TW576865B - A composition and method for selectively etching a silicon nitride film - Google Patents

A composition and method for selectively etching a silicon nitride film Download PDF

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TW576865B
TW576865B TW088114499A TW88114499A TW576865B TW 576865 B TW576865 B TW 576865B TW 088114499 A TW088114499 A TW 088114499A TW 88114499 A TW88114499 A TW 88114499A TW 576865 B TW576865 B TW 576865B
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etching
acid
ppm
composition
scope
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Thomas B Hackett
Zach Hatcher Iii
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Ashland Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • 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
    • 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

Description

五、發明説明（1 ) '〜一 87 背景 本發明係關於用於坐a (請先閱讀背面之注意事項再填寫本頁) 液。更❹m ^ 製造之㈣㈣水溶 出在氮…化…半、導刻水溶液，其顯示 飯刻選擇性增加。！Ub^導=置之純㈣氧化石夕的 M , ., 對一氧化矽的選擇性蝕刻作用係 :由：用-種含碟酸之餘刻浴溶液和一種含石夕組成物而完 ”中3隸成物係為易溶於㈣浴溶液者，例如六氟 納。為了本發明的目的，”易溶”係表示該隸成物在 至溫下與餘刻浴溶液均句地混和。姓刻浴溶液不含氫氟 酸、硝酸或其混合物或是含有第则族^之組成物。 技關拮藝說明 經濟部智慧財產局員工消費合作社印製 製造包含數層之組合+導體裝置一般需要數個基本處 理步驟。這些基本處理步驟包括：清洗、氧化、（大氣壓 和高壓）、微影（光蝕刻法、電子束及又_光）、以擴散和佈 植法進行塗佈、〉儿積（電子搶、濺射、化學氣相沉積⑴)、 低壓化學氣相沉積（LPCVD )以及電漿）、蝕刻（溼式化學及 乾式或電漿）以及測試。上述之一般技術係為該技藝所習 之。 本發明提供一種改良的、屋式化學钱刻法，其係增加氮 化矽之蝕刻率以及提高用於氮化矽-氧化矽組合半導體裳 置之氮化石夕對氧化石夕之熱構酸水溶液的餘刻選擇性。上述 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7
經濟部智慈財產局員工消費合作社印製 576865 五、發明説明（2) 方法之完成，係藉由將一種易溶的含矽组成物Γ 7, 、从观（例如六氟 石夕酸）加入於一種含磷酸之姓刻浴水溶液申。 像其他濕 式蝕刻法使用一種受熱的磷酸蝕刻浴，本發明人 < 3石夕組成 物易溶於含磷酸之蝕刻浴溶液中。而且，本發明之溶液不 含氫氟酸、硝酸或其混合物或含第ί或第π族元素之組 成物（例如矽酸鈉）。鈉、鎂及第I或第π族元素之存在 在許多半導體加工應用上是不希望以有的。 填酸#刻浴係在本技藝中為習知。Northern TeleeQm 有限公司之美國專M U.S· 4,092,211揭露一種在沸騰的磷 酸浴中透過二氧化矽光罩之孔隙蝕刻氮化矽的方法。該方 法降低了相對於氮化矽之二氧化矽的蝕刻率，其係藉由將 一種可溶性的矽酸鹽（例如矽酸鈉）加至磷酸中或者藉由 將細分的矽石加入於蝕刻液中。根據上述專利，加入可溶 性的矽酸鹽或矽石妨礙二氧化矽的蝕刻率，而未影響氮化 石夕的鍅刻率。Matsushita Electric之日本專利60137024揭 露除去由於蝕刻氮化矽（Si3N4)之副產物所形成的膜的 方法’其係先在水存在下受熱處理。在上述專利中所述之 以化學式SixNy〇z表示之殘餘副產物，則以含氟離子之磷 酸溶液蝕刻而去除。該發明之目的係為了以一種有效率的 方法除去氧化石夕層、氮化矽層以及氮化矽熱處理的副產物 膜。Hitachi有限公司之日本專利申請案JP63498〇8a揭露 了 種在氮化石夕膜除去期間抑制二氧化石夕膜餘刻率的方 法。该方法係根據該發明使用一種含矽之磷酸蝕刻液而完 (請先閲讀背面之注意事項再填寫本頁)
