JP4672400B2 - 過水素化ポリシラザン溶液およびそれを用いた半導体装置の製造方法 - Google Patents
過水素化ポリシラザン溶液およびそれを用いた半導体装置の製造方法 Download PDFInfo
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- JP4672400B2 JP4672400B2 JP2005065811A JP2005065811A JP4672400B2 JP 4672400 B2 JP4672400 B2 JP 4672400B2 JP 2005065811 A JP2005065811 A JP 2005065811A JP 2005065811 A JP2005065811 A JP 2005065811A JP 4672400 B2 JP4672400 B2 JP 4672400B2
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- element isolation
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- perhydrogenated polysilazane
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- 229920001709 polysilazane Polymers 0.000 title claims description 65
- 239000004065 semiconductor Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 227
- 235000012239 silicon dioxide Nutrition 0.000 claims description 112
- 239000000377 silicon dioxide Substances 0.000 claims description 112
- 238000002955 isolation Methods 0.000 claims description 53
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 32
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 23
- 230000001590 oxidative effect Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229910019001 CoSi Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Description
Void Free and Low Stress Shallow Trench Isolation Technology using P-SOG for sub 0.1μm Device (J. H. Heo et al.,2002 Symposium on VLSI Technology Digest of Technological Papers, pp132-133, 2002)
前記素子分離溝が設けられた前記半導体基板上に前述の過水素化ポリシラザン溶液を塗布して、過水素化ポリシラザン膜を形成する工程と、
前記過水素化ポリシラザン膜を、水蒸気を含む雰囲気中で酸化して二酸化シリコン膜を形成する工程と、
前記二酸化シリコン膜を選択的に除去して、前記素子分離溝の内部に前記二酸化シリコン膜を残置し、素子分離絶縁膜を形成する工程とを具備することを特徴とする。
前記ゲート絶縁膜、第1のゲート電極およびストッパー膜が順次形成された半導体基板に素子分離溝を形成する工程と、
前記素子分離溝が設けられた前記半導体基板上に請求項1に記載の過水素化ポリシラザン溶液を前記半導体基板上に塗布して、過水素化ポリシラザン膜を形成する工程と、
前記過水素化ポリシラザン膜を、水蒸気を含む雰囲気中で酸化して二酸化シリコン膜を形成する工程と、
前記ストッパー膜上の前記二酸化シリコン膜を選択的に除去して、前記素子分離溝の内部に前記二酸化シリコン膜を残置し、素子分離絶縁膜を形成する工程と、
前記ストッパー膜を除去して、前記第1の電極膜の表面を露出する工程と、
前記素子分離絶縁膜の上部を除去して、前記第1の電極膜の側面の上部を露出する工程と、
前記側面の上部が露出した第1の電極膜および前記上部が除去された素子分離絶縁膜の上に、電極間絶縁膜を介して第2のゲート電極膜を形成する工程とを具備することを特徴とする。
具体的には、過水素化ポリシラザンをジブチルエーテル溶媒に溶解してなる過水素化ポリシラザン溶液をスピンコート法により塗布し、ホットプレート上に載置して150℃3分のベーキングを施した。こうしてジブチルエーテル溶媒を揮発除去させて、膜厚500nmの過水素化ポリシラザン膜(PSZ膜)を形成し、SIMS測定を行なった。その結果を図1のグラフに示す。
図7乃至図10を参照して、STI埋め込み方法を例に挙げて本実施形態を説明する。
ここでは400℃15分の酸化処理を施して、過水素化ポリシラザン膜15を二酸化シリコン膜16に変化させた。
前述の実施形態1と同様の手法により、図9に示すように、二酸化シリコン膜11およびCMPストッパー膜12が形成されSTI溝13を設けたSi基板10上に、二酸化シリコン膜16を形成した。各膜は、実施形態1の場合と同様の材料を用いて、同様の膜厚で形成した。
