TW474004B - Semiconductor device incorporated therein high k capacitor dielectric and method for the manufacture thereof - Google Patents

Semiconductor device incorporated therein high k capacitor dielectric and method for the manufacture thereof Download PDF

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TW474004B
TW474004B TW089127725A TW89127725A TW474004B TW 474004 B TW474004 B TW 474004B TW 089127725 A TW089127725 A TW 089127725A TW 89127725 A TW89127725 A TW 89127725A TW 474004 B TW474004 B TW 474004B
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scope
pentoxide
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titanium
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Ki-Seon Park
Byoung-Kwan Ahn
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Hyundai Electronics Ind
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
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    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
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    • H01L21/314—Inorganic layers
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    • H01L21/02178—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
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    • H01L21/02112—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
    • H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02194—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing more than one metal element
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—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
    • H01L21/022—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 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides
    • H—ELECTRICITY
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L28/60—Electrodes
    • H01L28/75—Electrodes comprising two or more layers, e.g. comprising a barrier layer and a metal layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/60—Electrodes
    • H01L28/82—Electrodes with an enlarged surface, e.g. formed by texturisation
    • H01L28/90—Electrodes with an enlarged surface, e.g. formed by texturisation having vertical extensions
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B12/00—Dynamic random access memory [DRAM] devices
    • H10B12/30—DRAM devices comprising one-transistor - one-capacitor [1T-1C] memory cells
    • H10B12/31—DRAM devices comprising one-transistor - one-capacitor [1T-1C] memory cells having a storage electrode stacked over the transistor
    • H10B12/315—DRAM devices comprising one-transistor - one-capacitor [1T-1C] memory cells having a storage electrode stacked over the transistor with the capacitor higher than a bit line

