JP2009111382A - 遠隔プラズマcvdによりジシラン前駆体から高品質シリコン酸化膜を形成する方法 - Google Patents
遠隔プラズマcvdによりジシラン前駆体から高品質シリコン酸化膜を形成する方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 129
- 239000002243 precursor Substances 0.000 title claims abstract description 89
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 33
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 title claims description 15
- 238000000151 deposition Methods 0.000 claims abstract description 83
- 230000008021 deposition Effects 0.000 claims abstract description 73
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 66
- 239000010703 silicon Substances 0.000 claims abstract description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 238000000137 annealing Methods 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 37
- 229910021529 ammonia Inorganic materials 0.000 claims description 28
- 229910008045 Si-Si Inorganic materials 0.000 claims description 20
- 229910006411 Si—Si Inorganic materials 0.000 claims description 20
- 229910007991 Si-N Inorganic materials 0.000 claims description 16
- 229910006294 Si—N Inorganic materials 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 16
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000001722 carbon compounds Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 239000006227 byproduct Substances 0.000 claims 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 description 42
- 238000005229 chemical vapour deposition Methods 0.000 description 26
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 15
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- 230000009969 flowable effect Effects 0.000 description 12
- -1 methylcyclohexylsiloxane Chemical class 0.000 description 12
- 239000003989 dielectric material Substances 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000012686 silicon precursor Substances 0.000 description 7
- 229910008051 Si-OH Inorganic materials 0.000 description 6
- 229910006358 Si—OH Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008602 contraction Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Chemical group 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 150000002829 nitrogen Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000007845 reactive nitrogen species Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Chemical group 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PPUHGKQVCOLZPA-UHFFFAOYSA-N (acetyloxy-methyl-trimethylsilylsilyl) acetate Chemical compound CC(=O)O[Si](C)([Si](C)(C)C)OC(C)=O PPUHGKQVCOLZPA-UHFFFAOYSA-N 0.000 description 1
