TWI835883B - 以低電阻率金屬填充半導體元件中之凹陷特徵部的方法 - Google Patents
以低電阻率金屬填充半導體元件中之凹陷特徵部的方法 Download PDFInfo
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- TWI835883B TWI835883B TW108136852A TW108136852A TWI835883B TW I835883 B TWI835883 B TW I835883B TW 108136852 A TW108136852 A TW 108136852A TW 108136852 A TW108136852 A TW 108136852A TW I835883 B TWI835883 B TW I835883B
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- ZLZGHBNDPINFKG-UHFFFAOYSA-N chloro-decyl-dimethylsilane Chemical compound CCCCCCCCCC[Si](C)(C)Cl ZLZGHBNDPINFKG-UHFFFAOYSA-N 0.000 description 1
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- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
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- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
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Abstract
此處提供一種以低電阻率金屬填充凹陷特徵部的方法。所述方法包括提供圖案化基板,所述圖案化基板含有在第一層中形成之凹陷特徵部和暴露於凹陷特徵部中的第二層;及以表面改質劑預處理基板,所述表面改質劑相對於第一層而增加在第二層上的金屬沉積選擇性;利用氣相沉積法在基板上沉積金屬層,其中金屬層優先沉積於凹陷特徵部中的第二層上;並移除沉積在第一層上之金屬核,包括移除在場區域上以及於凹陷特徵部中的第一層之側壁上的金屬核,以在凹陷特徵部中的第二層上選擇性形成金屬層。可至少重複一次預處理、沉積和移除之步驟,以增加凹陷特徵部中的金屬層之厚度。
Description
〔相關申請案〕
申請案有關及主張2018年10月10日提出之美國臨時專利申請案序號第62/744,038號的優先權,其全部內容併入本文做為參考。
本發明有關半導體處理和半導體元件,且更具體地,有關以低電阻率金屬填充半導體元件中之凹陷特徵部的方法。
半導體元件含有填充的凹陷特徵部,例如在介電材料(例如層間介電質(ILD))中形成之溝道或通孔。由於凹陷特徵部底部之金屬層相對於介電材料係具有有限的金屬沉積選擇性,因此凹陷特徵部之選擇性金屬填充是有問題的。這使得難以在凹陷特徵部附近的場區域(水平區域)上以及凹陷特徵部之側壁上開始出現不想要的金屬核沉積之前,於自下而上的沉積製程中用金屬完全填充凹陷特徵部。
本發明之實施例敘述以低電阻率金屬填充半導體元件中的凹陷特徵部之方法。根據一實施例,所述方法包括提供圖案化基板,所述圖案化基板含有形成在第一層中的凹陷特徵部和暴露於凹陷特徵部中之第二層,及以表面改質劑預處理基板,該表面改質劑係相對於第一層而增加在第二層上的金屬沉積選擇性。所述方法更包括利用氣相沉積法將金屬層沉積於基板上,其中金屬層優先沉積在凹陷特徵部中的第二層上,及移除第一層上所沉積之金屬核,包括移除於凹陷特徵部中的第一層之場區域和側壁上者,以在凹陷特徵部中的第二層上選擇性形成金屬層。可至少重複一次預處理、沉積和移除之步驟,以增加凹陷特徵部中的金屬層之厚度。
