TWI353637B - An ultralow dielectric constant material as an int - Google Patents
An ultralow dielectric constant material as an int Download PDFInfo
- Publication number
- TWI353637B TWI353637B TW100109312A TW100109312A TWI353637B TW I353637 B TWI353637 B TW I353637B TW 100109312 A TW100109312 A TW 100109312A TW 100109312 A TW100109312 A TW 100109312A TW I353637 B TWI353637 B TW I353637B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- insulating material
- dielectric
- material layer
- hydrogen
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims description 56
- 239000010410 layer Substances 0.000 claims description 196
- 239000011810 insulating material Substances 0.000 claims description 80
- 239000002243 precursor Substances 0.000 claims description 56
- 239000001257 hydrogen Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 41
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 125000003342 alkenyl group Chemical group 0.000 claims description 27
- 239000003989 dielectric material Substances 0.000 claims description 27
- 239000011229 interlayer Substances 0.000 claims description 21
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 20
- 230000004888 barrier function Effects 0.000 claims description 19
- 150000002431 hydrogen Chemical class 0.000 claims description 18
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- 230000007306 turnover Effects 0.000 claims 1
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 28
- KAJRUHJCBCZULP-UHFFFAOYSA-N 1-cyclohepta-1,3-dien-1-ylcyclohepta-1,3-diene Chemical compound C1CCC=CC=C1C1=CC=CCCC1 KAJRUHJCBCZULP-UHFFFAOYSA-N 0.000 description 18
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- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 3
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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 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
- 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
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
- H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
-
- 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
- H01L21/02104—Forming layers
- 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
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Description
1353637 美國專利號 6,312,793、6,441,491、6,541,398 及 6,479,110 B2描述一多相(muitiphase)低k介電材料,係由石夕、碳’、氧 及氫元素組成之一基質相(matrixphase),以及主要由碳與氫 組成之另一相所構成。前述專利揭示之介電材料,1介; 不大於3.2。 ~ 美國專利號6,437,443描述一低k介電材料,具二個戋更 ^目’其中第一相由一 SiC0H材料形成。此低k ^電材料的 提供在一電漿加強化學氣相沉積(PECVD)腔體中,藉由將 夕:炭、氧及氫的第一前驅氣體,與至少-第二i驅氣 體反應’紅前喊體主要含有碳、氫原子並視需要含 氮及氧。 八管已有眾多低^電材料被揭示,仍持續需要研發一種 w電材料,介電常數不大於2 5,且在 製程溫度T具域力無安親。 ⑽1触使用之 【發明内容】 介電綠’以製造介數不大於2.5的一超低 亦即超低10材料。本發明提供之超低k材料更佳 2二二,約1,5至約2·5,且最佳的介電常數為約U至約 .。/思'除非特別聲明,所有的介電常數皆相對於真空而言。 本發明亦提供一方法以製造包含矽、碳、 材料’其係源自至少二種前驅物的混合,其中第 / R,,及口^雄邱)衍生物’具分子式&職”R,,,,R、 可以相同或不同,且係選自氫、烧基(a_及烷 1353637 氧基(alkoxy)。較佳的R、R’、R”及R’’’係相同的或不同的,且 係甲基(methyl)、乙基(ethyl)、甲氡基(methoxy)及乙氧基 (ethoxy)。較佳的第一前驅物包括但不限於:二乙氧基二曱基 石夕炫·(diethoxydimethyl silane)、二乙氧基曱基石夕烧 (diethoxymethylsilane,DEMS)、乙氧基三曱基石夕烧 (ethoxyltrimethylsilane) 、乙氧基二甲基矽烧 (ethoxydimethylsilane)、二甲氧基二曱基矽烷 (dimethoxydimethylsilane)、二甲氧基曱基石夕烧 (dimethoxymethylsilane)、三乙氧基矽烷(triethoxysilane)及三甲 氧基甲基石夕烧(trimethoxymethylsilane)。 本發明使用之第二前驅物係一有機化合物,選自:
Rl\ /R3 烯烴(alkenes) : r2 r4 ;
