TW202112786A - 產生含金屬或半金屬的膜之方法 - Google Patents
產生含金屬或半金屬的膜之方法 Download PDFInfo
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- TW202112786A TW202112786A TW109118970A TW109118970A TW202112786A TW 202112786 A TW202112786 A TW 202112786A TW 109118970 A TW109118970 A TW 109118970A TW 109118970 A TW109118970 A TW 109118970A TW 202112786 A TW202112786 A TW 202112786A
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- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000008569 process Effects 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 239000000758 substrate Substances 0.000 claims abstract description 46
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 12
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- 239000001257 hydrogen Substances 0.000 claims abstract description 11
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
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- 125000001424 substituent group Chemical group 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004145 cyclopenten-1-yl group Chemical group [H]C1=C(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000004639 dihydroindenyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000004587 thienothienyl group Chemical group S1C(=CC2=C1C=CS2)* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
Description
本發明係關於用於在基板上產生含金屬或半金屬的無機膜之方法,尤其原子層沉積法之領域。
隨著例如在半導體行業中正在進行的小型化發展,對基板上之薄無機膜之需求增加,同時對此類膜之品質的要求亦變得更加嚴格。薄金屬或半金屬膜用於不同用途,諸如障壁層、導電部件或罩蓋層。用於產生金屬或半金屬膜之若干方法為已知的。其中之一者為將成膜化合物自氣態沉積至基板上。為了在適度溫度下使金屬或半金屬原子變為氣態,必須例如藉由使金屬或半金屬與適合的配位體錯合來提供揮發性前驅物。此等前驅物需要對於蒸發足夠穩定,但另一方面其需要有足夠反應性以與沉積表面反應。
EP 3 121 309 A1揭示一種用於自參(二烷胺基)鋁前驅物沉積氮化鋁膜之方法。然而,該前驅物對於需要高品質膜之應用而言不夠穩定。
為了將所沉積之金屬或半金屬錯合物轉化成金屬或半金屬膜,通常必需使所沉積之金屬或半金屬錯合物暴露於還原劑。典型地,氫氣用於將所沉積之金屬或半金屬錯合物轉化成金屬或半金屬膜。雖然對於如銅或銀之相對貴金屬而言,氫氣相當好地起到了還原劑之作用,但其對於諸如鈦或鋁之更具正電性之金屬而言產生之結果不盡如人意。
WO 2013 / 070 702 A1揭示一種採用藉由二胺配位而作為還原劑之氫化鋁來沉積金屬膜之方法。雖然此還原劑通常產生良好結果,但對於一些要求高的應用,需要較高蒸氣壓、穩定性及/或還原電位。
D. Mukherjee等人在Chemical Communications,卷53(2017) 第3593-3496頁中揭示具有螯合配位體之氫化鋁錯合物。然而,作者並未意識到其用於製備含金屬或半金屬的無機膜之適合性,因為該化合物僅用於溶液中之有機合成。
