TW477828B - A method for depositing a silicon nitride layer - Google Patents

A method for depositing a silicon nitride layer Download PDF

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TW477828B
TW477828B TW089119754A TW89119754A TW477828B TW 477828 B TW477828 B TW 477828B TW 089119754 A TW089119754 A TW 089119754A TW 89119754 A TW89119754 A TW 89119754A TW 477828 B TW477828 B TW 477828B
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chamber
silicon nitride
nitride layer
temperature
pressure
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TW089119754A
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Ki-Young Kim
Kyung-Ho Hyun
Joong-Il An
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Samsung Electronics Co Ltd
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    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
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Description

A7 B7 477828 公告本 五、發明說明（1 ) 發明背景 發明範圍 本發明係關於一種用於在一具有一高壓閥之低壓化學 蒸氣沉積（於此之後以LPCVD稱之）室中沉積一種絕緣層之 方法，以及更特別關於一種方法，該方法關於在高壓低溫 之操作條件下，在沉積一氮化叾夕層之加工前，實施一氨處 理以作為一前處理，藉由該加工防止一整體操作時間之損 失。 習知技藝之描述 一般來說，一氮化矽層已因其一高介電強度、對雜質 擴散之優越屏障性質以及良好的化學穩定性，而被廣泛用 為高度積體電路之閘極介電體、擴散光罩以及鈍化膜。 同時，一氨處理已於沉積一氮化矽層Si3N4之加工前， 被實施作為一前處理步驟。該氮化矽層Si3N4來自一生成於 一晶圓上之一天然氧化物層Si02。該氨處理通常在高溫（例 如780°C)低壓（0.03ΤΟΠ·)之操作條件下實施。如果該前處理 在一低於780°C之溫度下實施，則較低層（例如一天然氧化 物層）之氮化作用，將無法有效地完成，因而導致一氨化矽 層之不適當沉積。 第la以及lb圖係一特徵圖，其用於說明當一傳統氨處 理實施在沉積一氮化矽層之方法中時之操作條件的改變， 該二圖分別包含：第la圖，其為一特徵圖，其用於說明該 室中隨時間前進而發生的溫度變化；以及第lb圖係一特徵 圖，其用於說明該室中隨時間前進而發生的壓力變化。參 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------Imp 裝--------訂--------- (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 經濟部智慧財產局員工消費合作社印製 477828 A7 B7 五、發明說明（2) 照附圖，一用以沉積一氮化矽層之傳統方法係被劃分成下 列4個步驟： 步驟一中，一晶圓係裝載入一晶舟，在LPCVD室溫為 準備溫度（例如，550°C)時將該晶舟置入該室。此時，該室 之該内部壓力係設定並保持在760Torr。用於該加工之該 室，應係設計成可使該室内部壓力控制在一少於〜2.25Τοπ· 的範圍内。 步驟二中是為了在該室之該内部部份製造一高度真空 狀態。該内部部份經以一低壓抽吸並經設定在一高於780 °C之溫度。降低該室之該内部壓力至Ο.