根據另一實施例,所述方法包括提供圖案化基板,所述圖案化基板含有形成在第一層中的凹陷特徵部和暴露於凹陷特徵部中之第二層,將含金屬層沉積在基板上,包括沉積於凹陷特徵部中,及從凹陷特徵部的底部和從凹陷特徵部附近之場區域各向異性地移除含金屬層,以在凹陷特徵部的側壁上形成含金屬層。所述方法更包括以表面改質劑預處理基板,所述表面改質劑相對於第一層而增加凹陷特徵部之側壁上的含金屬層以及第二層上的金屬沉積選擇性,利用氣相沉積法於基板上沉積金屬層,其中相對於凹陷特徵部附近的場區域,金屬層優先沉積於側壁的含金屬層上和凹陷特徵部中之第二層上,並移除沉積在場區域上的金屬核以在凹陷特徵部中選擇性形成金屬層。可至少重複一次預處理、沉積和移除之步驟,以增加凹陷特徵部中的金屬層之厚度。
根據另一實施例,所述方法包括提供圖案化基板,所述圖案化基板含有於材料中形成的凹陷特徵部;在基板上沉積金屬氮化物層,並包括沉積在凹陷特徵部中及凹陷特徵部附近之場區域上;及氧化場區域上之所述金屬氮化物層。所述方法更包括利用氣相沉積法在基板上沉積金屬層,其中金屬層優先沉積於凹陷特徵部中未被氧化之金屬氮化物層上,及移除沉積在場區域上的金屬核以於凹陷特徵部中選擇性形成金屬層。可至少重複一次沉積和移除之步驟,以增加凹陷特徵部中的金屬層之厚度。
根據另一實施例,所述方法包括提供圖案化基板,所述圖案化基板含有在材料中形成的凹陷特徵部;在基板上沉積金屬氧化物層,包括沉積在凹陷特徵部中及凹陷特徵部附近之場區域上;氮化場區域上以及凹陷特徵部中之所述金屬氧化物層;及氧化所述場區域上之該氮化金屬氧化物層。所述方法更包括利用氣相沉積法於基板上沉積金屬層,其中金屬層優先沉積在凹陷特徵部中未被氧化之氮化金屬氧化物層上;及移除沉積於場區域上的金屬核以在凹陷特徵部中選擇性形成金屬層。可至少重複一次沉積和移除之步驟,以增加凹陷特徵部中的金屬層之厚度。
根據另一實施例,所述方法包括提供圖案化基板,所述圖案化基板含有在材料中形成的凹陷特徵部;在基板上沉積金屬氧化物層,並沉積於包括凹陷特徵部中及凹陷特徵部附近之場區域上;及氮化場區域上之所述金屬氧化物層。所述方法更包括利用氣相沉積法於基板上沉積金屬層,其中金屬層優先沉積在場區域的氮化金屬氧化物層上;及移除沉積於凹陷特徵部中之金屬核,以在場區域上選擇性形成金屬層。可至少重複一次沉積和移除之步驟,以增加凹陷特徵部中的金屬層之厚度。
本發明之實施例提供於半導體元件的凹陷特徵部中選擇性形成低電阻率金屬之方法。所述方法可用於以低電阻率金屬完全填充凹陷特徵部。根據一實施例,利用氣相沉積法的金屬沉積選擇性按以下順序增加:含矽材料>含金屬層>金屬。沉積之金屬可例如包括Ru金屬、Co金屬、或W金屬。金屬沉積的培養時間在金屬上最短,而於含矽材料上最長。培養時間意指在沉積製程期間,直到金屬開始在表面上沉積之延遲。在一實施例中,這可用在相對於凹陷特徵部上方的表面,而優先在凹陷特徵部中形成金屬。含矽材料可包括SiO2
、SiON或SiN。SiO2
可作為層沉積或由Si之氧化所形成,例如藉由暴露至空氣、氧氣(O2
或O)、臭氧、或H2
O來形成。可將SiN沉積為層或藉由Si的氮化來形成SiN、例如藉由暴露至N或NH3
來形成。可將SiON作為層沉積或藉由氮化SiO2
、藉由SiN之氧化、或藉由Si的氧化和氮化來形成。含金屬層可包括金屬氧化物、金屬氮化物、金屬碳化物、金屬矽化物、金屬硫化物、或金屬磷化物。可藉由在Si上進行金屬沉積或於金屬上進行Si沉積來形成金屬矽化物,隨後進行熱處理,或在沉積製程期間形成金屬矽化物。金屬可例如包括Ru金屬、Co金屬、或W金屬。
圖1A-1F概要地顯示根據本發明之實施例的凹陷特徵部中之選擇性金屬形成的方法。金屬可例如選自由Ru金屬、Co金屬、和W金屬所組成之群組。圖案化基板1含有形成於第一層100中的凹陷特徵部110周圍之場區域101。凹陷特徵部110含有側壁103和具有外露表面104的第二層102。
根據一實施例,第一層100可包括介電材料,且第二層102可包括金屬層。介電材料可例如含有SiO2