快烴(alkynes): ^(ethers): R1—=—R2
;及
環氧乙烧類(oxiranes): R1、R2、R3、R4、R5及R6可為相同或不同,且係選自線 性的、分枝的、環狀的、多環的氫、烷基、烯(alkenyl)或烯基 (alkenyl group),且可被含有氧、氮或氟的各取代基官能化。 1353637 較佳的第二前驅物包括但不限於:環氧乙烧(ethylene oxide)、 環氧丙烧(propylene oxide)、環戊稀氧化物(cyclopentene oxide)、環氧異丁烧(isobutylene oxide)、2,2,3-三甲基環氧乙院 (2,2,3-trimethyloxirane)、丁二烯氧化物(butadienemonoxide)、 雙環庚二烯(bicycloheptadiene)、1,2-環氧-5-己稀 (l,2-epoxy-5-hexene) 、2-甲基-2-乙稀環氧乙院 (2-methyl-2-vinyloxirane) 、1-異丙環丁 -1,3-二烤 (l-isopropyl-cyclohexa-l,3-diene)及甲基第三 丁基醚 (tertbutylmethylether) ° 含矽烷衍生物之第一前驅物與第二有機前驅物的結合使 用’可有效地於氫化矽碳氧化物(SiCOH)基體中形成一孔洞 相’且氫化矽碳氧化物(SiCOH)薄膜之製備成本也較使用習知 之前驅物低。 含石夕烧衍生物之第一前驅物與第二有機前驅物的結合使 用’能使一多孔洞氫化石夕碳氧化物(SiC0H)介電質的伸張應力 降低(reduced tensile stress )。 本發明更提供一方法’在一平行平板式電漿加強式化學氣 相沉積(PECVD)反應器中,製造一超低k介電質,也提供 一方法製造一超低k材料,在電子結構之一後段製程(BE〇L) 内連線結構中,用作一層内或層間介電質。 在另一方面,本發明也提供一熱穩定超低匕材料,其具低 内應力’且介電常數不大於約2 5。超低k材料更佳的介電常 數約1.5至約2.5,域佳的介電常數約18至約2 25。 然而,在另一方面,本發明提供一電子結構,含有數層絕 緣材料,以在一後段製程(BE0L)線路結構中用作層内或層 間介電質’其中至少有兩層絕緣材料包含本發明之一超低k材 料。 再者本發明長^供一電子結構,其具數層本發明之超低k =料,以在一後段製程(BE0L)線路結構中用作層内或層間 介電質,且更包含至少一層介電帽蓋層(didectriccaplayer), 用作一反應式離子蝕刻(reactive i〇n etch,反^)停止層或一 化學機械研磨(chemicai_mechanicai p〇iish)停止層或一擴散 阻障層(diffusion barrier .layer )。 根據本發明的一種製造熱穩定介電材料的方法,此熱穩定 介=料具-基體’係包含n氧及氫原子,且提供一原 子級奈米多孔性(atomic level nan〇p〇r〇sity>在一較佳實施例 中’此介電材料具有主要由石夕、碳、氧及氫所構成之一基體。 ,發明更提供製造介電㈣的—方法,藉由將含碎、碳、氧及 虱,子之3石夕第一如驅氣體,與至少一含碳、氫原子及選擇性 的,、氟、及氮之含有機第二前驅氣體反應,在一電漿加強化 學氣相沉積(PECVD)反應器中。本發明之介電材料且一傅 利葉轉換紅外線(FTIR)光譜,其具一矽_氧吸收'頻帶 (absorptionband),可被解迴旋(deconv〇iuted)成三個蜂值。 ,發明更提供-電子結構(即基板(substfate)),具數層絕緣材 ^ ’以在一後段製程(BE〇L)線路結構中用作層内或層間介 電質,其中之絕緣材料可以是本發明之超低k薄膜。 在一較佳實施例中,提供製造一熱穩定超低k薄膜的方 1353637 法,包含下列步驟:提供一電漿加強化學氣相沉積(pECVD) 反應盗,在反應器中置入一電子結構(亦即基板);流入一包 含矽、碳、氧及氫原子之含矽第一前驅氣體至反應器中;流入 包含碳、氫原子及視需要的氧、氟及氮之含有機的一第二前驅 混合氣體至反應器中;以及在此基板上沉積一超低k薄膜。 較佳的第一前驅物選自石夕烧(silane,SiH4)衍生物,具分子 式SiRR’R’’R’’’,R、R’、R”及R,,,可以相同或不相同 ,且係選 自風、烧基(alkyl)及烧氧基(alkoxy),較佳的是曱基(methyl)、 乙基(ethyl)、甲氧基(methoxy)及乙氧基(ethoxy)。較佳的前驅 物包括·二乙軋基二甲基石夕烧(diethoxydimethylsilane)、二乙氧 基甲基矽烷(diethoxymethylsilane,DEMS)、乙氧基三曱基矽烧 (ethoxyltrimethylsilane)、乙氧基二曱基石夕烧 (ethoxydimethylsilane)、二甲氧基二曱基矽烷 (dimethoxydimethylsilane)、二甲氧基曱基石夕烧 (dimethoxymethylsilane)、三乙氧基矽烧(triethoxysilane)及三甲 氧基甲基矽烧(trimethoxymethylsilane)。 本發明使用之第二前驅物係一有機化合物,選自: 稀烴(alkenes) : R\=/R ; r2/ \r4 炔烴(alkynes) : r1 一=一Rz ; r' r4 醚(ethers) : R2-^o-^R5 ;及 R3 R6 -10· 1353637
環氧乙烧(oxiranes)類: 1^、112、113、尺4、尺5及116可為相同或不同,且係選自線 性的 '分枝的、環狀的、多環的氫、烷基、烯(alkenyl)或烯基 (alkenyl group) ’且可被含有氧、氮或氟的各取代基官能化。 較佳的第二前驅物包括環氧乙烧(ethylene oxide)、環氧丙烧 (propylene oxide)、環戊稀氧化物(cyclopentene oxide)、環氧異 丁烧(isobutylene oxide)、2,2,3-三甲基環氧乙烷 (2,2,3-trimethyloxirane)、丁二烯氧化物(butadienemonoxide)、 雙環庚二烯(bicycloheptadiene)(又名2,5-降冰片二浠 (2,5-11〇1'1)〇111&<^116))、1,2_環氧-5-己烯(1,2-6卩〇父>^5-116父6116)、2-甲基-2-乙缔環氧乙烧(2-methyl-2-vinyloxirane)、1 -異丙-環丁 -1,3-二烯(l-iSOpr〇py^CyCi〇hexa-l,3-diene)及曱基第三丁基鍵 (tertbutylmethylether) ° 本發明之沉積薄膜視需要可在不低於約300°C的溫度熱處 理’歷時(timeperiod)至少約0.25小時。另一種方式是,可 用紫外光(UV)或電子束(e-beam)處理本發明之沉積薄膜, 如美國專利申請號10/758,724中所述為例,其整體之内容於文 中納入作為參考。 本發明的方法可更包含提供一平行平板式反應器之步 驟’其—基板卡盤(chuck)具一區域約300cm2至800cm2, 且在基板與一上電極間具一間隙(gap)約lcm至約10cm。 另—種方式是,一多站(multi-station)反應器也可以用於 -11- 此溥膜之沉積。施加-高頻RP電力於其中一個電極,頻率約 12MHz (祕)至15MHz。可視需要施加一額外的低頻電力 於其中-個電極’該電力之頻率例如為2MHZ或更低 (350-450iCHz(千赫))。 熱處理步驟可在不高於約3〇〇°c的溫度下實行,歷時—第 厂時間週期’接著在不低_ 38(rc的溫度,歷時—第二時間 週期’第二時間週期較第一時間職長。第二時間週期可至少 是第-時間聊的約1G倍。可視需要藉由暴露輻射或 電子束熱處理薄膜’例如美國專利申請號10/758,724中所述。 