576865 五、發明説明（4 / 入氫氟酸、硝酸或其混合物或是含 發明之目的係為了提供一種組成物，：族之元素。本 發現的缺點。本發明之組成物顯示出增 /技藝中所 率，以及相對於二氧化矽之增 ：、乳化矽蝕刻 / &瑨加的虱化矽蝕刻選擇性。太 =二成物因為其成分液彼此相溶而容易製備。本發明 係提供—種以濕式化學餘刻法有效地增加相 對於乳化石夕之氮化矽餘刻率的方法。 發明詳沭 經 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 氮化石夕廣泛地用於半導體工業，其係作為阻撐層或頂 層以防止污染物擴散入半導體裝置。其亦作為於石夕局部氧 化法（LGCQS)之選擇性氧化阻劑，以便使氧化作用發 生於欲提供電晶體分離所需的範圍。氮化矽基本上是惰 f生緻拴的’並且不易蝕刻。可使用氫氟酸及前置氧化蝕 刻剑’但疋蝕刻率甚至在高溫下是相當低的，並且在極端 的條件下光敏電阻常受到不利的影響。另一個問題為，當 使用磷酸於蝕刻溶液時，磷酸則既蝕刻氧化矽也蝕刻氮化 矽。當需要選擇性蝕刻氮化矽時，共蝕刻是不希望有的。 先别所述之美國專利U.s· Patent 5,472,562指出，將一種 可/谷ϋ的石夕化合物加入於鱗酸、氫氟酸以及碼酸的餘刻溶 液中將有助於相對於石夕與氧化石夕之氮化石夕的钱刻選擇性。 但是額外的氫氟酸及硝酸的存在是不希望有的，並且在許 多情形中對半導體製程是有害的。在該技藝中所揭示之其 L 6 本紙210X297公釐 576865 五、發明説明（5) 他方法則提供加入石夕之剝除組成物以改良組成物的特性 一般而言’藉由將一種固態的含石夕材料（例如石夕晶 入於熱麟酸溶液可完成上诚古、土 , _ ^ 凡风上述方法。由於需要時間去消化 晶圓以及在姓刻液存在不τ溶的顆粒之緣&，故該方法β 不合需要的。 疋 本發明提供一種方&，以提高在組合半導體裝置中之 相對於氧化石夕之氮化石夕的蝕刻率，其係藉由在一種含碟醆 及易溶於姓刻纟溶液中之含石夕组成物之加&的水溶液中餘 刻該組合半導體裝置。本發明進一步提供一種水性蝕刻組 成，其中含有磷酸以及一種易溶於水性蝕刻組成物中之含 矽組成物。 經濟部智慧財產局員工消費合作社印製 根據本發明，氮化矽可選擇性地相對於二氧化矽進行 餘刻，其係藉由在一個含磷酸水溶液及含石夕組成物（易溶 於蝕刻浴中）之熱蝕刻浴中進行蝕刻操作。可使用工業級 的麟酸。一般而言，商業可利用之磷酸可利用者為8〇至85% 之水溶液。在一個較佳的電子級磷酸溶液的具體實施例 中’其中顆粒數小於1 00顆粒/ml且顆粒粒徑小於或等於〇. 5 微米，並且存在酸中之金屬離子含量係為ppm至ppb級。 這些種類的電子級磷酸之實例為購自Ashland Chemical之
CleanRoom⑧電子級藥品、cieanRoom LPTM、CleanRoom MBTM& CleanRoom GIGABIT⑧（GB )。沒有其他酸，例如 氫氟酸、硝酸或其混合物加入於蝕刻浴溶液中。 根據本發明將一種含矽組成物加入於蝕刻溶液中。該 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X 297公釐） 576865 五、發明説明（6 ) a矽組成物在室溫下易溶於水性蝕刻組成物中。在一個較 4的/、體實施例中’易溶之含矽的組成物為六氟矽酸 (I^SiF6 )。在一個較佳的具體實施例中，於蝕刻浴溶液 易’谷的a石夕組成物之存在量係由約16ppm至約 5〇〇Ppm。易溶的含矽組成物之濃度係以重量計（以總蝕 刻冷溶液為基準’係為每百萬份之存在於易溶組成物之矽 斤计算之伤數）。在一個更佳的具體實施例中，於蝕刻浴 /合液中之易溶的含矽組成物之存在量係由約16叩^至約 200ppm。在一個更佳的具體實施例中，易溶之含矽的 成物於蝕刻浴溶液中之存在量係為由約1〇〇ppm至約 ㈣PPm。進—步含第1或11族元素之切組成物除了作為 污染物外，並不存在於本發明之蝕刻浴溶液中。一個不希 望有的組成物之實例為石夕酸納 使蝕刻進行之蝕刻浴的溫度可以是任何讓氮化矽-氧 化矽蝕刻進行的溫度。此種蝕刻法通常在約丨8〇它下進行 本發明的-個優點為，可在任意溫度下進行㈣。當使用 根據本發明之水性磷酸蝕刻液時，可在低於15〇艽之溫产 下有效地進行㈣。根據本發明’進純刻之㈣浴溫^
較佳者係由約mt：至約18(rc。㈣浴溶液之溫度更佳者 係由約150°C至約160°C 已敘述本發明《，兹提出以下實例以$ 一步說明本發 明· 測量技術 1 __ 8 本紙張尺度適用中國國家標準（CNS ) A4規格（27〇^1^5Τ (請先閲讀背面之注意事項再填寫本頁)
576865
五、發明説明（7 ) 經濟部智慧財產局員工消費合作社印製 蝕刻率係使用橢圓測定儀（Plasmos Ellipsometer)測量 氣化物及氧化物厚度而決定。 —均勻性之計算式為 1- ( Max-Min/2 χ Average) x 100 糸現I置 個曰曰圓之49個不同位置而得，其中Max=最大 厚度，Min=最小厚度，Average =平均厚度。 晶圓製備 --決定餘刻率之晶圓 shN4_晶圓：於氧化物阻劑上之2〇〇11111之LPCVD氮化物 l〇〇nm之熱氧化物 實驗步驟 所有試驗係在1000級無塵室中之石英燒杯内以加熱板 加熱進行。在每一組試驗中係使用不同的溫度（150°C、160 C、1 7 0 C及1 8 0 °C )以相同的水浴持續加熱。於鱗酸加熱 期間’容器不加蓋。當水浴達到所欲之溫度時，Si3N4之 最初的钱刻率則係藉由將氮化物晶圓浸於水浴中1 〇分鐘而 決定。氧化物之蝕刻率則藉由30分鐘之第二個浸泡而決 定。用於試驗1之磷酸為購自Riedel-de-Haen之GB級8 5% 水溶液。用於試驗2至8之磷酸則為購自Ashland Chemical 之GB級85%水溶液。用於試驗9至12之磷酸則為購自 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公酱） I-------------訂-- (請先閱讀背面之注意事項再填寫本頁) 576865 A7 B7 五、發明説明（8 )