、例如氟化矽玻璃(FSG)之低介電常數(低k)材料、碳摻雜氧化物、聚合物、含SiCOH的低k材料、無孔隙低k材料、多孔隙低k材料、CVD低k材料、旋塗介電質(SOD)低k材料、或任何其他合適之介電材料,包括高介電常數(高k)材料。於一些範例中,凹陷特徵部110的寬度(臨界尺寸(CD))可在約10 nm與約100 nm之間、於約10 nm與約15 nm之間、在約20 nm與約90之間、或於約40 nm與約80 nm之間。在一些範例中,凹陷特徵部110的深度可於約40 nm與約200 nm之間 、或於約50 nm與約150 nm之間。在一些範例中,凹陷特徵部110可具有於約2與約20之間、或在約4與約6之間的深寬比(深度/寬度)。第二層102可包括低電阻率之金屬、例如Cu金屬、Ru金屬、Co金屬、W金屬、或其組合。於一範例中,第二層102可包括二或更多堆疊的金屬層。堆疊之金屬層的範例包括在Cu金屬上之Co金屬(Co / Cu)和於Cu金屬上的Ru金屬(Ru / Cu)。
所述方法包括以吸附在第一層100上之表面改質劑預處理圖案化基板1,並從而相對於第一層100而增加第二層102上的金屬沉積選擇性,並包括增加在側壁103上以及場區域101上的金屬沉積選擇性。表面改質劑之存在會阻礙金屬層在第一層100上的沉積,但是第二層102並沒有被改質。根據一實施例,圖案化基板1係藉由暴露至含有能夠在基板上形成自組裝單層(SAMs)之分子的反應物氣體而以表面改質劑進行預處理。SAM是分子組合物,其藉由吸附作用自發地形成於基板表面上,並組織成或多或少之大的有序區域(ordered domains)。SAM可包括擁有頭部基團、尾部基團、和功能性末端基團之分子,且SAM由在室溫或高於室溫下將頭部基團從氣相化學吸附至基板上、隨後為尾部基團的緩慢組織而形成。最初,在表面上之小分子密度下,被吸附物分子形成無序的分子團,或形成有序之二維「平躺相」(lying down phase),且經過幾分鐘至幾小時的時間,被吸附物分子便以較高之分子覆蓋率開始在基板表面上形成三維晶體或半晶體結構。頭部基團在基板上組裝在一起,而尾部基團則遠離基板組裝。根據一實施例,形成SAM的分子之頭部基團可包括硫醇、矽烷、或膦酸酯。矽烷的範例包括含有下列者的分子:C、H、Cl、F、和Si原子或C、H、Cl、和Si原子。分子之非限制性範例包括全氟癸基三氯矽烷(perfluorodecyltrichlorosilane) (CF3
(CF2
)7
CH2
CH2
SiCl3
)、全氟癸硫醇(perfluorodecanethiol) (CF3
(CF2
)7
CH2
CH2
SH)、氯癸基二甲基矽烷(chlorodecyldimethylsilane) (CH3
(CH2
)8
CH2
Si(CH3
)2
Cl)和叔丁基(氯)二甲基矽烷(tertbutyl(chloro)dimethylsilane) ((CH3
)3
CSi (CH3
)2
Cl))。
根據本發明的一些實施例,反應物氣體可含有含矽氣體,包括烷基矽烷、烷氧基矽烷、烷基烷氧基矽烷、烷基矽氧烷、烷氧基矽氧烷、烷基烷氧基矽氧烷、芳基矽烷、醯基矽烷、芳基矽氧烷、醯基矽氧烷、矽氮烷、或其任何組合。根據本發明之一些實施例,反應物氣體可選自二甲基矽烷二甲基胺(DMSDMA)、三甲基矽烷二甲基胺(TMSDMA)、雙(二甲基胺基)二甲基矽烷(BDMADMS)、和其他烷基胺矽烷。根據其他實施例,反應物氣體可選自N,O雙三甲基矽烷基三氟乙醯胺(bistrimethylsilyltrifluoroacetamide)(BSTFA)和三甲基矽烷基吡咯(trimethylsilyl-pyrrole)(TMS-吡咯)。
根據本發明的一些實施例,反應物氣體可選自矽氮烷化合物。矽氮烷是飽和之矽氮氫化物。其結構類似於矽氧烷,其中以-NH-取代-O。有機矽氮烷前驅物可進一步含有鍵結至Si原子之至少一烴基。烴基可例如是甲基、乙基、丙基、或丁基、或其組合。再者,烴基可以是環狀烴基、例如苯基。另外,烴基可以是烯基。二矽氮烷是具有與矽原子附接的1至6個甲基或具有與矽原子附接之1至6個乙基之化合物、或具有與矽原子附接的甲基和乙基之組合的二矽氮烷分子。
