the treatment temperature is about 60 ° C. The reaction speed of 矽## is greater than the kinetic reaction speed of tantalum nitride. Also, 'Amorphous Shixia et al. oxidizes with NOx as shown in the following formula to become yttrium oxide:

Si+NOx —Si〇2+N2 (式 41) 150469.doc -16· 201133619 名氧化矽與含有氧之氟系活性物質（COF2、〇ρ2、〇 等）反應而進行蝕刻（式32及式33)。 2 進而’於含有石夕之膜92包含碳化石夕（Sic)、氮氧化石夕 (SiON)、碳氧化石夕（Si〇c)、碳氮化i 別如7述—所示般與職反應而氧化：成：二 石夕° δ亥氧化石夕與含有氧之氟系活性物質（COF2、〇f2、〇2f2 等）反應而進行蝕刻（式32及式33): (式 42) (式 43) (式 44) (式 45)Si+NOx—Si〇2+N2 (Formula 41) 150469.doc -16· 201133619 The cerium oxide is etched by reacting with a fluorine-containing active material (COF2, 〇ρ2, yttrium, etc.) containing oxygen (Formula 32 and Formula 33) ). 2 Further, 'the film containing the shixi 92 contains carbon stone (Sic), oxynitride (SiON), carbon oxynitride (Si〇c), and carbonitride i as shown in 7 Oxidation by reaction: into: Ershixi ° δ oxime oxide is etched by reacting with oxygen-containing fluorine-based active material (COF2, 〇f2, 〇2f2, etc.) (Formula 32 and Formula 33): (Expression 42) ( Equation 43) (Equation 44) (Equation 45)

SiC+NOx->Si〇2+N2+c〇2 SiON+NOx-^Si〇2+N2 SiOC+NOx—>.Si〇2+N2 + CO: SiCN+NOx->Si〇2+N2+CO： 式32及式33所示之氧化矽之蝕刻反應速度大於上述實施 形態之處理條件下上述各含矽物（Si、SiC、Si〇N、si〇(：、SiC+NOx->Si〇2+N2+c〇2 SiON+NOx-^Si〇2+N2 SiOC+NOx->.Si〇2+N2 + CO: SiCN+NOx->Si〇2+ N2+CO: The etching reaction rate of cerium oxide represented by Formula 32 and Formula 33 is larger than the above-mentioned respective cerium contents (Si, SiC, Si〇N, Si〇 (:,

SiCN等）藉由含有氧之氟系活性物質而直接進行蝕刻之反 應速度。因此，該等含有矽之膜（si、Sic、Si〇N、Si〇c、The reaction speed of etching is directly performed by a fluorine-based active material containing oxygen by SiCN or the like. Therefore, these films containing bismuth (si, Sic, Si〇N, Si〇c,

SiCN等）亦可確貫提高姓刻速率。因此，可縮短钱刻之處 理時間’可於钮刻中減少環境氣體之水分吸附於被處理物 90之機會。進而’與蝕刻原料氣體實質上不含氫原子之效 果相加，可進一步抑制或防止有機膜之隆起或剝離。 圖2表示本發明之第2實施形態。第2實施形態係關於平 板顯示器用TFT之通道蝕刻。 應成為TFT之被處理物9〇a包含玻璃基板91。於玻璃基 板91上’自基板9 1側依序積層有閘極配線94、閘極絕緣膜 95、半導體膜96、金屬膜97、有機膜93。閘極配線94例如 150469.doc •17- 201133619SiCN, etc.) can also improve the rate of surnames. Therefore, it is possible to shorten the time of the money to reduce the chance that the moisture of the ambient gas is adsorbed to the object to be treated 90 in the button. Further, the effect of the etching source gas containing substantially no hydrogen atoms is added, and the swelling or peeling of the organic film can be further suppressed or prevented. Fig. 2 shows a second embodiment of the present invention. The second embodiment relates to channel etching of a TFT for a flat panel display. The object to be processed 9〇a to be the TFT includes the glass substrate 91. On the glass substrate 91, a gate wiring 94, a gate insulating film 95, a semiconductor film 96, a metal film 97, and an organic film 93 are sequentially laminated from the substrate 9 1 side. Gate wiring 94 such as 150469.doc •17- 201133619