ΟΤοπ*及升高其溫度 至如78(TC—般高，藉此使殘留在該室内之氣體釋出（例 如，蒸氣）。接著，增加該室之該内部壓力至〇.3Torr，該一 壓力對該氨處理係必須的。 步驟三中當降低該室之該内部溫度室如670°C (攝氏） 一般低時，該室内之内部壓力經設定如〇· 18Torr —樣大， 該一壓力為形成一氮化石夕層之所需。在前述操作條件下 (670°C之低溫以及〇.18Torr之低壓），沉積一氮化矽層。 步驟四中，在完成該氮化矽層沉積後，降低該室壓力 至Ο.ΟΤοιτ以釋出殘留在該室之氣體。然後，降低該室之該 内部溫度至550°C，即該初始之設定溫度，並使該室之内部 壓力回升至760Torr。結果，沉積一氮化矽層之所有製程就 此完成。 但是，如果該氮化紗層係在前述操作條件下形成，可 能會有下列問題存在於該沉積該氮化矽層之方法中。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------裝------ -丨訂-------— (請先閱讀背面之注意事項再填寫本頁) 477828 A7 五、發明說明（3 ) ^ 已知該氨處理係被當作〆^ \ γ用曰(例如’在一 晶圓上形成之一天然氧化物廣二:=前處理:但 是，如果該前處理係在如形成Μ二σ工的相同溫 度下實施(例如摘，則该較:作用不能有效 地完糕-所㈣減簡當的氮切層 沉積量。目前，該氨處理係不^避丨近乎78〇°C的高 溫下實施，以增加氮化的有妹$ 但是，如果該氨處理係在We高溫下施行，則殘留在 該室之氣體分子可在該室之内部溫度自其準備溫度550°c 到780°C之升高過程中被活化。最後，在該氨處理前之將該 室之内部壓力降低至其基礎真空狀怨〇·〇Τ〇ΓΓ的所耗費的 抽吸時間變長了。因為在該氨處理中的該室之内部溫度（例 如，780。〇，比在沉積一該氮化矽層之加工中來得高（例如 670。〇，所以需要歷經一段夠長的時間來使該室之内部溫 度自780°C降低至670°C。因此’存有一個問題，即沉積該 氮化矽層之所有加工而言需要一個較長的總體操作時間。 經濟部智慧財產局員工消費合作社印製 因此，諸如此一該整個操作時間中之損失可導致產量 的降低，以致於存有一種解決該傳統方法之該問題的急迫 要求。 發明摘要 因此，本發明之一目標是解決該前述問題以及提供一 種用以沉積一氮化矽層之方法，其令該氨處理係在高壓低 溫之操作條件下，於一具有一種高壓力閥之LPCVD室中實 施’藉此降低整個用於該氨處理操作所需之時間，而不會 本紙張尺度適用令_^?T^S)A4規袼（21〇 X 297公釐)_ 經濟部智慧財產局員工消費合作社印製 477828 A7 B7 五、發明說明（4 ) 任何降低氮化作用的有效性，以及防止該一用於沉積一種 氮化矽層加工之操作時間的損失。 為了達成該前述目標，設有一種用沉積一氣化碎層之 方法，該方包含下列步驟： 藉由置放一以一氧化物層形成之晶圓，在高壓低溫下 於一具有一高壓閥之LPCVD室中，實施一氨處理，以及 在如該氨處理中之相同溫度下沉積一氮化矽層。 此時，該低溫度是在一 670± 50°C之範圍中，以及該高 壓力是在一 5〜300Torr之範圍中。 因為在高壓低溫之操作條件下（例如，5〜300Τοιτ之壓 力以及670± 50°C之溫度）施行該氨處理，所以如果該氮化 矽層係在如實施該氨處理中之高壓低溫的相同操作條件 (例如，5〜300Torr的壓力以及670± 50°C的溫度）下沉積，則 有可能縮短該用於降低該室之該内部壓力至該基礎真空狀 態O.OTorr之抽吸時間。此外，因為應用於該氨處理之該溫 度係如同該沉積一氮化矽層加工之溫度，所以不需控制該 氨處理後的該室之該内部溫度，以防止一用於沉積一種氮 化矽層之該加工的整個操作時間中之損失。 圖示之簡要說明 從下列具有該相關附圖的具體實施例之描述來看，本 發明之目標以及態樣會變得明顯，其中： 第la以及lb圖，係用於說明，當一種氨處理係藉由一 種傳統方法實施時，該沉積一氮化矽層加工中操作條件變 化的特徵圖，其分別包含： 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝———訂--------- (請先閱讀背面之注意事項再填寫本頁)
(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 477828 A7 B7
