TW498483B - Borophosphosilicate glass incorporated with fluorine for low thermal budget gap fill - Google Patents

Borophosphosilicate glass incorporated with fluorine for low thermal budget gap fill Download PDF

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Publication number
TW498483B
TW498483B TW088116982A TW88116982A TW498483B TW 498483 B TW498483 B TW 498483B TW 088116982 A TW088116982 A TW 088116982A TW 88116982 A TW88116982 A TW 88116982A TW 498483 B TW498483 B TW 498483B
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Taiwan
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patent application
item
scope
fluorine
source
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TW088116982A
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English (en)
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Ashima B Chakravarti
Richard A Conti
Frank V Liucci
Darryl D Restaino
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Ibm
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  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

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498483 五、發明說明() 發明領 本發明係關於-種製造半導體元件的方法‘,特別係關 於在半導體元件上形成一層低溫、低黏度、摻雜了氟之硼 磷矽玻璃層(FBPSG)的方法。 發明背景: 在製造半導體電子元件組成物時,需將該組成物密封 於玻璃中或是以玻璃作為導電層間的界面。一般來說,該 玻璃層係為以化學氣相沉積(CVD)法沉積在組成物表面的 二氧化矽層。因業界持續需求更精細的電路圖案及更高的 電路密度,因此必需研發出在製造過程中能用來分隔半導 體表面、具改良性質的玻璃層。諸如高密度隨機動態存取 心憶體(DRAMs)或邏輯晶片等這類較高級的半導體元 件’對所有熱處理製程步驟的時間、溫度及環境要求也較 嚴格。 諸如删鱗碎玻璃(BPSG)薄膜或薄層這類的破璃層對 較高級DRAM元件的平坦化而言相當重要,這類較高級的 半導體元件的閘極高度及積體電路密度均較高。這類掺雜 玻璃的氧化層可降低玻璃層融點並使該層得以軟化並重 流’而於半導體元件表面上再創造出另一個平坦表面。一 般來說,該BPSG層可於其玻璃轉換溫度(約界於800-850 °C間)範圍内沉積後再重新回流。該玻璃轉換溫度乃是所 沉積玻璃開始回流的溫度。該破璃轉換溫度主要係與 BPSG之硼及磷濃度相關,且與沉積製程相關。 第5頁 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---------線一 經濟部智慧財產局員工消費合作社印製 498483 經濟部智慧財產局員工消費合作社印制衣 A7 B7 五、發明說明() 該重流溫度需低到足以繼續有效的執行製事,並避免 在製程中對半導體元件造成溫度傷害。隨著更精細的電路 圖案及更高電路密度的需求增加,因此亟需一種不會在該 玻璃氧化層或其表面缺陷上造成間隙,並能在半導體元件 表面上充填更小間隙的玻璃氧化層。迄今’用於導電層間 的BPSQ層可提供結構,寬度為〇·1 μπι及深寬比為6 : ;ι 之無間隙式的充填。 但是,對具有較高閘極高度及積體電路密度之DRAM 及邏輯晶片而言,亟需一種能在7 5 0 °C以下進行充填、深 寬比為6 : 1、不會損害晶片的無間隙式充填法。因此, 在降低DRAM及邏輯晶片之熱預算上’需降低製程中 BPSG層的黏度以提供結構一種深寬比為6 : 1之無間隙 式的充填方式。