TW202143328A - 用於調整膜應力之方法 - Google Patents
用於調整膜應力之方法 Download PDFInfo
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- TW202143328A TW202143328A TW110113550A TW110113550A TW202143328A TW 202143328 A TW202143328 A TW 202143328A TW 110113550 A TW110113550 A TW 110113550A TW 110113550 A TW110113550 A TW 110113550A TW 202143328 A TW202143328 A TW 202143328A
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- 238000000034 method Methods 0.000 title claims abstract description 76
- 239000000376 reactant Substances 0.000 claims abstract description 92
- 239000000758 substrate Substances 0.000 claims abstract description 83
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001039 wet etching Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 7
- 239000012634 fragment Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- NSYDOBYFTHLPFM-UHFFFAOYSA-N 2-(2,2-dimethyl-1,3,6,2-dioxazasilocan-6-yl)ethanol Chemical compound C[Si]1(C)OCCN(CCO)CCO1 NSYDOBYFTHLPFM-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 101000915175 Nicotiana tabacum 5-epi-aristolochene synthase Proteins 0.000 claims description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- DVSDDICSXBCMQJ-UHFFFAOYSA-N diethyl 2-acetylbutanedioate Chemical compound CCOC(=O)CC(C(C)=O)C(=O)OCC DVSDDICSXBCMQJ-UHFFFAOYSA-N 0.000 claims description 2
- SDIXRDNYIMOKSG-UHFFFAOYSA-L disodium methyl arsenate Chemical compound [Na+].[Na+].C[As]([O-])([O-])=O SDIXRDNYIMOKSG-UHFFFAOYSA-L 0.000 claims description 2
- 235000013616 tea Nutrition 0.000 claims description 2
- 101000735417 Homo sapiens Protein PAPPAS Proteins 0.000 claims 1
- 102100034919 Protein PAPPAS Human genes 0.000 claims 1
- 230000007423 decrease Effects 0.000 claims 1
- -1 iodine, hydrogen Chemical class 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 25
- 239000002243 precursor Substances 0.000 description 16
