JP2013187362A - 不揮発性半導体記憶装置 - Google Patents
不揮発性半導体記憶装置 Download PDFInfo
- Publication number
- JP2013187362A JP2013187362A JP2012051492A JP2012051492A JP2013187362A JP 2013187362 A JP2013187362 A JP 2013187362A JP 2012051492 A JP2012051492 A JP 2012051492A JP 2012051492 A JP2012051492 A JP 2012051492A JP 2013187362 A JP2013187362 A JP 2013187362A
- Authority
- JP
- Japan
- Prior art keywords
- hafnium
- insulating film
- film
- charge storage
- fullerene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 152
- 238000003860 storage Methods 0.000 title claims abstract description 137
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000010410 layer Substances 0.000 claims abstract description 62
- 239000002356 single layer Substances 0.000 claims abstract description 54
- 229910003472 fullerene Inorganic materials 0.000 claims description 84
- 239000000539 dimer Substances 0.000 claims description 33
- 238000009825 accumulation Methods 0.000 claims description 14
- 238000009413 insulation Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 301
- 239000000758 substrate Substances 0.000 description 86
- 238000000034 method Methods 0.000 description 80
- 229910052735 hafnium Inorganic materials 0.000 description 74
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 66
- 239000011159 matrix material Substances 0.000 description 46
- 238000005229 chemical vapour deposition Methods 0.000 description 42
- 125000004429 atom Chemical group 0.000 description 37
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 34
- -1 HfSiON Inorganic materials 0.000 description 31
- 229910004298 SiO 2 Inorganic materials 0.000 description 28
- 229910052710 silicon Inorganic materials 0.000 description 28
- 125000003184 C60 fullerene group Chemical group 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 23
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 20
- 229910052732 germanium Inorganic materials 0.000 description 18
- 229910052814 silicon oxide Inorganic materials 0.000 description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 16
- 238000000231 atomic layer deposition Methods 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000010931 gold Substances 0.000 description 13
- 229910003855 HfAlO Inorganic materials 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910004261 CaF 2 Inorganic materials 0.000 description 11
- 229910004140 HfO Inorganic materials 0.000 description 11
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 11
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 239000012212 insulator Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000002070 nanowire Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 238000004050 hot filament vapor deposition Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- 239000013638 trimer Substances 0.000 description 8
- 229910004542 HfN Inorganic materials 0.000 description 7
- 229910004129 HfSiO Inorganic materials 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000002052 molecular layer Substances 0.000 description 7
- 238000007740 vapor deposition Methods 0.000 description 7
- 229910019899 RuO Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 6
- IKMXSKDHYPICEK-UHFFFAOYSA-N N[Hf] Chemical class N[Hf] IKMXSKDHYPICEK-UHFFFAOYSA-N 0.000 description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 5
- 229910005866 GeSe Inorganic materials 0.000 description 4
- 229910005868 GeSeTe Inorganic materials 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000000995 aerosol-assisted chemical vapour deposition Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052955 covellite Inorganic materials 0.000 description 4