本發明之超低k薄膜的沉積步驟,可更包含下列步驟:設 定基板溫度從約25°C至約400。(:;設定高頻RF電力密度為約 0.05W/cm2 (瓦/平方公分)至約3 5 w/cm2 ;設定第一前驅物 流量^〇\¥以(6)為約5似111(每分鐘標準毫升)至約1〇〇〇似111; 设定第二前驅物流量為約5 seem至約1 〇〇〇sccm ;設定載子氣 體(carrier gas)氦流量為〇sccm至i〇〇〇sccm ;以及設定反應 器壓力為約50mtorr (晕托)至約8000mtorr。視需要加入一超 低頻電力於電漿,約〗〇W至約300W。 在另一較佳實施例令,提供製造一超低k薄膜的方法,包 含下列步驟:提供一具電漿加強的平行平板式化學氣相沉積 (chemical vapor d印osition )反應器;置入一預處理 (pre-processed)晶圓於一基板卡盤上,其具一區域從約 300cm2至約800cm2,且在晶圓與一上電極間維持一間隙從約 lem至約l〇cm ;流入一包含矽烧衍生物分子的第一前驅氣體 至反應器中’其具分子式SiRR,R,,R,,,,其中R、R,、R”及R,,, 12 B53637 係相同的或不同的’且係選自氫、烷基(alkyl)及烷氧基 (alkoxy),R、R’、R”及R”’每個皆獨立地為甲基(methyl)'乙 基(ethyl)、甲氧基(methoxy)或乙氧基(ethoxy);流入至少一第 二前驅氣體,包含有機分子自化合物群包括
Rl\ .R3 稀烴(alkenes) : 4 ; 炔烴(alkynes) : Rl—=一R2 ; 鍵(ethers) : ;及 環氧乙烧類(oxiranes) : R^/-\-R3 . R2 R4 ’ R1、R2、R3、R4、R5及R6可為相同或不同,且係選自線 性的、分枝的、環狀的、多環的氫、烷基、烯(alkenyl)或烯基 φ (alkenyl group),且可被含有氧、氮或氟的各取代基官能化; 且沉積一超低k薄膜在晶圓上。 此製程在沉積步驟後,可更包含熱處理薄膜的步驟,在不 低於約300C的溫度,歷時至少約〇25小時,或者在沉積後, W或電子束處理薄膜的步驟。㈣程更包含施加一虾能源 於晶,步=。熱處理步驟可更被實行在不高於約·。c的溫 ^歷日f第-時間職,且接著在不低於約獨。C的溫度, t厂第二時間週期’第二時間週期較第一時間週期長。第二 時間週期可至少是第—時間週期的約10倍。 -13· 1353637 所使用的矽烷衍生物前驅物可以是二乙氧基甲基矽烷 (diethoxymethylsilane,DEMS),且有機前驅物可以是雙環庚二 婦(bicycloheptadiene ’ BCHD)。超低k薄膜的沉積步驟可更包 含下列步驟:設定晶圓溫度約25^至約400°C ;設定一 RF能 源密度約〇.〇5W/cm2至約3.5W/cm2 ;設定矽烷衍生物流量約 5sccm至約lOOOsccm ;設定有機前驅物流量從約5sccm至約 lOOOsccm ;設定載子氣體氧流量從Osccm至lOOOsccm ;以及 設定反應器壓力從約50mtorr至約8000mtorr。此外,沉積步 驟可更包含設定雙環庚二烯(bicy cloheptadiene)對二乙氧基曱 基矽烷(diethoxymethylsilane)的流量比(flowrati〇)約 〇.1 至約 3,較佳為0.2至0.6。基板卡盤的傳導區域可藉由一因子X來 改變’藉由相同的因子X也會導致RF能源的改變。 然而,在另一較佳實施例中,提供製造一熱穩定超低匕介 電薄膜的方法,包含下列步驟:提供一平行平板式電漿加強化 學氣相沉積(PECVD)反應器;置入一晶圓於一基板卡盤上, 其具一傳導區域從約300 cm2至約800 cm2,且在晶圓與一上 電極間維持約lcm至約l〇cm 一間隙;流入前述矽烷衍生物與 有機分子的一前驅混合氣體至反應器中的晶圓上方,其溫度維 持從約25 C至約400°C,總流量約25sccm至約lOOOsccm,維 持反應器壓力在約lOOmtorr至約80〇〇mtorr ;沉積一介電薄膜 在晶圓上’ RF能源密度約〇.25W/Cm2至約3w/cm2 ;以及視需 要退火(annealing)此超低k薄膜在不低於約3⑻。c的溫度, 歷時至少約0.25小時。 。本發明的方法更包含—退火薄膜的步驟,係在不高於約 300 C的溫度’歷時一第-b夺間週期,且接著在不低於約38〇 -14- 1353637 一Λ二4間週期,其中第二時間週期較第-時 ^週』長。苐週期可被設定至少是第— 〇倍。錢衍生物可以是:乙氧基甲基石夕烧 (chethoxymethylsilane ’ DEMS),且有機前驅物可以是雙環庚二
本發明更指向-電子結構’其絲魏緣材料,以在一後 奴製程(BEOL)内連線結構中用作層内或層間介電質,内連 ,結構包括-預處理半導體基板,其具一第一金屬區:嵌在一 第絕緣材料層中’ -第-導體區域嵌在本發明超低k介電質 之一第二絕緣材料層中,本發明超低k介電質包含矽、碳氧 及氫,以及多樣性奈米級孔洞,且具一介電常數不大於約2 5 ; 第二絕緣材料層與第一絕緣材料層緊密接觸( 咖第-導舰域與第-金輕域電 communication);第二導體區域與第一導體區域電相連,且被 嵌入含本發明超低k介電質之一第三絕緣材料層中,第三絕緣 材料層與弟二絕緣材料層緊密接觸。此電子結構可更包^^一介
電帽蓋層,位在第二絕緣材料層與第三絕緣材料層之間。此電 子結構可更包含一第一介電帽蓋層,在第二絕緣材料層與第三 絕緣材料層之間,且一第二介電帽蓋層在第三絕緣材料層頂 上。 介電帽材料可以選自氧化碎(silicon oxide )、氮化石夕 (silicon nitride)、氮氧化石夕(silicon oxynitride)、氮碳化石夕(silicon carbon nitride ’ SiCN)、亂氧碳化發(silicon carbon oxynitride, SiCON)、而十火金屬石夕氮化物(refractory metal silicon nitride)(其 中之耐火金屬(refractory metal)係選自由钽(Ta)、鍅(Zr)、铪(Hi) -15- 1353637 及鎢(\\〇構成的群組)、碳化石夕(仙0011(^|)此)、摻雜碳的氧化 物(carbon doped oxide)或氫化矽碳氧化物(SiCOH)及其氫化化 &物(hydrogenated compounds)。第一與第二介電帽蓋層可選自 相同的介電材料群組。第一絕緣材料層可為氧化矽或氮化矽或 這些材料的摻雜變體’例如磷矽玻璃(phosph〇ms smeate glass ’ PSG)或爛鱗石夕玻璃(b0r0I1 phosphorus silicate glass, BPSG)。此電子結構可更包括一介電材料之一擴散阻障層,沉 積在絕緣材料第二與第三層之至少其中之一。此電子結構可更 包含一介電質,在第二絕緣材料層頂上,其用作一反應式離子 蝕刻(RIE)硬罩與研磨停止層,以及一介電擴散阻障層在此 介電反應式離子蝕刻硬罩與研磨停止層頂上^此電子結構可更 包含一第一介電反應式離子蝕刻硬罩/研磨停止層在此第二絕 緣材料層頂上,一第一介電反應式離子蝕刻硬罩/擴散阻障層 在此第一介電研磨停止層頂上,一第二介電反應式離子蝕刻硬 罩/研磨停止層在此第三絕緣材料層頂上,以及一第二介電擴 散阻障層在此第二介電研磨停止層頂上。此電子結構可更包含 與以上所提有相同材料之一介電帽蓋層,在超低^^介電質之一 層間’I電為與超低k介電質之一層内介電質之間。 、 【實施方式】 本發明揭示在一平行平板式電漿加強化學氣相沉 (PECVD)反應器巾,製造—_定超低介電f數薄膜的方 法。在健實施射揭示含有—氫化魏氧化物(hydfGgenated oxKhzedsiHccm carbon ’ SiCOH)材料為主體的一材料’包含在 -隨機共價麟(mndGmGGvalentlybGnded)晴㈣、碳、 氧及氫’且具不大於2·5的—介電常數,其更可含有分子級* 隙(m〇leCularscalevoids)’直徑約 〇 5 至2〇 奈米(__时s), -16- 1353637 =Η常數值降至約2·0以下。更佳之超低k薄膜的介電常 數約1·5至約2.5 ’且最佳的介電常數約! 8至約2〜 之超低k介電材料典型之特徵在於具一多相薄膜,其包括:^ 一相,主要由矽、碳、氧及氫構成;—第 構成之;以及多樣性奈米級孔洞。