所述方法更包括利用氣相沉積法在圖案化基板1上沉積金屬層106a,其中金屬層106a優先沉積於凹陷特徵部110中的第二層102上。金屬層106a可例如選自由Ru金屬、Co金屬、和W金屬所組成之群組。根據本發明的一實施例,可由化學氣相沉積(CVD)或原子層沉積(ALD)來沉積Ru金屬。含Ru之前驅物的範例包括Ru3
(CO)12
,(2,4-二甲基戊二烯基(2,4-dimethylpentadienyl))(乙基環戊二烯基(ethylcyclopentadienyl))釕(Ru(DMPD)(EtCp))、雙(2,4-二甲基戊二烯基)釕(Ru(DMPD)2
)、4-二甲基戊二烯基(4-dimethylpentadienyl))(甲基環戊二烯基(methylcyclopentadienyl))釕(Ru(DMPD)(MeCp))、和雙(乙基環戊二烯基)釕(Ru(EtCp)2
)、以及這些和其他前驅物之組合。
如圖1B所概要地顯示,金屬沉積可能不是完全選擇性的,且金屬核107a可沉積在側壁103和場區域101上。與金屬層106a不同,金屬核107a可形成非連續層,其中金屬核107a中之金屬總量小於金屬層106a中的金屬量。
在一範例中,使用CO載體氣體中之Ru3
(CO)12
前驅物而利用CVD來沉積Ru金屬。於以表面改質劑預處理基板之後,在介電材料中的凹陷特徵部之底部的Cu金屬層上沉積約15-20 nm之Ru金屬的厚度之後,於介電材料上觀察到Ru金屬核。這說明Ru金屬在不同材料上沉積的選擇性有限,以及於Ru金屬在介電表面上開始沉積之前,難以用Ru金屬選擇性沉積和填充比約15-20 nm深的凹陷特徵部。觀察到由CVD形成之Ru金屬沉積速率依次降低:金屬>金屬氮化物或氮化金屬氧化物>金屬氧化物或氧化的金屬氮化物> ILD,其中Ru金屬沉積速率於金屬表面上最高而在ILD表面上最低。這可利用於在不同材料上優先進行Ru金屬沉積。ILD包括含有矽、碳、或矽和碳兩者之介電化合物。範例包括SiO2
、SiON、SiN、SiCOH、Si、SiC和C。
所述方法更包括從圖案化基板1移除金屬核107a,以於凹陷特徵部110中的第二層102上選擇性形成金屬層106a。這是概要地顯示在圖1C中。較佳是在金屬核107a變得太大且更難以有效地移除之前就進行移除。於一範例中,可由使用反應性離子蝕刻(RIE)法進行蝕刻來移除Ru金屬核107a,例如使用電漿激發的O2
氣體並可選地添加含鹵素之氣體(例如Cl2
)。
可至少重複一次預處理、沉積、和移除的步驟,以增加沉積在凹陷特徵部110中之金屬的厚度。這是概要地顯示於圖1D中,其中附加金屬層106b優先沉積在金屬層106a上,且附加金屬核107b沉積於側壁103上和場區域101上。此後,如圖1E中所示,移除附加之金屬核107b。在一範例中,可重複預處理、沉積和移除,直到凹陷特徵部110完全以金屬填充為止。這在圖1F中概要地顯示。其中以金屬層106a-106c填充凹陷特徵部110。
於凹陷特徵部中的選擇性Ru金屬形成之製程範例包括使用TMSDMA氣體暴露進行的預處理,其中將TMSDMA液體汽化並用N2
氣體稀釋,基板溫度在約180°C至約250°C之間,製程室壓力約5 Torr,且暴露時間為10秒,無電漿激發。Ru金屬CVD製程包括含有Ru3
(CO)12
+ CO(例如,氣體流量比為約1:100),基板溫度於約135℃至約180℃之間(例如約160℃),製程室壓力在約1mTorr與約20mTorr(例如約5mTorr)之間,及400秒的暴露時間,沒有電漿激發,其於金屬表面上沉積約20 nm之Ru金屬。Ru金屬移除製程包括使用含有O2
和Cl2
的蝕刻氣體(例如,約100:1之氣體流量比);於約室溫至約370°C(例如約370°C)之間的基板溫度;使用電容耦合電漿源之電漿激發,將約1200W的RF功率施加至頂部電極,並將約0W至約300W(例如0W)之間的RF功率施加至底部電極(基板夾具);製程室壓力約5mTorr;及40秒的暴露時間,以移除相當於約5 nm之Ru金屬核。
圖7顯示在圖案化基板上的凹陷特徵部中具有選擇性Ru金屬形成之SEM影像。所接收的圖案化基板於W金屬膜上含有凸起之SiO2