因此,本發明之目標為提供一種用於製備膜中含較少雜質之含金屬或半金屬的無機膜之方法。方法材料應容易處置;特定言之,應有可能以儘可能少之分解將其蒸發。此外,方法材料不應在方法條件下在沉積表面處分解,但同時應具有足夠反應性以參與表面反應。所有反應副產物應為揮發性的,以避免膜污染。另外,應有可能調整方法使得方法材料中之金屬或半金屬原子為揮發性的或併入膜中。此外,該方法應為通用的,以使得其可適用於產生大範圍之不同金屬,包括正電性金屬或半金屬膜。
此等目標係藉由用於製備含金屬或半金屬的無機膜之方法達成,該方法包含
(a)將含金屬或半金屬的化合物自氣態沉積至固體基板上,及
(b)使該固體基板與呈氣態之通式(I)、(II)或(III)化合物接觸
其中A為NR、NR 2
、PR、PR 2
、O、OR、S或SR,
E為N、NR、P、PR、O或S,
N為1、2或3,
R為烷基、烯基、芳基或矽烷基,及
R'為氫、烷基、烯基、芳基或矽烷基,以及
A、E及n經選擇以使得通式(I)、(II)或(III)化合物為電中性的。
本發明進一步係關於通式(I)、(II)或(III)化合物之用途,其用作氣相沉積法中之還原劑。
本發明之較佳具體實例可見於實施方式及申請專利範圍中。不同具體實例之組合落入本發明之範圍內。
根據本發明之方法適用於製備含金屬或半金屬的無機膜。在本發明之上下文中,無機係指含有至少5 wt%、較佳至少10 wt%、更佳至少20 wt%,尤其至少30 wt%之至少一種金屬或半金屬的材料。無機膜典型地含有僅呈碳化物相形式之碳,該碳化物相包括混合碳化物相,諸如氮化物之碳化物相。無機膜中並非碳化物相之部分的碳之碳含量較佳地小於5 wt%,更佳小於1 wt%,尤其小於0.2 wt%。含金屬或半金屬的無機膜之較佳實例為金屬或半金屬氮化物膜、金屬或半金屬碳化物膜、金屬或半金屬碳氮化物膜、金屬或半金屬合金膜、金屬間化合物膜或含有其混合物之膜。藉由根據本發明之方法製備之膜含有金屬或半金屬。膜有可能含有一種金屬或半金屬或超過一種金屬及/或半金屬。金屬包括Li、Be、Na、Mg、Al、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Rb、Sr、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、In、Sn、Cs、Ba、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Hf、Ta、W、Re、Os、Ir、Pt、Au、Hg、Tl、Bi。半金屬包括B、Si、Ge、As、Sb、Se、Te。較佳地,金屬或半金屬比Cu更具電正性,更佳地比Ni更具電正性。特定言之,金屬或半金屬為Ti、Ta、Mn、Mo、W、Ge、Ga、As、In、Sb、Te、Al或Si。
固體基板可為任何固體材料。此等材料包括例如金屬、半金屬、氧化物、氮化物及聚合物。基板亦有可能為不同材料之混合物。金屬之實例為鋁、鋼、鋅及銅。半金屬之實例為矽、鍺及砷化鎵。氧化物之實例為二氧化矽、二氧化鈦及氧化鋅。氮化物之實例為氮化矽、氮化鋁、氮化鈦及氮化鎵。聚合物之實例為聚對苯二甲酸伸乙酯(PET)、聚乙烯萘-二甲酸(PEN)及聚醯胺。
固體基板可具有任何形狀。此等形狀包括薄片板、膜、纖維、各種尺寸之粒子及具有溝槽或其他壓痕之基板。固體基板可具有任何尺寸。若固體基板具有粒子形狀,則粒子之尺寸可在低於100 nm至若干公分,較佳1 μm至1 mm範圍內。為了避免粒子或纖維在含金屬或半金屬的化合物沉積至其上時彼此黏著,較佳使其保持處於運動中。此可例如藉由攪拌、藉由旋轉鼓輪或藉由流體化床技術來達成。
根據本發明,使固體基板與呈氣相之通式(I)、(II)或(III)化合物接觸。通式(I)、(II)或(III)化合物中之R'為氫、烷基、烯基、芳基或矽烷基,較佳為氫或烷基,尤其為氫、甲基或乙基。R'可彼此相同或不同。較佳地,所有R'均相同。
烷基可為直鏈或支鏈的。直鏈烷基之實例為甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基。支鏈烷基之實例為異丙基、異丁基、第二丁基、第三丁基、2-甲基-戊基、新戊基、2-乙基-己基、環丙基、環己基、二氫茚基、降莰基。較佳地,烷基為C1
至C8
烷基,更佳C1
至C6
烷基,尤其C1
至C4
烷基,諸如甲基、乙基、異丙基或第三丁基。
烯基含有至少一個碳碳雙鍵。該雙鍵可包括R'藉以鍵結至分子之其餘部分的碳原子,或其可置於距R'鍵結至分子之其餘部分之位置更遠處。烯基可為直鏈或支鏈的。雙鍵包括R'藉以鍵結至分子之其餘部分之碳原子的直鏈烯基之實例包括1-乙烯基、1-丙烯基、1-正丁烯基、1-正戊烯基、1-正己烯基、1-正庚烯基、1-正辛烯基。雙鍵置於距R'鍵結至分子之其餘部分之位置更遠處的直鏈烯基之實例包括1-正丙烯-3-基、2-丁烯-1-基、1-丁烯-3-基、1-丁烯-4-基、1-己烯-6-基。雙鍵包括R'藉以鍵結至分子之其餘部分之碳原子的支鏈烯基之實例包括1-丙烯-2-基、1-正丁烯-2-基、2-丁烯-2-基、環戊烯-1-基、環己烯-1-基。雙鍵置於距R'鍵結至分子之其餘部分之位置更遠處的支鏈烯基之實例包括2-甲基-1-丁烯-4-基、環戊烯-3-基、環己烯-3-基。具有超過一個雙鍵之烯基的實例包括1,3-丁二烯-1-基、1,3-丁二烯-2-基、環戊二烯-5-基。