Ashland Che mi cal之MB級85%水溶液。六氟石夕酸為25%之 水溶液。試驗11所含之矽係以Si〇2之形式加入，其係藉由 將3公克之Si〇2加入於100ml之HJO4中，並且將該組合物 加入一個8公升之磷酸蝕刻浴中，並放置過夜。經過放置 過夜後，當加熱至150°C時Si〇2沒有完全溶解。表1顯示在 不同溫度下12個試驗之結果。所紀錄之結果包括對於si3N4 及Si02蝕刻率及蝕刻均勻性，以及蝕刻的選擇性。 H2SiF0之加入造成SisN4全面的餘刻率增加。隨著溫 度的增加，對沒有添加物之碟酸以及含六氟石夕酸之水浴而 言，其氮化物對氧化物的選擇性降低。在試驗1 2中將HF 將入磷酸中，顯示氧化物及氮化物之餘刻率皆增加，且氮 化物對氧化率之蝕刻選擇性降低。在試驗1丨以Si〇2加入之 矽對氮化物膜之蝕刻率沒有可察覺到的效果。試驗丨丨之蝕 刻率比得上水浴中僅存在磷酸之蝕刻率。 (請先閱讀背面之注意事項再填寫本頁) 訂
經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 576865
7 7 A B 五、發明説明（9 ) 表1 氮化物及氧化物基質之蝕刻率以及氮化物對氧化物之選擇性 氮化物 氧化物 T 試驗添加劑 （°c) 蝕刻率 均勻性 (nm/min) (%) 蝕刻率均勻性選擇性 (nm/min) (%) 95.8 25.38 95 25.68 92 9.63 150 3.3±0.14 97.5 160 5.65±0.07 97 180 10.3+0.07 94.4 —2— υ ο ο ο 5 6 7 8 lx H 11 6 4 2 7 2 7 1 . . ..3 3 5 5 1 7 7 7 9 9 9 9 9 9 2 0 · 1 3 土0 0.22 土 0.02 1.07土Ο 0；02— 0.23 0.49 0.87 6 2 8 5 8 8 7 7 9 9 9 9 2 2 5 4 5 0 5 3 150 160 170 180 5 6 4 9 J 6 6 9 4 6 6 6 6 4 9 9 9 9 5 7 0.15 0.18 0.23 0.6 5 3 2 7 7 7 9 9 9 96.6 3 7 8 5 3 6 7 6 2 3 2 1 4 1 6ppm H2SiF6 150 160 180 5.65+0.07 7.55±0.07 10.6土0.2 5 7 3 6 5 3 9 9 9 0.17+0 (K25±0.02 0.72 士 0.02 5 3 • . 3 5 5 9 9 9 33.24 30.2 14.65 5 50ppm 1 50 7.34 96.1 H2SiF6 160 9.09 93.9 170 10.2 95 180 10.7 94.1 5 7 8 2 4 8 ο ο ο ο 3 4 7 8 8 7 6 7 9 9 9 9 5 4 7 6 12 3 2 1 6 lOOppm H2SiF6 150 10.5 160 12.5 170 13.4 180 15.25 9 • 9 7 6 18 8 8 2 7 2 3 0 17 3 ο ο ο 1 2 8 7 4 7 7 6 5 9 9 9 9 462.3 73.56 18.63 11.46 lOOppm H2SiF6 150 160 170 180 8.6 10.0 11.7 13.7 9 1.2 94.0 94.4 81.9 -0.01 0.19 0.46 0.82 6 5 6 7 7 7 9 9 9 96.9 52.6 25.4 16.7 1 50ppm H2SiF6 150 160 170 180 2 9 2 8.3 4 8 1i Is 16 6 8 7 9 0 2 6 8 9 3 -0.08 0.07 0.69 1.24 /513 6 6 6 3 9 9 9 9 8 008515 I ------ITJ--I-- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 9 200ppm H2SiF6 ο ο ο ο 5 6 7 8 15.0 9.3 15.4 14.0 36.4 83.1 92.3 80.8 -0.34 97.8 00 0.01 96.3 930 0.43 97.1 35.8 0.96 95.2 14.6 1 1 500ppm H2SiF6 150 160 170 180 4 0 5 4 4 4 II <1 It )5 • 7 12 9 /IV 9 95.3 3 6 2 8 •202 -00 1 2 7 7 6 9 9 9 9 4 1 005514 4 6 lOOppm Si02 160 170 180 5.2 7.24 14.8 0 6 9 8 6 7 9 9 8 0.00 0.06 0.29 98.7 98.5 98.7 121 5 1
12 相當於 1 OOppm H2SiF6之 HF ο ο ο ο 5 6 7 8 3 4 4 9 8 6 84 82 20 2.4 1.89 2.1 2.24 82 89 88 89 5 7 2 4 4 7 9 7 5 7 6 8 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 11