特徵部。凸起的SiO2
特徵部約113 nm高、約31 nm寬,且隔開約87 nm。凸起之SiO2
特徵部形成凹陷特徵部,其深度約113 nm,且寬度約87 nm。所述圖面顯示沉積製程的結果,所述沉積製程包括以含有TMSDMA之表面改質劑預處理圖案化基板、使用Ru3
(CO)12
+ CO的Ru金屬CVD沉積步驟、及使用電漿激發之O2
氣體+ Cl2
氣體的Ru金屬蝕刻步驟,其從凹陷特徵部的側壁移除Ru金屬核。施行四次之預處理、Ru金屬沉積、和Ru金屬核移除之製程。所述圖面說明Ru金屬選擇性形成在凹陷特徵部中,且於凹陷特徵部的側壁上或在經蝕刻之SiO2
特徵部的頂部表面上均不存在Ru金屬核。於凹陷特徵部中形成之Ru金屬的厚度約69 nm,且填充約61%的凹陷特徵部之體積。
圖2A-2F概要地顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法。圖1A已複製如圖2A中之圖案化基板2。所述方法包括提供圖案化基板2,其含有形成在第一層100中的凹陷特徵部110和暴露於凹陷特徵部110中之第二層102。如圖2B中所示,所述方法包括將含金屬層111沉積在圖案化基板2上,包括沉積在凹陷特徵部110中及在凹陷特徵部110附近的場區域101上。含金屬層111可為保形的,且於一些範例中,含金屬層111可包括金屬氧化物、金屬氮化物、或其組合。金屬氧化物可例如包括Al2
O3
、TiO2
、HfO2
、或MnO2
,且金屬氮化物可例如包括AlN、TiN、HfN、或MnN。
此後,如圖2C中所示,所述方法更包括從凹陷特徵部110之底部和從凹陷特徵部110附近的場區域101各向異性地移除含金屬層111,以在凹陷特徵部110之側壁103上形成含金屬層111。所述方法更包括以表面改質劑預處理圖案化基板2,所述表面改質劑吸附於第一層100上,包括吸附在場區域101上,從而增加於凹陷特徵部110的側壁103上之含金屬層111上及相對於第一層100上的第二層102上之金屬沉積選擇性。
所述方法更包括利用氣相沉積法將金屬層112沉積在圖案化基板2上,其中金屬層112優先沉積於側壁103上的含金屬層111上、及相對於凹陷特徵部110附近之場區域101而在凹陷特徵部110的底部之第二層102上。金屬層112可例如選自由Ru金屬、Co金屬、和W金屬所組成的群組。如圖2D中所概要地顯示,金屬沉積可能不是完全選擇性的,且金屬核113可沉積於場區域101上。與金屬層112不同,金屬核113可形成非連續層,其中金屬核113中之金屬總量小於金屬層112中的金屬量。根據圖2D中所示之實施例,金屬層112可完全填充凹陷特徵部110。如圖2E中所示,所述方法更包括移除沉積在凹陷特徵部110附近的第一層100之場區域101上的金屬核113,以於凹陷特徵部110中選擇性形成金屬層112。
根據另一實施例,金屬層112可未完全填充凹陷特徵部110,並可至少重複一次預處理、沉積和移除以增加凹陷特徵部110中所沉積之金屬的厚度。根據一實施例,可重複預處理、沉積和移除,直到以金屬完全填充凹陷特徵部110為止。
圖3A-3E概要顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法。圖1A已被複製為圖3A中之圖案化基板3。所述方法包括提供圖案化基板3,所述圖案化基板3含有在材料中形成的凹陷特徵部110。於一範例中,所述材料可包括暴露在凹陷特徵部110中之第一層100和第二層102。如圖3B中所示,所述方法更包括於圖案化基板3上沉積金屬氮化物層114,包括沉積在凹陷特徵部110中及於凹陷特徵部110附近的場區域101中。金屬氮化物層114可以是保形的,且在一些範例中,金屬氮化物層114可包括AlN、TiN、HfN或MnN。
此後,所述方法更包括氧化場區域101上之金屬氮化物層114,以形成氧化的金屬氮化物層115。如本文所使用,氧化製程將氧加入金屬氮化物層114之至少一表面區域。如圖3C中所概要地顯示,金屬氮化物層114亦可於凹陷特徵部110的開口附近在凹陷特徵部110中氧化。氧化金屬氮化物層114之步驟可使用電漿激發的O2
