409306 A7 B7 經濟部智慧財產局貝工消費合作社印製 五、發明説明（ 技術領域 本發明係有關於半導體裝置的製造領域等適用之乾蝕 刻方法，特別是有關於對氮化矽系材料層—邊確保很大的 選擇性一邊乾姓刻氧化;g夕系材料層之方法。 背景技術 近年隨著超大型積體電路，極大型積體電路等能看得 見那樣的半導體裝置之高積體化及高性能化之進展，絕緣 膜的乾蝕刻其中，強烈期望所達成之技術也不會犧牲高各 向異性、高速性、高選擇性、低損傷性、低污染性等諸要 求中的任一項。 氧化石夕系材料之乾蝕刻係使用習知的三氟甲烷混合氣 、四氟化碳/氫混合氣、四氟化碳/氧混合氣、六氟化二碳， 二氟甲院 昆合氣等的氟代烴系化合物作為組成的主體之蝕 刻氣體°此即’（a)包含於氟代烴系化合物的碳原子在氧 化梦系材料（以下’有稱為矽氧X ;典型的有χ=2)層的表面 生成原子間結合能量很大的碳-氧結合，有作為切斷或減 低梦-氧結合之作用’能生成;5夕氧χ層的主蝕刻種類之 碳氟X根式（典型的係χ=3) ’更且（C)藉控制蝕刻反應系之碳 /氟比（碳原子數與氟原子數之比）使碳化系聚合物的堆積 量最適合’也由於可達成對抗蝕劑保護層或頭道材料層之 高選擇性等之理由。 另外，此處所稱的頭道材料層主要的是指矽基片、聚 矽軻層、聚氧化膜等之矽系材料層。 氮化矽（以下，有稱為矽χ氮y ;典型的係x=3，y = 4)也 t .装 .IT;%. (請先閲讀背面乏注意事項再填寫本頁)409306 A7 B7 Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (Technical Field The present invention relates to dry etching methods applicable to the field of semiconductor device manufacturing and the like, and particularly to silicon nitride-based material layers— The method of engraving and oxidizing while ensuring a large selectivity is a material layer. Background Art In recent years, with such large integrated circuits, very large integrated circuits, and the like, such high-concentration semiconductor devices can be seen. In the advancement of high-performance and high-performance, dry etching of insulating films, it is strongly expected that the achieved technology will not sacrifice any of the requirements of high anisotropy, high speed, high selectivity, low damage, and low pollution. One. Dry etching of oxidized stone materials is based on the conventional trifluoromethane gas mixture, carbon tetrafluoride / hydrogen gas mixture, carbon tetrafluoride / oxygen gas mixture, dicarbon hexafluoride, and difluoromethane. Fluorinated hydrocarbon compounds such as Kunhe Gas are used as the main etching gas of the composition. This means that ((a) carbon atoms contained in fluorinated hydrocarbon compounds are oxidized in dream-type materials (hereinafter referred to as silicon oxide X; typical) Χ = 2) The surface of the layer generates a carbon-oxygen bond with large interatomic bonding energy, which can be used to cut or reduce the dream-oxygen bond. It can be generated; fluorocarbon X radical formula of the main etching type of the oxygen x layer Typical system χ = 3) 'Moreover, (C) The carbon / fluorine ratio (ratio of the number of carbon atoms to the number of fluorine atoms) of the etching reaction system is controlled to optimize the accumulation amount of the carbonized polymer. The reason for the high selectivity of the resist protection layer or the head material layer. In addition, the head material layer referred to here mainly refers to a silicon-based material layer such as a silicon substrate, a polysilicon layer, and a polyoxide film. Silicon nitride (hereinafter referred to as silicon x-nitrogen y; typical system x = 3, y = 4) also t. Installed. IT;%. (Please read the lack of attention on the back before filling in this page)
409306 A7 B7______ 五、發明説明（2 ) 適用於矽’裝置之一種絕緣膜材料。矽X氮y層的乾蝕刻也 是適用與矽氡X層之蝕刻同樣的氣體組成。但是’藉對矽 氧X層將離子、輔助反應作為主體之機構蝕刻，按照矽X氮 y層係使氟基作為主蝕刻種類之游離基反應機構蝕刻，蝕 刻速度也比妙氧X層快。 矽、裝置的製造步驟之中，有需要矽氧X層與矽X氮y 之間的高選擇钱刻步驟。再者，隨著裝置之微細化 '複雜 化、矽X氮y層為防止蝕刻損傷作為蝕刻停止層形成於種種 地方之事例在增加中，因此，產生有必要在砍X氮y層上高 選擇兹刻£夕氧X層。 具體上，譬如為降低過度蝕刻時之基月損傷在基片的 表面或介入薄的矽X氮y層’或形成具有所謂氡氮氧（矽氧χ 層/矽X氮y層/矽氧X層）構造之洗口絕緣膜，或在澆口電極 的表面層壓矽X氮y層時，該上面所施行的矽氧X層之蝕刻 非確實的停止在矽X氮y層之表面不可。 經濟部智慧財產局員工消費合作社印製 m n I I n ϋ I 私―i I 訂 c請先聞讀背面之注意事項再填寫本頁) 可是’層壓的不同材料之間的高選擇蝕刻一般在兩材 料層之原子間結合能量之值差異越大越容易。可是，梦氧 X層與碎X氛y層的情形’石夕-氧結合與；e夕-氮結合的原子間 結合能量之值由於比較接近’高選擇蝕刻就困難了。 