Claims (1)

  1. 576865 本 告 公 六 圍範利 專請 申 8 8 8 8 A B c D f/ 專利申請案第88114499號 ROC Patent Appln. No.88114499 修正後無劃線之申請專利範圍中文本-附件㈡ Amended Claims in Chinese - Encl.fll) (民國92年l2月州日送呈） (Submitted on December , 2003) 10 15 20 5. 經濟紙智慧財產局員工消費合作社印製 25 h —種蝕刻半導體裝置的方法，其中氮化矽相對於二氧 化矽之蝕刻率選擇性提高，該方法係包括： 於一種熱的蝕刻水溶液中蝕刻該半導體裝置，該 餘刻水溶液實質上由以下成分組成： A. 鱗酸，和 B · 六氣碎酸。 2·根據申請專利範圍第丨項之方法 °C至約180°C之溫度下進行。 3 ·根據申清專利範圍第1項之方法 在量係由約16ppm至約500ppm。 4·根據申請專利範圍第1項之方法 在量係由約1 OOppm至約200ppm。 一種水性蝕刻組成物，其實質上係由以下之成份組 成： A. 磷酸，和 B. 六氟矽酸。 根據申請專利範圍第5項之水性蝕刻組成物，其中六氣 矽酸之存在量係由約16ppm至約500ppm。 根據申請專利範圍第5項之水性蝕刻組成物，其中鱗酸 係為85%水溶液。 其中蝕刻係於約150 其中含碎組成物之存 其中含矽組成物之存
    88251B-接 -12 - 576865 8 8 8 8 A B c D 六、申請專利範圍 8.根據申請專利範圍第5項之水性蝕刻組成物，其中磷酸 係為電子級之85%水溶液。 經 濟 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 -13 -
    本紙張尺度適用中國國家標準(CNS)A4規格（210x297公釐）
TW088114499A 1998-08-28 1999-08-25 A composition and method for selectively etching a silicon nitride film TW576865B (en)

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