第la圖，其係—種用於說明該室内隨時間前進而發生 的溫度變化之特徵圖；以及第關，其係用於說明該室内 隨時間改變而發生之壓力變化的特徵圖； 當一種氨處理係藉由一本發明之方法實施時，第仏以 及2b圖係用於說明，在沉積—氮切層之該加工中之操作 條件變化的特徵圖，其分別包含·· 第2a圖，其係一種用於說明該室内隨時間前進而發生 的溫度變化之特徵圖；以及第_，其係用於說明該室内 隨時間前進而發生的壓力變化之特徵圖；以及 第3圖係一圖表，其用於說明分別在第“及沁圖與第仏 及2b圖之操作條件下形成之平均氮化矽層沉積量之比較。 發明之詳細說明 、<從下列具有該相關之附圖的一詳細較佳具體實施例描 述來看，本發明之目標以及態樣會變得明顯。第h以及沘 ，係特徵圖，其用於說明當一種氨處理係藉由本發明方法 貫施時，該沉積一氮化矽層加工中操作條件變化的特徵 圖’其分別地包含： 第2a圖，其係一種用於說明該室内隨時間前進而發生 =溫度變化之特徵圖；以及第2b圖，其係用於說明該室内 間前進而發生的壓力變化之特徵圖；關於該附圖，此 處提供一用於在本發明中沉積一氮化矽層的方法，其包含4 個下列步驟： ^在步驟I，將一晶圓載於一晶舟上，接著在該LPCVD 至的準備狀態之溫度（例如，550。〇下將該晶舟置入一該
本氏張尺度相巾_家標準(CNS)A< .4規格（210 X 297公釐） 477828 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（6) 中。此時，該室之該内部壓力係設定並保持在760Torr。該 LPCVD室應具有一種高壓力閥以控制其内部壓力在一可 尚達〜lOOOTorr的寬廣範圍。此處不會更進一步描述關於該 具有一種高壓力閥之LPCVD室，該LPCVD室已廣泛用於一 沉積一種層的加工。 在步驟II，為了製造該室之該内部部份的一種高高真 空狀態，所以實施一低壓力抽吸以及提高該室之該内部溫 度至670°c。如本發明之一具體實施例，該室之該内部溫度 如弟2a圖所示是維持在670°C，但是一種在670± 5〇°C之範 圍内的變異可能會產生。於其溫度係保持在670〇Ct，降低 該室之該内部壓力至O.OTorr，藉此釋出殘留在該室之該之 所需。即使將該室之該内部壓力維持在如第沘圖所示之 5.0Torr ’仍可能應用在該5.0〜3〇〇T〇rr之範圍内之任何程度 的壓力。接著在該前述操作條件（67(rc的低溫度〇£以及 5.0T〇rr的高壓力）下施行該氨處理。在完成該氨處理後，該 室之該内部溫度係保持在670°C下，使該室之該内部溫度暴 降至O.OTorr，以釋出殘留在該室之該氣體。 在步驟III，當該室之該内部溫度保持67〇。(：時，提高 該室之該内部壓力至〇.l8Torr，該壓力為用於沉積一種ι 化矽層加工之所需。在該前述操作條件下，沉積一種氮化 石夕層。 在步驟IV，在該沉積一氮化矽層加工後，使該室之該 内部溫度暴降O.OTorr以釋出殘留在該室之該氣體。接著降 低該室之該内部溫度至其初始之設定值以及提高該室之該 (請先閱讀背面之注意事項再填寫本頁) —1 i^i I —HI 1^1 11 a— 1 ·
477828 A7 ____ Β7 五、發明說明（7) 〜 一 ~ 内部壓力至760加。結果’用於_—種氮化物層之該所 有步驟就此完成。 如果如此這般地沉積該氮化石夕層，則該氨處理係在高 壓低溫（例如5〜300T〇rr的壓力以及67〇± 5〇<t的溫度）下實 施，而非在低壓高溫（例如0.3T〇rr的壓力〇f以及78〇。〇的， 度）下實施，以至於該抽吸所花之用於降低該室之該内部^ 力至基礎真空狀態的O.Oltoir之日夺間，可在本發明之該方法 中縮短。相較於該要求用於該氨處理之該低壓高溫操作條 件的傳統方法，本發明之該方法中之該氨處理所需的該溫 度從78代降至67G± 5_度以藉此有效蘭制殘留在 該室之氣體分子的活化。更甚者，該氨處理中所需之該溫 度條件和一種氣化石夕層之該加工的沉積是相同的，以致於 在完成後不需要降低該室之該内部溫度，藉此使防止用於 該沉積-種氮化石夕層加工之該全部操作時間中的任何損失 f為可月b。換句活s兒，因為有可能使所需用於該沉積一種 氮化石夕層步驟之所有該操作時間明顯縮短，所以係在產量 上有所改良，。 表此外丄確定的是一實驗，其所有操作時間，全花在本 2明之该刖述操作條件沉積該氮化石夕層加工之過程，則該 貫驗可比在該傳統方法下進行縮短近72分鐘。 、同時確定的是該氨處理之該氮化作用，比在該傳統方 法之780 C鬲溫度下，係在該前述操作條件下更有效地完成 在本I明。第3圖顯不—種證明本發明中氮化作用有效性之 實驗結果。 --------si (請先閱讀背面之注音？事項再填寫本頁) — 丨！訂-丨---1111 經濟部智慧財產局員工消費合作社印製