可藉由增加重流溫度來降低BPSG層的 黏度,但此為不欲求的方式,或是藉由增加BPSG層中 硼、磷摻雜物濃度來降低BPSG層的黏度。此外,所沉 積間隙的大小(亦即,在薄膜被退火重流並降低或去除間 隙前)也需愈小愈好。隨著一窄小特徵之深寬比增加及可 允許的熱預算降低之際,減低所沉積間隙之體積大小也 變得愈加重要。 已知摻雜氟可增加 BPSG層的表面張力並降低黏 度,但僅能在深寬比高達6 : 1時才能提高低溫下的充填 特性。但是,對硼及磷這兩種摻雜物而言,每一種摻雜 物濃度均限於5 %以下,因為當濃度超過此值時會造成沉 積後的表面長出硼酸或硼磷酸晶體。基於後續關於光 第6頁 >紙張尺度適flT中國國家標準(CNS)A4規格(210 X 297公釐) -----------装--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) A7 B7 五'發明說明( 刻、反應性離子蚀刻及化學機械研磨製程這麵積_ 程的考量,因此表面結晶乃是不欲求的現象。 丹者 知摻雜物濃度也會導致薄膜變得潮濕。 由於前技的不足及缺點,因此本發明的目標之— 供一種在諸如半導體晶圓等基材上形成氟化之哪_ 璃的方法,該晶圓基材並具有改良的沉積間隙充填考寺 較低的重流溫度,且不會產生結晶缺陷。 本發明的另一目標係提供一種形成具有更佳間 填能力之硼磷矽玻璃的方法,以提供結構深寬比大於 之無間隙充填。 本發明的其他優點及目的部分為顯而易知的,部 在將過說明書的記載内容後變得明顯。 化過 ,増 係提 矽破 性及 隙充 6:1 分則 f請先閱讀背面之注咅?事項再填寫本頁) >裝 經濟部智慧財產局員工消費合作社印製 發明目的及概诫: 習知技蟄人士將能輕易藉由本發明的說明了解本發 明之上述目的及其他優點。本發明的主要目的係提供一種 在化學氣相沉積室中以下列步驟於一半導體基材上形成 一摻雜了氟的氧化玻璃層的方法,該方法至少包含下列步 驟: (a) 提供一半導體基材於一室中; (b) 提供一氣態的矽來源; (c) 提供一氣態的氧來源; (d) 提供一氣態的氟來源; (e) 提供一氣態的硼來源; 第7頁 表紙張尺度適用中國國家標準(CNS)A4規格(2i〇x 297公f ---—訂---------線. 498483 A7 B7 驟 層 五、發明說明( (0提供一氣態的嶙來源,· (g) 將氣體來源注入一氣相沉積室中;且 (h) 在48〇_65〇°C的溫度及200-750托耳(torr)略低於 大乳壓的情況下,於一半導體元件上沉積一層摻 雜了氟的氧化破璃層。 〉方法較好疋更包含了讓氣體來源物互相反應的步 以便於半導體儿件上沉積一層摻雜了氟的氧化玻璃 邊万法更包含—步驟’該步驟係讓沉積於半導體元 件上摻雜了 #1的氧化破璃層# 48G_725 t的溫度下重 /儿在重"IL 7騍中可包括蒸氣退火(steam annealing)。該 重流步驟及步騾(h)較好是同時進行。 以 於步驟(a)中,诗& μ & )中邊+導體元件可至少包含一邏輯曰 片、一隨機動態存取記情鹘曰 科卵 取記憶體之組合晶片。“或一㈣與隨機動態存 較好疋’步驟(b)中的氣態矽來源至少包含 矽:較好:,步驟⑷中的氣態氟來源係選自氟化三乙: 矽圪_氟矽烷、三氟矽烷及四氟矽烷。當步 虱 氣態氣來源至少包含三氣我或四氣錢時,中的 掺雜了氟的氧化破璃層沉積於半導體元件之前—層 電漿。最好是,步驟⑷中的氣態氟來源至少包括^產生 較好疋,步驟(e)中的氣態硼來源係 基硼酸鹽、三甲基硼酸鹽及其混合物中。較好η ,-乙 ⑴中的氣態铸來源係選自四乙基鱗酸鹽、一,驟 二乙基磷 第8頁
表紙張尺度 t關家#297 /JiT (請先閱讀背面之注意事項再填寫本頁) π裝·-------訂---------線. 經濟部智慧財產局員工消費合作社印製 A7 - -—-------—」B7 _ 五、發明說明() 酸鹽、及其混合物。 幸乂好疋彳參雖了氟的氧化玻璃層可充填深寬比在7 : (請先閱讀背面之注意事項再填寫本頁) 、上之半導元件中深寬比值(aspect ratios)高的間 隙。 較好是’步驟(g)至少包含將各氣態來源分別注入反應 至中。最好疋,步驟(g)至少包含在將氣態來源物注入化學 氣相沉積ί #,先將石夕&氣來源預混合成第一注入氣流, 並將硼及磷來源預混合成第二注入氣流。 較好是,步騾(h)係在約550_65〇t的溫度下進行。 較好疋’步驟(c)中的氣態氧來源係選自臭氧、氧氣 /臭氧混合物及過氧化氫。 較好是’所得摻雜了氟的氧化玻璃層内所含的硼量 約等於5.0%或以下,所含的磷量約等於4〇%或以下,所 含的氟量約等於2 · 0 %或以下。 最後步驟(h)可在半導體元件上產生一層沉積層,或是 在後續仍可繼續進行處理之該半導體元件上產生一層平 坦化的中間層。 經濟部智慧財產局員工消費合作社印製 本發明的另一目的係關於一種在半導體晶圓上充填 高深寬比間隙的方法,該方法至少包含下列步驟: U)提供一深寬比大於7 :丨之半導體晶圓;及 (b)以氟化的硼磷矽玻璃來充填間隙。 