- 238000010926 purge Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical compound CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VMSHTUXEAVQEKB-UHFFFAOYSA-N [Si].C(C)(C)N(C(C)C)[SiH3] Chemical compound [Si].C(C)(C)N(C(C)C)[SiH3] VMSHTUXEAVQEKB-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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Abstract
所提供者係一種調整膜應力之方法。在一實施例中,藉由在第一步驟中循序且交替地供應第一反應物及第二反應物,而在基板上形成第一膜,並藉由在第二步驟中供應第三反應物至第一膜,而將第一膜轉化成第二膜。第二膜之膜應力係藉由控制第一步驟對第二步驟的比率來進行調整。
Description
本揭露提供一種用於處理基板之方法,更具體地,一種用於調整形成於基板上之膜的應力之方法。
基板及形成於其上的膜可在高溫製程中經受熱處理而產生應力。此可導致基板變形(諸如翹曲(warpage)或開裂(crack))、或膜剝離、或裝置性質劣化。第1圖顯示膜的應力可如何導致膜的剝離或者基板的斷裂或變形。
本揭露提供一種用於處理一基板之方法。更具體地,本揭露提供一種用於調整一膜的一應力之方法。
根據一實施例,一第一膜可藉由在一第一步驟中循序且交替地供應一第一反應物及一第二反應物而形成在基板上。第一膜可藉由在一第二步驟中供應一第三反應物而轉化成一第二膜。第二反應物可經活化。第三反應物可經活化並對第一膜具反應性。第二膜之應力可藉由控制第一步驟對第二步驟的循環比率來進行調整。
根據另一實施例,一第一膜可藉由在一第一步驟中循序且交替地供應一第一反應物及一第二反應物,而形成在具有作為一硬遮罩的一圖案之基板上。第一膜可藉由在一第二步驟中供應一第三反應物而轉化成一第二膜。第二反應物可經活化。第三反應物可經活化並對第一膜具反應性。在50°C下形成之硬遮罩的濕式蝕刻率可與在300°C或更高溫度下形成之氧化矽硬遮罩的濕式蝕刻率幾乎相同。
根據另一實施例,一第一膜可藉由在一第一步驟中循序且交替地供應一第一反應物及一第二反應物而形成在一基板背側上,並可藉由在一第二步驟中供應一第三反應物而轉化成一第二膜。第二反應物可經活化。第三反應物可經活化並對第一膜具反應性。一第三膜可在高溫下形成於基板前側上。可在處理基板之後蝕除第二膜。
根據另一實施例,提供一種具有一待填充間隙之基板,且間隙可以一第一膜填充。一第二膜可藉由在一第一步驟中循序且交替地供應一第一反應物及一第二反應物而形成在第一膜上,並可藉由在一第二步驟中供應一第三反應物而轉化成一第三膜。第二反應物可經活化。第三反應物係經活化並對第二膜具反應性。
根據本揭露之基板處理方法提供調整膜應力以及防止及/或抑制由於膜或基板之應力而發生的基板變形或膜剝離之方法。
第2圖係根據一實施例之製程流程,且第2圖之細節係描述如下。
-裝載基板(101):可將基板裝載至反應空間中之基板支撐(substrate support)上。基板支撐(substrate support)支撐了基板,並對基板提供熱能,以保持基板溫度處於指定溫度。
-形成第一膜(201):第一膜可藉由交替且循序地供應第一反應物及第二反應物至基板而形成在基板上。第一反應物可以是含有Si元素之前驅物,且第二反應物可藉由射頻功率來活化。第二反應物可不與第一反應物起化學反應。例如,第一反應物可以是胺基矽烷(aminosilane)前驅物。第二反應物可以是非活性氣體(諸如Ar、或He、或其組合)。在此步驟中,第一反應物可藉由電漿來解離(dissociated)及打斷,並吸附至基板上。由於在第一反應物與第二反應物之間可不存在化學反應,經吸附至基板上的膜可包含經解離或打斷的第一反應物分子之片段(fragments)(例如矽(Si)、碳(C)、氮(N)、氯(Cl)、碘(I)、烷基配位基(例如 Cn
H2n+1