477828 經濟部智慧財產局員工消費合作社印製 A7 Β7 五、發明說明（8 ) 第3圖是一種用於說明氮化矽層平均沉積量的比較 圖，該圖係在該第la以及lb圖以及第2a圖之操作條件下分 別地形成的。整體而言，氮化作用係已知該一種氮化矽層 沉積量之比例。在第3圖中，係該氮化矽層沉積量於該氨處 理之該過程中一室之該内部壓力中的改變之比較與評估。 在該前述圖中REF代表之部份，表示藉由低〇.3T〇rr的 壓力以及780°C的高溫（根據第1圖所示的該傳統方法）之操 作條件下，該氨處理中沉積之該氮化石夕層量已經施行。另 一方面，該圖的其他符號，表示在該超過2.5丁0汀的高壓力 以及670°C的低溫（如示於第2圖之本發明的一種具體實施 例）之操作條件下氨處理沉積的氮化矽層： 此時，參考的符號T、C以及B分別地代表該LPCVD室 頂部、中部以及底部的一種氮化矽層沉積厚度。此外，參 考的符號T(D/R)、C(D/R)以及B(D/R)分別代表一在該 LPCVD室之該頂部、中部以及底部每分鐘氮化矽層沉積之 厚度。 如該圖所示，在該低壓面溫（780 C ’ 0 ·3 Torr)之操作條 件下，該室個別區域（例如該LPCVD室之頂部、中部以及 底部）的該氮化矽層沉積量經測量為1·.7、ι·3以及11〇。另 一方面，如果溫度以及壓力係分別設定在67〇°C以及超過 5Torr，則確定的是該室所有區域的該氮化；g夕層沉積量要^匕 REF的來得高。換句話說，在同於670°C的溫度下，如果今 室之該内部壓力係5Τ0Π*，則該室個別區域之該氮化石夕層沉 積量經測量為1.8、1.4以及1·16，而，而如果該室之兮内部 (請先閱讀背面之注音？事項再填寫本頁)
477828 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（9) 壓力係lOTorr，則該室個別區域之該氮化矽層沉積量經測 量為1.8.1.4以及1.20。 關於該前述實驗結果，可確定的是，在該第2a以及2b 圖之操作條件下之該氮化矽層沉積量，要比第la以及lb圖 的量更有效。 因此，經發現藉由本發明之方法，用於沉積一種氮化 矽層之氮化作用，在該製造一種半導體裝置（特別是一種電 容器）之加工中，更有效地造成一種較高的介電效應，藉此 使該介電層更薄以及得到一種額外的效用，即在一種電容 器之崩潰電壓（BV)方面有所進展。 當本發明以一種較佳的具體實施例的角度來說明時， 那些習於此藝者會認知到本發明可在該附加的請求項的範 圍及精神中進行改變來實行。 如上所述，本發明之該方法中有一益處，即該沉積一 種氮化矽層之一種加工前的氨處理，係在該高壓低溫的操 作條件下，於一種具有一種高壓力閥之LPCVD室中實施’ 藉此縮短用於該氨處理所需之整個操作時間而不會降低任 何氮化作用的有效性，並防止沉積一種氮化矽層之該所有 步驟中之該操作時間中的損失。 ------------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -12-

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  1. 4/7828 申叫專利範圍 l 一種用於沉積一氮化矽層之 如一矿、t ’套’其包含τ列步驟： 在尚Μ低溫下，藉由蔣一 — - 晶圓置放於一個具有一高_^有—氧化物層之 -個氨處理’及⑽閥upcvD室中，實施 在相同於該氨處理中之溫度下沉積-個氮化石夕 層0 2.如申請專利範圍第1項之方法，其中該低溫係位在— 為670± 50°C之範圍中。 3·如申請專利範圍第！項之方法，其中該高壓係位在一 為5〜300Torr之範圍中。 訂 4.如申請專利範圍第1項之方法，其中該氧化物層係一 種天然氧化物層。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）
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US6326322B1 (en) 2001-12-04

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