步驟(b)更可包含下列步驟: U)提供一氣態的四氧乙基矽來源; (b)提供一氣態的氧來源; ____ 第9頁 表紙張尺度適用中國:標準(CNS)A4規格⑵〇 x 297公釐)'~~ --- 498483 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明() (C)提供一氣態的氟來源,其係選自氟化三乙氧矽 乾、二氟碎燒、三氟碎燒及四氟碎燒; (d) 提供一氣態的硼來源’其係選自三乙基硼酸鹽、 三甲基硼酸鹽及其混合物; (e) 提供一氣態的鱗來源,其係選自四乙基嶙酸鹽、 膦、三乙基磷酸鹽、及其混合物;和 (f) 於約480-65 0°C及約200-700托耳下,以氣相沉 積法沉積該絕緣玻璃層。 其中該絕緣玻璃層中含重量百分比約為5 〇0/。或5.0%以下 的棚,約4.0%以下的磷,及約〇.1 %-2.〇%的氟,且幾乎不 含任何間隙。 該方法更可包含將絕緣玻璃層在約700。(:至725。(:的 溫度下退火的步驟。 本發明的另一項目的係關於在半導體晶圓上形成一 層絕緣層的方法,該方法至少包含以下步騾: (a) 提供一半導體晶圓複數個高深寬比的間隙; (b) 提供一氣態的矽、氟、爛、磷及氧來源,以便在 約480-6 50°C及約200-760托耳的壓力下,以每 分鐘約400-1 000A的速率,藉由化學氣相沉積法 將第一層絕緣玻璃層沉積於晶圓上; (c) 以内含重量百分比約為5 · 0 %或5.0 %以下的侧、 約4.0%以下的磷及約0.1 %-2.0%的氟之第一層絕 緣玻璃層來充填間隙;且 (d) 以化學氣相沉積法將第二層絕緣玻璃層沉積於 第10頁 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) 498483 A7
經濟部智慧財產局員工消費合作社印製 五、發明說明() 晶圓表面上,該第二層絕緣玻璃層内所含之棚、 氟及嶙濃度較第一層絕緣玻璃層内濃度為低。 較好是,該矽來源物係以約10.8至32.25 seem的速 率流進反應室中,更好是以内含四氧乙基石夕的形式、並以 約1 8 · 8 s c c m的速率流進反應室中。較好是’該氟來源物 係以約2.5 0至9 · 8 5 seem的速率流進反應室中’更好是以 内含氟化三乙氧基矽烷的形式、並以約6.2 seem的速率流 進反應室中。較好是,該硼來源物係以約3.07至12.27 seem 的速率流進反應室中’更好是以内含三乙基删故鹽的形 式、並以約7 · 7 s c c m的速率流進反應室中。較好是,該磷 來源物係以約2 · 5 0至9.8 5 seem的速率流進反應室中’更 好是以内含三乙基磷酸鹽的形式、並以约4 · 9 s c c m的速率 流進反應室中。 較好是,步驟(d)至少包含以化學氣相沉積法將一未摻 雜的玻璃層沉積於一晶圓表面上。 該方法更可包括以低於700°C的溫度將第一及第二絕 緣玻璃層退火的步驟。 圖式簡單說明: 本發明所提出的特點具新穎性。附圖係為闡述本發之 用’因此並未以實際尺寸繪出。但可藉由附圖說明來了解 本發的組織及其操作方法。 第1圖為典型半導體晶圓在沉積一層絕緣玻璃層之前 的部分剖面示意圖。 —------.一 —_^ 第”頁 本紙張尺度適標準(CNS)A4藏721〇 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) « — — — III— 一(口T I .! I I 1 I I I . A7 經濟部智慧財產局員工消費合作社印製 五、發明說明() 弟2圖^爵右* ϋ , 則技所沉積的絕緣玻璃層之半導體晶圓 的邵分剖面示意圖。 第3圖為具有本發明幾乎不含任何間隙及表面缺限之 絕緣玻璃層的丰!_ 反曰曰Β]的部分剖面示意圖。 昨圖為用於本發明中、壓力在大氣壓以下之化學氣 相沉積室的剖面圖。 還號對照諸Bg| : 10 矽基材 15 多矽閥導電極 20 絕緣玻璃層 22 間隙 24 表面結晶 30 FBPSG 層 40 反應室 45 晶圓 50 基座 55 蓬頭 發明詳細說明: 以下,係依據圖示來詳細說明本發明之較佳實施例。 、據本發明所製成的F B p s G係可作為半導體元件之 取、、、的絕緣層或中間的介電絕緣層,這類半導體元件包括 堵如互補金屬氧化物半導體(CM〇S)或其他晶片或亟需具 重流特性之絕緣層的電子元件等。在此,,,半導體元件,,一 詞係包括任何一種前述开 ^ ^ 月J边7L件,包括DRAM晶片、邏輯晶 片、及DRAM與邏輯晶片組合。 如第1圖所示’在一半導體元件之矽基材1〇表面上 形成了數個金屬合金或多矽閥導電極15。矽基材1〇可包 参紙張尺度適用中關家標準(CNS)A4規格(21: 第12頁 x 37公釐) (請先閱讀背面之注意事項再填寫本頁) ▼裝--------訂---------線.