最近，對氮化矽系材料層一邊維持高選擇性一邊蝕刻 氧化矽系材料層之方法有幾個建議7譬如，特開平6 275568 號公報係提供離子密度10”離子/立方公分以上之等離子在 可能生成的蝕刻裝置内，生成一般式碳乂氧7(但是，χ，y 係自然數，滿足ySx+2之關係^ )表示的氟化烴系化合物 本纸^通用十國國家梂準（〇«)八4说格（210><297公釐)' ------ 409306 A7 ________Β7 五、發明説明（3 ) 作為主體之蝕刻氣體的等離子體，將形成於矽^氮丫系材料 層上面之矽氧X系材料層選擇性的蝕刻之方法。 特開平8-31797號公報係提供在氮化矽系材料層上面 形成氧化矽系材料層之基月上，當選擇性地蝕刻該氧化石夕 系材料層時’施行實際上只將前述氧化矽系材料層蝕刻之 精確蝕刻步驟，係將八氟環丁烷那樣的氟代烴系化合物作 為主體使用的蝕刻氣體之乾蝕刻，蝕刻前述氧化矽系材料 層之殘餘部份之過度蝕刻步驟係使用包含前述氟代烴系化 合物與含有氮之有機矽化合物之蝕刻氣體施行乾蝕刻之方 法。 依上述建議之技術’氧化矽系材料與氧化矽系材料之 選擇性蝕刻具有高選擇比及優越的面内均一性變成可能作 乾蝕刻。可是，在基片的平坦部雖可確保高的選擇比，但 在隅角部選擇比的水平是相當的低，選擇比的面内並不均 一报難說能令人充份的滿意》 發明之宣告 經濟部智慧財產局員工消費合作社印製 11 L^111 11L. (I (請先閲讀背面之注$項再填寫本頁} 本發明之目的係提供在氮化梦系材料上面形成氧化矽 系材層構成的基片上乾钱刻該氧化石夕系材料之方法，可顯 著的提高選擇性，且能充份降低選擇比面内不均一之一種 方法。 發明家們係使用種種含有氟之化合物重覆蝕刻的結果 ，作為蝕刻氣體使用八氟環戊烯、全氟（代）環烯烴，且全 氟（代）環烯烴中具有氣原子的不純物之含有量極度的抑低 ’發現有效的能達成上述目的，至完成本發明。 本紙張尺度適用中國國家標準（CNS } A4規格（210X297公釐） 广 -6 經濟部智慧財產局員工消費合作社印製 409306 A7 B7五、發明説明（4 ) 於是，依本發明，在氮化矽系材料層上面形成氧化矽 系材料層之基片上選擇性乾蝕刻該氟化矽系材料層之方法 其中， 其特徵在於提供一種使用具有氣原子不純物的含有量在 1,000百萬分率以下之全氟（代）環烯烴作為蝕刻氣體之選 擇性乾蝕刻方法。 為實施發明之較佳的形態 本發明其中所使用含全氟（代）環烯烴之乾蝕刻用氣體 係乾蝕刻其中，只要藉等離子體可發生氟基就可，全氟（ 代）環烯烴之碳數雖沒有特別的限定，通常3〜8，較理想 的係4〜6，最理想的係5。 作為全氟（代）環烯烴之具體例，可舉出全氟（代）環丙 烯；全氟（代）環丁烯，全氟（代）環戊烯，全氟（代）環己烯 ，全氟（代）環庚烯，全氟（代）環辛烯，全氟（代）-1-曱基環 丁烯，全氟（代）-3-f基環丁烯，全氟（代）-1-甲基環戊烯， 全氟（代）-3-甲基環戍烯等。其中，全氟（代）環丁烯*全氤 (代）環戊烯，全氟（代）環己烯，全氟（代）環丁烯，全氟（代） 環戊烯，全氟（代）-3-甲基環丁烯，全氟（代）-1-甲基環戊烯 ，全氟（代）-3-甲基環戊烯等較為理想，全氟（代）環戊烯最 為理想。 全氟（代）環烯烴類通常將對應之含氣的環狀碳氫化合 物作為原料藉氟化作用反應製造。譬如，八氣環戊烯作為 原料之有機溶媒中，與氟化鉀反應製造。理所當然的在反 應生成物中混有氟化反應完全未進行之反應中間體或副生 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） _ 7 _ (請先聞锛背面之注意事項再填寫本頁) 409306 a7 B7 五、發明説明（5 ) 物，雖也依反應條件及反應終了後之精製條件，但作為目 的之八氣環戊烯係隨著具有氮原子的各種化合物作為不純 物*作為代表性的含有氣原子化合物之例，可列舉出氣 -2,3,3,4,4,5,5-七氣環戊稀，1-3-二氯-2,3,4,4,5,5-六氟1環戊 烯，1-3,4-三氣-2,3,4,5,5-五氟環戊烯，1 —氣_1，2,2,3,3,4,4,5,5 -九氟（代）環戊烷，1，4-二氣-2,3,3,4,5,5-六氟環戊烯及14,4-三氣-2,3,3,5,5-五氟環戊烯等。 本發明其中’其特徵在於使用全氟（代）環烯烴作為蝕 刻氣體及包含於該全氟（代）環烯烴具有氣原子之不純物濃 度抑制在1000百萬分率以下這些點*藉滿足這樣的要件， 在氮化矽系材料層上面形成氡化矽系材料層構成的基片上 能具有高選擇性的蝕刻。 具有氣原子之不純物的濃度非在1000百萬分率以下不 可’期望盡可能降低。其濃度理想的係1 〇〇百萬分率以下 ，要理想的係10百萬分率以下，最理想的係百萬分之1以 下。 具有氣原子之不純物之不純物，通常藉利用與全I ( 代）環烯烴類之沸點差之蒸餾由全氟（代）環烯烴類除去。 理想的係將氟化作用反應生成物以水洗淨並乾燥後，在常 壓下惰性氣體環境下施行蒸餾。全氟（代）環烯烴中含有氯 原子之不純物的含有量藉氣相色譜法分析能測定。 依希望，在由全氟（代）環烯烴所構成之蝕刻氣體，作 為乾蝕刻用氣體’可以應用含有一般所使用之種種的氣體 。作為那樣的氣體，譬如可舉出氧氣、氮氣、氬氣、氫氣 本紙張尺度適用中國國家梂準（CNS > A4規格（210X297公釐） I---------.''^-- (請先閱謓背面之注意事項再填寫本頁)409306 A7 B7______ 5. Description of the invention (2) An insulating film material suitable for silicon ’devices. The dry etching of the silicon X nitrogen y layer is also applicable to the same gas composition as the etching of the silicon X layer. However, by using the silicon-oxygen X layer to etch ions and auxiliary reactions as the main mechanism, the fluorine-based free radical reaction mechanism is used to etch in accordance with the silicon X-nitrogen y layer system, and the etching speed is also faster than that of the oxygen-X layer. Among the manufacturing steps of silicon and devices, there is a need for a high-selection engraving step between a silicon oxide X layer and a silicon X nitrogen y. In addition, as the device becomes more sophisticated, the number of cases where the silicon X-nitrogen y layer is formed as an etch stop layer to prevent etching damage is increasing. Therefore, it is necessary to select a high level of the X-nitrogen y layer. Here are the X layers. Specifically, for example, in order to reduce the damage of the base month during over-etching, a thin silicon X-nitrogen-y layer is interposed on the surface of the substrate, or a so-called nitrogen-oxygen layer (silicon-oxide x layer / silicon-X-nitrogen layer / silicon-oxide X) is formed. When the silicon X-nitrogen y layer is laminated on the surface of the gate electrode, the etching of the silicon-oxygen X layer may not stop on the surface of the silicon-nitrogen y layer. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, mn II n ϋ I Private ―i I Order c, please read the precautions on the back before filling out this page) However, the high choice of etched between different materials is generally between two The larger the difference in the value of the bonding energy between atoms in the material layer, the easier it is. However, in the case of the dream oxygen X layer and the broken X atmosphere y layer, the value of the inter-atomic bonding energy of the stone-oxygen bond and the nitrogen-nitrogen bond is relatively close to the high selective etching, which makes it difficult. Recently, there have been several suggestions on a method for etching a silicon oxide-based material layer while maintaining a high selectivity for the silicon nitride-based material layer. For example, Japanese Patent Application Laid-Open No. 6 275568 provides a plasma having an ion density of 10 ”ions / cm 3 or more. In the etching device that may be generated, a fluorinated hydrocarbon compound represented by the general formula carbohydrate 7 (however, χ, y are natural numbers and satisfy the relationship of ySx + 2 ^) ^ General ten countries' national standards (〇 «) Eight-four grid (210 > < 297 mm) '------ 409306 A7 ________B7 V. Description of the invention (3) The plasma of the etching gas as the main body will be formed in silicon ^ nitrogen-based materials A method for selective etching of a silicon oxide X-based material layer on a layer. Japanese Patent Laid-Open No. 8-31797 provides a method for forming a silicon oxide-based material layer on a silicon nitride-based material layer. In the case of the oxidized stone material layer, the precise etching step of actually etching only the aforementioned silicon oxide material layer is performed, which is dry etching and etching using an fluorinated hydrocarbon compound such as octafluorocyclobutane as a main body. The aforementioned silica-based material The over-etching step of the remaining portion of the material layer is a dry etching method using an etching gas containing the aforementioned fluorohydrocarbon-based compound and an organic silicon compound containing nitrogen. According to the above-mentioned recommended technique, 'silicon oxide-based materials and silicon oxide-based materials The selective etching has a high selection ratio and excellent in-plane uniformity, making dry etching possible. However, although a high selection ratio can be ensured in the flat portion of the substrate, the level of the selection ratio in the corner portion is quite low. The selection ratio is not uniform, and it is difficult to say that it can be fully satisfied. Announcement of invention Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 11 L ^ 111 11L. (I (Please read the note on the back side before Fill out this page} The object of the present invention is to provide a method for engraving the oxidized stone material on the substrate formed by forming a silicon oxide material layer on the nitrided dream material, which can significantly improve the selectivity and can sufficiently One method to reduce the