- WDFIBGBTIINTHZ-UHFFFAOYSA-N CCO[SiH2][SiH3] Chemical compound CCO[SiH2][SiH3] WDFIBGBTIINTHZ-UHFFFAOYSA-N 0.000 description 1
- SHYMOZPBUNMINW-UHFFFAOYSA-N CO[SiH2]C1CCCCC1 Chemical compound CO[SiH2]C1CCCCC1 SHYMOZPBUNMINW-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- VARCERBLAQWSHW-UHFFFAOYSA-N cyclohexyl-methoxy-methylsilane Chemical compound CO[SiH](C)C1CCCCC1 VARCERBLAQWSHW-UHFFFAOYSA-N 0.000 description 1
- IRRVTIDUSZWLNF-UHFFFAOYSA-N cyclopentylsilane Chemical compound [SiH3]C1CCCC1 IRRVTIDUSZWLNF-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LVBHDLYSVWFICY-UHFFFAOYSA-N diethyl-methyl-trimethylsilylsilane Chemical compound C[Si]([Si](CC)(CC)C)(C)C LVBHDLYSVWFICY-UHFFFAOYSA-N 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- BPAOHKKCAPEUMS-UHFFFAOYSA-N disilanyl acetate Chemical compound CC(=O)O[SiH2][SiH3] BPAOHKKCAPEUMS-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- MEBNNDGCPRQQBQ-UHFFFAOYSA-N methoxy(silyl)silane Chemical compound CO[SiH2][SiH3] MEBNNDGCPRQQBQ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002831 nitrogen free-radicals Chemical class 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 1
- 239000012713 reactive precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 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
- 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
- H01L21/02274—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 in the presence of a plasma [PECVD]
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Abstract
【解決手段】基板を収容する堆積チャンバ内にシリコンを含有する前駆体を導入することを含み、シリコンを含有する前駆体は少なくとも2つのシリコン原子を含む。さらに、堆積チャンバの外側に位置する遠隔プラズマシステムを用いて少なくとも1つのラジカル窒素前駆体を生成する。さらに、堆積チャンバにラジカル窒素前駆体を導入することを含み、ラジカル窒素およびシリコン含有前駆体は反応して基板上にシリコンおよび窒素含有膜を堆積する。さらに、蒸気環境内でシリコンおよび窒素含有膜をアニーリングしてシリコン酸化膜を形成することを含み、蒸気環境は水および酸蒸気を含む。
【選択図】図1
Description
Claims (39)
- 基板上にシリコンおよび窒素含有膜を堆積する方法であって、
前記基板を収容する堆積チャンバに、少なくとも2つのシリコン原子を含むシリコン含有前駆体を導入するステップと、
前記堆積チャンバの外側に位置する遠隔プラズマシステムを用いて少なくとも1つのラジカル窒素前駆体を生成するステップと、
前記堆積チャンバに前記ラジカル窒素前駆体を導入するステップと、
を備え、
前記ラジカル窒素およびシリコン含有前駆体が反応し、前記基板上に前記シリコンおよび窒素含有膜を堆積する方法。 - 原子状窒素の生成が前記遠隔プラズマシステム内でアンモニアをプラズマに曝露させるステップを備え、前記アンモニアの少なくとも一部が前記ラジカル窒素前駆体に分解する、請求項1に記載の方法。
- 前記ラジカル窒素前駆体が化学式NHXを有し、式中xが0、1または2である、請求項1に記載の方法。
- 前記シリコンを含有する前駆体がジシラン前駆体またはポリシラン前駆体を含む、請求項1に記載の方法。
- 前記シリコン含有前駆体がアルコキシジシラン、アルコキシ−アルキルジシランおよびポリシランから成る群より選択される、請求項1に記載の方法。
- 前記シリコンおよび窒素含有膜がシリコン炭窒化膜を含む、請求項1に記載の方法。
- 前記シリコンおよび窒素含有膜がSi−N(H)−Si結合を含む膜を含む、請求項1に記載の方法。
- 前記方法が、前記シリコンおよび窒素含有膜をアニーリングしてシリコン酸化膜を形成するステップをさらに備える、請求項1に記載の方法。
- 前記アニーリングが蒸気を含む雰囲気内で実施される、請求項8に記載の方法。
- 前記アニーリングが酸蒸気を含む雰囲気内で実施される、請求項8に記載の方法。