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Description

474004 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明（1 發明領娀 本發明係與半導體裝置有關，詳言之，係與結合高κ介電 質做爲電容介電質膜之半導體裝置有關。 先前技藝揣i 如眾所週知，動態隨機存取記憶體至少具備一個由一個 電晶體與一個電容器所組成之記憶胞，其積體程度較高之 王因係經微量化造成之尺寸縮減。然而，縮減記憶胞之面 積仍屬所需。 爲達成此需求，已提出之電晶體結構頗多，諸如穿圳型 或堆疊型電容，其在記憶裝置中爲三維空間配置，俾減少 電客所需佔有之記憶胞面積。然而，三維空間配置之電容 製造過程十分冗長，造成製造成本昴貴。因此，極需要新 型的記憶體裝置，其可減少所需記憶胞面積，而確保所需 之貧料容t，且無須複雜的製造步驟。 爲達成此需求，已引進諸如五氧化二妲或類似的高&介電 質，做爲電容之薄膜，以取代習知之氧化矽膜或氮化矽膜 。然而，由於五氧化二釦層在後續的熱處理製程中長成圓 柱型結構，此長成之五氧化二鈕會造成高漏電流。因此， 在記憶體裝置中，採用五氧化二鈕層做爲電容薄膜實屬不 易。 、、 爲克服述問題，已有人提出可選擇以金屬有機化學汽 相沉積法（MOC VD)，將諸如氧化二鈕（Ta2〇)/二氧化鈦或氧 •化二姮/氧化鋁之多層介電質做爲電容薄膜。然而，金屬有 機化學汽相沉積法會使得外來物質殘留在電容薄膜上。此 --------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) -~ -4- ^___I_ 經濟部智慧財產局員工消費合作社印製 474004 A7 B7 發明說明（） 結果迫使需在電容薄膜上施行高溫熱處理，使其依序產生 電容薄膜中之缺陷與高漏電流。 仍需要持續研發可與半導體製程相容之具低漏電流之高K 介電質。 發明概述 因此，本發明之目的之一係爲提供一種結合其電容之介 電質爲高K介電質之半導體裝置。 本發明之另一目的係爲提供一種結合其電容之介電質爲 高K介電質之半導體裝置之製造方法。 依本發明之觀點之一，所提供之用於記憶體裝置之半導 體裝置，包括：配有半導體基座之主動陣列、多個成型於 半導體基座上之電晶體，以及與電晶體導電連結之導體塞 ;數個成型於導體塞上方之底部電極；成型於底部電極之 上之合成以及成型於合成膜上之氧化鋁膜。 依本發明之另一觀點，所提供之用於記憶體裝置之半導 體裝置製造方法，此方法所含步驟包括：a)製備主動陣列 ，其配置至少一個電晶體、多個與電晶體導電連結之導體 塞，以及成型於導體塞週邊之絕緣層；b)形成主動基礎上 方之導體層；c)依預定组態定樣導體層，從而產生數個底 部電極；d)形成底部電極上之（五氧化二鈀）x (二氧化鈦）y合 成層，X、>y分別表示分子比例；e)形成（五氧化二姮）x (二氧 化鈦）y合成層上之介電層；f)定樣介電層與（五氧化二妲）x (二氧化鈦）y合成層爲預設組態，半導體裝置從而得之。 圖示簡述 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ▼裝--------訂---------線泰 474004 A7 五、發明說明（3 ) 參閲附圖及後續之較佳具體實施例之描述，本發明之上 述與其它目的及特性即顯而易見，其中： 圖1所示爲依本發明提出之半導體裝置剖面圖。 圖2A至2G所示爲依本發明提出之半導體記憶裝置製造方 法之簡略剖面圖。 較佳具體實施例之詳地 圖1與2A至2G所示爲用於記憶體裝置之半導體裝置1〇〇剖 面圖，及其依本發明之較佳具體實施例提出之製造方法剖 面圖。需注意出現在圖1與2入至2(}之類似部件均以類似參 考代號表之。 圖1中提供所發明之半導體裝置100剖面圖包括主動陣列 與電容結構。主動陣列包含矽基座102、成型於矽基座 上頂端心電晶體、用來隔絕這些電晶體之絕緣區、複晶 塞116、位立線118與字元線12〇。所有的電晶體均具擴散區 106、閘極氧化層1〇8、閘極線ιι2與侧壁114。 在半導體裝置1〇〇中，位元線118與擴散區1〇6之一導電連 結’俾施予電位。所有的電容結構均經複晶塞ιΐ6與其它擴 政區106導電連結。雖然位元線⑴實際上延伸於左、右方 來旁路複晶塞116,圖中並未顯示位元線118的這些部份。 私谷結構可與金屬線(未圖示)相連，俾於該處施加一定電 位。一 - 所有的％谷結構均包含較低電極125、成型於較低電極 極層130與成型於第一較高電極層上之第二較高電極層 -6 - 本紙張尺度適用t7國國家標準（CNS)A4 4格（210 X 297公£3----— (請先閱讀背面之注意事項再填寫本頁) -裝--------訂---------· 經濟部智慧財產局員工消費合作社印製 474004