芳基包括芳族烴,諸如苯基、萘基、蒽基、菲基;及雜芳族基團,諸如吡咯基、呋喃基、噻吩基、吡啶基、喹啉基、苯并呋喃基、苯并噻吩基、噻吩并噻吩基。若干此等基團或此等基團之組合亦為可能的,如聯苯、噻吩并苯基或呋喃基噻吩基。芳基可例如藉由鹵素(如氟、氯、溴、碘);藉由假鹵素(如氰離子、氰酸根、硫氰酸根);藉由醇;烷基鏈或烷氧基鏈取代。芳族烴為較佳的,苯基更佳。
矽烷基為典型地具有三個取代基之矽原子。較佳地,矽烷基具有式SiX3
,其中X彼此獨立地為氫、烷基、芳基或矽烷基。有可能所有三個X均相同或兩個X相同且剩餘的X不同,或所有三個X彼此不同,較佳地所有X均相同。烷基及芳基係如上文所描述。矽烷基之實例包括SiH3
、甲基矽烷基、三甲基矽烷基、三乙基矽烷基、三正丙基矽烷基、三異丙基矽烷基、三環己基矽烷基、二甲基-第三丁基矽烷基、二甲基環己基矽烷基、甲基-二異丙基矽烷基、三苯基矽烷基、苯基矽烷基、二甲基苯基矽烷基、五甲基二矽烷基。
通式(I)或(II)化合物中之A為NR、NR2
、PR、PR2
、O、OR、S或SR,亦即攜載一或兩個取代基R之氮原子、攜載一或兩個取代基R之磷原子、氧原子、攜載取代基R之氧原子、硫原子或攜載取代基R之硫原子。R為烷基、烯基、芳基或矽烷基。如針對上文所描述之R',適用相同定義。較佳地,R為烷基或矽烷基,更佳為甲基、乙基、異丙基、第二丁基、第三丁基或三甲基矽烷基,尤其為甲基或乙基。通式(I)或(II)化合物中之所有A可彼此相同或不同。
通式(II)或(III)化合物中之E為N、NR、P、PR、O或S,亦即氮原子、攜載取代基R之氮原子、磷原子、攜載取代基R之磷原子、氧原子或硫原子。上文所描述之R之定義適用。通式(II)或(III)化合物中之所有E可彼此相同或不同。
有可能所有R及R'均為單獨取代基。可替代地,有可能兩個R或兩個R',或一個R'與一個R一起形成環,較佳地四員至八員環,尤其五員環或六員環。
根據本發明,通式(I)、(II)或(III)化合物中n(其為結合至鋁原子之氫原子之數目)為1、2或3,較佳為1或2,尤其為1。
根據本發明,A、E及n經選擇以使得通式(I)、(II)或(III)化合物為電中性的。若A為NR、PR、O或S,則A向配位體提供陰離子供體原子,而若A為NR2
、PR2
、OR或SR,則其提供中性供體原子。若E為N或P,則E提供陰離子供體原子,而若E為NR、PR、O或S,則其提供中性供體原子。為了使通式(I)、(II)或(III)化合物電子顯現中性,陰離子供體原子之數目加鍵結至鋁原子之氫原子之數目需要為3以抵消Al3+
原子之電荷。
參考此等通式之通式(I)化合物之較佳實例在下表中給出。
Et表示乙基。
編號 | 化學式 | R | R' |
Ia-1 | Ia | CH3 | H |
Ia-2 | Ia | CH3 | H CH3 |
Ia-3 | Ia | CH3 | CH3 |
Ia-4 | Ia | CF3 | H |
Ia-5 | Ia | CH3 | H CF3 |
Ia-6 | Ia | Et | H |
Ia-7 | Ia | Et | H CH3 |
Ia-8 | Ia | Et | Et |
Ib-1 | Ib | CH3 | H |
Ib-2 | Ib | CH3 | H CH3 |
Ib-3 | Ib | CH3 | CH3 |
Ib-4 | Ib | CF3 | H |
Ib-5 | Ib | CH3 | H CF3 |
Ib-6 | Ib | Et | H |
Ib-7 | Ib | Et | H CH3 |
Ib-8 | Ib | Et | Et |
Ic-1 | Ic | CH3 | H |
Ic-2 | Ic | CH3 | H CH3 |
Ic-3 | Ic | CH3 | CH3 |
Ic-4 | Ic | CF3 | H |
Ic-5 | Ic | CH3 | H CF3 |
Ic-6 | Ic | Et | H |
Ic-7 | Ic | Et | H CH3 |
Ic-8 | Ic | Et | Et |
Id-1 | Id | CH3 | H |
Id-2 | Id | CH3 | H CH3 |
Id-3 | Id | CH3 | CH3 |
Id-4 | Id | CF3 | H |
Id-5 | Id | CH3 | H CF3 |
Id-6 | Id | Et | H |
Id-7 | Id | Et | H CH3 |
Id-8 | Id | Et | Et |
Ie-1 | Ie | CH3 | H |
Ie-2 | Ie | CH3 | H CH3 |
Ie-3 | Ie | CH3 | CH3 |
Ie-4 | Ie | CF3 | H |
Ie-5 | Ie | CH3 | H CF3 |
Ie-6 | Ie | Et | H |