- 前記アニーリングが約20℃から約900℃の範囲の温度で実施される、請求項8に記載の方法。
- 前記アニーリングがオゾン(O3)を含む雰囲気内で実施される、請求項8に記載の方法
- 前記アニーリングが、約20℃から約600℃の範囲の温度で前記基板を紫外線光に曝露するステップをさらに備える、請求項12に記載の方法。
- 前記アニーリングが分子状酸素(O2)を含む雰囲気内で実施される、請求項8に記載の方法
- 前記アニーリングが、約20℃から約600℃の範囲の温度で原子状酸素(O)を含む雰囲気内で実施される、請求項8に記載の方法。
- 基板上にシリコン酸化膜を形成する方法であって、
堆積チャンバ内に基板を提供するステップと、
前記堆積チャンバに結合された遠隔プラズマシステムを用いて複数のハイドロニトレンラジカルを生成するステップと、
少なくとも1つのSi−Si結合を含むシリコン含有前駆体を堆積チャンバに導入するステップと、
前記堆積チャンバに複数のハイドロニトレンラジカルを導入するステップであって、前記ハイドロニトレンラジカルとシリコン含有前駆体とが反応して前記基板上に第1膜を堆積し、前記第1膜が複数のS−N(H)−Si結合を含む、ステップと、
蒸気雰囲気内で前記第1膜をアニーリングするステップと、
前記基板上に、複数のSi−O−Si結合を含む第2膜を形成するステップと、
を備える方法。 - 複数のハイドロニトレンラジカルを生成する前記ステップが、前記遠隔プラズマシステム内でアンモニアをプラズマに曝露させる工程を備え、前記アンモニアの少なくとも一部が前記複数のハイドロニトレンラジカルに分解する、請求項16に記載の方法。
- 前記シリコン含有前駆体がジシラン前駆体またはポリシラン前駆体を含む、請求項16に記載の方法。
- 前記第1膜が流動特性を備えるヒドロキシル基をさらに含む、請求項16に記載の方法。
- 前記第1膜を前記アニーリングする前記ステップが、約20℃から約900℃の範囲の温度で実施される、請求項16に記載の方法。
- 前記蒸気雰囲気が水蒸気および酸蒸気を含む、請求項16に記載の方法。
- 第2膜を形成する前記ステップが、前記水蒸気を使用して、前記第1膜内の前記複数のSi−N(H)−Si結合の少なくとも一部を複数のSi−O−Si結合の第1部分に変換する工程を備える、請求項21に記載の方法。
- 第2膜を形成する前記ステップが、前記酸蒸気を使用して、前記水蒸気と未反応のヒドロキシル基と反応に触媒作用を及ぼすことにより反応性OH基を形成し、前記複数のSi−O−Si結合の少なくとも第2部分をもたらす工程をさらに備える、請求項21に記載の方法。
- 前記酸蒸気が塩酸または酢酸を含む、請求項21に記載の方法。
- 前記第2膜が前記第1膜より高密度を有する、請求項16に記載の方法。
- 基板上のシリコン酸化層を硬化する方法であって、
半導体処理チャンバおよび基板を提供するステップと、
前記基板の少なくとも一部の上に重なるシリコン酸化層を形成するステップであって、前記シリコン酸化層が形成の副産物として炭素種を含む、ステップと、
前記半導体処理チャンバに塩基蒸気を導入するステップであって、前記塩基蒸気が前記シリコン酸化層と反応して前記シリコン酸化層から前記炭素種を除去する、ステップと、
前記半導体処理チャンバから前記塩基蒸気を除去するステップと、
を備える方法。 - 前記塩基蒸気がアンモニアを含む、請求項26に記載の方法。
- 前記シリコン層がアルコキシシランプロセスを使用して堆積される、請求項26に記載の方法。
- 前記シリコン酸化層がプラズマCVDプロセスを使用して堆積される、請求項26に記載の方法。
- 塩基蒸気を導入する前記ステップが、アンモニアガスを前記半導体処理チャンバに流し込む工程をさらに備える、請求項26に記載の方法。
- 前記塩基蒸気が触媒として機能し、前記シリコン酸化層内の反応を完成する、請求項26に記載の方法。
- 前記蒸気が酸と水の混合物である、請求項26に記載の方法。
- 前記蒸気が分子状酸素(O2)をさらに含む、請求項26に記載の方法。
- 前記蒸気が遠隔で生成されるラジカル原子状窒素をさらに含む、請求項26に記載の方法。
- 前記塩基蒸気とシリコン酸化層との間の前記反応が約60℃から約600℃の間で実施される、請求項26に記載の方法。
- 前記反応が約300℃で実施される、請求項25に記載の方法。
- 前記処理チャンバが、前記シリコン酸化層との前記反応の間が約1トールから760トールの圧力を有する、請求項26に記載の方法。
- 前記処理チャンバが約40トールの圧力を有する、請求項37に記載の方法。
- 前記アニーリングが約200℃から約1050℃の範囲の温度で実施される、請求項8に記載の方法。
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KR101042788B1 (ko) | 2011-06-20 |
US20110014798A1 (en) | 2011-01-20 |
TW200927979A (en) | 2009-07-01 |
US8242031B2 (en) | 2012-08-14 |
CN101418438B (zh) | 2013-05-01 |
EP2053143A3 (en) | 2009-09-02 |
TWI506158B (zh) | 2015-11-01 |
SG152183A1 (en) | 2009-05-29 |
US20090104755A1 (en) | 2009-04-23 |
EP2053143A2 (en) | 2009-04-29 |
US7867923B2 (en) | 2011-01-11 |
CN101418438A (zh) | 2009-04-29 |
KR20090040870A (ko) | 2009-04-27 |
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