、相,主要由碳與氫 要產生-超低k熱穩定薄膜,需要有一特定幾何形狀的沉 積反應器,以及特定的成長條件。舉例而言,在平行平板式反 應器中’基板卡盤的一傳導區域應約為300cm2至約_ cm2, 基板與一上電極間應具一間隙為約lcm至約1〇cm。施加一即 能源於基板。根據本-發明,超低k薄膜係形成自一矽烷衍生 物,例如二乙氧基甲基矽烷(DEMS)與一第二前驅物的混合, 第二前驅物係一有機分子,選自以下各化合物組成之群組:
稀煙(alkenes):
快烴(alkynes): 謎(ethers): R1—^-R2
;及 環氧乙烧類(oxiranes):
其中,R1、R2、R3、R4、R5及R6可為相同或不同,且係 選自線性的、分枝的、環狀的、多環的氫、烷基、烯(alkenyl) 或烯基(alkenyl group),且可被含有氧、氮或II的各取代基官 •17- 1353637 月匕化’例如雙環庚二烯(bicycloheptadiene,BCHD),在特定反 應條件下與—特定型態之沉積反應ϋ中。本發明之超低k薄膜 ^可在不低於約300。(:的溫度下被熱處理,歷時至少約〇25小 或者為降低介電常數。在沉積或熱處理後,此薄膜也可用 uv或電子束處理。在後沉積(口〇对_4印〇伽〇11)處理步驟中, 源自第二前驅氣體(或混合氣體)之分子碎片(m〇lecule fragments)’包含碳與氫以及選擇性的(〇pti〇naUy)氧原子, 可會熱分解,且可會被轉變成較小分子,從薄膜中被釋放。藉 由分子碎X的轉變過程與釋放,在薄膜中可會選擇性地會發^ 出些空隙。薄膜密度會因此而減小,介電常數與折射率 (refractive index )也會跟著降低。
本發明提供製備一具超低k (即小於約2.5)材料的方法, 其適用於一後段製程(BEOL)線路結構之整合。本發明之超 低k薄膜更佳之介電常數約丨.5至約2 5為,且最佳之介電常 數為約1.8至約2.25。製備本發明之薄膜,可選擇至少二個適 合的前驅物,以及如以下所述之製程參數的一特定組合。較佳 的第一前驅物係選自矽烷(silane,SiH4)衍生物,具分子式 SiRR’R”R”’,R、R’、R”及R”’可以是相同或不同/且係選^ 氫、烷基(alkyl)及烷氧基(alkoxy),較佳為曱基(methyl)、乙基 (ethyl)、曱氧基(methoxy)及乙氧基(ethoxy)。較佳的前驅物包 括.一乙氧基一TSsi^^Xdiethoxydimethylsilane)、二乙氧基甲 基石夕烧(diethoxymethylsilane,DEMS)、乙氧基三甲基石夕燒 (ethoxyltrimethylsilane)、乙氧基二曱基矽烷 (ethoxydimethylsilane)、二曱氧基二曱基矽烷 (dimethoxydimethylsilane)、二甲氧基曱基矽烷 (dimethoxymethylsilane)、三乙氧基矽烷(trieth〇xysilane)及三甲 -18- 氧基甲基石夕炫〇3111^1;110乂丫11161:11)45他116)。 本發明使用之第二前驅物係一有機化合物選自: R'\ R3 v=< 烯經(alkenes) : R2/ xr4 ; 块烴(alkynes) : Rl ~~=一r2 ; • R\ R4 峻(ethers) : r2;^~0~^:R5 •,及 R3 R6 R^/〇V R3 環氧乙烧類(oxiranes) : ; R1、R2、R3、R4、R5及R6可為相同或不同,且係選自線 性的、分枝的、環狀的、多環的氫、烧基、烯(alkenyl)或烯基 (alkenyl group),且可被含有氧、氮或氟的各取代基官能化。 鲁 再者’其他原子像是例如硫、石夕,或其他鹵素(halogens)可 被包含在第二前驅物分子中。在這些種類中,最適合的係環氧 乙烷(ethylene oxide)、環氧丙烷(propylene oxide)、環戊缚氧化 物(cyclopentene oxide)、環氧異丁烷(is〇butylene oxide)、2,2 3- 三曱基環氧乙院(2,2,3-trimethyl〇xirane)、丁二稀氧化物 〇31血(^狀111〇11(^(^)、雙環庚二烯(1^7〇1〇1^〖&(^1^)、1,2-環氧 -5-己烯(l,2-epoxy-5-hexene)、2-甲基-2-乙烯環氧乙烷 (2-methyl-2-vinyloxirane) 、1-異丙-環丁 -1,3-二烯 (1-isopropyl-cyclohexa-l, 3-diene)及曱基第三 丁基趟 (tertbutylmethyldher)〇 -19- 1353637 如圖一所示,平行平板式電漿加強化學氣相沉積 (PECVD)反應器10係用於2〇〇mm晶圓製程的類型。反應 器1〇的内直徑X約是13英吋,而高度Y約是8.5英吋。基 板卡盤12的直徑約是]〇 8英对。反應氣體經由一氣體分配板 (gas distribution plate,GDP) 16 導入反應器 10 中,此氣體分
配板與基板卡盤12之間的間距z約是1英吋,且反應氣體係 經由一 3英吋排出埠(exhaustp〇rt) 18被排出反應器。奸 能源20被連接至氣體分配板(GDP) 16,其在電性上係與反 應器10絕緣,且基板卡盤12是接地的。為了實用目的,反應 器所有的其他部分皆是接地的。在一不同的實施例中,即能 源20可被連接至基板卡盤12 ’並被傳送至基板22。此中,基 板獲得一負偏壓(negative bias ),其值取決於反應器的幾何形 狀與電漿參數。在另—實施例中,可以使用超過—個能源。^ 例而言,二個能源可以操作在相同的处頻率,或者—個可^ 作在低頻、一個在高頻。這二個能源可都被連接至相同的電^ 或者至不_電極。在另—實施财,处能源在沉
^斷斷續續地產生脈衝波。沉積低㈣膜期間被控制的製程變 數係RF能源密度、前驅物混合與流量、反應器中的壓力 ^間,及基板溫度。(加_晶圓卡盤的溫度控制著基板撕 很爆不^月尺⑺工地又令、迥的笫一與第二 =定製程錄結合,可製備本發明之較 含:約5至約40原子百分比的石夕;約5至約7G原包 石厌’ 0至約5。原子百分比的氧;以及約5至約 =的 的氫。在本發明的某些實施例中,碳含量可以高至約刀比 -20- 1353637 在一薄膜的一沉積製程期間,被控制的主要製程變數係 RF能源、前驅物的流量、反應器壓力及基板溫度。根據本發 明’以下提供以一第一前驅物二乙氧基曱基矽^ (diethoxymethylsilane,DJEMS)與一第二前驅物雙環庚二= (bicycloheptadiene,BCHD)沉積薄膜的數個範例。在某此範 例中,二乙氧基甲基矽烷(DEMS)前驅物蒸汽用氦(或氬 載子氣體,以傳送至反應H中。可視需要地,將沉積後之薄膜 在400C熱處理,以減小k。另一種方式是,用或電子束 處理薄膜以減小k並增加交聯(cross_iinking),如美國專利申 請號10/758,724中所述為例。熱處理可以單獨進行,或與 在’724申請案中之其中一個處理方法併用。 /、不