問極絕緣膜95例如由SiN 由Cr、Ta等高熔點金屬所構成 所構成。 半導體膜96例如由非晶石夕 構成。半導體膜96包括基板 91側之臈部分9以與金屬膜9 盔去换灿▲ 』< 腰〇Ρ分96b。膜部分96a 為未掺雜有雜質之非摻雜非 雜質刑&曰 夕分96b為摻雜有P等 '士非曰曰石夕。半導體膜96之厚度例如為2〇〇nm〜300 :工。η型非晶石夕96b之膜厚例如為⑼⑽〜⑽⑽左 右0 金屬膜97成為TFT之信號配線。金屬膜97例如由mi 等金屬所構成。有機膜93包含光阻劑。以有機彭3為遮罩 對金屬膜97之與通道料相對叙部分進行㈣。藉此， 通道部分之η型非晶矽膜96b露出。於第2實施形態中，上 述通道部分之n型非晶石夕膜96b成為姓刻對象之含有石夕之 膜。. 於電漿蝕刻裝置丨之蝕刻氣體供給系統3中，將含有 CF4(氟系原料）、〇2、&之蝕刻原料氣體導入至放電空間 中使其電水化，生成钮刻氣體。將上述触刻原料氣體之 各成分之體積含有率較好的是設為CL為2〇%〜8〇%，A為 7°/〇〜60°/。’ 〇2為5。/。〜60%，更好的是設為€卩4為40%〜80%， A為7%〜40%，Ο!為5%~40%。可將eh與沁及〇2之總計之 體積流量比設為。？4:(]^2+〇2)=30:70〜80:20，較好的是設為 CF4:(N2 + 〇2)=50:50〜80:20，可將N2與02之體積流量比設為 N2:〇2 = 1〇:9〇~90:10。被處理物90之設定溫度較好的是設為 超過50°C且l〇〇°C以下，更好的是設為60t〜80。(：。 150469.doc •18· 201133619 a蝕刻原料氣體中幾乎或完全不含水（h2〇)。因此’蝕刻 亂體中幾乎或完全不含HF及水（Ha)。將該蝕刻氣體噴附 至被處理物90A上。蝕刻氣體與n型非晶矽膜961^之露出部 刀接觸。藉此，引起構成膜96b之非晶矽之蝕刻反應（式 3式24 '式41、式32、式33)。如圖2之雙點劃線所示， 於蝕刻深度到達n型非晶矽膜96b與非摻雜非晶矽膜96a之 邊界附近時，彳τ止蝕刻。藉此，可對通道部分之η型非晶 矽膜96b進行蝕刻’且可留置非摻雜非晶矽膜96a。 蝕刻非晶矽膜96b時之被處理物9〇A之溫度較好的是設為 超過5〇 C且loot以下，更好的是調節為6〇t：〜川它。藉 此，可提高非晶矽之蝕刻速率（參照實施例8及圖7)。且可 防止有機膜93發生熱變性。 稭由將被處理物90A之溫度及蝕刻原料氣體之各成分之 流量比設定為上述對於非晶矽之合適的範圍，可增大非晶 矽對於SiN之選擇比。因此，於通道蝕刻時可抑制對siN膜 95進行蝕刻。 蝕刻氣體中幾乎或完全不含HF& H2〇 ,因此可避免氟經 離子化而浸透至有機膜93中’可避免有機膜93之界面密著 力下降。因此，可防止有機膜93之隆起及剝離，可維持有 機膜93與金屬膜97之密著狀態。進而，可避免金屬膜97藉 由HF而溶解（蝕刻）。藉此，可形成良好之通道部分。 本發明並不限定於上述實施形態，只要不變更發明之主 旨則可實施各種改變。 例如’有機膜93亦可構成被處理物90之基材91。 150469.doc 201133619 亦可藉由使被處理物9G之周邊之環境氣體乾燥，而抑制 或防止％ i兄氣體中之水分吸附於被處理物列。 圖1所示之電隸刻裝置！為被處理物90配置於電極間空 間23之外側之所謂遙距式電聚處理裝置，亦可為被處理: 魏置於電極間空間23之㈣，電渡直接照射至被處理物 90上之所謂直接式電漿處理裝置。 [實施例1 ] 以下’說明實施例。本發明並不限定於以下實施例。 實施例i中’將CF4、氧(〇2)、氮(N2)之混合氣體作為蚀 刻原料氣體，研究氮切膜之㈣速率。银刻原料氣體之 各成分之流量如下所示：The gate insulating film 95 is made of, for example, SiN composed of a high melting point metal such as Cr or Ta. The semiconductor film 96 is composed of, for example, an amorphous stone. The semiconductor film 96 includes a meandering portion 9 on the side of the substrate 91 to be exchanged with the metal film 9 』 』 < lumbosacral portion 96b. The film portion 96a is a non-doped non-impurity impurity which is not doped with impurities, and is not doped with P et al. The thickness of the semiconductor film 96 is, for example, 2 〇〇 nm to 300: work. The film thickness of the n-type amorphous slab 96b is, for example, (9) (10) to (10) (10). The left metal film 97 serves as a signal wiring of the TFT. The metal film 97 is made of, for example, a metal such as mi. The organic film 93 contains a photoresist. The organic film 3 is used as a mask to perform a cross-section on the metal film 97 and the channel material (4). Thereby, the n-type amorphous germanium film 96b of the channel portion is exposed. In the second embodiment, the n-type amorphous stone film 96b of the channel portion is a film containing the stone of the surname. In the etching gas supply system 3 of the plasma etching apparatus, an etching raw material gas containing CF4 (fluorine-based raw material), ruthenium 2, and & is introduced into a discharge space to be electrolyzed to generate a button gas. The volume content of each component of the above-mentioned etchant material gas is preferably set to CL of 2% by weight to 8% by weight, and A is 7 ° / 〇 to 60 ° /. ’ 〇 2 is 5. /. ~60%, better is set to €4 for 40%~80%, A for 7%~40%, Ο! for 5%~40%. The volumetric flow ratio of the total of eh to 沁 and 〇2 can be set. ? 4: (] ^ 2+ 〇 2) = 30: 70 ~ 80: 20, preferably set to CF4: (N2 + 〇 2) = 50: 50 ~ 80: 20, the volume flow of N2 and 02 The ratio is set to N2: 〇2 = 1〇: 9〇~90:10. The set temperature of the workpiece 90 is preferably more than 50 ° C and not more than 10 ° C, more preferably 60 t to 80. (: 150469.doc •18·201133619 a The etching raw material gas is almost or completely free of water (h2〇). Therefore, 'the etching body is almost or completely free of HF and water (Ha). The etching gas is sprayed to On the object to be processed 90A, the etching gas is brought into contact with the exposed portion of the n-type amorphous germanium film 961, thereby causing an etching reaction of the amorphous germanium constituting the film 96b (Expression 4, Equation 24, Formula 32, Formula 33) As shown by the alternate long and two short dashes line in Fig. 2, when the etching depth reaches the vicinity of the boundary between the n-type amorphous germanium film 96b and the non-doped amorphous germanium film 96a, the 彳τ is etched. Part of the n-type amorphous germanium film 96b is etched' and the undoped amorphous germanium film 96a may be left. The temperature of the object to be treated 9A when the amorphous germanium film 96b is etched is preferably set to exceed 5 〇C. Further, it is adjusted to 6 〇t: 〜 川. It is possible to increase the etching rate of the amorphous ruthenium (see Example 8 and Fig. 7) and prevent the organic film 93 from being thermally denatured. By setting the flow rate ratio of the temperature of the workpiece 90A and the components of the etching source gas to the above-mentioned suitable range for the amorphous crucible, it is possible to increase The ratio of amorphous germanium to SiN is selected. Therefore, etching of the siN film 95 can be suppressed during channel etching. The etching gas contains almost no or completely no HF & H 2 , so that fluorine can be prevented from permeating to the organic film 93 by ionization. In the middle, the adhesion of the organic film 93 can be prevented from decreasing. Therefore, the embossing and peeling of the organic film 93 can be prevented, and the adhesion between the organic film 93 and the metal film 97 can be maintained. Further, the metal film 97 can be prevented from being HF by HF. Dissolving (etching), a good channel portion can be formed. The present invention is not limited to the above embodiment, and various modifications can be made without changing the gist of the invention. For example, the organic film 93 can also constitute the object to be processed 90. Substrate 91. 150469.doc 201133619 It is also possible to suppress or prevent moisture in the gas of the % i brother from being adsorbed to the object to be treated by drying the ambient gas around the object to be treated 9G. The so-called remote type electropolymerization processing apparatus in which the workpiece 90 is disposed on the outer side of the interelectrode space 23 may be processed: (4) placed in the interelectrode space 23, and the electric light is directly irradiated to the object to be processed 9 The direct plasma processing apparatus of 0. [Example 1] The following is a description of the examples. The present invention is not limited to the following examples. In Example i, 'CF4, oxygen (〇2), nitrogen (N2) The mixed gas is used as an etching source gas to study the rate of the nitrogen film. The flow rate of each component of the silver-cut material gas is as follows:

CF4 : 0.2 SLMCF4 : 0.2 SLM

〇2 ： 0.2 SLM〇 2 : 0.2 SLM

N2 · 0.4 SLM 因此，蝕刻原料氣體之各成分之含有率係CF4為2 V01% ’ 〇2為25 V〇1% ’ N2為50 v〇1%。飿刻原料氣體之露黑 溫度為-45。(：以下，蝕刻原料氣體之含水量實質上為零 [生成步驟] 藉由電漿生成部20於大氣壓下將上述蝕刻原料氣體 (CF4+〇2+N2)電漿化，生成蝕刻氣體。電漿生成部2〇之電 漿放電條件如下所述： 電極間空間2 3之厚度：1 m m 40 kHz，脈衝 電極21、21間之施加電壓：γρρ= 13 kV， 150469.doc -20· 201133619 噴出喷嘴24之開口寬度（與圖1之紙面正交之方向之尺 寸）為 100 mm。 [餘刻反應步驟] 將於5 cm見方之玻璃基材91上覆膜有氮化矽膜92之被處 理物90放置於平台2上，使之移動至喷出部24之下方後， 於靜止之狀態（固定處理方法）下，自喷出部24喷附上述蝕 刻氣體。處理時間為1分鐘。被處理物9 〇之溫度為室溫。 如圖3所示’測定氮化矽膜之蝕刻速率，結果為280 nm/min。為於半導體裝置或液晶顯示裝置之製造步驟中可 充分實用之蝕刻速率。 [比較例1 -1 ] 作為比較例，將混合有Cf4、氧（〇2)、氬（Ar)之蝕刻原料 氣體於與實施例1相同之電漿處理條件下電漿化，且以與 實施例1相同之固定處理方法、處理時間、溫度條件對與 實施例1相同構造之被處理物9〇進行蝕刻反應步驟。蝕刻 原料氣體之各成分之流量如下所述··N2 · 0.4 SLM Therefore, the content ratio of each component of the etching source gas is CF 4 of 2 V01% ' 〇 2 is 25 V 〇 1% ' N 2 is 50 v 〇 1%. The blackening temperature of the raw material gas is -45. (The following is the case where the water content of the etching source gas is substantially zero. [Production step] The etching source gas (CF4 + 〇 2+ N2) is plasma-formed by the plasma generating unit 20 under atmospheric pressure to generate an etching gas. The plasma discharge conditions of the generating portion 2 are as follows: Thickness of the space between the electrodes 2 3: 1 mm 40 kHz, applied voltage between the pulse electrodes 21, 21: γρρ = 13 kV, 150469.doc -20· 201133619 ejection nozzle The opening width of 24 (the dimension in the direction orthogonal to the plane of the paper of Fig. 1) is 100 mm. [Residual reaction step] The processed object of the tantalum nitride film 92 is coated on the glass substrate 91 of 5 cm square. After the 90 is placed on the stage 2 and moved to the lower side of the discharge portion 24, the etching gas is sprayed from the discharge portion 24 in a stationary state (fixed processing method). The processing time is 1 minute. 9 The temperature of the crucible is room temperature. As shown in Fig. 3, the etching rate of the tantalum nitride film is measured, and the result is 280 nm/min, which is a practically applicable etching rate in the manufacturing steps of a semiconductor device or a liquid crystal display device. Comparative Example 1-1] As a comparative example, Cf4 was mixed. The etching source gas of oxygen (〇2) and argon (Ar) was plasma-formed under the same plasma treatment conditions as in Example 1, and the same treatment method, treatment time, and temperature conditions as in Example 1 were carried out. In the same manner, the workpiece 9 of the same structure was subjected to an etching reaction step. The flow rate of each component of the etching source gas was as follows.

Cp4 : 0.2 SLMCp4 : 0.2 SLM

°2 : 0.2 SLM°2 : 0.2 SLM

Ar : 0.4 SLMAr : 0.4 SLM

[比較例1-2] 作為其他比較例’於蝕刻氣體中進一步添加臭氧（〇3)。 六、氧係以氧（〇2)為原料藉由臭氧發生器而生成。來自臭氧 叙生益之輸出氣體（〇2 + 〇3)之流量為0.2 SLM，其臭氧濃度 為〇 。另外，將與上述比較例1 _ 1相同組成之姓刻原 150469.doc 21 201133619 料氣體(CF4 . 〇·2 SLM ’ 〇2 : 0.2 SLM，Ar : 0_4 SLM)於與 貫 Η相同之電聚處理條件下藉由電漿生成部20而電漿 化 < 繼而’將來自電激生成部20之氣體與來自臭氧發生器 之狀體（〇2+〇3)混合’將該混合氣體喷附於被處理物90 上’以與實施例1相同之固定處理方法、處理時間、溫度 條件對與實％例i相同構造之被處理物9〇進行飯刻反應步 驟。 、圖3係將實施例1及上述2個比較例W、i-2之㈣速率[Comparative Example 1-2] As another comparative example, ozone (〇3) was further added to the etching gas. 6. Oxygen is produced by using an ozone generator using oxygen (〇2) as a raw material. The flow rate of the output gas (〇2 + 〇3) from Ozone is 2.2 SLM and its ozone concentration is 〇. In addition, the same composition as the above Comparative Example 1 _ 1 was originally engraved 150469.doc 21 201133619 material gas (CF4 . 〇 · 2 SLM ' 〇 2 : 0.2 SLM, Ar : 0_4 SLM) in the same electropolymerization as the cross The plasma is generated by the plasma generating unit 20 under the processing conditions < and then 'mixing the gas from the electric generating unit 20 with the object from the ozone generator (〇2+〇3)' to squirt the mixed gas The workpiece 9 was subjected to a rice-meal reaction step in the same manner as in Example 1 except that the same treatment method, treatment time, and temperature conditions as in Example 1 were carried out. Figure 3 shows the rate of (IV) of Example 1 and the above two comparative examples W and i-2.

進仃比較者。根據實施例i，可獲得相對於比較例Μ、W 而為約25倍高之高速触刻速率。確認到與經由比較例卜2 之利用臭乳之氧化作用相比，經由實施例！之利用氧化氛 (N〇X)之氧化作用者㈣刻速率之提昇^十分明顯。 [實施例2] 於實施例2中，如下所示 、 伏·做刻原枓軋體中之CF4及〇2 之流量為固定，改轡n 曰 玄έ 支氮之机置，研究氮化矽膜之蝕刻速 率。蝕刻原料氣體之各成分之流量如下所述：Enter the comparator. According to the embodiment i, a high-speed etch rate of about 25 times higher than that of the comparative example Μ, W can be obtained. It was confirmed that it was compared with the oxidation by the use of the scented milk by the comparative example 2, via the examples! The use of the oxidizing atmosphere (N〇X) of the oxidation effect (four) the rate of increase ^ is very obvious. [Example 2] In Example 2, as shown below, the flow rates of CF4 and 〇2 in the original ruthenium rolling body were fixed, and the niobium of n 曰 έ έ , , , , , , , The etching rate of the film. The flow rate of each component of the etching source gas is as follows:

CF4 : 0.2 SLMCF4 : 0.2 SLM

〇2 : 〇.2 SLM〇 2 : 〇.2 SLM

n2 : °~1.5 SLM 即，將蝕刻原料氣體（CF4+〇2+n 或奶1Λ ,〇 2)之各成分之含有率於 CF4為約 10 νο〗％〜5〇 ν〇ι% n .. Qn 丨 V〇I〇/〇〜50 vol%，N2為 〇〜約80 vol%之範圍内谁 …… 麵到原料氣體中之⑽ 氧之體積流罝比為CFV 〇 =丨.7 Λ AST ΐλ ir & 2 ·。刻原料氣體之露點溫度 CT，韻刻原料氣體之含水量實質上為零。 I50469.doc •22- 201133619 [生成步驟] 藉由電漿生成部20於大氣壓下將上述蝕刻原料氣體電漿 化，生成蝕刻氣體。電漿生成部2〇之電漿放電條件如下所 述： 電極間空間23之厚度：1 mm 電極21、21間之施加電壓：Vpp = 13 kV ’ 40 kHz，脈 衝波 噴出喷嘴24之開口寬度（與圖丨之紙面正交之方向之尺 寸）為 100 mm。 [蝕刻反應步驟] 將於5 cm見方之玻璃基材91上覆膜有氮化矽膜92之被處 理物90放置於平台2上，—邊使其於噴出部之下方往復 通過複數次（掃描處理方法），一邊自喷出部Μ喷附上述蝕 刻氣體。被處理物9〇之搬送速度為4 m/min。被處理物9〇 之溫度為室溫。 將往復之單程移動作為丨次掃描，進行5〇次掃描。其 後，測疋氮化矽膜之蝕刻量，將其除以掃描次數（5〇次）， 算出每1次掃描之蝕刻速率。 將實施例2之結果示於圖4。 若將姓刻原肖氣體（CF4+〇2+N2)之各成&之含有率設為 CF^ 10 vol%〜4〇 v〇1%左右，ι〇 ν〇ι%〜4〇 ⑽。/❶左右， A為20 v〇U〜8〇 v〇p/。左右，則可獲得一定程度高之蝕刻 速率右°又為0卩4為1〇 v〇i%〜35 ν〇ι%左右，〇2為1〇 ν〇ι%〜 5 V〇l/〇左右，為30 vol%〜80 v〇l%左右，則可獲得較高 150469.doc •23 - 201133619 之姓刻速率。τ — 牛進而’於含氮率為40 vol。/。〜70 v〇l%左右之 範圍内可充分提高㈣彳速率。於含氮率為5G vol%〜60 v〇l%左右之範圍内可使蝕刻速率變為最大。 [實施例3] 於實施例3中，對包含有機膜93之被處理物9〇進行蝕刻 處理研九對有機膜93之影響^作為被處理物9〇，使用於 5 cm見方之玻璃基材91上積層有氮化矽膜％、有機膜μ之 樣本3有矽之膜92設為氮化矽膜，有機膜93設為丙浠酸 系樹脂膜。 敍刻原料氣體之各成分之流量如下所述：N2 : °~1.5 SLM That is, the content of each component of the etching source gas (CF4+〇2+n or milk 1Λ,〇2) is about 10 νο 〗 〖~5〇ν〇ι% n .. Qn丨V〇I〇/〇~50 vol%, N2 is 〇~about 80 vol% of the range... face to the raw material gas (10) The volumetric flow ratio of oxygen is CFV 〇=丨.7 Λ AST ΐλ ir & 2 ·. The dew point temperature of the raw material gas is CT, and the water content of the raw material gas is substantially zero. I50469.doc • 22-201133619 [Generation step] The etching source gas is plasma-formed by the plasma generating unit 20 under atmospheric pressure to generate an etching gas. The plasma discharge conditions of the plasma generating portion 2 are as follows: Thickness of the interelectrode space 23: 1 mm Applied voltage between the electrodes 21, 21: Vpp = 13 kV '40 kHz, the opening width of the pulse wave ejection nozzle 24 ( The dimension in the direction orthogonal to the plane of the paper is 100 mm. [Etase Reaction Step] The object to be treated 90 having the tantalum nitride film 92 coated on the glass substrate 91 of 5 cm square is placed on the stage 2, and is reciprocated several times under the ejection portion (scanning) In the treatment method, the etching gas is sprayed from the discharge portion. The conveyance speed of the workpiece was 9 m/min. The temperature of the treated material was 室温. The reciprocating one-way movement is performed as a one-time scan, and five times of scanning is performed. Thereafter, the etching amount of the tantalum nitride film was measured, and this was divided by the number of scans (5 times) to calculate the etching rate per one scan. The results of Example 2 are shown in Fig. 4. If the content of each of the original gas (CF4+〇2+N2) is set to CF^10 vol%~4〇 v〇1%, ι〇 ν〇ι%~4〇 (10). /❶, A is 20 v〇U~8〇 v〇p/. Left and right, a certain degree of high etching rate can be obtained. Right is 0卩4 is 1〇v〇i%~35 ν〇ι% or so, 〇2 is 1〇ν〇ι%~ 5 V〇l/〇 , from 30 vol% to 80 v〇l%, you can get a higher rate of 150469.doc •23 - 201133619. τ — cattle and then have a nitrogen content of 40 vol. /. The range of ~70 v〇l% can be fully increased (4) 彳 rate. The etching rate can be maximized within a range of from about 5 G vol% to about 60 v 〇 1%. [Example 3] In Example 3, the object to be treated 9 containing the organic film 93 was subjected to an etching treatment to effect the influence on the organic film 93. As the object to be treated 9, used for a glass substrate of 5 cm square. A film 92 having a tantalum nitride film % and a sample 3 of an organic film μ laminated on 91 is a tantalum nitride film, and the organic film 93 is a propionic acid resin film. The flow rate of each component of the raw material gas is as follows:

Cp4 : 0.2 SLMCp4 : 0.2 SLM

°2 : 0.2 SLM°2 : 0.2 SLM

n2 : 0.4 SLM 因此，蝕刻原料氣體之各成分之含有率係（：匕為25 02為25 vol%，乂為5〇 v〇1%。蝕刻原料氣體之露點 溫度為-45°C以下，蝕刻原料氣體之含水量實質上為零。 [生成步驟] 藉由電t生成部20於大氣壓下將上述蝕刻原料氣體 (CF4+〇2+N2)電漿化，生成钮刻氣體。電漿生成部2〇之電 漿放電條件如下所述： 電極間空間23之厚度：i mm 電極21、21間之施加電壓：Vpp=13 kV，4〇 kHz，脈 衝波 噴出喷嘴24之開口寬度（與圖1之紙面正交之方向之尺 150469.doc -24* 201133619 寸）為 1 00 mm。 [蝕刻反應步驟] 將覆膜有氮化矽膜之被處理物90放置於平台2上，使之 移動至喷出部24之下方後，於靜止之狀態（固定處理方法） 下，自喷出部24喷附上述蝕刻氣體。處理時間設為以下6 個。 處理時間：5秒、10秒、20秒、60秒、90秒、120秒 被處理物90之溫度設為以下3個。被處理物90之加熱係 隔著平台2而進行。N2 : 0.4 SLM Therefore, the content of each component of the etching source gas is (25 为 25 vol%, 乂 5 〇 v 〇 1%. The dew point temperature of the etching source gas is -45 ° C or less, etching The water content of the material gas is substantially zero. [Production Step] The etching source gas (CF4 + 〇 2+ N2) is plasma-formed by the electric t generating unit 20 at atmospheric pressure to generate a button gas. The plasma generating unit 2 The plasma discharge conditions of the crucible are as follows: Thickness of the interelectrode space 23: i mm The applied voltage between the electrodes 21, 21: Vpp = 13 kV, 4 kHz, the opening width of the pulse wave ejection nozzle 24 (Fig. 1 The ruler of the paper surface orthogonal direction 150469.doc -24* 201133619 inch) is 100 mm. [Etase reaction step] The object to be treated 90 having the tantalum nitride film is placed on the stage 2, and moved to the spray. After the lower portion 24, the etching gas is ejected from the ejecting portion 24 in a stationary state (fixed processing method). The processing time is set to six. Processing time: 5 seconds, 10 seconds, 20 seconds, 60 The temperature of the workpiece 90 in seconds, 90 seconds, and 120 seconds is set to the following three. The heating system of the workpiece 90 The platform 2 is carried out.