氣體來施行,其中凹陷特徵部110之小開口限制電漿激發的O2
氣體穿透進入凹陷特徵部110。這將金屬氮化物層114的氧化限制在場區域101和凹陷特徵部110之上部。
所述方法更包括利用氣相沉積法在基板上沉積金屬層116,其中金屬層116優先沉積於凹陷特徵部110中未被氧化之金屬氮化物層114上。吾人相信優先的金屬沉積係由於相對於在氧化之金屬氮化物層115上,在金屬氮化物層114上有更短的金屬沉積之培養時間。如圖3D中所概要地顯示,金屬沉積可能不是完全選擇性的,且金屬核123可沉積在場區域101上。與金屬層116不同,金屬核123可形成非連續層,其中金屬核123中之金屬總量小於金屬層116中的金屬量。
根據圖3D中所示之實施例,金屬層116可完全填充凹陷特徵部110,其中避免了金屬氮化物層114的氧化。如圖3E所示,所述方法更包括移除沉積在凹陷特徵部110附近之第一層100的場區域101上之金屬核123,以於凹陷特徵部110中選擇性形成金屬層116。
根據另一實施例,在避免金屬氮化物層114氧化的情況下,金屬層116可能不會完全填充凹陷特徵部110,並可重複至少一次沉積和移除步驟以增加凹陷特徵部110中所沉積之金屬層116的厚度。根據一實施例,可重複沉積和移除步驟,直到以金屬層116完全填充凹陷特徵部110。
圖4A-4F概要顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法。圖1A已被複製為圖4A中之圖案化基板4。所述方法包括提供圖案化基板4,所述圖案化基板4含有材料中所形成的凹陷特徵部110。於一範例中,所述材料可包括第一層100和暴露在凹陷特徵部110中之第二層102。如圖4B中所示,所述方法更包括將金屬氧化物層117沉積於圖案化基板4上,包括在凹陷特徵部110中及於凹陷特徵部110附近的場區域101上。金屬氧化物層117可以是保形的,且在一些範例中,金屬氧化物層117可包括Al2
O3
、TiO2
、HfO2
、或MnO2
。
此後,所述方法更包括氮化在場區域101上和凹陷特徵部110中的金屬氧化物層117,以形成氮化之金屬氧化物層118。如本文所用,氮化製程將氮加入金屬氧化物層117的至少一表面區域。如圖4C中所概要地顯示,氮化金屬氧化物層118可以是保形的。可使用熱氮化製程(例如,在沒有電漿之情況下進行NH3
退火)來進行氮化金屬氧化物層117的步驟,所述方法有效地氮化整個金屬氧化物層117之厚度的至少一部分,包括凹陷特徵部110中。
此後,所述方法更包括氧化場區域101上之氮化金屬氧化物層118,以形成氧化的氮化金屬氧化物層119。如本文中所使用的,氧化製程將氧加入氮化金屬氧化物層118之至少一表面區域。氧化所述氮化金屬氧化物層的步驟可使用電漿激發之O2
氣體施行,其中凹陷特徵部110的小開口限制電漿激發之O2
氣體穿透進入凹陷特徵部110。如此便將氮化的金屬氧化物層的氧化限制在場區域101及凹陷特徵部110之上部。這在圖4D中概要地顯示。
所述方法更包括利用氣相沉積法於圖案化基板4上沉積金屬層120,其中金屬層120優先沉積在凹陷特徵部110中未被氧化之氮化金屬氧化物層118上。吾人相信優先的金屬沉積係由於相對在氧化之氮化金屬氧化物層119上,在氮化的金屬氧化物層上有更短的金屬沉積之培養時間。
如圖4E中所概要地顯示,金屬沉積可能不是完全選擇性的,且金屬核121可沉積在場區域101上之氧化的氮化金屬氧化物層119上。與金屬層120不同,金屬核121可形成非連續層,其中金屬核121中之金屬總量小於金屬層120中的金屬量。
根據圖4E中所示之實施例,金屬層120可完全填充凹陷特徵部110,其中避免了氮化金屬氧化物層118的氧化。如圖4F中所示,所述方法更包括移除沉積於凹陷特徵部110附近之第一層100的場區域101上之金屬核121,以在凹陷特徵部110中選擇性形成金屬層120。