non-uniformity of the selection ratio. The inventors repeated the etching using various fluorine-containing compounds, and used octafluorocyclopentene and perfluorinated (substituted) rings as the etching gas. Olefins, and the extremely low content of impure substances with gas atoms in perfluorinated (substituted) cyclic olefins was found to be effective in achieving the above-mentioned objectives, and to complete the present invention. This paper size applies the Chinese National Standard (CNS} A4 Specification ( 210X297mm) Canton-6 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 409306 A7 B7 V. Description of Invention (4) Thus, according to the present invention, a silicon oxide-based material layer is formed on a substrate on the silicon nitride-based material layer. The method for selectively dry-etching the fluorinated silicon-based material layer is characterized in that it provides a selective dry etching method using perfluoro (substituted) cycloolefin having an impurity content of gas atoms of 1,000 parts per million or less as an etching gas. Etching method. In order to implement the preferred form of the invention, the present invention uses a dry etching gas system for dry etching containing a perfluoro (substituted) cycloolefin. As long as a fluorine group can be generated by plasma, the perfluoro (substituted) cycloolefin can be used. Although the carbon number is not particularly limited, it is usually 3 to 8, more preferably 4 to 6, and most preferably 5. Specific examples of perfluoro (substituted) cycloolefins include perfluoro (substituted) cyclopropene; perfluoro (substituted) cyclobutene, perfluoro (substituted) cyclopentene, perfluoro (substituted) cyclohexene, Perfluoro (substituted) cycloheptene, perfluoro (substituted) cyclooctene, perfluoro (substituted) -1-fluorenylcyclobutene, perfluoro (substituted) -3-f-based cyclobutene, perfluoro (substituted ) -1-methylcyclopentene, perfluoro (substituted) -3-methylcyclopinene, etc. Among them, perfluoro (substituted) cyclobutene * perfluorinated (substituted) cyclopentene, perfluoro (substituted) cyclohexene, perfluoro (substituted) cyclobutene, perfluoro (substituted) cyclopentene, perfluoro (substituted) Substituted) -3-methylcyclobutene, perfluoro (substituted) -1-methylcyclopentene, perfluoro (substituted) -3-methylcyclopentene, etc. are more desirable, perfluoro (substituted) cyclopentene Most ideal. Perfluorinated (substituted) cyclic olefins are usually produced by fluorination using the corresponding gas-containing cyclic hydrocarbons as raw materials. For example, octa-cyclopentene is produced by reacting with potassium fluoride in an organic solvent. As a matter of course, the reaction product is mixed with reaction intermediates or byproducts that have not undergone the fluorination reaction at all. The paper size is Chinese National Standard (CNS) A4 (210X297 mm) _ 7 _ (Please first read the Note this page, please fill in this page again) 409306 a7 B7 V. Invention description (5) Although the reaction conditions and the purification conditions after the end of the reaction also depend on the purpose of the eight gas cyclopentene series with various compounds with nitrogen atoms Impurities * As examples of typical compounds containing gas atoms, gas-2,3,3,4,4,5,5-heptacyclocyclopentane, 1-3-dichloro-2,3,4 , 4,5,5-hexafluoro1cyclopentene, 1-3,4-trigas-2,3,4,5,5-pentafluorocyclopentene, 1-gas_1, 2, 2, 3 , 