▲、詳細而言,根據,724申請案’沉積的薄膜視需要可以用一 能源處理,以穩定此薄膜並改善其特性(電性、機械性、黏性》 最後可得-最佳化_。適合的能源包減源、化學源、紫外 光(UV)、電子束、微波及電漿。前述能源的各種組合也可以 用^本發財。本發明個源侧來修飾沉積介電質的石夕 -¾鍵結麟(bondingnetworic)、修飾材射的其他鍵结、引 的化碳交聯,以及在某些狀況下移除碳氫相,綜合前 j有的修飾,可得—較高的彈性模數(dast—)、- =的硬度、或-較低的内應力、或以上所述特性的結合。一 模數或較低的應力皆可得—較低的裂變傳播速度,較 回、數與較低應力的結合係較佳的能源處理結果。 熱源包括任何來源,像是例如一發熱元件 (heating 犠1^、或紐’可以加熱沉積之介電材料從約3G()°C至約 ’皿度。此熱源紐係能夠加熱沉積之介電材料約35〇 -21 - 43〇C的溫度。熱處理製程可被實行在多種時間週期, ^力1刀知至約3〇〇分鐘。此熱處理步驟一般被執行在一惰 ί1生氣體中例如氦與氬^熱處理步驟可稱作—退火步驟,此中 使用了快賴社、火爐(&_6)退火雷機火或尖峰 (spike)退火條件。 兔外光處理步驟的執行^^利用可以產生約5⑻奈米至約 150奈米波長的光源來照射(irradiate)基板,祕關溫度維 持在25 C至50(rc ’較佳的溫度為30(TC至45(TC。大於370 ^米的輻射能不足轉離或活化重要_結,波絲圍以150 奈,至370奈米較佳。由文獻資料與在沉積薄膜上測得的吸收 光谱’本發明已得知小於m奈米的輻射並不適用此係由於 氫化石夕碳氧化物(SiCOH)薄膜的降解(degradati〇n)。再者,相 巧於1M)奈米至310奈米的範圍,31〇奈米至37〇奈米的能量 範圍較不實用’此係由於31G奈米至37G奈米之每個光子 (phmon)相對低的能量。在15〇奈米至31〇奈米的範圍中, /儿積4膜之吸收光譜有最佳重疊(〇veriap),且薄膜特性(像 是例如疏水性)降解最小,故可視需要被選用作^光譜一最 有效區,以改變氫化矽碳氧化物(Sic〇H)的特性。 一電子束處理步驟的執行’係利用一能夠在晶圓上方產生一 均勻電子通量(electron flux)的能源,其電力從G 5 keV (仟 電子伏特)至25keV ’且電流密度從〇丨至丨⑽mien)Amp/cm2 (微安培/平方公分)(較佳為1至5 micr〇Amp/cm2),晶圓溫 度維持在25°C至500。(:,較佳的溫度為^(^^至45〇〇c。在電 子束處理步驟中。使用之較佳的電子劑量為5〇至5〇〇 m_coulombs/cm‘(微庫侖/平方公分),最佳為1〇〇至3〇〇 microcoulombs/cm2 地產:ΓΐΤ行’係利用能夠產生原子氫以及選擇性 露基繼。嫌的電絲 2—_====罐度維持在
_ίίΐ!步驟的執行’係藉由導入-氣體至-可以產生電 “二二,J"之後其轉變為電聚。可以用於㈣處理的氣 =ΐ例如氬、氮、氦、_或氪㈣,其中 •里5 '、子虱的相關來源、甲烧(methane)、甲基石夕烧 ^ _^1Sllane)曱基的相關來源及其混合物。電漿處理氣體的 机里β視使用的反應器系統而改變。腔體壓力可以在至 2〇torr的範圍中,但壓力操作的較佳範圍在i至⑴咖。電 處理步驟歷時-咖週期,—般從約1/2至約1()分鐘,然而 在本發明中可用較長的時間週期。 …'
〇 一,用—处或微波能源來產生上述的電漿。RF能源可 操作在鬲頻範圍(約l〇〇w或更大的等級);低頻範圍(小於 250W)或者可用兩者的組合。高頻電力密度可以在〇 1至 2,0W/cm2的範圍中,但操作的較佳範圍在〇 2至丨〇w/em2。 低頻電力密度可以在0.1至i.OW/cm2的範圍中,但操作的較 佳範圍在0.2至〇.5W/cm2。選定的電力層級必須夠低,以避免 暴露的介電表面(小於5奈米去除(removal))有顯著的濺擊钱 刻。 為使本發明之沉積製程能成功完成’使用的沉積條件也是 -23- 1353637 關鍵的。舉例而言,晶圓溫度為約25¾至約42〇t:,且較佳為 約60°C至約35〇°c。处能源密度為約0.05W/cm2至約 3.5W/cm2 ’且較佳為約〇 25W/cm2至約lw/cm2。在較佳的製 程中’射頻電力同時施加於氣體導入板(喷頭)(13.6MHZ頻 率與約35〇W的電力(然而可用200W至450W))及晶圓卡盤 (13.6MHz頻率,約100W的電力(然而可用50W至200W))。 如此技藝者所習知’本發明也可使用不同的頻率(〇26、 0.35、0.45MHz) 〇 二乙氡基曱基矽烷(DEMS)反應氣體流量約5sccm至 lOOOsccm ’且較佳為約25sccm至約200sccm。雙環庚二烯 (BCHD)反應氣體流量約5sccm至約1 〇〇〇sccm,且較佳約 lOsccm至約120sccm。以使用液態前驅物輸送(deHvery )時, 每個前驅物的液態流量在500_5000毫克/分鐘(mg/minute)的 範圍中。視需要可以添加氦,且較佳的氦流量在丨〇〇_2〇〇〇sccm 的範圍中,然而在本發明中也可用其他流量。沉積製程期間的 反應器壓力一般為約50mtorr至約l〇〇〇〇mt〇rr。 使用一多站(multistation)沉積反應器時,基板區域係指 每個個別的基板卡盤,且各氣體的流量係指一個個別的沉積 站。因此,輸入反應器的總流量與總電力要乘以反應器内沉積 站總數。 在進行後續。之整合製程前,沉積薄膜是穩定的。執行穩定 製程可在約300°C至約430。(:一火爐退火步驟中,歷時一時間 週期約0.5小時至約4小時。穩定製程也可在一快速熱退火製 程中執行,溫度向於約300°C。穩定製程也可在一 υγ或電子 -24- 執ΐ,溫度高於’。根據本發明所得到的着之 以形成無數的其他裝置。 乾例依據本發明還可 32頂Hi建立在—絲板32上的電子裝置30。在石夕基板 第-令麗成絕緣材料層34 ’ 一第—金屬區36嵌入兑中。在 二it上實行化學機械研磨(CMP)製程後:、-薄膜 蓋^未^ ^在層34與層38之間加上—額外的介電帽 此二一絕緣材料層34可由氧化梦、氮化石夕、這 r够㈣麵鱗_祕。超低k薄 乂净、由一微衫(Photolith嗯aohy)製程圖荦化,而導 (cwT^ ° 40 將超低上ί-声',:】學氣相沉積(PECVD)製程 _ #膜第一層44 >儿積在第-超低k薄膜38斑第-壤碑 彳導體層4G可由—金屬傳導材料或—非金屬傳導材 例而言’可使用一金屬傳導材料例如滅銅,或- T…導材料滅或多祕。第—導體4G與第—金屬區36 可電相連。 ^第二超低!^薄膜層44巾進行—光微影製程後,形成一 触—¥虹區50,接著疋第二導體材料的—沉積製程。第二導 5〇也可纟金屬材料或—非金屬材料沉積類似沉積第一 -25· 1353637 導體層40的材料。第二導體區5〇與第一導體區4〇可 ^系般入在超似絕緣鮮二層44卜超低⑽膜第連盘 第一絕緣材料層38緊密接觸。在此特定範例中,第 枓層38根據本發明係一超低k材料,用作—勒介料才 而第二絕緣材料層,亦即,超低k _ 44,卿時 =與-層間介電f。基於超低k薄膜的低介電常數第—絕ς 曰38與第二絕緣層44可具極佳的絕緣特性。
圖五顯示本發明之電子裝置60,類似圖四所示電子裝 30,但是有額外的介電帽蓋層62沉積在第一絕緣材料層犯與 第二絕緣材料層44之間。介電帽蓋層62適合由一材料形成: =氧化石夕、氮化碎、氮氧化♦、碳化碎、氮碳化邦iCN)、石夕 碳氧化物(SiCO)、修飾過的超低k及其氫化化合物,以及耐火 巧石夕氮化物’其中此财火金屬係選自由组皆铪及鶴構成 的群組。此外,介電帽蓋62伽作—擴散阻障層防止第一 導體層40擴散到第二絕緣材料層4钟,或擴散到較低層中, 特別是進入層34與層32。