被處理物溫度：室溫（RT，Room Temperature)、50°C、 80°C 表1係總結各處理時間及各被處理物溫度下之有機膜93 之隆起及剝離狀況之檢查結果而得出者。 [表1] 蝕刻氣體照射時間 5秒 10秒 20秒 60秒 90秒 120秒 基 室溫 〇 〇 Δ X X X 板 50°C 〇 〇 〇 〇 Δ Δ 溫 度 80°C 〇 〇 〇 〇 〇 〇 〇：無有機膜之隆起及剝離 △:於一部分發生有機膜之隆起 x:發生有機膜之剝離 藉由使用HF及含水量實質上為零之蝕刻氣體，而即使 喷附時間為1 0秒左右，亦未發現有機膜之隆起及剝離。另 外，於使用在CF4中添加H20進行電漿化而生成之HF之蝕 150469.doc -25- 201133619 刻反應（式2、式3)中，即使h2〇之添加量以露點溫度計而 為0 C左右’亦自開始喷附含有HF之蝕刻氣體起數秒便發 生有機膜之隆起。 若至溫下處理時間變長’則大氣中之水分吸附於被處理 物90上之可能性變高，引起有機膜之隆起及剝離。然而， 確認到藉由加熱被處理物9〇，而即使處理時間變長，亦可 抑制或防止有機膜之隆起及剝離。 [實施例4] 於實施例4中’使蝕刻原料氣體（CF4 + 02+N2)之總流量及 A流量為固定，改變eh與A之流量比，研究氮化矽之蝕 刻速率。餘刻原料氣體之總流量為8 SLM。cf4與〇2之總 計流量為0.4 SLM(固定）。&之流量為〇.4 SLM(固定）。將 蝕刻原料氣體之各成分之含有率於CF4為約12 v〇1%〜約45 v〇l%，〇2為約 5 v〇l%〜約 38 vol%，n2為 5〇 v〇1%(固定）之範 圍内進行調節。CL與〇2之總計與A之體積流量比為 (CF4+〇2):N2 = 50:50。蝕刻原料氣體之露點溫度為_45r以 下’姓刻原料氣體之含水量實質上為零。 [生成步驟] 藉由電桌生成部20於大氣壓下將上述蝕刻原料氣體電漿 化，生成蝕刻氣體。電漿生成部2〇之電漿放電條件如下所 述： 電極間空間23之厚度：1 mm 電極21、21間之施加電壓：Vpp=13 kv，4〇 kHz，脈 衝波 150469.doc -26- 201133619 喷出噴嘴24之開口寬度（與圖1之紙面正交之方向之尺 寸）為 100 mm。 [蚀刻反應步驟] 將於5 cm見方之玻璃基材91上覆膜有氮化矽膜92之被處 理物90放置於平台2上，使之移動至喷出部24之下方後， 於靜止之狀態（固定處理方法）下，自喷出部24噴附上述蝕 刻氣體，測定蝕刻速率。處理時間為1分鐘。被處理物9〇 之溫度為室溫。 圖5係以CF4與〇2之流量比為橫軸對蝕刻速率之測定結果 進行表示者。於實施例4之所有流量比範圍内，可獲得一 定程度之姓刻速率。於相對於CF*與〇2之總計之〇2之比例 為25 vol%〜60 vol%之範圍内，可獲得較高之蝕刻速率。 進而於〇2之比例為40 vol%〜60 vol%之範圍内，可充分提 高蝕刻速率。即，於相對於蝕刻原料氣體之總流量而 為20 vol%〜38 v〇i%左右，〇2為12 v〇1%〜3〇 v〇1%左右之範 圍内，可獲得較南之蝕刻速率。進而，於相對於蝕刻原料 氣體之總流量而CF4*20 v〇l%〜30 v〇1%左右，〇2為2〇 vol%〜30 v〇1%左右之範圍内，可充分提高蝕刻速率/於〇2 較少之範圍及少之範圍内㈣速率變得較低。認為 其原因在於cof2、〇f2、〇2F2等含有氧之氟系、活性物質之 生成量減少。 [實施例5] 於實施例5中’將氮化石夕作為钱刻對象。準備於玻璃基 板91上覆膜有氮化矽之樣本9〇。樣本9〇之大小為別 150469.doc •27- 201133619 mmx50 mm。將該樣本90設置於電漿蚀刻裝置1之平台2 上，喷附蝕刻氣體。 樣本90之溫度為90°C。 蝕刻原料氣體之各成分之流量如下所述：Temperature of treated material: room temperature (RT, Room Temperature), 50 ° C, 80 ° C Table 1 summarizes the inspection results of the aging and peeling conditions of the organic film 93 at each treatment time and the temperature of each treated object. By. [Table 1] Etching gas irradiation time 5 sec 10 sec 20 sec 60 sec 90 sec 120 sec Base 〇〇 Δ XXX Plate 50 ° C 〇〇〇〇 Δ Δ Temperature 80 ° C 〇〇〇〇〇〇〇: None Uplift and peeling of the organic film Δ: ridge of the organic film occurs in part x: peeling of the organic film occurs by using HF and an etching gas having a water content of substantially zero, even if the spraying time is about 10 seconds, The bulging and peeling of the organic film were found. In addition, in the HF etch 150469.doc -25-201133619 reaction (Formula 2, Formula 3) generated by adding H20 to CF4 for plasma formation, even if the amount of h2〇 is 0 ° C with a dew point thermometer The left and right 'the ridges of the organic film also occur from the start of spraying the etching gas containing HF for several seconds. If the treatment time becomes longer when the temperature is lowered, the possibility that the moisture in the atmosphere is adsorbed on the object to be treated 90 becomes high, causing the bulging and peeling of the organic film. However, it was confirmed that by heating the object to be treated, even if the treatment time is long, the swelling and peeling of the organic film can be suppressed or prevented. [Example 4] In Example 4, the total flow rate of the etching source gas (CF4 + 02 + N2) and the A flow rate were fixed, and the flow ratio of eh to A was changed to investigate the etching rate of tantalum nitride. The total flow of the raw material gas is 8 SLM. The total flow of cf4 and 〇2 is 0.4 SLM (fixed). The traffic of & is S.4 SLM (fixed). The content of each component of the etching source gas is about 12 v〇1% to about 45 v〇l% in CF4, about 5 v〇l% to about 38 vol%, and n2 is 5〇v〇1%. Adjust within the range of (fixed). The ratio of the total flow of CL to 〇2 to the volume flow ratio of A is (CF4 + 〇 2): N2 = 50:50. The dew point temperature of the etching source gas is _45r or less. The water content of the material gas is substantially zero. [Production Step] The electricity source generating unit 20 plasmas the etching raw material gas under atmospheric pressure to generate an etching gas. The plasma discharge conditions of the plasma generating portion 2 are as follows: Thickness of the interelectrode space 23: 1 mm Applied voltage between the electrodes 21, 21: Vpp = 13 kv, 4 kHz, pulse wave 150469.doc -26- 201133619 The opening width of the discharge nozzle 24 (the dimension in the direction orthogonal to the plane of the paper of Fig. 1) is 100 mm. [Etution Reaction Step] The object to be treated 90 having the tantalum nitride film 92 coated on the glass substrate 91 of 5 cm square is placed on the stage 2, and moved to the lower side of the discharge portion 24, and then left still. In the state (fixed processing method), the etching gas was sprayed from the discharge portion 24, and the etching rate was measured. The processing time is 1 minute. The temperature of the treated material was 室温. Fig. 5 shows the measurement result of the etching rate on the horizontal axis by the flow ratio of CF4 to 〇2. Within the range of all flow ratios of Example 4, a certain degree of surname rate can be obtained. A higher etching rate can be obtained in the range of 25 vol% to 60 vol% with respect to the ratio of *2 of the total of CF* and 〇2. Further, in the range of 40 vol% to 60 vol% in the range of 〇2, the etching rate can be sufficiently increased. That is, it is about 20 vol% to 38 v〇i% with respect to the total flow rate of the etching source gas, and 〇2 is in the range of about 12 v〇1% to 3〇v〇1%, and a southerly etching can be obtained. rate. Further, the etching rate can be sufficiently increased in the range of about 4 〇 vol% to 30 v 〇 1% with respect to the total flow rate of the etching source gas, and CF4*20 v〇l% to 30 v 〇 1% or so. / Yu 〇 2 Less range and less (4) The rate becomes lower. The reason for this is considered to be that a fluorine-containing system containing oxygen such as cof2, 〇f2, or 〇2F2 has a reduced amount of active material produced. [Embodiment 5] In Example 5, the nitrite was used as a money engraving object. A sample of tantalum nitride 9 覆 was prepared on the glass substrate 91. The size of the sample 9〇 is 150469.doc •27- 201133619 mmx50 mm. The sample 90 is placed on the stage 2 of the plasma etching apparatus 1, and an etching gas is sprayed. Sample 90 has a temperature of 90 °C. The flow rate of each component of the etching source gas is as follows:

cf4 : 0.3 SLM 〇2 ·· 0.1 SLM n2 : 0.2 SLM 触刻原料氣體之露點溫度為-45°C以下，蝕刻原料氣體 之含水量實質上為零。 電漿生成部20之電漿放電條件如下所述： 電極間間隙23之厚度：1 mm 輸入電力：325 W(將直流130 V、2.5 A轉換為脈衝） 電極2i、2i間之施加電壓及頻率：Vpp=15 kv，4〇 kHz 喷出喷嘴24之開口寬度（與圖1之紙面正交之方向之尺 寸）為 100 mm。 蝕刻時間為60 sec ’於膜92未完全除去之階段停止蝕 刻。 藉由 XPS(X-ray photoelectron Spectroscopy，X射線光電 子光譜儀）對蝕刻處理前與處理後之樣本9〇之表面之組成 進行刀析。作為XPS，使用Krat〇s公司製造之型號 165 〇 將分析結果示於表2。 处里則之樣本之表面組成係氧為36 24%，氮為， + ;此處理後之樣本之表面組成係氧為M W%，氣為 150469.doc •28· 201133619 1.81%。 [表2]Cf4 : 0.3 SLM 〇 2 ·· 0.1 SLM n2 : 0.2 SLM The material temperature of the etched material gas is -45 ° C or lower, and the water content of the etching source gas is substantially zero. The plasma discharge conditions of the plasma generating portion 20 are as follows: Thickness between the interelectrode gaps 23: 1 mm Input power: 325 W (converts direct current 130 V, 2.5 A into pulses) Applied voltage and frequency between the electrodes 2i, 2i : Vpp = 15 kv, 4 kHz The opening width of the discharge nozzle 24 (the dimension in the direction orthogonal to the plane of the paper of Fig. 1) is 100 mm. The etching time was 60 sec' to stop etching at the stage where the film 92 was not completely removed. The composition of the surface of the sample before and after the etching treatment was subjected to knife analysis by XPS (X-ray photoelectron spectroscopy). As XPS, the model number 165 manufactured by Krat〇s was used. The analysis results are shown in Table 2. The surface composition of the sample is 36 24% oxygen, nitrogen is +, and the surface composition of the treated sample is M W%, and the gas is 150469.doc •28·201133619 1.81%. [Table 2]

Cls Ols —'-ίϋ-L Si2p FIs 處理前 9.10 36.24 ___2169 28.78 1.19 處理後 6.18 62.57 ------- 1.81 25.49 3.95 [%] 圖6係表示實施例5之樣本之處理前與處理後之χρ§光譜 之測定結果者。 處理前Si-N鍵之蜂值顯著出現，但處理後si-N鍵之峰值 幾乎沒有，取而代之’ Si-Ο鍵之峰值顯著出現。 根據以上結果可明確’蝕刻時引起氮化矽之氧化反應。 [實施例6 ] 於實施例6中，將氮化矽（SiNx)作為蝕刻對象，研究蝕 刻原料氣體（CF4 + 〇2+N2)之各成分之流量比與蝕刻速率之 關係。準備於玻璃基板91上覆膜有包含氮化矽之膜92之樣 本90。各樣本90之大小為50 mmX50 mm。將樣本90設置於 電漿蚀刻裝置1之平台2上’噴附蝕刻氣體。 以蝕刻原料氣體之總流量成為i SLM之方式將蝕刻原料 氣體之3種成分之流量如表3所示般相互調節。蝕刻原料氣 體之露點溫度為-45。(：以下，蝕刻原料氣體之含水量實質 上為零。 樣本90之設定溫度為i〇(rc。 電漿生成部20與樣本基板90之相對移動速度為1〇 mm/sec ° 電4生成部2 0之電聚條件如下所述： 150469.doc -29- 201133619 電極間間隙23之厚度：1 mm 輸入電力：325 W(將直流130 V、2.5 A轉換為脈衝） 電極21、21間之施加電壓及頻率：Vpp=15 w，4〇^ζ 噴出噴嘴24之開口寬、度（與圖丨之紙面正交之方向之尺 寸）為 100 mm。 將實施例6之蝕刻速率之測定結果示於表3。表3之蝕刻 速率係使樣本90相對於電漿生成部2〇而於圖i之左右方向 單程移動僅1次時之蝕刻量β [表3]Cls Ols —'-ίϋ-L Si2p FIs Before treatment 9.10 36.24 ___2169 28.78 1.19 After treatment 6.18 62.57 ------- 1.81 25.49 3.95 [%] Figure 6 shows the pre-treatment and post-treatment of the sample of Example 5. Χρ§ Spectrum measurement results. The bee value of the Si-N bond before the treatment occurred remarkably, but the peak of the si-N bond after the treatment was almost absent, and the peak of the 'Si-Ο bond was prominently changed. From the above results, it is clear that the oxidation reaction of tantalum nitride is caused during etching. [Example 6] In Example 6, the relationship between the flow ratio of each component of the etching source gas (CF4 + 〇 2+ N2) and the etching rate was investigated by using tantalum nitride (SiNx) as an object of etching. A sample 90 containing a film 92 of tantalum nitride is formed on the glass substrate 91. Each sample 90 has a size of 50 mm X 50 mm. The sample 90 is placed on the stage 2 of the plasma etching apparatus 1 to spray the etching gas. The flow rates of the three components of the etching raw material gas were adjusted as shown in Table 3 so that the total flow rate of the etching raw material gas became i SLM. The dew point temperature of the etching source gas is -45. (The following, the water content of the etching source gas is substantially zero. The set temperature of the sample 90 is i 〇 (rc. The relative moving speed of the plasma generating unit 20 and the sample substrate 90 is 1 〇 mm/sec ° The electropolymerization conditions of 20 are as follows: 150469.doc -29- 201133619 Thickness of interelectrode gap 23: 1 mm Input power: 325 W (converts direct current 130 V, 2.5 A into pulse) Application between electrodes 21, 21 Voltage and frequency: Vpp=15 w, 4〇^ζ The opening width and degree of the discharge nozzle 24 (the dimension in the direction orthogonal to the plane of the paper) are 100 mm. The measurement results of the etching rate of Example 6 are shown in Table 3. The etching rate of Table 3 is the etching amount β when the sample 90 is moved one-way with respect to the plasma generating portion 2 in the left-right direction of Fig. i [Table 3].

根據上述結果可確認，若將蝕 d席枓fL體中之CF4設為 7〜80體積％、N2設為7〜80體積％、 2 °又马5〜60體積％，則 可以一定程度之蝕刻速率蝕刻Si 進而，若將蝕刻原料 氣體中之〇2設為45體積％以下、 較好的疋3 0體積％以下、 更好的是20體積％以下，則可被仅a > J確保咼餘刻速率。 [實施例7] 150469.doc -30. 201133619 於實施例7中，將非晶石夕（a_si)作為钱刻對象，研究姓刻 原料氣體（CF4+〇2+N2)之各成分之流量比與㈣速率之關 係。準備於玻璃基板91上覆膜有包含非W之膜92之樣本 90。將樣本崎置於電㈣刻裝μ之平台2上喷附钱刻 氣體。其他處理條件與實施例6相同。 將實施例7之姓刻速率之測定結果示於表4。表4之姓刻 速率係使樣本9〇柄對於電漿生成部2〇而於圖i之左右方向 單程移動僅1次時之蝕刻量。 [表4]According to the above results, it was confirmed that the CF4 in the etched d 枓fL body is 7 to 80% by volume, N2 is 7 to 80% by volume, and 2° is 5 to 60% by volume, which can be etched to some extent. In the rate of etching Si, if the enthalpy 2 in the etching source gas is 45% by volume or less, preferably 3% by volume or less, more preferably 20% by volume or less, it is ensured by only a > J The rate of the moment. [Example 7] 150469.doc -30. 201133619 In Example 7, amorphous stone (a_si) was used as a money engraving object, and the flow ratio of each component of the raw material gas (CF4+〇2+N2) was studied. (4) The relationship between rates. A sample 90 containing a non-W film 92 is prepared on the glass substrate 91. The sample is placed on the electric (four) engraved μ platform 2 to squirt the gas. Other processing conditions were the same as in Example 6. The results of the measurement of the surname rate of Example 7 are shown in Table 4. The surname rate in Table 4 is the amount of etching when the sample 9 shank is moved to the plasma generating portion 2 in the left-right direction of Fig. i. [Table 4]