3,4,4,5,5 -Ninefluoro (substituted) cyclopentane, 1,4-digas-2,3,3,4,5,5-hexafluorocyclopentene and 14,4-tri Gas-2,3,3,5,5-pentafluorocyclopentene and so on. The present invention is characterized in that it uses perfluoro (substituted) cycloolefin as an etching gas and the concentration of impurities contained in the perfluoro (substituted) cycloolefin having gas atoms is suppressed to less than 1000 parts per million * by satisfying such points Essentially, a substrate made of a silicon nitride-based material layer formed on the silicon nitride-based material layer can be etched with high selectivity. It is desirable that the concentration of the impurities having gas atoms is not less than 1,000 parts per million, and it is desirable to reduce it as much as possible. The ideal concentration is less than 100 parts per million, the ideal concentration is less than 10 parts per million, and the most ideal part is less than 1 part per million. Impurities with gas atoms are usually removed from perfluorinated (cyclic) cycloolefins by distillation using a boiling point difference from that of all (substituted) cycloolefins. Ideally, the fluorination reaction product is washed with water and dried, and then distilled under an inert gas atmosphere at normal pressure. The content of impurities containing chlorine atoms in perfluorinated (cyclic) cycloolefins can be determined by gas chromatography analysis. It is desired that, as an etching gas composed of a perfluorinated (substituted) cyclic olefin, as a dry etching gas', a gas containing a variety of commonly used gases can be used. Examples of such gases include oxygen, nitrogen, argon, and hydrogen. This paper is sized to the Chinese National Standard (CNS > A4 (210X297 mm) I ---------. '' ^ -(Please read the notes on the back of 謓 before filling this page)
’IT 經濟部智慧財產局貝工消費合作社印製 40930δ Α7 --^ Β7 五、發明説明（6 ) 、-氧化碳、二氧化唉、氧化氮及氧化硫等。再者控制 钱刻氣體的氟與碳之原子比作為目的，可添加氩化氟代烴 系氣體作為像這樣的添加氣體，譬如，可列舉三氣化碳 氫氣-氟化碳_氫氣等。該等的添加氣想單獨使用也可 ，或组合2種以上使用也佳。添加氣體的量雖依㈣村料 波及氣趙的程度而有所不同，但通常以包含全氣（代）環稀 煙的乾蚀刻用氣趙100重量份為基準在4〇重量份以下，理 想的係2 5重量份以下。 本發明之乾蝕刻方法其中，作為蝕刻時照射的等離子 逋。應用產生離子/立方公分以上高密度領域者。特別 疋10〜10離子/立方公分程度之密度。越能發現高性 能，形成微細的結構上較理想。等離子體的密度過度的小 時，作為本發明之目的特別是高的蝕刻速度，高的氧化矽 系材料層的選擇性無法達成，而且由於沈澱生成聚合獏的 情況較多，並不理想β 經濟部智慧財產局員工消費合作社印製 藉習知所使用的並行平板型或磁控管型之反應性離子 蝕刻方式之乾蝕刻係一般不適於實現上述那樣的高密度領 域之等離子體。作為用以實現上述那樣高密度領域的等離 子體之方法可推薦螺旋狀波方式，高頻率感應方式，ECR( 電子回旋加速器共鳴）方式，TCP(變壓器耦合等離子體）方 式及ICP(感應耦合等離子體）方式。 本發明之乾蝕刻方法其中，在上述乾蝕刻用氣體及依 希望併用包含其他氣體的氣體組成物之蝕刻時的壓力沒有 必要選擇特別的範圍，一般係在真空脫氣之蝕刻裝置内導 本紙張尺度適用中國國家標丰（CNS ) A4说格（210X297公庚) Z --- 409S06 Α7 Β7 五、發明説明（7 ) 入10托〜1(Τ5托程度那樣壓力的氣體组成物β理想的係1〇-2托 〜103托。 在蝕刻處理時’被蝕刻基體的溫度，縱令是以加熱或 冷卻裝置控制於任意的溫度也佳，實際上即使不控制也可 。控制時，基體的溫度係通常是攝氏〇度〜約攝氏3〇〇度， 理想的係攝氏50度〜攝氏150度’更理想的係攝氏7〇度〜 攝氏130度，最理想的係在攝氏8〇度〜攝氏1〇〇度之範圍選 擇。藉控制這樣的溫度，一如具有高的對聚矽酮選擇性及 對光致抗姓劑選擇擇性那樣’南速敍刻就變為可能。被鞋 刻基體之溫度「實際上不控制的蝕刻」係在蝕刻中，在完 全不控制被蝕刻基體之溫度時，指在被姓刻基體到達的溫 度之± 30%以内’理想的係土20%以内，更理想的係土 1 〇〇/0 以内之溫度施行餘刻。因而，對應於蚀刻時急劇的發熱雖 以急速冷卻那樣操作可免除的，但直到取出被蝕刻基體為 止包含有除冷程度的操作。如此’實際上無需控制被蝕刻 基體之溫度’其溫度只要能保持與上述控制時的溫度同樣 ，便有操作上顯著的益處。 姓刻處理的時間雖有10秒〜10分之程度，但依本發明 之方法’通常，由於可能高速蝕刻，從提高生產性的觀點 來看也在10秒〜3分鐘較為理想。 以下就實施例’具體的說明本發明。但是，本發明其 範圍並不限定於該等的實施例。 製造例1 由公知的方法，將八氯環戊烯在二甲基甲酰胺中與氟 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ----------.^--- (請先閱说背面之注-^項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 409306 Α7 Β7 五、發明説明（8 ) 化钟反應得到合成八氟環戊烯。在蒸餾精製後以氣相色譜 法分析時’含氣原子之不純物1，42〇百萬分率（樣品丨）包含 在内* 將該八氟環戊烯500克以50克的超純水洗淨2次。經乾 燥後’使用包括有相當60層的蒸餾塔之蒸餾裝置以回流比 1精密蒸德過。該精密蒸餾係在常壓，氮氣環境下施 行。