圖六顯示本發明之另一不同電子裝置7〇的實施例。在電 子裝置70中,使用二層額外的介電帽蓋層乃與%,其可用 作一反應式離子蝕刻(RIE)遮罩與化學機械研磨(CMp)研 磨停止層。第—介電帽蓋層72沉積在第-絕緣材料層38頂 上。"電層72的作用’係為平坦化第一導體層4〇之化學機械 研磨製程提供-停止點(endpGint)。研磨停止層72可由一適 合的介電材航積,如氧缺、氮切、氮氧切、碳化石夕、 石夕碳氧化物(sico)、氮碳化邦iCN)、經修飾之超低k及其氫 化化合物’以及耐火金屬魏化物,其巾此耐火金屬係選自由 •2(5- 1353637 f、錯、餘及鎢構成的群組。介電層72的上 的水平高度相同。為了相同目的,可加上—第弟= 74在第二絕緣材料層44頂上。 弟一 ”包層 圖七顯示本發明另-更不同電子裝置8〇的實施 不同的實施例中’沉積-額外的介電層82,因此將第1 材料層44分隔為二層84與86。層内與層間介電層44,如^ ^所不,因此被分隔為層内介電層84與層間介電層%
^㈣與内連線94間的分界線(b_daiy )上,如圖八所示。 再儿積-額外的擴散阻障層96於上面的介電層74頂上。此不 同之電子錢8〇實施例提供_外優點,翁介電層82用作 一反應式離子侧(RIE) _停止,以提供極佳的内連線深 度控制’以便對導體阻抗(resistance)有較佳的控制。 以下所列範例,係為示範本發明之超低k介電薄膜的製 造’並展示此等範例可得到的好處: 、
【範例一】 在此範例中,參照圖一,首先準備一晶圓,經由一開缝閥 (slit valve) 14將此晶圓置入反應器10中,且視需要以氬氣 預蝕刻(pre-etched)此晶圓。在此晶圓製備製程中,晶圓溫 度被設定在約18(TC,而氬流量被設定在約25sccm,以達到約 lOOmtorr的壓力。接著打開一 rf能源至約125W,歷時約6〇 秒。然後關閉RF能源與氬氣流。 一乙氧基甲基石夕烧(DEMS)前驅物被送入反應器中。要沉 積本發明之超低k薄膜’首先建立二乙氧基曱基矽烷(DEMS) •27· 1353637 與雙環庚二烯(BCHD)氣體流至必要的流量與壓力,亦即,二 乙氧基曱基矽烷(DEMS)約4sccm與雙環庚二烯(BCHD)約 3sccm ’以及約500mtorr的壓力。接著打開一 RF能源至約 30W ’歷時一時間週期約50分鐘。然後關閉RF能源與氣體 流。接著自反應器10將晶圓移出。 為減小沉積薄膜的介電常數,且更為改善其熱安定性,亦 即,為使其在溫度高於300t時能穩定,此薄膜需後處理(post treated)以蒸發其揮發性成分(v〇iatiiecontents),並且在尺寸 上(dimensionally)穩定薄膜。此後處理製程可由下列步驟在 一退火火爐中實行。首先,以流量約1〇公升/分鐘的氮淨化火 爐約5分鐘(薄膜樣本置於一裝載站(i〇a(j stati〇n)中)。接著將 薄膜樣本轉移至火爐反應器中,開始加熱薄膜至約28〇。〇的後 退火循環’加熱率約5°C/分鐘,維持在約280。(:歷時約5分鐘, 以約5C/分鐘的第二加熱率加熱至約4〇〇°C,維持在約400°C 歷時約4小時’關閉火爐,並讓薄膜樣本冷卻至低於約1〇〇〇c 的溫度。一適合的第一維持溫度可從約28(y>c至約3〇〇〇c,而 一適合的第二維持溫度可從約3〇(TC至約400T:。由此得到的 薄膜具介電常數1.81。另一種方式是,可在約3〇〇°c用UV或 電子束處理薄膜歷時至多30分鐘。 現在參照圖二討論第一實施例之結果。圖二所示係得自一 超低k薄膜之傅利葉轉換紅外線(FTIR)光譜,此薄膜係根 據本發明製備自二乙氧基曱基矽烷(DEMS)與雙環庚二烯 (BCHD)的混合。此光譜顯示石夕-氧吸收頻帶在約 1000-1100cm、石夕-甲基吸收峰值(咖哪如叩池)在約mg cnT1及碳-氫吸收峰值在約2900_3000 cm-i。超低k薄膜之傅利 •28· 1353637 葉轉換紅外線(FTIR)光譜的-個特性,係_氧峰值可被解 迴旋為在1141cm·1、1064 cm·丨及l〇3〇cm-丨的三個峰值,尤如 圖一之示意圖所示。 【範例二】 在此範例中,在與範例一相同的設備中製備一晶圓。首 先,將晶圓置入反應器中。晶圓溫度被設定在約18〇。〇。二乙 氧基甲基矽炫(DEMS)前驅物被送入反應器中。要沉積本發明 之超低k薄膜,首先建立二乙氧基曱基矽烷(0£1^幻與丁二烯 氧化物(butadienemonoxide ’ BMO)的氣體流至必要的流量與壓 力’亦即’二乙氧基甲基碎炫(DEMS)約1 seem與丁二婦氧化 物(BMO)約4sccm ’以及約500mtorr的壓力。接著打開一 Rp 能源至約30W ’歷時一時間週期約50分鐘。然後關閉RF能 源與氣體流。接著自反應器10將晶圓移出。 接著以範例一所述相同的方法處理薄膜。得到的薄膜具介 電常數1.77。 【範例三】 在此範例中,在與範例一相同的設備中製備一晶圓。首 先,將晶圓置入反應器中。晶圓溫度被設定在約180°C。二乙 氧基甲基矽烷(DEMS)前驅物被送入反應器中。要沉積本發明 之超低k薄膜,首先建立二乙氧基甲基矽烷(DEMS)與2-甲基 乙烯環氧乙烧(2-methyl-2-vinyloxirane,MVOX)的氣體流至 想要的流量與壓力,亦即,二乙氧基曱基矽烷(DEMS)約2sccm 與2-曱基-2-乙烯環氧乙烷(MVOX)約3sccm,以及約500mtorr 的壓力。接著打開一 RF能源至約30W,歷時一時間週期約 -29- =。。然後’能源錢體㈣著自反應器10將晶 接著以範例-所述相同的方法處理薄膜。 得到的薄膜具介電常數2,08。 【範例四】 在此Ιϋ別中,在- 8英忖商用電聚加強化學氣相沉積 (PECVD)②備巾製備—晶圓。首先,將晶圓置人反應腔體 中。晶圓溫度被設定在約20(TC。用氦作載子氣體,二乙氧基 甲基矽烷师厘呂你展戊烯氧化物㈣咖伽如㈢硫⑶⑺同 時被送入反應巾。要沉積本發明之超低k缚膜,首先建立二 乙氧基甲基魏(DEMS)、環戊稀氧化物(cp〇)及氦的氣體流至 想要的流篁與壓力’亦即,二乙氧基甲基矽划加卿約 7〇SCCm、環戊烯氧化物(〇>〇)約32〇sccm及氦約最_,以 及約200〇mt〇rr的壓力。接著打開一处能源至約3〇〇w,歷時 -時間週期約10分鐘。然後關閉即能源與氣體流。接著自 反應腔體將晶圓移出。 接著以範例一所述相同的方法處理薄膜。得到的薄膜具介 電常數2.19。 現在參照圖三討論結果。圖三所示係得自一超低k薄膜之 傅利葉轉換紅種(FTIR)规,此薄麟製備自二乙氧基 曱基石夕烧(DEMS)/環戊烯氧化物(CP〇)及氦。此光譜顯示石夕^ 吸收頻帶在約lOOO-UOOcm-1、矽-甲基吸收峰值在約 -30- 1353637 及石厌-氫吸收峰值在約2900-3000 cm-1 〇超低k薄膜之傅利葉轉 換紅外線(FTIR)光譜的一個特性,係矽_氧峰值可被解迴旋 為在】132cm、1058 cn^及1024cmf丨的三個峰值,如圖三之 • 特別示意圖所示。 • 為穩定超低k薄膜,也可用一快速熱退火(rapid thermal annealing ’ RTA)製程。根據本發明得到的薄膜,具介電常數 k小於約2.5的特性’且能熱穩定地整合在一後段製程(be〇l) 内連線結構中,其一般製程在至多約40(TC的溫度。因此,採 用本發明之教示可容易地生產邏輯與記憶裝置之後段製程中 用作層内與層間介電質之薄膜。 因此,根據本發明之方法與形成的電子結構,在以上所述 與圖四至圖八附加圖面中已完整示範。須強調圖四至圖八所示 電子結構之範例,僅用來例示本發明的方法,其亦可應用於益 數電子裝置的製造。 〜、…' % 熟此技藝者已習知,使用液態質量流控制時,列在上述四 個製程範例中之氣體流單位,可代換為液態流單位。 