Τ7〇1·〇 J Α7 五、發明說明() 含或不包含姆丰壤轉- 千令随7L件處理非常必要的額外的薄層。本 月對界於,木寬比(深丨比上寬度)在6 : 1以上之閥導電極 勺溝木或通道最具應用價值,其中通道寬度(,,w,,)約為 〇·〇5 μΓη,且”d,,係為通遒深度。 參閱第2圖,所示為未能為商界接受的一種前技積體 私路結構,位於基材1〇上的絕緣玻璃層2〇,具有一内含 門隙22和/或表面結晶24之閥導電極1 $。位於閥導電極 1 5間的溝渠或通道必需以絕緣玻璃層完全充填,且不能留 下月顯的間隙或表面缺陷。一般當摻雜了硼及磷的絕緣玻 璃層之摻雜物濃度大於10%時,就會生成表面結晶24。 一般係以化學氣相沉積加上重流來形成絕緣玻璃 層典型的情況是’將絕緣玻璃層重流可降低間隙的數 目但疋,重流後的結構表面仍可能出現表面結晶。此外, W技中硼、磷含量大於5%之絕緣玻璃層通常都很潮濕。 第3圖顯示一依據本發明方法製成並具有絕緣玻璃層 的半導體元件。一半導體基材10,其上有一系列的閥極或 是升高的線1 5,在該閥極或是升高的線上覆有依本發明方 法製成的FBPSG層30。該FBPSG層30上幾乎不含任何 氣泡或表面缺陷,且此類型覆有破璃層的電子元件乃是電 子製造業者所欲求的。在略低於大氣壓下的化學氣相沉積 室中進行製作,該FBPSG層較好是含有濃度等於5%或略 低於5%的硼,濃度略低於4%的磷,及濃度約為〇1_2〇% 的氟。該略低於大氣壓下的化學氣相沉積室較好是能讓本 發明的氣態前驅物能由沉積室的頂端被導入室中,此 σ 乃疋 第13頁 (請先閱讀背面之注意事項再填寫本頁) 擎裝---- 訂---------線| 經濟部智慧財產局員工消費合作社印製 498483 五、發明說明( 習知的 經濟部智慧財產局員工消費合作社印製 併入本發明BPSG層的氣係藉由氣態的麟及棚捧雜物 及以氟來源㈣(較好是氟化乙氧形成的。該氣態 反應物也可包括一軋態的氧來源,該氣態的氧來源可包含 臭氧、臭氧及氧氣的混合物、或過氧化氫。由製程操作的 觀來看,職體混合物中—般也會包含一諸如氬氣、氮氣 或氦氣的惰性載體氣體。 最好疋’孩氣癌碎來源乃是四氧乙基矽(TE〇s)。該氣 怨硼及磷來源物可包括任何—種内含硼或磷的氣體。該氣 態硼及磷來源物也可包括不會干擾FBpsG層形成的其他 物負’该其他物質並能在特定的製程壓力及溫度範圍下分 解及與TEOS及氟來源一起與氧氣來源物共同反應。較好 是’這類氣怨棚及磷來源物屬於内含有機硼及磷的氣體, 並能在分解溫度下分解後與其他殘存的氣體組成一起被 反應室中用來保持真$的真空系統揮發並移除。 這類测、磷氣體更好是也包括三乙基硼酸鹽(TEB)、 三甲基硼酸鹽(TMB)、膦、三乙基磷酸鹽(TEP0)及其類似 物與混合物。最好是,這類硼、磷氣體分別是TEB及 TEPO,因為這兩種氣體最有效。氟氣體較好是氟化三乙 氧基矽烷(FTES)、二氟矽烷、三氟矽烷及四氟硬烷;最好 是F T E S。當氟氣體為四氟碎坑及三氟碎垸^時,必須在沉 積室中點燃一種電漿,以便將FBPSG層沉積於基材上。 一般以習知的液體注入系統而將反應物蒸氣來源與 諸如氮氣、氬氣或氦氣等惰性載體氣體混合。一般來說, 第u頁 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---- — — — — — — 經濟部智慧財產局員工消費合作社印制衣 498483 A7 ______ B7 __ 五、發明說明() 液體注入系統係使用加壓液體管線來傳輸一液體反應物 至一洞穴中,該液體反應物於該洞穴中被蒸發氣化,而後 導入反應室中。如果所需導入反應室的氣體混合物超過1 種’先將每一種液體單獨氣化後再以氣體混合物方式注 入。也可將氣體反應物和或蒸發的液體反應物單獨注入反 應室中。該反應物蒸氣彼此反應後會在基材上形成FBPSG 層並充填其中的間隙。 第4圖示出反應室4 0,其内有四種氣體反應物分別經 由蓬頭55注入反應室40中。晶圓45係經由基座50加熱 到約4 8 0 °C至6 5 0 °C的反應溫度。反應室中的壓力約在2 〇 〇 至7 6 0托耳間。或者,一種較好的方法係將删及磷掺雜物 氣體來源與適當的惰性載體氣體混合成一種注入氣流,而 TEOS及FTES至少包括另一種注入氣流。