根據上述結果可確訪、，芒 〜右將蝕刻原料氣體中之CF4設为 謂體料、N2設為7〜8。體積％、〇2設為5〜6〇體積％，貝: 1,押疋3^度之姓刻速率触刻非晶碎。進而，若將触刻馬 料氣體中之CF4設為2〇體籍0/μ Χτ 體積/°以上、Ν2設為60體積％以下， 則可確保高蝕刻速率。谁According to the above results, it is confirmed that the CF4 in the etching raw material gas is set as the body material, and N2 is set to 7 to 8. The volume %, 〇 2 is set to 5 to 6 〇 vol%, and the shell: 1, the 疋 疋 3 ^ degree of the surname rate is engraved with amorphous. Further, when the CF4 in the etchant gas is set to 2 Å body volume 0/μ Χ volume/° or more and Ν 2 is 60 vol% or less, a high etching rate can be secured. Who

^ ^ 進而，右將蝕刻原料氣體中之CF 设為40體積％以上、Ν 為〇體積/0以下、〇2設為4〇體賴 150469.doc -31 - 201133619 %以下，則可確實獲得高蝕刻速率。 [實施例8] 於實施例8中，將非晶石夕（a_Si)作為敍刻對象。準備於玻 璃基板91上覆膜有包含非晶石夕之膜92之樣本列。樣本9〇之 大小為50 mmx50 mm。將該樣本9〇設置於電漿蝕刻裝置】 之平口 2上，喷附蝕刻氣體。藉由加熱器4而於3 〇亡〜1⑽π 之範圍内調節樣本90之溫度。 姓刻原料氣體之各成分之流量如下所述.·^ ^ Further, the CF in the etching source gas is set to 40% by volume or more, Ν is 〇 volume/0 or less, and 〇2 is set to 4 〇 赖 150469.doc -31 - 201133619 % or less, and the height can be surely obtained. Etching rate. [Example 8] In Example 8, amorphous australis (a_Si) was used as a target. A sample row containing a film of amorphous austenite 92 is prepared on the glass substrate 91. The sample size is 50 mm x 50 mm. The sample 9 was placed on the flat opening 2 of the plasma etching apparatus, and an etching gas was sprayed. The temperature of the sample 90 is adjusted by the heater 4 within a range of 3 〇 〜 1 (10) π. The flow rate of each component of the raw material gas is as follows.

CF4 : 0.2 SLMCF4 : 0.2 SLM

〇2 ·· 0.2 SLM〇2 ·· 0.2 SLM

N2 : 0.2 SLM 姓刻原料氣體之露點溫度為_45t以下，㈣原料氣體 之含水量實質上為零。 電梁生成部2 0之電毅放電條件如下所述： 電極間間隙23之厚度：1 mm 輸入電力：325 W(將直流130¥、2.5A轉換為脈衝） 電極21、21間之施加電壓及頻率：Vpp = 15 kv，4〇 kHz 喷出喷嘴24之開口寬度（與圖紙面正交之方向之尺 寸）為 100 mm。 圖7係表示各溫度條件下之蝕刻速率之測定結果者。 可確認即使於常溫附近（3(rc左右）亦可蝕刻非晶矽。 若超過50°C，則蝕刻速率大幅提昇。尤其K6〇t〜8(rc 之溫度範圍内可充分提高蝕刻速率。 即使於超過、1〇(TC下，亦可獲得充分之蝕刻速 150469.doc -32- 201133619 率。 因此於蝕刻對象之含有矽之膜92為非晶矽之情形時， 。的疋。於恤度δ周節步驟中將才皮處理物之溫度設為超過 5〇C 1〇〇C ’更好的是設為60°C〜80°C。 進而於任何溫度條件下均未確認到遮罩9 3之隆起 離。 [產業上之可利用性] 本發月例如可適用於液晶顯示裝置之偏光膜之製造或半 導體裝置之製造。 【圖式簡單說明】 圖1表不本發明之第丨實施形態，且係電漿蝕刻裝置之概 略構成圖； 圖2係表示本發明之第2實施形態之概略構成圖； 圖3係表示實施例1、比較例1-1、比較例1-2之钱刻速率 之測定結果之圖表； 圖4係表示實施例2中之相對於蝕刻原料氣體中之含氮率 之氮化矽膜之蝕刻速率的測定結果之圖表； 圖5係表示實施例4中之相對於蝕刻原料氣體中之與 氧之流量比之氮化矽膜之蝕刻速率的測定結果之圖表； 圖ό係表示實施例5中之氮化矽之處理前及處理後之表面 原子之分析結果之光譜圖；及 圖7係表示實施例8中之非晶矽之蝕刻速率之溫度依賴性 之測定結果之圖表。 【主要元件符號說明】 I50469.doc •33- 201133619 1 電漿蝕刻裝置 2 支持部 3 蝕刻氣體供給系統 4 溫度調節機構 10 蝕刻原料氣體供給系統 11 氟系原料供給部 12 氧供給部 13 氮供給部 20 電漿生成部 21 電極 22 電源 23 電極間之電漿空間 24 喷出喷嘴 90 > 90A 被處理物 91 基材 92 含有矽之膜 93 有機膜 94 閘極配線 95 閘極絕緣膜 96 非晶矽膜（含有矽之膜） 96a 非摻雜非晶矽膜 96b 摻雜有雜質之非晶矽膜 97 金屬膜 150469.doc -34-N2: 0.2 SLM The raw material gas has a dew point temperature of _45t or less, and (4) the water content of the material gas is substantially zero. The electric discharge condition of the electric beam generating portion 20 is as follows: Thickness of the interelectrode gap 23: 1 mm Input electric power: 325 W (converting direct current 130 ¥, 2.5 A into a pulse) The applied voltage between the electrodes 21 and 21 and Frequency: Vpp = 15 kv, 4 〇 The opening width of the discharge nozzle 24 (the dimension orthogonal to the plane of the drawing) is 100 mm. Fig. 7 is a graph showing the results of measurement of the etching rate under each temperature condition. It was confirmed that the amorphous yttrium can be etched even at around normal temperature (3 (around rc). If it exceeds 50 ° C, the etching rate is greatly improved. Especially in the temperature range of K6 〇 t 8 (r), the etching rate can be sufficiently increased. When the temperature exceeds 1 〇 (TC, a sufficient etching rate of 150469.doc -32-201133619 can also be obtained. Therefore, when the film 92 containing ruthenium is amorphous, the 疋 疋. In the δ-week step, the temperature of the rind treatment is set to be more than 5 〇C 1 〇〇C ', and it is more preferably 60 to 80 ° C. Further, no mask is confirmed at any temperature. [Industrial Applicability] This is applicable, for example, to the manufacture of a polarizing film of a liquid crystal display device or the manufacture of a semiconductor device. [FIG. 1 shows a third embodiment of the present invention. FIG. 2 is a schematic configuration diagram of a second embodiment of the present invention; FIG. 3 is a diagram showing the constitution of the first embodiment, the comparative example 1-1, and the comparative example 1-2. Graph of the measurement result of the rate; FIG. 4 shows the relative etching source in Example 2. FIG. 5 is a graph showing the etch rate of the tantalum nitride film in the ratio of the flow rate of oxygen to the etching source gas in Example 4; A graph showing the results of the measurement of the surface atoms before and after the treatment of the tantalum nitride in Example 5; and FIG. 7 shows the etching rate of the amorphous germanium in Example 8. Graph of measurement results of temperature dependence. [Description of main component symbols] I50469.doc • 33- 201133619 1 Plasma etching apparatus 2 Support part 3 Etching gas supply system 4 Temperature adjustment mechanism 10 Etching material gas supply system 11 Fluorine-based raw material Supply unit 12 Oxygen supply unit 13 Nitrogen supply unit 20 Plasma generating unit 21 Electrode 22 Power supply 23 Electrostatic space between electrodes 24 Ejection nozzle 90 > 90A Substance 91 Substrate 92 Membrane containing ruthenium 93 Organic film 94 Pole wiring 95 gate insulating film 96 amorphous germanium film (film containing germanium) 96a non-doped amorphous germanium film 96b amorphous germanium film doped with impurities 97 metal film 150469.doc -34-