)、及氫(H)片段、及/或其混合物)。第一膜的第一層可化學吸附至基板。第二層可沉積在第一膜上方,並可包含那些片段的堆疊。第一膜可藉由經活化的第二氣體來緻密化(densified)。同樣地,經活化的第二氣體可有助於第一氣體的解離。此第一步驟可重複「M」次。
-將第一膜轉化成第二膜(301):第三反應物可供應至形成在基板上之第一膜。第三反應物可由射頻功率活化,並與第一膜起化學反應。第三反應物可以是含氧氣體,更佳地,第三反應物可以是氧。在此步驟中,第一膜可轉化成第二膜。由於經活化之第三反應物與第一膜起化學反應,第一膜可轉化成第二膜。例如,第二膜可以是SiO2
膜。此第二步驟可重複「N」次。
在第2圖中,第一步驟201對第二步驟301之循環比率可大於5、較佳地大於20、或更佳地大於50。例如,第一步驟201可重複50次,且第二步驟301可重複一次。進一步地,第一步驟201及第二步驟301可作為群組循環或超循環重複「X」次(至少一次),以在第一膜厚度增加時更加地促成第一膜轉化成第二膜。
第3圖係第2圖之製程流程的示意圖。第3圖之第一步驟及第二步驟分別對應於第2圖之第一步驟201、第二步驟301。在第3圖之第一步驟中,第一層可藉由循序且交替地供應第一反應物及第二反應物來形成。例如,第二反應物可藉由射頻功率來活化。
在另一實施例中,第二反應物可如第3圖所示般連續地供應。在第3圖中,第一步驟可重複「M」次(至少一次),隨後進行第二步驟。在第3圖之第二步驟中,可供應並由電漿活化第三反應物,且第二步驟可重複「N」次(至少一次)。第一步驟對第二步驟之循環比率(也就是M/N)可大於5、較佳地大於20、或更佳地大於50。經活化的第三反應物可將第一膜轉化成第二膜。例如,第一反應物可以是含Si前驅物,第二反應物可以是Ar,且第三反應物可以是氧。作為第一反應物之含矽前驅物可以是下列中之至少一者:DIPAS(SiH3
N(iPr)2
)、TSA((SiH3
)3
N)、DSO((SiH3
)2
)、DSMA((SiH3
)2
NMe)、DSEA((SiH3
)2
NEt)、DSIPA((SiH3
)2
N(iPr) )、DSTBA((SiH3
)2
N(tBu) )、DEAS(SiH3
NEt2
)、DTBAS(SiH3
N(tBu)2
)、BDEAS(SiH2
(NEt2
)2
)、BDMAS(SiH2
(NMe2
)2
)、BTBAS(SiH2
(NHtBu)2
)、BITS(SiH2
(NHSiMe3
)2
)、TEOS(Si(OEt)4
)、SiCl4
、HCD(Si2
Cl6
)、3DMAS(SiH(N(Me)2
)3
)、BEMAS(SiH2
[N(Et)(Me)]2
)、AHEAD(Si2
(NHEt)6
)、TEAS(Si(NHEt)4
)、Si3
H8
、DCS(SiH2
Cl2
)、SiHI3
、SiH2
I2
、或其混合物。作為第三反應物之氧氣可以是O2
、O3
、CO2
、H2
O、NO2
、及N2
O、或其混合物中之至少一者。
第一膜可以是由電漿緻密化之Si前驅物分子的片段堆疊,並可藉由氧電漿來轉化成作為第二膜之SiO2
。換言之,步驟1可以是源塗佈(source coating)步驟,且步驟2可以是氧處理步驟。在第3圖中,步驟2之電漿條件可改變。例如,射頻功率可以提供為具有某一工作比的脈衝,以減少對基板或子層(sublayer)的損壞。
如第4圖所示,當以脈衝提供射頻功率時,實際射頻功率供應時間b對射頻脈衝之單位循環時間a的比率(也就是b/a)係定義為工作比。在根據本揭露概念之另一實施例中,射頻功率可以提供為具有10%至75%之工作比範圍的脈衝。
第5圖係根據本揭露概念之另一實施例。在第一步驟中,可以連續模式供應電漿,但在第二步驟中,可以具有某一工作比的脈衝模式供應電漿。但以脈衝供應電漿並未受限於此。在另一實施例中,可以脈衝供應電漿至第一步驟及第二步驟中之至少一者。
表1係根據第3圖之一實施例的實驗條件,其中可以連續模式供應電漿,其中可不以脈衝供應電漿。
表1:一實施例之實驗條件
項目 | 條件 | |
製程溫度(°C) | 室溫至150°C(較佳地50至150°C) | |
製程壓力托耳((Torr)) | 1.0至5.0(較佳地2.0至3.0托耳) | |
Si前驅物 | DIPAS(二異丙基胺基矽烷(diisopropylaminosilane)) | |
反應物 | O2 | |
吹掃氣體 | Ar | |
形成第一膜之第一步驟 | ||