前述の実施形態2における二酸化シリコン膜16の緻密化は、STI溝13内に埋め込んだ後に行なうこともできる。本実施形態においては、実施形態1と同様の手法により、図10に示すように、二酸化シリコン膜11およびCMPストッパー膜12が形成されたSi基板10のSTI溝13内に、二酸化シリコン膜16を埋め込んだ。緻密化前の二酸化シリコン膜16をCMPするので、実施形態2の場合よりも過水素化シラザン膜の絶対量が少ないため残存するC量も少なく、デバイス特性を悪化させにくいという点で有利である。
図14乃至図18を参照して、本実施形態を説明する。
前述の実施形態4と同様の手法により、図16に示すように、ゲート絶縁膜18、ゲート電極膜19およびCMPストッパー膜12が形成されSTI溝13を設けたSi基板10上に、二酸化シリコン膜16を形成した。各膜は、実施形態1の場合と同様の材料を用いて、同様の膜厚で形成した。
前述の実施形態5における二酸化シリコン膜16の緻密化は、STI溝13内に埋め込んだ後に行なうこともできる。本実施形態においては、実施形態4と同様の手法により、図17に示すように、ゲート絶縁膜18、ゲート電極膜10およびCMPストッパー膜12が形成されたSi基板10のSTI溝13内に、二酸化シリコン膜16を埋め込んだ。緻密化前の二酸化シリコン膜16をCMPするので、実施形態5の場合よりも過水素化シラザン膜の絶対量が少ないため残存するC量も少なく、デバイス特性を悪化させにくいという点で有利である。
103…poly−Si電極; 10…シリコン基板; 11…二酸化シリコン膜
12…CMPストッパー膜; 13…素子分離溝; 15…過水素化ポリシラザン膜
16…二酸化シリコン膜; 17…緻密化した二酸化シリコン膜
18…ゲート絶縁膜; 19…第1のゲート(浮遊ゲート)電極膜
20…電極間絶縁膜; 21…第2のゲート(制御ゲート)電極膜。
Claims (5)
- ブタノール濃度が30ppm以下のジブチルエーテルと、前記ジブチルエーテルに溶解された過水素化ポリシラザンとを含有することを特徴とする過水素化ポリシラザン溶液。
- 半導体基板に素子分離溝を形成する工程と、
前記素子分離溝が設けられた前記半導体基板上に請求項1に記載の過水素化ポリシラザン溶液を塗布して、過水素化ポリシラザン膜を形成する工程と、
前記過水素化ポリシラザン膜を、水蒸気を含む雰囲気中で酸化して二酸化シリコン膜を形成する工程と、
前記二酸化シリコン膜を選択的に除去して、前記素子分離溝の内部に前記二酸化シリコン膜を残置し、素子分離絶縁膜を形成する工程とを具備することを特徴とする半導体装置の製造方法。 - 半導体基板上に、ゲート絶縁膜、第1のゲート電極およびストッパー膜を順次形成する工程と、
前記ゲート絶縁膜、第1のゲート電極およびストッパー膜が順次形成された半導体基板に素子分離溝を形成する工程と、
前記素子分離溝が設けられた前記半導体基板上に請求項1に記載の過水素化ポリシラザン溶液を前記半導体基板上に塗布して、過水素化ポリシラザン膜を形成する工程と、
前記過水素化ポリシラザン膜を、水蒸気を含む雰囲気中で酸化して二酸化シリコン膜を形成する工程と、
前記ストッパー膜上の前記二酸化シリコン膜を選択的に除去して、前記素子分離溝の内部に前記二酸化シリコン膜を残置し、素子分離絶縁膜を形成する工程と、
前記ストッパー膜を除去して、前記第1の電極膜の表面を露出する工程と、
前記素子分離絶縁膜の上部を除去して、前記第1の電極膜の側面の上部を露出する工程と、
前記側面の上部が露出した第1の電極膜および前記上部が除去された素子分離絶縁膜の上に、電極間絶縁膜を介して第2のゲート電極膜を形成する工程と
を具備することを特徴とする半導体装置の製造方法。 - 前記二酸化シリコン膜を選択的に除去する前に、前記二酸化シリコン膜を緻密化する工程を具備することを特徴とする請求項2または3に記載の半導体装置の製造方法。
- 前記半導体基板の前記素子分離溝内に残置された前記二酸化シリコン膜を緻密化することを特徴とする請求項2または3に記載の半導体装置の製造方法。
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JP2013042067A (ja) | 2011-08-19 | 2013-02-28 | Toshiba Corp | 半導体装置およびその製造方法 |
JP2013089859A (ja) | 2011-10-20 | 2013-05-13 | Toshiba Corp | 半導体装置の製造方法 |
JP5667961B2 (ja) | 2011-11-04 | 2015-02-12 | 株式会社東芝 | 半導体装置の製造方法 |
US10020185B2 (en) | 2014-10-07 | 2018-07-10 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, silica layer, and electronic device |
KR101833800B1 (ko) | 2014-12-19 | 2018-03-02 | 삼성에스디아이 주식회사 | 실리카계 막 형성용 조성물, 실리카계 막의 제조방법 및 상기 실리카계 막을 포함하는 전자 소자 |
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