氧氣也可與上 述氣流之一或兩者混合在一起。 在一較佳實施例中,係使用約50(TC的沉積溫度,該 溫度可提供所沉積之FBPSG層於沉積製程中同步進行重 流。由於此同步重流過程中,無論深寬比值為高或低的晶 圓間隙均可在無需進一步重流退火的情況下進行充填。無 論所使用沉積條件為何,在典型沉積製程後通常都需要在 5 0 0-725 °C的溫度下進行退火。但是,間隙深寬比值低的 半導體基材可能不需要後續的退火程序或是重流來完全 充填間隙。如此可提高操作效率並降低製程成本。此外, 本發明製程溫度係遠低於DRAMs及多數邏輯晶片之熱預 % ° ……、 第15頁 (請先閱讀背面之注意事項再填寫本頁) 訂---------線i 經濟部智慧財產局員工消費合作社印製 498483 A7 B7___ 五、發明說明() 沉積室中的氣體反應物流速,對TEOS而言,較好是 界於每分鐘32.25- 75.26標準立方釐米(sccm^,最好是 約5 3.8 seem ;對FTES而言較好是界於約6.15-61.5 sccm 間’最好是約12·3 seem;對TEPO而言較好是界於約 2.5-9.85 seem間,最好是約4.9sccm;對TEB而言較好是 界於約1 5.34-30.70 seem間,最好是約23.0 seem ;且氧氣 /臭氧混合物係以每分鐘約2 - 6標準立方升(s 1 m)的速率流 動,最好是約4 slm。由於這些參數,因此沉積速率約為 每分鐘2,000-6,000A。一般來說,所使用反應物流速需能 使FBPSG層的組成分中含約2·0-5·0%的硼、2.0-4.0%的磷 及約0.1-2.0%的氟。 本發明的另一實施例至少包括一種兩步驟的方法,該 方法可充填半導體晶圓中深寬比值大於6 : 1的間隙。使 用同樣的氣體反應物,可以每分鐘約600Α之較低的沉積 速率沉積一 FBPSG層。一般來說,所得FBPSG層之硼及 磷濃度為硼濃度等於或略低於5.0%,而磷濃度約為 4.〇%,氟濃度則約界於0.1-2.0%間。該FBPSG層幾乎可 完全充填深寬比值大於6 : 1、寬度約為500 A的間隙。該 FBPSG層係在壓力約低於大氣壓、600托耳、及約500°C 的化學氣相沉積室沉積出來的。 氣體反應物係以下列流速流進反應室中:對矽而言, 流速約為1 〇.80至32.25 seem ’ TEOS流速最好是18·8 seem;對氟而言,流速約為2.50至9.85 seem,FTES流速 最好是6.2 seem ;對磷而言’流速約為2·5至9·85 sccm, 第16頁 >紙張尺度適用中國國家標準(CNS)A4規格(21^297公爱) ---------------------訂---------線 . (請先閱讀背面之注意事項再填寫本頁) 498483 A7 __________B7 ___ 五、發明說明() TEPO流速最好是4.9 seem ;對硼而言’流速約為3.07至 12.27 seem,TEB流速最好是7_7 seem;且臭氧/氧氣的流 速約為4.0 slm,且反應室中所含臭氧重量百分比約為 12%。 在沉積FBPGS層後,接著是沉積一層厚度至少為3000 A至6000A的絕緣玻璃層。此較厚的層可充填寬約5000人 的大間隙,並可覆蓋整個晶圓表面並將其平坦化。此厚的 絕緣層中並不一定需要含摻雜物,或是可含低量的硼、 磷、及氟,其所含摻雜物濃度遠低於其下層FBPGS層之 摻雜物濃度。在沉積該厚的絕緣層後’可於700°C或略低 於700°C的溫度下進行蒸氣退火。同樣的,此製程溫度係 遠低於DRAMs及多數邏輯晶片之熱預算。 實施例 本發明的FBPGS層係依上述第一實施例之製程於化 學氣相沉積室中進行,亦即,應用材料公司的 P5000 SABPSG反應室。以下附表比較了前技的BPSG層與本發 明之FBPSG層,兩者分別以沉積層型式或經退火程序處 理後之層來充填間隙的結果。 以具深寬比約為1 : 1、且寬度約為〇·3μπι間隙的半 導體晶圓作為前技BPSG層與本發明FBPSG層品質的比 較。所沉積之層係於480°C、200托耳壓力下進行。 