製程時間(秒) | 源饋送(S1) | 0.05至2.0秒(較佳地0.1至1.0秒) |
源吹掃(S2) | 0.05至2.0秒(較佳地0.1至1.0秒) | |
電漿開啟(S3) | 0.05至2.0秒(較佳地0.1至1.0秒) | |
吹掃(S4) | 0.05至2.0秒(較佳地0.1至1.0秒) | |
S1至S4循環 | 50至200個循環(較佳地100至150個循環) | |
氣體 流量率(單位時間標準毫升數(sccm)) | 源載體Ar | 100至10,000 單位時間標準毫升數(較佳地600至1,200 單位時間標準毫升數) |
吹掃Ar | 1,000至10,000 單位時間標準毫升數(較佳地3,000至6,000 單位時間標準毫升數) | |
電漿條件 | 射頻(RF)功率(瓦(W)) | 100至1,000瓦(較佳地200至400瓦) |
射頻頻率 | 13至100百萬赫茲(MHz)(較佳地27至60百萬赫茲) | |
將第一膜轉化成第二膜之第二步驟 | ||
製程時間(秒) | 預吹掃(S5) | 0.05至5.0秒(較佳地0.5至5.0秒) |
電漿開啟(S6) | 0.05至3.0秒(較佳地0.1至2.0秒) | |
吹掃(S7) | 0.05至2.0秒(較佳地0.1至1.0秒) | |
S5至S7循環 | 1至10個循環(較佳地1至5個循環) | |
氣體 流量率(單位時間標準毫升數) | 反應物(O2 ) | 50至1000 單位時間標準毫升數(較佳地200至500 單位時間標準毫升數) |
吹掃Ar | 1,000至10,000 單位時間標準毫升數(較佳地3,000至6,000 單位時間標準毫升數) | |
電漿 | 條件 射頻功率(瓦) | 100至1,000瓦(較佳地200至500瓦) |
射頻頻率 | 13至100百萬赫茲(較佳地27至60百萬赫茲) |
第6圖顯示根據第一步驟對第二步驟之循環比率的膜應力。在第6圖中,藉由在其中交替且循序地提供含矽前驅物及氧電漿以形成SiO2
膜之正規製程(normal process)於室溫下所形成的SiO2
膜可具有109.8百萬帕(MPa)的拉伸應力,但根據本揭露概念之SiO2
膜之應力可根據第一步驟對第二步驟的循環比率而改變。
在第一步驟中,可交替且循序地將作為第一反應物之含Si前驅物及作為第二反應物之Ar電漿提供至基板,以形成由元素及經解離之Si前驅物的配位基之片段所組成的第一膜。
在第二步驟中,可將作為第三反應物之氧電漿提供至第一膜,以將第一膜轉化成作為第二膜之SiO2
膜。在一實施例中,第一步驟對第二步驟的循環比率可以是50。例如,第一步驟可以是50個循環,且第二步驟可以是一個循環。在另一實施例中,第一步驟對第二步驟的循環比率可以是100。例如,第一步驟可以是100個循環,且第二步驟可以是一個循環。
第7圖顯示在實行第一步驟及第二步驟之後的膜組成。如第7圖所示,在第6圖之50:1及100:1的循環比率條件下所形成之SiO2
膜例如具有理想配比(stoichiometric)的SiO2
膜組成,而無來自氮、碳、及氫、或其混合物之片段的其他元素。此意指第一膜實質上可藉由作為第三反應物之氧電漿來轉化成第二膜。
如第6圖所示,第一膜之膜應力具有-74.8百萬帕之壓縮應力,但隨著氧電漿的提供及第一膜經轉化成第二膜,膜應力轉為拉伸應力。同樣地,步驟1對步驟2之循環比率越高,SiO2
膜之拉伸應力越高。也就是說,SiO2
膜之應力可藉由控制第一步驟對第二步驟的循環比率而適當地調整。因此,可設定最佳製程條件或循環比率以防止基板變形及膜剝離(例如翹曲、開裂等)。因此,可藉由控制循環比率來形成具有目標應力的膜。
在另一實施例中,可實行此製程以引入應力控制膜。例如,若在反應器中以高溫處理基板,使其經受壓縮應力或拉伸應力,則基板可能會變形或斷裂或者可能在其中發生膜剝離或開裂。在此情況下,可將應力控制膜引入基板背側,以抵消基板的壓縮應力或拉伸應力。應力控制膜可以是在處理基板之前藉由根據前述之第2圖及第3圖之方法所形成之具有壓縮應力或拉伸應力的膜。也就是說,應力控制膜的應力可藉由調整源塗佈步驟對電漿處理步驟的循環比率來抵消基板的應力。因此,應力控制膜可在基板的高溫處理期間抑制基板變形及基板上之膜中的開裂。第8圖顯示引入應力控制膜之製程流程。