五、發明說明（ 經濟部智慧財產局員工消費合作社印製 ^第二介電層128配置於第一介電層126與第—較高電杨 層130間。較低電極125之材質以選自包括複晶碎、鹤、氮 '、Χ^4Ι’1Χ)、氮化鈥、銷、备、銀與類似材質群 、且中車又佳，而第二較高電極層132之材質則以選自包括複晶 =、鎢、氮化鎢、Χ矽化鎢（WS1x)與類似材質群組中較佳。曰 第一介電層126亦可以原子層沉積法，由（五氧化二妲）。η (二氧化鈦）〇心製得。在較佳具體實施例中，第二介電層 =8係由氧化鋁製得，而第一較高電極層13〇則以氮化鈦^ 侍，以增進第二介電層128與第二較高電極層132間之黏著。 圖2Α至2G所示爲依本發明提出之半導體記憶裝置中電容 結構140製造方法之簡略剖面圖。 半導體裝置I製造程序啓始於主動陣列丨丨〇之製備，包括 矽基座102、絕緣區104、擴散區1〇6、閘極氧化層1〇8、閘 極線112、童]壁114、位元線118、複晶塞110與字元線丨22， 如圖2A所示。.位元線118與擴散區1〇6之一導電連結，俾施 予私位。所有的複晶塞！丨6均分別與其它擴散區i 〇6導電連 結。雖然位兀線11 8實際上延伸於左、右方來旁路複晶塞 11 6，圖中並未_示位元線丨丨8的這些部份。電容結構1可 與金屬線（未圖示）相連，俾於該處施加一定電位。絕緣層 122係由如硼磷矽酸鹽玻璃（BpSG)之材質製成。 接下來為步驟爲：以半導體製程將較低電極125成型於主 動陣列110之上，所有的較低，電極125均以此方式與相對應 足複晶塞116導電連結，如圖2B所示。較低電極125之材質 以選自包括複晶矽、鎢、氮化鎢、X矽化鎢、氮化鈦、鉑、 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ·裝--------訂---------^_wi (請先閱讀背面之注意事項再填寫本頁) 474004 A7 五、發明說明（ 名如、敏與類似材質群組中較佳。 &後，以原子層沉積法將第一介電層126成型於較低電極 125與主動陣列110之上。第一介電層126以（五氧化二包）χ (-氧化欽）y製得較佳，其中之χ、讀、以莫爾百分率表之。 在此較佳具體實施例中，\爲〇 92、丫爲〇 〇2。（五氧化二姮）〇92 (氧化欽）G.Μ製得之第一介電層126可以下列步驟形成：a) 反應槽之溫度範圍維持在約25(rc至約3〇(rc ; b)依序將第一 與第二源氣體引入反應槽中，以形成五氧化二鈕薄層；为 依序將第三與第四源氣體引入反應槽中，以形成五氧化二 鈕薄層上之二氧化鈦薄層；d)重複步驟!^與c)，形成五氧化 二鈕與二氧化鈦堆疊層；以及e)加熱堆疊層之溫度範圍在 約40(TC至約55(TC，（五氧化二以（二氧化欽）y介電層從而 得之。 在此具ft:實施例中，如以五乙醇鈕做爲第一 源氣體，第二源氣體可爲選自包括水蒸氣（H2〇）、氧氣 、氧化二氮（N2〇)氣體、醇類（cxHyOH)氣體與類似材質群組 中之氣體。在另一方面，以氯化妲（TaC15)做爲第一源氣體 ;第二源氣體可爲選自包括水蒸氣、氧氣、氧化二氮氣體 、醇類氣體與類似材質群組中之氣體。在步·驟b)中，所来 成之五氧化二鈕薄層厚度以低於或等於丨〇埃較佳。以四氣 化欽（TiCi；)做爲第三源氣體，第四源氣體可爲選自包括水 洛氣、氧氣、氧化一氮氣體或類似材質群組中之氣㈣。在 步驟c)中，所形成之二氧化鈦薄層厚度以低於或等於5埃較 佳。需注意到步驟e)可在較高電極成型後再執行。 (請先閱讀背面之注意事項再填寫本頁) 裝--------訂·--------· 經濟部智慧財產局員工消費合作社印製 -8- 474004 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（
(五氧化二备、 ί ^ η λ, X Q·92 (―乳化鈦）0.〇8堆疊層之厚度範圍在約 lOOi矢至約200埃齡社 _ ^ .. 心 。而注忍到步躁b)與步驟c)之循環要控 > 爲2 y爲〇.〇8。在步驟b)後，本發明之較佳具體實 =例包括將第—惰性氣體引入反應槽中α.ι·Η)秒，俾驅除殘 :在反應槽中之第—與第二源氣體之步驟。在步驟^後， ^ 1兒g 126之成型更包括將第二惰性氣體引入反應槽中 〇心俾驅除殘存在反應槽中之源氣體與第—惰性氣體 之步驟。 舲堆&層定樣爲預定組態，如圖2C所示。 、接下來的步驟中，第二介電層⑶成型於第一介電層126 、 固2D所示。在此較佳具體實施例中之第二介電層 ⑶係以原子層沉積法’由諸如氧化銘之高K介電材質製成。 多閲圖2E，例如以氮化碳製得之第一較高電極層130，係 以原子層笟積法，成型於第二介電層128之上，以增進第二 :電層128與第二較高電極層132間之黏著。在此較佳具體 貝她例中I原子層沉積法採用四氯化鈦及氨（NH4)，做爲反 應源氣體。 之後，第一較鬲電極層132成型於第一較高電極層130之 如圖2F所tf。第二較高電極層132由選自包括複晶矽、 鎢、氮化鎢、X矽化鎢與類似材質群組中較佳。 沭後扣第一較鬲電極層132、第一較高電極層13〇、第二 介％層128，以及第一介電層126定樣爲記憶體區塊。 最後，例如以硼磷矽酸鹽玻璃製得之絕緣層15〇，其係採 仃堵如電漿化學蒸鍍汽相沉積法成型於電容結構140之上， 裝--------訂---------^9. (請先閱讀背面之注意事項再填寫本頁)
本紙張尺度適財國國家標準（CNS)A4規格（210 X 297公爱 474004
五、發明說明（7 並採用諸如化力學拋光（CMP)的方法，使並 2G所示。 ’、 一 ，如圖 藉由採行（五氧化(二氧化鈥)y與氧化純爲電容人 電質，本發明可提升電容介電之總介電係數，以： 流。很明顯地，(五氧化二以(二氧化欽、之採用：使‘ 總介電《增力”且氧化鋁可避免較高電核與其間之介面 發生反應’漏電流因而減少。 雖然本發明已於相關之特定具體實施例中描述，熟悉此 技藝者應可瞭解，在不偏離下列專利申請 發明謝，不同的變化與修正均屬可行執圍所疋出〈本 --------^--------- (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制衣 ο 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）