藉蒸德得到的各蒸餾分以氣相色譜法分析，測定含氣 原子不純物之含有量，這樣做，混合已知含氣不純物之含 有量的蒸館分’調製不純物之含有量有不同的3種樣品。 包含在該樣品中含氣原子之不純物的含有量再度以氣相色 議法測定時’係730百萬分率（樣品2)，2百萬分率（樣品3) ’ 0‘05百萬分率（樣品4)。 實施例1 在本實施例其中’將具有所謂氧氮氧（矽氧乂層/矽?4氮 y層/矽氧X層）構造之層間絕緣膜蝕刻並開口得到接觸孔a 接著’說明本實施例作為蝕刻樣品使用之晶片的構成 。首先’在矽基片上’形成矽3氮4頭道膜層，接著形成矽 氧2層間絕緣膜第1層。更且，在上述矽氧2層間絕緣膜第j 層上面’摹製矽3氮4蝕刻停止層。該蝕刻停止層係使用抗 钱劑保護層，藉摹製形成開口寬度約〇_6微米的開口部者 。更且，在矽3氮4蝕刻停止層上面係全面被膜形成矽氧2 層間絕緣膜第2層，在最上層係形成具有一定圖型之抗姓 劑保護層。 另外，抗蝕劑保護層係開口寬度約2微米的開口部係 本紙張尺度埴用中國國家標準（CNS > Α4規格（210 X 297公釐） _ π i :k-- (請先閱请背面之注意事項再壤寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 mm 經濟部智慧財羞局貝工消費合作社印製 A7 B7 五、發明説明（10 ) 刻。 其結果，矽3氮4頭道膜層及矽3氮4蝕刻停止層上之氧 化矽絕緣膜層以一定的圖型能非常良好的蝕刻.再者，秒 3氮4蝕刻停止層之開口邊緣部完全未能蝕刻，變形也完全 不能觀察的，不認為聚合物往孔壁沈澱。 比較例1 使用製造例之樣品1，其他與實施例1同樣的施行蝕刻 其結果’碎3氮4餘刻停止層之開口部係與氧化石夕絕緣 膜層同樣的被蝕刻’未能維持一定的孔徑。特別是，石夕3 氮4蝕刻使停止層之邊緣部有顯著的變形，認為聚合物往 孔壁沈澱。 以上’雖說明有關於本發明3個具體例，但本發明絲 毫不限定於該等之例。不用說當然，樣品晶片之構成，蝕 刻條件’使用之蝕刻裝置或蝕刻氣體的種類有可能適當的 變更。 產業上之利用可能性 依本發明之乾蝕刻方法，氧化矽系材料層與氮化矽系 材料層之間之蝕刻具有高的選擇性變成可能實現。 因而’本發明係按照微細的設計規則而設計，較適於 具有高集成度及高性能的半導體裝置之製造·> 本紙張尺度適用中國國家梂準（CNS ) A4規格（210X297公釐） ^^1 i n 11-- ^^1 n ^ 1^1 HI -I I ^^1 XV .¾ ·ν» (請先閲請•背面之注意事項再填寫本頁)’Printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 40930δ Α7-^ Β7 V. Description of the invention (6), -Carbon oxide, thorium dioxide, nitrogen oxide, sulfur oxide, etc. Furthermore, for the purpose of controlling the atomic ratio of fluorine to carbon of the coin-cut gas, an argon-fluorinated hydrocarbon-based gas can be added as such an additive gas, and examples thereof include tri-gasified carbon hydrogen-carbon fluoride-hydrogen. These additive gases may be used alone or in combination of two or more. Although the amount of the added gas varies depending on the extent to which the gastrointestinal material has spread to the gas source, it is usually less than 40 parts by weight based on 100 parts by weight of the gas source for the dry etching including the whole gas (generation) ring thin smoke.的 系 2 5 5 parts by weight or less. In the dry etching method of the present invention, plasma erbium is irradiated during etching. Applications that produce ions / cubic centimeters or more in high density fields. In particular, it has a density of about 10 to 10 ions per cubic centimeter. The higher the performance is found, the more ideal it is to form a fine structure. When the plasma density is excessively small, the object of the present invention, especially the high etching rate, the high selectivity of the silicon oxide-based material layer cannot be achieved, and since precipitation of polymerized hafnium is often generated, it is not ideal. Β Ministry of Economic Affairs The Intellectual Property Bureau employee consumer cooperative prints dry etching systems using parallel plate type or magnetron type reactive ion etching methods that are conventionally used, which are generally not suitable for achieving the above-mentioned high-density plasma. As a method for realizing the above-mentioned high-density plasma, a spiral wave method, a high-frequency induction method, an ECR (electron cyclotron resonance) method, a TCP (transformer coupled plasma) method, and an ICP (inductively coupled plasma) method are recommended. )the way. In the dry etching method of the present invention, it is not necessary to select a specific range of the pressure during the etching of the dry etching gas and a gas composition containing other gases as desired, and the paper is generally guided in a vacuum degassing etching apparatus. The scale is applicable to China