在第8圖中,第一膜可藉由在第一步驟中供應第一反應物及第二反應物而形成在基板背側上。接著,第一膜可藉由在第二步驟中供應第三反應物而轉化成第二膜。第二膜之應力可藉由控制第一步驟對第二步驟的循環比率來進行調整,且第二膜可充當應力控制膜。製程序列係更詳細地描述於第2圖及第3圖中,因此在本文中省略其詳細描述。之後,第三膜可形成於基板前側上。在完成製程之後,應力控制膜(也就是第二膜)可藉由含氟蝕刻劑(諸如CF4
)來移除。藉由實行此製程,可抑制基板之變形或斷裂以及第三膜中之開裂或損壞。
第8圖之製程可非原位(ex-situ)執行。例如,此製程可在其中具有複數個反應器之室中實行。例如,基板可藉由循序地從一個反應器轉移至另一者以實行第8圖的各步驟來進行處理。
第9圖顯示第8圖之實施例。在第9A圖中,第二膜或應力控制膜2可在低溫(例如室溫)下形成於基板1之背側上。接著,目標第三膜3可在高溫下形成於基板1之前側上。基板之應力可藉由將具有壓縮應力或拉伸應力之應力控制膜引入至基板1的背側來抵消。
在第9A圖中,可藉由在基板1的背側上形成具有壓縮應力之應力控制膜2來抵消基板之拉伸應力,因此可抑制基板的變形或斷裂或者基板上之第三膜3中的開裂。
在第9B圖中,可藉由在基板1的背側上形成具有拉伸應力之應力控制膜2來抵消基板之壓縮應力,因此可抑制基板的變形或斷裂或者基板上之第三膜3中的開裂。
藉由在低溫下將一膜轉化成另一膜,而控制膜應力提供另一技術優勢。SiO2
硬遮罩(hardmask)可用在半導體裝置製造之圖案化製程中。但隨著裝置收縮,裝置上的膜厚度變得更薄,且熱預算(thermal budget)變成嚴重的問題,因為其導致子層損壞、電子跨裝置結構的異常遷移、及裝置失效。因此,可能需要低溫下的SiO2
硬遮罩製程具有與現有高溫製程下所形成者相同的膜性質。因此,根據本揭露之發明概念可提供其之解決方案。
第10圖顯示根據另一實施例之用於在基板圖案上形成硬遮罩的製程流程。
在第10圖之第一步驟101中,可將具有圖案結構之基板裝載至基板支撐。在第10圖的第二步驟301中,可在基板圖案上形成第一膜。第一膜可根據前述之第2圖及第3圖中的方法形成,因此在本文中將省略詳細描述。在第二步驟301之後,可在第三步驟501中將第一膜轉化成第二膜。第一膜至第二膜的轉化可根據前述之第2圖及第3圖中的方法實行,因此在本文中將省略詳細描述。
第11圖顯示根據第10圖及現有方法形成之SiO2
膜的濕式蝕刻率(wet etch ratio,WER)。濕式蝕刻率係在以100:1的比率稀釋於去離子水(deionized water,DIW)中的氫氟酸(HF)中實行。
在第11圖中,各製程條件之細節係描述如下。
-A:藉由正規電漿增強原子層沉積(PEALD)方法而在50°C下形成SiO2
膜,其中可交替且循序地提供二異丙基胺基矽烷(DIPAS,diisopropylaminosilane)前驅物及氧電漿。
-B:前驅物沉積。含Si膜可在50°C下藉由交替且循序地供應二異丙基胺基矽烷矽前驅物及Ar電漿而形成。
-C:藉由實行交替且循序地供應二異丙基胺基矽烷前驅物及Ar電漿的50個循環以及氧電漿的一個循環,以轉化成SiO2
膜而在50°C下形成SiO2
膜。
-D:藉由正規電漿增強原子層沉積方法而在300°C下形成用於硬遮罩應用的SiO2
膜,其中可交替且循序地提供二異丙基胺基矽烷前驅物及氧電漿。
如第11圖之A所示,藉由正規電漿增強原子層沉積方法而在50°C下形成之SiO2
膜具有175.84埃(Å)/分鐘之高濕式蝕刻率,換言之,低濕式蝕刻抗性。但在B條件下,藉由供應二異丙基胺基矽烷前驅物及Ar電漿,而在50°C下形成之含Si膜且具有極低的濕式蝕刻率,換言之,高濕式蝕刻抗性。但如C所示,氧處理及50°C下之含Si膜至SiO2
膜的所得轉化使濕式蝕刻率增加至更接近條件D所示之在300°C下形成之SiO2
膜的濕式蝕刻率。在另一實施例中,藉由進一步控制第一步驟對第二步驟的循環比率,在50°C下形成之SiO2
膜的濕式蝕刻率可與在300°C或更高溫度下形成之SiO2
膜的濕式蝕刻率幾乎相同。換言之,藉由調整前驅物沉積步驟對電漿處理步驟之循環比率,可在低溫下達成在高溫(例如300°C或更高溫度)下可達成的膜性質,減少裝置的熱預算。因此,本揭露的發明概念可針對低溫製程的需求提供解決方案。第11圖亦顯示可藉由調整前驅物沉積步驟對電漿處理步驟之循環比率而在低溫下實現具有不同濕式蝕刻率的膜,且此可使各種應用得以實現。