根據另一實施例,金屬層120可不完全填充凹陷特徵部110,其中避免了氮化金屬氧化物層118的氧化,並可至少一次重複沉積和移除步驟以增加沉積於凹陷特徵部110中之金屬層120的厚度。根據一實施例,可重複沉積和移除步驟,直到以金屬層120完全填充凹陷特徵部110。
圖5A-5D概要顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法。圖5A顯示含有在材料500中形成凹陷特徵部510的圖案化基板5,其中凹陷特徵部含有側壁503和底部502。所述方法包括於圖案化基板5上沉積金屬氧化物層504,包括沉積在凹陷特徵部510中及於凹形特徵部510附近之場區域501上。這概要地顯示在圖5B中。
所述方法更包括於場區域101上氮化金屬氧化物層504。如本文所用,氮化製程將氮加入金屬氧化物層504的至少一表面區域,以形成氮化之金屬氧化物層505。這概要地顯示在圖5C中。可使用電漿激發的含氮氣體(例如,N2
或NH3
)來施行氮化金屬氧化物層504之步驟,其中凹陷特徵部510的小開口限制電漿激發之含氮氣體穿透進入凹陷特徵部510。
所述方法更包括利用氣相沉積法將金屬層506沉積於圖案化基板5上,其中金屬層506優先沉積在場區域501上之氮化金屬氧化物層505上。如圖5D中所概要地顯示,金屬沉積可能不是完全選擇性的,且金屬核507可沉積於凹陷特徵部510中之金屬氧化物層504上。
所述方法更包括移除凹陷特徵部510中所沉積的金屬核507,以在場區域501上選擇性形成金屬層506。這概要地顯示於圖5E中。可至少重複一次沉積和移除之步驟,以增加場區域501上的金屬層506之厚度。
圖6A-6D概要顯示根據本發明的另一實施例之凹陷特徵部中的選擇性金屬形成之方法。在一範例中,顯示於圖6A中,圖案化基板6可包括3D NAND元件的一部分。所述方法包括提供圖案化基板6,其在材料600中含有經蝕刻的直立特徵部610和經蝕刻之水平特徵部601。經蝕刻的直立特徵部610可為錐形的,使頂部附近之開口大於底部附近的開口。在一範例中,材料600可包括SiO2
或SiN。所述方法更包括氮化經蝕刻之直立特徵部610和經蝕刻的水平特徵部601,以形成氮化層602。氮化之製程可包括熱氮化製程(例如,於沒有電漿的情況下之NH3
退火),其將經蝕刻的直立特徵部610和經蝕刻之水平特徵部601兩者氮化。此後,所述方法包括電漿處理(例如,Ar電漿),其從經蝕刻的直立特徵部610移除氮化層602,同時保留經蝕刻之水平特徵部601中的氮化層602。所得的圖案化基板6顯示於圖6B中。所述方法更包括利用氣相沉積法將金屬層603沉積在圖案化基板6上,其中相對於經蝕刻之直立特徵部610,金屬層603優先沉積在經蝕刻的水平特徵部601中之氮化層602上。這概要地顯示於圖6C中。施行氣相沉積,直到金屬層604也完全填充經蝕刻的直立特徵部610。選擇性金屬沉積是由於在氮化層602上的金屬沉積速率比於未氮化之經蝕刻直立特徵部610上的金屬沉積速率更高。這允許經蝕刻之直立特徵部610和經蝕刻的水平特徵部601之完全金屬填充而沒有任何空隙。
在諸多實施例中已揭示以低電阻率金屬填充半導體元件中的凹陷特徵部之方法。對本發明實施例之先前敘述的呈現係為了說明和敘述之目的。其並非意欲窮舉或將本發明限制於所揭示之精確形式。此敘述和隨後的請求項包括僅用於敘述的目的之術語,且不應解釋為限制性的。相關領域之技術人員可理解到根據以上教導,許多修改和變動是可能的。本領域技術人員將認識到圖面中所示之諸多部件的諸多等效組合和替代。因此,意圖使本發明之範圍不受此詳細敘述所限制,而是由所附請求項所限制。
1:基板
2:基板
3:基板
4:基板
5:基板
6:基板
100:第一層
101:場區域
102:第二層
103:側壁
104:暴露表面
106a:金屬層
106b:金屬層
106c:金屬層
107a:金屬核
107b:金屬核
110:凹陷特徵部
111:含金屬層
112:金屬層
113:金屬核
114:金屬氮化物層
115:金屬氮化物層
116:金屬層
117:金屬氧化物層
118:金屬氧化物層
119:金屬氧化物層
120:金屬層
121:金屬核
123:金屬核
500:材料
501:場區域