第17頁 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) 1 n ϋ·· an ·.—」fl 1· n 1 I afli n I ! * 秦 l 經濟部智慧財產局員工消費合作社印製 498483 A7 B7 五、發明說明() 經濟部智慧財產局員工消費合作社印製 表I 沉積層 層 [B] [P] [F] 結果 (wt%) (wt%) (wt%) BPSG 4.5 4.2 - 明顯間隙 FBPSG 4.5 4.0 2.0 幾無間隙 前技的BPSG層出現明顯間隙,而本發明FBPSG層則幾乎 沒有任何間隙。 以具深寬比約為8 : 1、且寬度約為〇 · 〇 4 μ m間隙的半 導體晶圓作為前技B P S G層與本發明F B P S G層經乾燥氧化 退火程序處理後其品質的比較。所沉積之層係於4 8 〇 、 200托耳壓力下進行。 表η 經退火虛理後的絕n 層 [B] (wt%) [P] (wt%) [F] (wt%) 退火溫度 (°C ) 退火時間 (分鐘) 結果 BPSG 4.6 4.0 _ 850 25 明顯間隙 FBPSG 4.4 4.0 2.0 750 30 幾無間隙 前技之BPSG層需於約850t下退火25分鐘。前技絕緣層 於咼溫退火後’仍出現無法為商界接受的明顯間隙。本發 明之FBPSG層則於約750。(:下退火30分鐘後即可製造出 幾無任何間隙的絕緣層,可直接用於後續製程或當成最終 第18頁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公髮) -------------------^--------- (請先閱讀背面之注意事項再填寫本頁) 498483 A7 ___ __ 五、發明說明() 介電層來使用。 本發明可達成上述各項目標。依本發明方法沉積的 FBPSG層無論是否經退火,均具有優異的間隙充填性質, 可充填深寬比高達6 : 1之間隙。所得FBPSG層所需重流 溫度較低,因此可避免製程中因高溫導致的晶圓傷害。因 本發明FBPSG層的低黏度,因此無需增加硼、磷摻雜物 濃度,因此也可降低出現表面結晶缺陷的機率並使潮濕度 維持在最低狀態。 本發明已藉由上述貫施例作了詳盡說明,需知在不悖 離本發明精神範疇下,可對本發明作許多修改或變化,這 些修改或變化應仍視為涵蓋於本發明範轉内。 (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 貰 9 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公釐)

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  1. 498483
    經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 1 · 一種於化學氣相沉積元件上形成一層 掺雜了氟的氧化玻璃層的方法至少包含下列 步騾: (a) 提供一半導體元件於一室中; (b) 提供一氣態的碎來源, (c) 提供一氣態的氧來源, (d) 提供一氣態的氟來源, (e) 提供一氣態的硼來源, ⑴提供一氣態的磷來源, (g) 將氣體來源注入一氣相沉積室中;且 (h) 在480-650T:的溫度及200·750托弄(t〇r〇之低於 大氣壓的情況下,於一半導體元件上沉積一層 掺雜了氟的氧化玻璃層。 2. 如申請專利範圍第1項所述之方法,其更包含在 4 8 0-72 5 °C的溫度下於該半導體基材上重流該摻雜氧 化玻璃層的步驟。 3. 如申請專利範圍第2項所述之方法’其中該重流步驟 至少包含蒸氣退火。 4. 如申請專利範圍第2項所述之方法’其中該重流步驟 與步驟(h)係同時發生。 第20頁 本紙張尺度適用中國國家標準(CNS ) Μ規格(210Χ297公釐) ---------^裝------訂 I----- (請先閱讀背面之注意事項再填寫本頁) 498483 8 8 8 8 ABCD 六、申請專利範圍 5.如申請專利範圍第i項所述=方法’其中步驟⑷之該 半導體元件至少包括/遽輯0曰片 (請先閱讀背面之注意事項再填寫本頁) 6·如申請專利範圍第i項所述之方法其中步驟(a)之該 半導體元件至少包括一動態隨機存取記憶體晶片。 