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000001928 direct liquid injection chemical vapour deposition Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 238000000038 ultrahigh vacuum chemical vapour deposition Methods 0.000 description 4
- 238000000927 vapour-phase epitaxy Methods 0.000 description 4
- 229910005829 GeS Inorganic materials 0.000 description 3
- 229910004541 SiN Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- OBLUVCTYGGZPPW-UHFFFAOYSA-N 2-methoxyethyl 3,5-dioxoheptaneperoxoate Chemical compound C(CC(CC(CC)=O)=O)(=O)OOCCOC OBLUVCTYGGZPPW-UHFFFAOYSA-N 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- DQNVAXRKWKAIIR-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Hf](C1(C=CC=C1)CC)(C1(C=CC=C1)CC)C1(C=CC=C1)CC Chemical compound C(C)C1(C=CC=C1)[Hf](C1(C=CC=C1)CC)(C1(C=CC=C1)CC)C1(C=CC=C1)CC DQNVAXRKWKAIIR-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
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- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
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- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 2
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- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- AJLACKNAMZBNEJ-UHFFFAOYSA-J hafnium(4+) pentanoate Chemical compound [Hf+4].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O AJLACKNAMZBNEJ-UHFFFAOYSA-J 0.000 description 2
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- 238000012856 packing Methods 0.000 description 1
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Abstract
【解決手段】実施の形態の不揮発性半導体記憶装置は、半導体層と、半導体層上に形成される第1の絶縁膜と、第1の絶縁膜上に形成され、0.5モノレイヤ以上1.0モノレイヤ未満のC60フラーレンを有する電荷蓄積膜と、電荷蓄積膜上の第2の絶縁膜と、第2の絶縁膜上の制御電極と、を備える。
【選択図】図1
Description
電荷蓄積膜も、電荷蓄積特性を維持しながら薄膜化することが望まれる。
本実施の形態の不揮発性半導体記憶装置は、半導体層と、半導体層上に形成される第1の絶縁膜と、第1の絶縁膜上に形成され、フラーレンを含む電荷蓄積膜と、電荷蓄積膜上の第2の絶縁膜と、第2の絶縁膜上の制御電極と、を備えている。
本実施の形態の不揮発性半導体記憶装置は、BiCS(Bit−Cost Scalable)技術を用いた3次元構造以外の3次元構造を備える点で、第1の実施の形態と異なっている。電荷蓄積膜をはじめメモリセルにおける膜の積層構造部分については、第1の実施の形態と基本的に同様である。したがって、第1の実施の形態と重複する内容については記述を省略する。
本実施の形態の不揮発性半導体記憶装置は、平面型のNAND型のメモリセル構造を備える点で、第1の実施の形態と異なっている。電荷蓄積膜をはじめメモリセルにおける膜の積層構造部分については、第1の実施の形態と基本的に同様である。したがって、第1の実施の形態と重複する内容については記述を省略する。
本実施の形態の不揮発性半導体記憶装置は、半導体層と、半導体層上に形成される第1の絶縁膜と、第1の絶縁膜上に形成され、分子またはクラスタを含み、電荷蓄積時に分子またはクラスタの二量体が形成される電荷蓄積膜と、電荷蓄積膜上の第2の絶縁膜と、第2の絶縁膜上の制御電極と、を備えている。
本実施の形態の不揮発性半導体記憶装置は、BiCS(Bit−Cost Scalable)技術を用いた3次元構造以外の3次元構造を備える点で、第4の実施の形態と異なっている。電荷蓄積膜をはじめメモリセルにおける膜の積層構造部分については、第4の実施の形態と基本的に同様である。したがって、第4の実施の形態と重複する内容については記述を省略する。
本実施の形態の不揮発性半導体記憶装置は、平面型のNAND型のメモリセル構造を備える点で、第4の実施の形態と異なっている。電荷蓄積膜をはじめメモリセルにおける膜の積層構造部分については、第4の実施の形態と基本的に同様である。したがって、第4の実施の形態と重複する内容については記述を省略する。
第1の実施形態に係る半導体記憶装置100を作製した。
第4の実施形態に係る半導体記憶装置300を作製した。
上記電荷蓄積膜中には近接したクラスタ対が見られた。
第4の実施形態に係る半導体記憶装置300を作製した。
第5の実施形態に係る半導体記憶装置を作製した。この半導体記憶装置は、いわゆるVG(vertical gate)−NANDである。
12 基板絶縁膜
14 制御電極(ゲート電極)
16 制御電極間絶縁膜
18 積層体
20 半導体層
22 トンネル絶縁膜(第1の絶縁膜)
24 電荷蓄積膜
24a フラーレン
24b マトリクス材
26 ブロック絶縁膜(第2の絶縁膜)
40 孔
100 不揮発性半導体記憶装置
Claims (7)
- 半導体層と、
前記半導体層上に形成される第1の絶縁膜と、
前記第1の絶縁膜上に形成され、0.5モノレイヤ以上1.0モノレイヤ未満のC60フラーレンを有する電荷蓄積膜と、
前記電荷蓄積膜上の第2の絶縁膜と、
前記第2の絶縁膜上の制御電極と、
を備えることを特徴とする不揮発性半導体記憶装置。 - 前記C60フラーレンが2分子の短距離秩序を備え、かつ、長距離秩序を備えないことを特徴とする請求項1記載の不揮発性半導体記憶装置。
- 前記電荷蓄積膜への電荷蓄積時に、前記C60フラーレンの二量体が形成されることを特徴とする請求項1または請求項2記載の不揮発性半導体記憶装置。
- 半導体層と、
前記半導体層上に形成される第1の絶縁膜と、
前記第1の絶縁膜上に形成され、0.3モノレイヤ以上0.5モノレイヤ以下のC70フラーレンを有する電荷蓄積膜と、
前記電荷蓄積膜上の第2の絶縁膜と、
前記第2の絶縁膜上の制御電極と、
を備えることを特徴とする不揮発性半導体記憶装置。 - 前記C70フラーレンが2分子の短距離秩序を備え、かつ、長距離秩序を備えないことを特徴とする請求項4記載の不揮発性半導体記憶装置。
- 前記電荷蓄積膜への電荷蓄積時に、前記C70フラーレンの二量体が形成されることを特徴とする請求項4または請求項5記載の不揮発性半導体記憶装置。
- 半導体層と、
前記半導体層上に形成される第1の絶縁膜と、
前記第1の絶縁膜上に形成され、分子またはクラスタを有し、電荷蓄積時に、前記分子または前記クラスタの二量体が形成される電荷蓄積膜と、
前記電荷蓄積膜上の第2の絶縁膜と、
前記第2の絶縁膜上の制御電極と、
を備えることを特徴とする不揮発性半導体記憶装置。
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