藉由將一膜轉化成另一膜而控制膜應力可在間隙填充製程中提供另一技術優勢。在第12圖中,覆蓋頂表面的膜1可由於膜應力(例如第12A圖所示的拉伸應力)而剝離。但將應力控制膜引入至膜的頂表面可抑制膜剝離,如第12B圖所示者。
在第12B圖中,以第一膜1填充間隙,且第二膜或應力控制膜2可藉由在第一步驟中供應第一反應物及由電漿活化之第二反應物而形成,且第二膜可在第二步驟中轉化成第三膜。第三膜3之應力可藉由控制第一步驟對第二循環的循環比率來進行調整。製程的細節先前係在第2圖及第3圖中描述,因此在本文中將省略其詳細描述。
第13圖顯示第12圖之製程流程,其中可在步驟101處裝載具有間隙結構之基板,隨後在步驟301處以第一膜填充間隙。可在步驟501處於第一膜上形成第二膜,隨後在步驟701處將其轉化成第三膜。
1:基板
2:膜
3:膜
101:步驟
201:步驟
301:步驟
501:步驟
701:步驟
a:單位循環時間
b:供應時間
S1:源饋送
S2:源吹掃
S3:電漿開啟
S4:吹掃
S5:預吹掃
S6:電漿開啟
S7:吹掃
本揭露之某些實施例的上述及其他態樣、特徵、及優點將從結合隨附圖式的下列描述而更加明白,其中:
第1圖係膜的應力感生(stress-induced)剝離及基板變形的視圖。
第2圖係根據一實施例的基板處理流程圖。
第3圖係根據一實施例的製程流程示意圖。
第4圖係工作比之定義的示意圖。
第5圖係根據另一實施例的製程流程示意圖。
第6圖係顯示根據步驟1對步驟2的循環比率之SiO2
膜應力的圖。
第7圖係SiO2
膜組成的視圖。
第8圖係根據另一實施例的基板處理流程的視圖。
第9圖係根據另一實施例的製程示意圖。
第10圖係根據另一實施例的基板處理流程圖。
第11圖係顯示在各種條件下之SiO2
膜之濕式蝕刻率的圖。
第12圖係根據另一實施例的製程示意圖。
第13圖係根據另一實施例的基板處理流程圖。
101:步驟
201:步驟
301:步驟
Claims (41)
- 一種用於調整一膜應力之方法,包括: 將一基板裝載至一基板支撐上; 在一第一步驟中於該基板上形成一第一膜,該第一步驟包括: 供應一第一反應物;以及 供應一第二反應物,其中該第一反應物及該第二反應物係循序且交替地供應; 藉由在一第二步驟中將一第三反應物供應至該第一膜,而將該第一膜轉化成一第二膜,其中該第一步驟對該第二步驟之循環比率係大於5,以調整該第二膜之應力。
- 如請求項1之方法,其中該第二反應物係由一射頻功率而活化。
- 如請求項2之方法,其中該第二反應物係Ar、及He、或其混合物中之至少一者。
- 如請求項3之方法,其中該第二反應物使該第一膜緻密化,且該第一膜包括該第一反應物之複數個片段。
- 如請求項1之方法,其中該第三反應物係由一射頻功率活化,並與該第一膜起化學反應。
- 如請求項1之方法,其中該第一步驟係重複至少一次,且該第二步驟係重複至少一次, 其中該第一步驟及該第二步驟係循序地重複至少一次。
- 如請求項1之方法,其中該第一反應物係含矽氣體。
- 如請求項1之方法,其中該第二反應物係Ar、及He、或其混合物中之至少一者。
- 如請求項1之方法,其中該第三反應物係含氧氣體。
- 如請求項7之方法,該含矽氣體係下列中之至少一者:DIPAS(SiH3 N(iPr)2 )、TSA((SiH3 )3 N)、DSO((SiH3 )2 )、DSMA((SiH3 )2 NMe)、DSEA((SiH3 )2 NEt)、DSIPA((SiH3 )2 N(iPr) )、DSTBA((SiH3 )2 N(tBu) )、DEAS(SiH3 NEt2 )、DTBAS(SiH3 N(tBu)2 )、BDEAS(SiH2 (NEt2 )2 )、BDMAS(SiH2 (NMe2 )2 )、BTBAS(SiH2 (NHtBu)2 )、BITS(SiH2 (NHSiMe3 )2 )、TEOS(Si(OEt)4 )、SiCl4 、HCD(Si2 Cl6 )、3DMAS(SiH(N(Me)2 )3 )、BEMAS(SiH2 [N(Et)(Me)]2 )、AHEAD(Si2 (NHEt)6 )、TEAS(Si(NHEt)4 )、Si3 H8 、DCS(SiH2 Cl2 )、SiHI3 、SiH2 I2 、或其混合物。
- 如請求項9之方法,其中該含氧氣體係下列中之至少一者:O2 、O3 、CO2 、H2 O、NO2 、及N2 O、或其混合物。