7·如申請專利範圍第1項所述之方法/、中步驟(a)之該 半導體元件至少包括一遂輯與動態隨機存取記憶體 之組合晶片。 8 · 如申請專利範圍第1項所述之方法’其中步驟(b)之氣 態碎來源至少包括四氧乙基梦(tegs)。 9· 如申請專利範圍第1項所述之方法’其中步驟(d)之氣 態氟來源係選自氟化之三乙氧基碎燒、二氟矽烷、三 氟石夕垸、及四氟矽烷。 經濟部智慧財產局員工消費合作社印製 10·如申請專利範圍第1項所述之方法,其中該氣態氟來 源至少包含三氟矽烷或四氟矽烷,且其中步驟(h)之電 漿係於該摻雜了氟之氧化玻璃層被沉積在該半導體 元件前所產生的。 1 1.如申請專利範圍第1項所述之方法,其中步驟(d)之氣 態氟來源至少包含氟化之三乙氧基矽烷。 第21頁 本紙張尺度適用中國歐家標準(CNS )八4祕(210X297公酱) 一-- 498483 經濟部智慧財產局員工消費合作社印製 Λ8 B8 C8 D8 " __________________夂、申請專利範圍 1 2 .如申請專利範圍第1項所述之方法,其中步驟(e)之氣 態硼來源係選自氟化之三乙基棚酸鹽、三甲基硼酸鹽 及其混合物中。 13.如申請專利範圍第丨項所述之方法’其中步驟(f)之氣 態磷來源係選自四乙基璘酸鹽、膦、三乙基磷酸鹽、 及其混合物中。 14·如申請專利範圍第1項所述之方法’其中該摻雜了氟 之氧化玻璃層可充填半導體元件上深寬比大於7: 1 之高深寬比間隙。 15·如申請專利範圍第1項所述之方法’其中步驟(g)至少 包含將該氣體來源分別注入該反應室中。 16·如申請專利範圍第1項所述之方法’其中步驟(g)至少 包含在將各氣體來源注入化學氣相沉積室前,預先將 該矽及氟來源混合成第一注入氣流’並預先將該硼及 磷來源混合成第二注入氣流° 1 7.如申請專利範圍第1項所述之方法,其中步驟(h)係發 生於550。(:至65 0°C的溫度下。 1 8·如申請專利範圍第1項所述之方法’其中步騾(c)中的 第22頁 本紙張尺度適用中國國家標準(CNS〉Α4規格(210Χ297公釐) (請先閱讀背面之注意事 1·. •項再填· 裝--I •寫本頁) 、1T 4 498483 Λ 8 Β8 C8 D8 六、申請專利範圍 氧氣來源係選自臭氣、氧氣/臭氣混合物、及過氧化 氫中。 (請先閱讀背面之注意事項再填寫本頁) 19. 如申請專利範圍第1項所述之方法,其中該摻雜了氟 之氧化玻璃層中含有重量百分比為5.0%或5.0%以下 的砸1。 20. 如申請專利範圍第1項所述之方法,其中該摻雜了氟 之氧化玻璃層中含有重量百分比4 · 0 %以下的磷。 21. 如申請專利範圍第1項所述之方法,其中該摻雜了氟 之氧化玻璃層中含有重量百分比為 0.1 %至 2.0%的 氟。 22. 如申請專利範圍第1項所述之方法,其中步驟(h)係於 該半導體元件上形成一最終的沉積層。 經濟部智慧財產局員工消費合作社印製 23. 如申請專利範圍第1項所述之方法,其中步騾(h)係於 該半導體元件上形成一平坦的中間沉積層,且更包含 後續繼續處理該半導體元件的步驟。 24. 如申請專利範圍第1項所述之方法,其更包含讓氣體 來源互相反應以於該半導體元件上沉積一層摻雜了 氟之氧化玻璃層的步驟。 第23頁 本紙張尺度適用中國國家標準(CNS )"a4規格(210X297公釐) 498483 A8 B8 C8 D8 六、申請專利範圍 (請先閱讀背面之注意事項再填寫本頁) 2 5. —種充填半導體晶圓上高深寬比值間隙的方法,該方 法至少包含下列步驟: (a) 提供一間隙深寬比值大於7 : 1之半導體晶圓; 且 (b) 以氟化之硼磷矽酸鹽玻璃來充填該間隙。 26. 如申請專利範圍第25項所述之方法,其中步驟(b)至 少包含下列步驟: (a) 提供一氣態的四氧乙基矽來源; (b) 提供一氣態的氧氣來源; (c) 提供一氣態的氟來源,其係選自氟化的三乙氧基 矽烷、二氟矽烷、三氟矽烷、及四氟矽烷; (d) 提供一氣態的硼來源,其係選自氟化之三乙基硼 酸鹽、三甲基硼酸鹽及其混合物中; (e) 提供一氣態的磷來源,其係選自四乙基磷酸鹽、 膦、三乙基磷酸鹽、及其混合物中;且 經濟部智慧財產局員工消費合作社印製 (f) 於480-650°C及200-750托耳壓力下,以氣相沉 積法沉積該絕緣玻璃層。 