National Standards (CNS) A4 grid (210X297 hectares) Z --- 409S06 Α7 Β7 V. Description of the invention (7) The gas composition β ideal system with a pressure of 10 Torr ~ 1 (T5 Torr) 1〇-2 Torr to 103 Torr. The temperature of the substrate to be etched during the etching process is preferably controlled by a heating or cooling device at an arbitrary temperature. In fact, it is not necessary to control. The temperature of the substrate is controlled during the control. It is usually 0 ° C ~ 300 ° C, the ideal range is 50 ° C ~ 150 ° C. The more ideal range is 70 ° C ~ 130 ° C, and the most ideal range is 80 ° C ~ 1 ° C. 〇 Degree range selection. By controlling such a temperature, as with high selectivity to polysilicone and photoselective anti-surname agent selection, 'Nansu Narration becomes possible. The temperature of the substrate engraved by the shoe "Actually out of control "Etching" refers to the fact that when the temperature of the substrate to be etched is not controlled at all, it means that it is within ± 30% of the temperature reached by the substrate engraved by the last name ', which is within 20% of the ideal soil, and more preferably 100%. For the rest of the time, the temperature should be within / 0. Therefore, the rapid heat generation during etching can be eliminated by rapid cooling, but the cooling degree operation is included until the substrate to be etched is removed. In this way, 'there is actually no need to control the The temperature of the etching substrate, as long as the temperature can be maintained at the same temperature as the above-mentioned control, will have significant operational advantages. Although the processing time of the last name is about 10 seconds to 10 minutes, according to the method of the present invention, generally, Since high-speed etching is possible, it is also desirable from the viewpoint of improving productivity to be 10 seconds to 3 minutes. Hereinafter, the present invention will be specifically described with reference to examples. However, the scope of the present invention is not limited to these examples. Manufacturing Example 1 The octachlorocyclopentene in dimethylformamide and fluorine were applied by a known method. This paper is sized to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ------- ---. ^ --- (please read the note on the back-item ^ before filling out this page) Order Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 409306 Α7 Β7 V. Description of the invention (8) The chemical reaction was synthesized Octafluorocyclopentene. Includes 1,42 million parts per million (samples) of impurities containing gas atoms when analyzed by gas chromatography after distillation and refining. 500 grams of this octafluorocyclopentene is divided into 50 G of ultrapure water was washed twice. After drying, it was distilled using a distillation device including a distillation column with a considerable 60 layers at a reflux ratio of 1. The precision distillation was performed under normal pressure and nitrogen environment. Each distillation fraction obtained by Germany was analyzed by gas chromatography to determine the content of impurities containing gas atoms. In this way, three types of samples with different contents of impurities were prepared by mixing the steaming ingredients with known contents of gas impurities. . When the content of impurities containing gas atoms contained in this sample was measured again by