- 如請求項1之方法,其中該第二膜包括氧化矽。
- 如請求項4之方法,其中該第一反應物之該等片段係矽、碳、氮、氯、碘、氫、及烷基、或其混合物中之至少一者。
- 如請求項1之方法,其中隨著該第一步驟對該第二步驟之循環比率增加,該第二膜之一拉伸應力增加。
- 如請求項1之方法,其中隨著該第一步驟對該第二步驟之循環比率減小,該第二膜之一壓縮應力增加。
- 如請求項5之方法,其中一射頻功率係使用10%至75%之一工作比,而以脈衝供應。
- 如請求項1之方法,其中該基板包括一圖案,且該第二膜係形成在該圖案上之一硬遮罩,其中該第一步驟及該第二步驟係在50°C或更低溫度下實行。
- 如請求項17之方法,其中藉由控制該第一步驟對該第二步驟之循環比率來調整該第二膜之一濕式蝕刻率。
- 如請求項18之方法,其中該第二膜之該濕式蝕刻率與在300°C或更高溫度下形成之氧化矽硬遮罩的濕式蝕刻率幾乎相同。
- 如請求項17之方法,其中該第二膜係一氧化矽硬遮罩。
- 一種用於調整一膜應力之方法,包括: 將一基板裝載至一反應器之一基板支撐上; 藉由在一第一步驟中循序且交替地供應一第一反應物及一第二反應物,而在該基板之一背側上形成一第一膜; 藉由在一第二步驟中將一第三反應物供應至該第一膜,而將該第一膜轉化成一第二膜; 在該基板之一前側上形成一第三膜; 從該基板之該背側移除該第二膜,其中該第一步驟對該第二步驟之循環比率係大於5,以調整該第二膜之一應力。
- 如請求項21之方法,其中該第二膜之一應力抵消該基板之一應力。
- 如請求項21之方法,其中該第三膜係在300°C或更高溫度下形成。
- 如請求項21之方法,其中該基板係藉由在具有複數個反應器的一系統中循序地從一反應器轉移至另一反應器來進行處理。
- 如請求項21之方法,其中該第二反應物係由一射頻功率而活化。
- 如請求項21之方法,其中該第三反應物係由一射頻功率而活化,並與該第一膜起化學反應。
- 如請求項21之方法,其中該第一反應物係含矽氣體。
- 如請求項21之方法,其中該第二反應物係Ar、及He、或其混合物中之至少一者。
- 如請求項21之方法,其中該第三反應物係包括氧的一氣體。
- 如請求項21之方法,其中該第二膜係氧化矽。
- 如請求項21之方法,其中該第一步驟係重複至少一次,且該第二步驟係重複至少一次,且該第一步驟及該第二步驟係作為一群組循環,而循序地重複至少一次。
- 一種用於調整一膜應力之方法,包括: 將一基板裝載至一基板支撐上; 在該基板上形成一第一膜; 在該第一膜上形成一第二膜,包括: 在一第一步驟中交替且循序地供應一第一反應物及一第二反應物。 藉由在一第二步驟中將一第三反應物供應至該第二膜,而將該第二膜轉化成一第三膜, 其中該第一步驟對該第二步驟之循環比率係大於5,以調整該第二膜之一應力。
- 如請求項32之方法,其中該第二反應物係由一射頻功率而活化。
- 如請求項32之方法,其中該第三反應物係由一射頻功率而活化,並與該第二膜起化學反應。
- 如請求項32之方法,其中該第三膜之一應力抵消該第一膜之一應力。
- 如請求項32之方法,其中該第一反應物係含矽氣體。
- 如請求項32之方法,該第二反應物係Ar、及He、或其混合物中之至少一者。
- 如請求項32之方法,該第三反應物係含氧氣體。
- 如請求項32之方法,其中該第三膜係氧化矽。
- 如請求項32之方法,其中該第一步驟係重複至少一次,且該第二步驟係重複至少一次;且 該第一步驟及該第二步驟係作為一群組循環,而循序地重複至少一次。
- 如請求項32之方法,其中該基板具有待填充之一間隙,且該間隙係填充有該第一膜。
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- 2021-04-15 KR KR1020210049493A patent/KR20210130646A/ko active Search and Examination
- 2021-04-16 US US17/233,382 patent/US20210327714A1/en active Pending
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CN113529054A (zh) | 2021-10-22 |
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