其中該絕緣玻璃層中含重量百分比為5.0%或 5.0%以下的硼,重量百分比 4.0%以下的磷,及重量 百分比0.1 %-2.0%的氟,且幾乎不含任何間隙。 27. 如申請專利範圍第26項所述之方法,其更包含讓氣 第24頁 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 498483 A8 B8 C8 D8 申請專利範圍 體來源互相反應以於該半導體元件上沉積一層摻雜 了氟之氧化玻璃層的步驟。 (請先閱讀背面之注意事項再填寫本頁) 28. 如申請專利範圍第26項所述之方法,其更包含將該 絕緣玻璃層於700°C至725 °C的溫度下退火的步驟。 29. 一種在半導體晶圓上形成一層絕緣層的方法,該方 法至少包括下列步驟: (a) 提供一半導體晶圓複數個高深寬比的間隙; (b) 提供一氣態的矽、氟、硼、磷及氧來源,以便在 J0-650°C及200-750托耳的壓力下,以每分鐘 kp〇-l,0〇〇A的速率,藉由化學氣相沉積法將 第緣玻璃層沉積於晶圓上; (c) 以内含j量百分比為5.0%或5.0%以下的硼、重 量百分比 4.0%以下的磷及重量百分比為 0.1%-2.0%的氟之第一層絕緣玻璃層來充填間隙;且 (d) 以化學氣相沉積法將第二層絕緣玻璃層沉積於 晶圓表面上,該第二層絕緣玻璃層内所含之硼、 氟及磷濃度較第一層絕緣玻璃層内濃度為低。 經濟部智慧財產局員工消費合作社印製 498483 A8 B8 C8 D8 申請專利範圍 至少包括四氧乙基矽,並 反應室中。
    .8 s c c m的速率流進 3 2.如申讓、專利範圍第29項所述之方法,其中該氟來源 物係 · 5 0至9 · 8 5 s c c m的速率流進反應室中。
    3 3 ·如申請專利竣29項所述之 至少包括氟化三乙氧基矽烷,並 率流進反應室中。
    該氟來源 seem白勺 3 4.如@請專利範圍第29項所述之方法,其中該硼來源 物係: .07至12.27 seem的速率流進反應室中
    35.如申請專邱^獨第29項所述 至少包括三乙基硼酸鹽,並 進反應室中。
    其中該硼來源 seem的速率流 ---- --mu 1^1 m —ϋ ml m ml ϋ ml mu \ Ψ flm mi —ϋ— ϋϋ am (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
    36.如' ^專利範圍第29項所述之方法,其中該磷來源 * 係成、譏 $0至9.85 seem的速率流進反應室中 3 7.如申請專利範圍第29項所 至少包括三乙基磷酸鹽,並 進反應室中。
    其中該磷來源 seem的速率流 第26頁 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) 498483 A 8 B8 C8 D8 六、申請專利範圍 (請先閱讀背面之注意事項再填寫本頁) 38.如申請專利範圍第29項所述之方法,其中步驟(d)至 少包含以氣相沉積法於該晶圓表面上沉積一未經捧 雜的玻璃層。 3 9.如申請專利範圍第29項所述之方法,其更包含於700 °C或700°C以下的溫度將該第一及第二絕緣玻璃層退 火的步驟。 40.如申請專利範圍第29項所述之方法,其更包含,在 步驟(b)後,讓氣體來源互相反應以於該半導體晶圓上 沉積一層摻雜了氟之氧化玻璃層的步騾。 經濟部智慧財產局員工消費合作社印製 第27頁 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)
TW088116982A 1998-12-11 1999-10-01 Borophosphosilicate glass incorporated with fluorine for low thermal budget gap fill TW498483B (en)

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