由於已用例示方式描述本發明,故應瞭解專業術語 (terminology)的使用係在於文字說明之本質,而不在於限制°。 再者,本發明之較佳實施例與數個不同的實施例已特別地 顯說明如上,熟此技藝者可了解,在不悖離本發明之精神 與範疇下,可應用這些教示於本發明之其他可的變體中。 -31- 1353637 依本發明之實施例所主張之專屬權利在以下所附申請專 利範圍中。 【圖式簡單說明】 本發明之4述目的、特性與優勢藉由詳細說明與所附圖式 可清楚瞭解,其中: 圖一顯示可用於本發明之一平行平板式化學氣相沉積反 應器之剖面圖。 、 圖二顯示本發明之一超低k材料的傅利葉轉換紅外線 (F〇uner Tmnsf0rm Infrared,FTIR)光譜,其係沉積自二乙氧基 甲基矽烷(DEMS)與雙環庚二烯(BCHD)的混合。 ⑽齡本發明之^—超低k材料之傅繼轉換紅外線 ^ R)光睹,其係沉積自二乙氧基甲基矽烷(DEMS)與環戊 烯氧化物(CPO)的混合。 ❿ 圖四係依據本發明,顯示一電子裝置之放大剖面圖,其具 超低k材料之-層时電層與—層間介電層。 阻障發明,顯示當圖四電子結構具一額外的擴散 阻障)丨電巾自盍層,位於超低k__頂上時之放大剖面圖。 離子t ,顯相五料結額外的反應式 障’於研磨停止層頂上^ 式離=?===3_個額外的反應 料薄膜頂上。 所朴止介電層,位在層間超低k材 -32- 1353637 圖八係依據本發明,顯示圖七電子結構具數個額外的反應 式離子蝕刻(RIE)硬罩/研磨停止介電層沉積,位在多相 (multiphase)材料薄膜頂上。 【主要元件符號說明】 10反應器 12基板卡盤 14縱向閥 16氣體分配板 18排出埠 20RF能源 22基板 30電子裝置 32矽基板 34第一絕緣材料層 36第一金屬區 40第一導體層 44超低k薄膜第二層 50第二導體區 38超傳k薄膜 60電子裝置 70電子裝置 62介電帽蓋 72第一介電帽蓋層 74第二介電帽蓋層 80電子裝置 82介電層 84層内介電層 92内連線 94内連線 96擴散阻障層 86層間介電層 -33-
Claims (1)
1353637 七、申請專利範圍: 1. 一種介電材料,包含矽、碳、氧及氫元素,該介電材料具一隨 機共價鍵結(random covalently bonded )三度空間網路結構 (tri-dimentional network structure),其介電常數不大於 2.5,且具 有一傅利葉轉換紅外線(FTIR)光譜,其之一矽-氧吸收頻帶被解 迴旋(deconvoluted)成三個峰值,該矽、碳、氧及氩元素衍生自 一第一前驅物,具分子式SiRR’R’’R’,,,其中R、R’、R,,及R,’, 為相同或不同,且係選自氫、烧基及燒氧基;以及一第二前驅, 係具以下各分子式之一: 稀烴(alkenes): 块烴(alkynes):
R1 R1 ^(ethers) : r2RJ^_〇^5 ;及
環氧乙烧類(oxiranes)
其中’1^、111、112、114、尺5及尺6為相同或不同,且係選自氫、 燒基、烯(alkenyl)或烯基(alkenyl group)。 -34- 1 .如請求項1所述之介電材料’其中該隨機共價鍵結三度空間網 2 路結構包含矽-氧、矽-碳、矽_氫、碳_氫及碳_碳鍵。 3. 如請求項i所述之介泰 1時是熱穩定的。 $料’射該介電材料在溫度至少43〇 4. 如請求項】所述之介 米級孔洞。 W ,其申該介電材料更包含多樣性奈 6· -種後段製程(BEOL)内遠绩姓媒^ (BEOL)之絕緣體、帽蓋構’包含用作—後段製程 含石夕、碳、氧及氫元素,層的—介騎料,該介電材料包 其介電fϋλππ,B、^機共價鍵結三度空刺路結構, ' *具有一傅利葉轉換紅外線(FTIR)光譜, ^ rfn f被解迴縣三個雜,财、碳、氧及氫元素 储生自具分子式SiRR,R,,R,”的一第一前驅物,其中R、r,、R” 及R,”為相同或不同,且係選自氫、絲及燒氧基;以及一第二前 驅物,係具以下各分子式之一: 稀烴(alkenes): 块煙(alkynes): R1—s一~R2 . S^(ethers) : r3 H5 ; 及
環氧乙烷類(〇xiranes): -35· 1353637 产其其二广^^七七及^為相同或不同’且係選自气 烷基、烯(alkenyl)或烯基(aikenyl抑叩)。 目氧、 電 二-種具數層絕騎料以在—線路結構巾祕層喊層 貝的電子結構,包含: 一預處理半導體基板,具一第一金屬區,鑛入 材料層中; 絕緣 一第-導歷’触人由—超低k材料臟之—第 料層中’該超低k材料包含石夕、碳、氧及氮,以及多樣性太半 孔洞,該超低k材料料大於約2.5的—介電錄,以及—傅^ 轉換紅外線^獲)光譜,其,·氧吸㈣較解减為三個| 值’該矽、碳、氧及氫元素係衍生自具分子式別狀’尺”尺”’的一第 一前驅物,其中R、R’、R”及R’’,為相同或不同,且係選自氫、 烷基及烷氧基;以及一第二前驅物,係具以下各分子式之<-·· R· R3 烯烴(alkenes) : ^ \___/ r2’—\r4 R2 快烴(alkynes) : Rl ;及 R1 r4 越(ertiers) : r2-^V-〇- 〆 環氧乙烧(oxiranes)類:Ri''~7^-R3 R2 R4 其中’1^、112、113、尺4、尺5及116為相同或不同,且係遽自~ 烧基、稀(alkenyl)或稀基(alkenyl group),該第二絕緣材料層與^ -36- 1353637 -絕緣材料層緊雜觸(intimate e_et),該第―導魏與該第 一金屬區電相連(electrical communication);以及 一第二導體區,係與該第-導體區電相連且被嵌人含該超低k 材料之-第三絕緣材料層中’該第三絕緣材料層與該第二絕緣材 料層緊密接觸。 9. 如請求項7所述之電子結構,更包含 該第二絕緣材料層與該第三絕緣材料層之間;以及一=介= 蓋層,位於該第三絕緣材料層頂上。 10.如請求項8所述之電子結構,其中該介電帽蓋由—材料所形 成,該材料選自氧切、氮切、氮氧切、敎金屬魏化物 sllrn nitride)、碳切、碳氮切、碳氧化石夕、 摻雜反的魏物及其含纽合物賴成之群組。 所述之電子結構’其巾剌火金屬魏化物包括一 ^m^m"!〇ry meta〇 ? #iS ^ ^(Ta)'#(Zr)' 之電子結構’其巾該第—介電帽蓋層與該第二 石々、ΐϊ曰由一材料形成,該材料選自氧化石夕、氮化石夕、氮氧化 的氧化物'綱 -37- 14. 丄 下所述^電子結構’其中該第一絕緣材料層係選自以 silicate sla 一氧化石夕、氮化石夕、•夕玻璃(phosphorus BPSG) ' ^^^^(boron phosphorus silicate glass ^ BPSG)、及此等材料之各種其他經摻雜之變體。 層,位結構,更包含-介電·之擴散阻障 位在辟—絕緣材料層與該第三絕緣材料層至少其中一上。 應式_刻 :,阻障層,於該反應式二二及層- 17.如請求項7所述之電子結構,更人 刻(RIE)硬罩/研磨停止層 反應式離子蝕 擴散阻障層 層頂上。 介電擴散阻障層,於魅—人絕緣材料層頂上,·一第-磨停止層頂上;—“介電;子餘刻(_)硬罩/研 止層★,於該第三絕緣材料層頂二以及硬罩/研磨停 於該第一介電反應式離子钱刻硬罩/研磨丨停止 18.如請求項7所述之電子結構, 似材料之-侧介«與-超似㈣ 19. 一種 電 具數層絕緣材料以在一線路結構中用作層内或層間介 -38- 1353637 質的電子結構,包含: ’係嵌入一第一絕緣 一預處理半導體基板,具一第一金屬區 材料層中; 加楚至少個第一導體區係嵌入由一超低k材料形成之至少-個苐二絕緣材料層t,該超低k材料主要_、碳、氧及Μ 及多樣性奈米級孔洞所構成,該超似材料具不大於約2 8的 電常數’以及-傅利葉轉換紅外線(FTIR)光譜其一石 頻帶被解迴旋為三個峰值,财、破、氧及氫元素翁 八