gas chromatography, it was 730 parts per million (sample 2), 2 parts per million (sample 3), and 0 0 05 parts. Rate (sample 4). Example 1 In this example, an "interlayer insulating film having a so-called oxynitride layer (silicon oxide layer / silicon oxide layer / silicon oxide layer / silicon oxide X layer) structure is etched and opened to obtain a contact hole a." Next, this embodiment is explained. The structure of a wafer used as an etching sample is exemplified. First, a silicon 3 nitrogen 4 head film layer is formed 'on a silicon substrate', and then a first layer of a silicon oxide 2 interlayer insulating film is formed. Furthermore, a silicon 3 nitrogen 4 etch stop layer is formed on the silicon dioxide 2 interlayer insulating film j-th layer. The etch stop layer is formed of an opening portion having an opening width of about 0-6 micrometers by using a protective layer of an anti-money agent. In addition, the silicon 3 nitrogen 4 etching stop layer is fully coated to form a second layer of a silicon oxide 2 interlayer insulating film, and a protective layer with a certain pattern is formed on the uppermost layer. In addition, the resist protective layer has an opening width of about 2 micrometers. The opening size is based on the paper standard (CNS > A4 size (210 X 297 mm)) _ π i: k-- (Please read it first. (Notes on the back are written on this page again.) Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives of the Ministry of Economic Affairs, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Shellfish Consumer Cooperative, A7, B7. 5. The description of the invention (10) is engraved. As a result, Silicon 3 The silicon oxide insulating film layer on the nitrogen 4 head film layer and the silicon 3 nitrogen 4 etch stop layer can be etched very well with a certain pattern. In addition, the opening edge of the second 3 nitrogen 4 etch stop layer has not been etched at all. No deformation can be observed at all, and the polymer is not considered to be deposited on the pore wall. Comparative Example 1 Sample 1 of the manufacturing example was used, and other etching was performed in the same manner as in Example 1. As a result, the opening of the crushed 3 nitrogen 4 stop layer was left. It is etched in the same way as the insulating layer of oxidized stone. 'A certain pore size cannot be maintained. In particular, the etched stone 3 and nitrogen 4 caused significant deformation of the edge of the stop layer, and it is believed that the polymer precipitated on the hole wall. Above' Although there are three specific aspects of the present invention Examples, but the present invention is not limited to these examples. Needless to say, the structure of the sample wafer, the etching device used for the etching conditions, or the type of the etching gas may be appropriately changed. Industrial application possibilities according to the present invention With the dry etching method, it becomes possible to achieve high selectivity in etching between the silicon oxide-based material layer and the silicon nitride-based material layer. Therefore, the present invention is designed in accordance with the fine design rules and is more suitable for high integration. Manufacturing of high-performance semiconductor devices > This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ^^ 1 in 11-- ^^ 1 n ^ 1 ^ 1 HI -II ^^ 1 XV .¾ · ν »(Please read the note on the back before filling this page)