Claims (1)

  1. 經濟部智慧財產局員工消費合作社印製 474004 A8 B8 -~_____D8___ 六、申請專利範圍 1 ·—種用於記憶胞之半導體裝置，其包括： 配有半導體基座之主動陣列、多個成型於半導體基座 上之電晶體，以及與該等電晶體導電連結之導體塞； 數個成型於導體塞上方之底部電極； 成型於底邵電極上之合成膜；以及 成型於合成膜上之氧化鋁（Al2〇3)膜。 2.如申請專利範圍第1項之半導體裝置，其中之底部電極之 材質可選自包括複晶矽、鎢、氮化鎢、χ矽化鎢、氮化飲 、銘、条、敏與類似材質之群組中。 3 .如申請專利範圍第2項之半導體裝置，其中之合成膜係以 原子層沉積法，由（五氧化二妲丸92 (二氧化鈦）gq8製得。 4.如申請專利範圍第3項之半導體裝置，更包括氮化鈦膜， 以及完滿成型於氧化鋁膜上之較高電極。 5 一種用於記憶體裝置之半導體裝置製造方法，此方法所 含步驟包括： a) 製備主動基礎，其配置至少一個電晶體、多個與電 晶體導電連結之導體塞，以及成型於導體塞週邊之絕 層； 、、 b) 形成主動基礎上方之導體層； c) 依預足組怨足樣導體層，從而產生數個底部電極； d) 形成底邵電極上之（五氧化二鈕）χ(二氧化鈦）y合成 層，X ? y分別表示分子比例； e) 形成（五氧化二鈕）χ (羊氧化鈦夂合成層上之介電層 ;以及： -11 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------0^--------訂---------綠 (請先閱讀背面之注意事項再填寫本頁) __ 474004 A8 B8 C8 D8
    、申請專利範圍 6. 7. f)足樣介電層與（五氧化二妲）χ(二氧化鈦）y合成層爲 預設組態。 如申請專利範圍第5項之方法，其中之底部電極之材質可 局選自包括複晶矽、鎢、氮化鎢、χ矽化鎢、氮化鈦、鉑 、如、敏與類似材質之群組中。 如申請專利範圍第5項之方法，其中之步驟幻包括步驟： dl)依序將第一與第二源氣體引入反應槽中，以形成五 氧化二备薄層； d2)依序將第三與第四源氣體引入反應槽中，以形成五 氧化二包薄層上之二氧化鈦薄層； d3)重複步驟di)與步驟J2)，形成五氧化二备與二氧化 鈦堆疊層；以及 ' d4)加熱堆疊層之溫度範圍在約4〇(rc至約55〇。〇，（五氧 化二鼓）χ(二氧化鈦）y合成層從而得之。 8. 如申請專利範圍第7項之方法，其中如以五乙醇鈕 (Ta(C2H5〇)5)做爲第一源氣體，第二源氣體可選自包括水 蒸氣、氧氣、氧化二氮氣體、醇類（CxHy〇H)氣體與類似 氣體之群組中。 9. 如申請專利範圍第8項之方法，更包括維持反應槽之溫度 範圍在約250X：至約350°C之步驟。 10. 如申請專利範圍第7項之方法，其中之五氧化二鈕薄層厚 度低於>或等於1〇埃。 1.如申μ專利範圍第7項之方法，其中如以四氯化鈦做爲第 三源氣體，第四源氣體可選自包括水蒸氣、氧氣、氧化 -12· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐 --------------------訂---------線 PAW. (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制衣 474004 A8 d —----- -58__ 六、申請專利範圍 一氮氣體或類似氣體之群組中。 U·如申請專利範圍第：^項之方法，其中之二氧化鈦薄層厚 度低於或等於5埃。 13. 如申請專利範圍第7項之方法，其中之（五氧化二妲、μ (二氧化鈦）G 堆疊層之厚度範圍在約1〇〇埃至約2〇〇埃。 14. 如申請專利範圍第7項之方法，其中步驟心）與步騍们）之 循環要控制在X爲0.92以及y爲0.08。 15. 如申請專利範圍第7項之方法，在步驟dl)後，更包括將 第一惰性氣體引入反應槽中0.1 -10秒，俾驅除殘存在反 應槽中之第一與第二源氣體之步驟。 16. 如申請專利範圍第15項之方法，在步驟d2)後，更包括將 第一惰性氣體引入反應槽中〇. 1 〇秒，俾驅除殘存在反 應槽中之源氣體與第一惰性氣體之步驟。 17·如申請專利範圍第7項之方法，其中之介電層包括氧化 鋁。 二 18. 如申請專利範圍第Π項之方法，更包括（五氧化二鉅）χ(二 氧化钕）y合成層與介電層之熱處理，以及在氧化二氮存 在的狀況下’採用之溶爐溫度範圍在約6 〇 〇 °C至約8 5 0 °C 之步驟。 19. 如申請專利範圍第18項之方法，更包括氮化鈦層完滿成 型於介電層上之步驟。 20. 如申貧專利範圍第7項之方法，其中如第一源氣體爲五氯 化叙，第二源氣體可選自包括水蒸氣、氧氣、氧化二氮 氣體或類似氣體之群組中。 -13- 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） ---------------------^---------^ (請先閲讀背面之注意事項再填寫本頁)
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US7012001B2 (en) 2006-03-14
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KR100705926B1 (ko) 2007-04-11
US20020020869A1 (en) 2002-02-21
US20040082126A1 (en) 2004-04-29

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