502:底部
503:側壁
504:金屬氧化物層
505:金屬氧化物層
506:金屬層
507:金屬核
510:凹陷特徵部
600:材料
601:水平特徵部
602:氮化層
603:金屬層
604:金屬層
610:直立特徵部
當結合附圖考慮時,透過參考以下詳細敘述,本發明及其許多附帶優點將變得更好瞭解,而可輕易獲得對本發明及其許多附帶優點的更完整理解,其中:
圖1A-1F概要地顯示根據本發明之實施例的凹陷特徵部中之選擇性金屬形成的方法;
圖2A-2E概要地顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法;
圖3A-3E概要地顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法;
圖4A-4F概要地顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法;
圖5A-5E概要地顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法;
圖6A-6D概要地顯示根據本發明之另一實施例的凹陷特徵部中之選擇性金屬形成的方法;和
圖7顯示在圖案化基板上之凹陷特徵部中形成有選擇性Ru金屬的SEM影像。
1:基板
100:第一層
101:場區域
102:第二層
103:側壁
106a:金屬層
107a:金屬核
110:凹陷特徵部
Claims (9)
- 一種形成半導體元件的方法,該方法包含:提供圖案化基板,該圖案化基板含有形成在第一層中之凹陷特徵部和暴露於該凹陷特徵部中的第二層;以表面改質劑預處理該基板,該表面改質劑相對於該第一層而增加在該第二層上的金屬沉積選擇性;此後,利用氣相沉積法將金屬層沉積於該基板上,其中該金屬層優先沉積在該凹陷特徵部中之該第二層上,且該沉積更在該凹陷特徵部中之該第一層的側壁上和一場區域上形成金屬核;移除該第一層上所沉積的該金屬核以在該凹陷特徵部中之該第二層上選擇性形成該金屬層;及至少重複一次該預處理、該沉積和該移除,以增加該凹陷特徵部中之該金屬層的厚度。
- 如請求項1之形成半導體元件的方法,其中該預處理包括在該第一層上形成自組裝單層(SAMs)。
- 如請求項1之形成半導體元件的方法,其中該金屬層選自由Ru金屬、Co金屬、和W金屬所組成之群組,且該第二層選自由Cu金屬、Ru金屬、Co金屬、W金屬、及其組合所組成的群組。
- 一種形成半導體元件的方法,該方法包含: 提供圖案化基板,該圖案化基板含有形成在第一層中之凹陷特徵部和暴露於該凹陷特徵部中的第二層;將含金屬層沉積在該基板上,包括沉積於該凹陷特徵部中;從該凹陷特徵部之底部和從該凹陷特徵部附近的場區域各向異性地移除該含金屬層,以在該凹陷特徵部之側壁上形成該含金屬層;以表面改質劑預處理該基板,該表面改質劑相對於該第一層而增加該凹陷特徵部的該側壁上之該含金屬層以及該第二層上之金屬沉積選擇性;利用氣相沉積法於該基板上沉積金屬層,其中相對於在該凹陷特徵部附近的該場區域,該金屬層優先沉積於該凹陷特徵部中之該側壁之該含金屬層上以及該第二層上;及移除沉積在該場區域上之金屬核以在該凹陷特徵部中選擇性形成該金屬層。
- 如請求項4之形成半導體元件的方法,更包含:至少重複一次該預處理、該沉積和該移除,以增加該凹陷特徵部中之該金屬層的厚度。
- 如請求項4之形成半導體元件的方法,其中該預處理包括在該第二層上形成自組裝單層(SAMs)。
- 如請求項4之形成半導體元件的方法,其中該金屬層選自由Ru金屬、Co金屬、和W金屬所組成之群組,且該第二層選自由Cu金屬、Ru金屬、Co金屬、W金屬、及其組合所組成的群組。
- 如請求項4之形成半導體元件的方法,其中該含金屬層含有金屬氧化物、金屬氮化物、或其組合。
- 如請求項8之形成半導體元件的方法,其中該金屬氧化物包括Al2O3、TiO2、HfO2或MnO2,且該金屬氮化物包括AlN、TiN、HfN、或MnN。
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