Claims (1)

201133619 七、申請專利範圍： ^•-種含有石夕之膜之钱刻方法，其係對包含可藉由氧化氮 (職）氧化之含有⑪之収有_之被處理物中之上述 ， a有矽之膜進仃蝕刻者，該蝕刻方法之特徵在於包含： 生成^驟其係將實質上不含氫原子之#刻原料氣體 導入至接近大氣壓之電漿空間中，生成钮刻氣體；及 蝕刻反應步驟’其係使上述韻刻氣體接觸上述被處理 物； 上述姓刻原料氣體含有7〜晴積％之不含氫原子之氣 系原料、7〜80體積％之氮（N2)、5〜6〇體積％之氧⑴2)。 2·如請求们之蝕刻方法’其十上述蝕刻原料氣體含有“ 體積％以下之氧。 3.如請求们之钮刻方法，其中上述姓刻原料氣體含有儿 體積％以下之氧。 4·如請求们之㈣方法，其中上述氟系原料及氧之總計 與氮之體積流量比為70:30〜20:80，且上述氟系原料與氧 之體積流量比為75:25〜40:60。 5_ :請求項4之姓刻方法，其中上述姓刻原料氣體之上述 '、原料及氧之總計與氮之體積流量比為6m。 6·=求項4之㈣方法’其中上述飯刻原料氣體之上述 #二原料及氧之總計與氮之體積流量比為50:50〜4〇:6〇。 ，糸項4之蝕刻方法’其中上述蝕刻原料氣體之上述 乳系原料與氧之體積流量比為60:40〜40:60。 青长項1之蝕刻方法，其中上述蝕刻原料氣體含有2〇 150469.doc 201133619 體積/〇以上之上述氟系原料、6〇體積〇/〇以下之氣。 9·如請求項8之蝕刻方法，直中上诚名 。 八甲上述蝕刻原料氣體含有40 積％以上之上述氟系原料、4〇體積％以下之氮、體 積％以下之氧。 10.如請求項!之蝕刻方法，其中上述含有矽之膜包含矽 (=、氮切（SiNx)、碳化邦⑹、氮氧切（si〇N)、 碳氧化矽（SiOC)、碳氮化矽（SiCN)之任—種。 11·如請求項1至7中任一項之触刻方法，其中上述含有石夕之 膜包含氮化矽（SiNx)。 12·如請求項丨、8或9之蝕刻方法，其中上述含有矽之膜包 含非晶碎。 13. 如請求項1至10中任一項之蝕刻方法’其進而包含將上 述被處理物之溫度設為^。(:〜丨⑼它之溫度調節步驟。 14. 如請求項12之蝕刻方法，其中將上述被處理物之溫度設 為超過50°C〜lOOt：。 15. 如請求項I2之蝕刻方法，其中將上述被處理物之溫度設 為 6〇t：〜8〇t：。 16.如請求項12之蝕刻方法’其中上述被處理物包括依序積 層之包含非晶石夕之上述含有矽之膜、金屬膜及上述有機 膜’於上述含有矽之膜之上述金屬膜侧之膜部分中推雜 有雜質’藉由上述蝕刻氣體對上述膜部分進行叙刻。 150469.doc201133619 VII. Scope of application for patents: ^•- A method for engraving a film containing Shi Xi, which is the above-mentioned object containing a substance containing 11 which can be oxidized by nitric oxide. The etching method is characterized in that: the etching method comprises: generating a material gas which is substantially free of hydrogen atoms and introducing it into a plasma space close to atmospheric pressure to generate a button gas; The etching reaction step 'contacts the rhyme gas with the object to be treated; the raw material gas of the last name contains 7% to % of a gas-based raw material containing no hydrogen atom, and 7 to 80% by volume of nitrogen (N2), 5 ~ 6 〇 vol% of oxygen (1) 2). 2. The etching method of the requester's tenth etching raw material gas contains "% by volume or less of oxygen. 3. As claimed in the button carving method, wherein the above-mentioned raw material gas contains oxygen below 5% by volume. The method of (4), wherein the ratio of the total volume of the fluorine-based raw material and oxygen to the volume flow of nitrogen is 70:30 to 20:80, and the volume flow ratio of the fluorine-based raw material to oxygen is 75:25 to 40:60. 5_ : The method of claim 4 of claim 4, wherein the ratio of the above-mentioned raw material gas to the raw material gas and the volumetric flow ratio of the total amount of the raw material and the oxygen to the nitrogen is 6 m. 6·=Requirement 4 (4) Method 'The above-mentioned rice cooking material gas The volume ratio of the total amount of the raw materials and oxygen to the volume of nitrogen is 50:50 to 4:6 〇. The etching method of the item 4, wherein the volume ratio of the above-mentioned emulsion raw material to the volume of oxygen of the etching raw material gas is The etching method of the cyan term 1 wherein the etching source gas contains 2 〇 150469.doc 201133619 vol/y of the above fluorine-based raw material, and 6 〇 volume 〇/〇 or less. · As claimed in item 8, the method of etching is straightforward. The etching raw material gas contains 40% by mole or more of the fluorine-based raw material, and 4% by volume or less of nitrogen or less by volume of oxygen. 10. The etching method according to claim 2, wherein the film containing ruthenium contains ruthenium (= Nitrogen cut (SiNx), carbonized state (6), oxynitride (si〇N), cerium oxycarbide (SiOC), bismuth carbonitride (SiCN). 11 · Any of claims 1 to 7 The method of etching, wherein the film containing the diarrhea comprises lanthanum nitride (SiNx). 12. The etching method of claim 丨, 8 or 9, wherein the film containing ruthenium comprises amorphous ruthenium. The etching method of any one of items 1 to 10, which further comprises the step of setting the temperature of the object to be treated to (.: 丨 (9) the temperature adjustment step. 14. The etching method of claim 12, wherein The temperature of the object to be treated is set to exceed 50 ° C to 100 t: 15. The etching method of claim 1 , wherein the temperature of the object to be treated is set to 6 〇 t: 〜 8 〇 t: 16. The etching method of 12 wherein the above-mentioned processed object comprises the above-mentioned laminated layer containing amorphous rock The film, the metal film, and the organic film 'in the film portion on the side of the metal film containing the ruthenium film are etched with impurities'. The film portion is etched by the etching gas. 150469.doc
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