子式SiRR,R,,R,,,的一第一前驅物,其中R、R,、R,,及r,”為相= 或不同,且係選自氫、絲及燒氧基;以及—第二前驅物 以下各分子式之一: 八
稀烴(alkenes): 炔烴(alkynes) : r1 一三 R2 ; 2r!\ r4 •醚(ethers) : ;及
環氧乙烷類(oxiranes): 其中,1^、112、尺3、尺4、115及尺6為相同或不同,且係選自氫、 烧基、烯(alkenyl)或稀基(alkenyl group),該至少一個第二絕緣材料 層之一與該第一絕緣材料層係緊密接觸(intimate contact ),該至 少一個第一導體區之一與該第一金屬區電相連(electrical -39- 1353637 communication)。 嫩—軸麯,位於每 21如請求項W所述之電子結構更包含 f母個該至少一個第二絕緣材料層之間;以及」第電=二 層’位在該最上面之第二絕緣材料層的頂上。 ”電中目盍 22.如請求項21所述之雷早έ士接 二介電帽蓋由-超低kf_成。“—介電帽蓋層與該第 構,其愧第—介侧制與該第 盍層係由_更的(modified)超低w料形成。 述US結構)中該介電帽蓋由-材料形成, 括 2質6的一電種^層料以在—線路結射_内或層間介電 一預處理半導體基板, 材料層中; 具一第一金屬區,係嵌入一第 絕緣 1353637 一〒-導體區’嵌人—第二絕緣材料層 層與該第-絕緣材料層緊密接觸,該第—=第二絶緣材料 電相連·,-第二導體區,係與該第—導體區該第-金屬區 第二絕緣材料層中,該第三絕緣材料層與 络且被丧入一 接觸; 萆—、,色緣材料層緊密 層之間 ,以及、^ ' ”:曰。亥 第二絕緣材料 介電帽ί層第一 氧及氫,以及多樣性==該: (FTIR)光/之—介電錄’以及—翻雜換紅外線 石:3本/ 及收頻帶’其被解迴旋為三個峰值;該矽、 ΐ中R、C何生,自具分子式·,R”R,”的—第一前驅物, 、 及R為相同或不同,且係選自氫、燒基及烧氧 基’以及-第二前,崎,係具以下各分子式之一· 烯烴(alkenes): R R2 炔烴(alkynes) : r> R3 R4 •R2 R 醚(ethers) : r2^_〇 及 〇 環氧乙炫(oxiranes)類: RLym3 R2 -41 , 1353637 其中,1^、112、尺3、尺4、尺5及&6為相同或不同,且係選 炫*基、烯(alkenyl)或烯基(alkenyl group)。 2質7的一層料喊_魏、轉+㈣層喊層間介電 貝的電子結構,包含: 兒 材料2處理半導體基板,具―第—金屬區’係嵌人—第—絕緣 —第一導體區’欽一第二絕緣材料層中,該第二絕緣材 層與該第一絕緣材料層緊密接觸,該第一導體區與該第一金屬區 電相連; °° …—第二導體區與該第一導體區電相連,且被嵌入一第三絕緣 材料層中,該第三絕緣材料層與該第二絕緣材料層緊密接觸;以 及 —擴散阻障層,係由一材料形成,該材料包含一超低k介電 材料,係位在該第二絕緣材料層與該第三絕緣材料層之至少其中 一個上’該超低k材料包含石夕、碳、氧及氫,以及多樣性奈米級 • 孔洞’該超低k材料具不大於約2.5的一介電常數,以及一傅利葉 轉換紅外線(FTIR)光譜具一矽-氧吸收頻帶,其被解迴旋為三個 導值;該矽 '碳、氧及氫元素係衍生自具分子式SiRR,R,,R,1 — 第一前驅物,其中R、R,、R”及R,,,為相同或不同,且係選自氫、 统基及院氧基,以及一第二前驅物,係具以下各分子式之一:
烯烴(alkene。: •42· 1353637 R2 炔烴(alkynes) : Rl ;及 R1 R4 fel(ethers) : R2_\ 〇-Z-r5 〆 R6 1 0 3 環氧乙烧類(oxiranes) : R'^~V^R 其中,1^、112、113、114、1^及尺6為相同或不同’且係選自氣、 烧基、稀(alkenyl)或烯基(alkenyl group)。 28. —種具數層絕緣材料以在一線路結構中用作層内或層間介電 質的電子結構,包含: 一預處理半導體基板,具一第一金屬區,係嵌入一第一絕緣 材料層中; 一第一導體區,嵌入一第二絕緣材料層中,該第二絕緣材料 層與該第一絕緣材料層緊密接觸,該第一導體區與該第一金屬區 _ 電相連; ' 。° 第體區與⑧第-導體區電相連,且被喪人—第三絕緣 材料層中,該第三絕緣材料層與該第二絕緣材料層緊密接觸;、 離:Τ(_硬罩/研磨停止層,位於該第二絕 :擴散轉層,錄觀應式料射 碟、氧及氫,—二=二=約 丄刀:>Dj/ 2 5介電常數’以及—傅利葉轉換紅外線(FTIR)光諸,具-石夕-氧吸_帶’祕迴旋為三個峰值;财、碳、氧及氫元素係 衍生^具分子式SiRR,R,,R,’,的一第一前驅物其中R、R,、R” 及R為相同或不同’且係選自氫、院基及烷氧基以及一第二前 驅物,係具以下各分子式之一: 烯烴(alkenes;) R1 R2
R3 R4 •R2 炔烴(alkynes> : R1 Rl R4 及 il(ethers) : ; 環氧乙烧(oxiranes) :rS^Vr3 R2 r4 其中,R、R、R、R4、R5及R6為相同或不同,且係選自氫、 烧基、稀(alkenyl)或烯基(alkenyl group;)。 29· —種具數層絕緣材料以在一線路結構中用作層内或層間介電 質的電子結構,包含: 曰/ 一預處理半導體基板,具一第一金屬區,係嵌入一第一絕緣 材料層中; -第-導體區,嵌人-第二絕緣材料層中,該第二絕緣材料 層與該第-絕緣材料層緊密接觸,該第_導體區與該第一金屬區 電相連;-第二導體區與該第-導體區電相連,且被嵌入〆第三 -44 - ^53637 、、巴緣材料層中’該第三絕緣材料層與該第二絕騎料層緊密接觸; —第一反應式離子蝕刻(RIE)硬罩/研磨停止層 -絕緣材料層頂上; 位於料 /研磨停 1層H阻障層’位於該第—反應式離子钱刻(RIE)硬罩 —-第二反應式離子糊(RJE)硬罩/研磨停止I,位於該第 二絕緣材料層頂上;以及 /研紅第散轉層,位概第二反就料_ (_硬罩 止層頂上’其中該反應式離子侧(Rffi)硬罩/研磨停止 石障層由一,k介電材料形成,該超低k材料包含 電常Γ及多巧生奈米級孔洞’該超低k材料具-介 ^ % ;、.以及一傅利葉轉換紅外線(FTIR)光譜具一 矽-氧吸收頻帶,其被解迴旋為三 . 象㈠一备 係衍生自具分子式贈R”R,”的1及風兀素, 及R,,,為相同或不同,且係選自氫、广=g ’其中R、R、R 驅物,係具以下各分子式之風烧基及烧氧基,以及一第二前 稀煙(alkenes): R1、 R2 .R3 、R4 R2 炔煙(alkynes) : R1 R1、 R2 _(ethers) : R; -R5 :及 〇 環氧乙烧類(oxiranes):
R3 -45· 1353637
其中,1^、尺2、1^、1^、尺5及尺6為相同或不同,且係選自氫、 烧基、稀(alkenyl)或烯基(alkenyl group)。 30.如請求項29所述之電子結構,更包含一介電帽蓋層,係由一 材料形成,此材料包含該超低k介電材料,該超低k介電材料位 於一層間介電層與一層内介電層之間。 -46-
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CN1950932A (zh) | 2007-04-18 |
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MM4A | Annulment or lapse of patent due to non-payment of fees |