Ie-7 | Ie | Et | H CH3 |
Ie-8 | Ie | Et | Et |
If-1 | If | CH3 | H |
If-2 | If | CH3 | H CH3 |
If-3 | If | CH3 | CH3 |
If-4 | If | CF3 | H |
If-5 | If | CH3 | H CF3 |
If-6 | If | Et | H |
If-7 | If | Et | H CH3 |
If-8 | If | Et | Et |
Ig-1 | Ig | CH3 | H |
Ig-2 | Ig | CH3 | H CH3 |
Ig-3 | Ig | CH3 | CH3 |
Ig-4 | Ig | CF3 | H |
Ig-5 | Ig | CH3 | H CF3 |
Ig-6 | Ig | Et | H |
Ig-7 | Ig | Et | H CH3 |
Ig-8 | Ig | Et | Et |
Ih-1 | Ih | CH3 | H |
Ih-2 | Ih | CH3 | H CH3 |
Ih-3 | Ih | CH3 | CH3 |
Ih-4 | Ih | CF3 | H |
Ih-5 | Ih | CH3 | H CF3 |
Ih-6 | Ih | Et | H |
Ih-7 | Ih | Et | H CH3 |
Ih-8 | Ih | Et | Et |
Ij-1 | Ij | CH3 | H |
Ij-2 | Ij | CH3 | H CH3 |
Ij-3 | Ij | CH3 | CH3 |
Ij-4 | Ij | CF3 | H |
Ij-5 | Ij | CH3 | H CF3 |
Ij-6 | Ij | Et | H |
Ij-7 | Ij | Et | H CH3 |
Ij-8 | Ij | Et | Et |
Ik-1 | Ik | CH3 | H |
Ik-2 | Ik | CH3 | H CH3 |
Ik-3 | Ik | CH3 | CH3 |
Ik-4 | Ik | CF3 | H |
Ik-5 | Ik | CH3 | H CF3 |
Ik-6 | Ik | Et | H |
Ik-7 | Ik | Et | H CH3 |
Ik-8 | Ik | Et | Et |
Im-1 | Im | CH3 | H |
Im-2 | Im | CH3 | H CH3 |
Im-3 | Im | CH3 | CH3 |
Im-4 | Im | CF3 | H |
Im-5 | Im | CH3 | H CF3 |
Im-6 | Im | Et | H |
Im-7 | Im | Et | H CH3 |
Im-8 | Im | Et | Et |
針對通式(I)化合物中之一些的合成描述於例如藉由C. Jones之Journal of the Chemical Society,Dalton Transactions,卷1996,第829-833頁中。。
參考此等通式之通式(II)化合物之較佳實例在下表中給出。
Et表示乙基,Ph表示苯基。
編號 | 化學式 | R | R' | ||
IIa-1 | IIa | CH3 | H | ||
IIa-2 | IIa | CH3 | H CH3 | ||
IIa-3 | IIa | CH3 | CH3 | ||
IIa-4 | IIa | CF3 | H | ||
IIa-5 | IIa | CH3 | H CF3 | ||
IIa-6 | IIa | Et | H | ||
IIa-7 | IIa | Et | H CH3 | ||
IIa-8 | IIa | Et | Et | ||
IIb-1 | IIb | CH3 | H | ||
IIb-2 | IIb | CH3 | H CH3 | ||
IIb-3 | IIb | CH3 | CH3 | ||
IIb-4 | IIb | CF3 | H | ||
IIb-5 | IIb | CH3 | H CF3 | ||
IIb-6 | IIb | Et | H | ||
IIb-7 | IIb | Et | H CH3 | ||
IIb-8 | IIb | Et | Et | ||
IIc-1 | IIc | CH3 | H | ||
IIc-2 | IIc | CH3 | H CH3 | ||
IIc-3 | IIc | CH3 | CH3 | ||
IIc-4 | IIc | CF3 | H | ||
IIc-5 | IIc | CH3 | H CF3 | ||
IIc-6 | IIc | Et | H | ||
IIc-7 | IIc | Et | H CH3 | ||
IIc-8 | IIc | Et | Et | ||
IId-1 | IId | - | H | ||
IId-2 | IId | - | H CH3 | ||
IId-3 | IId | - | CH3 | ||
IId-4 | IId | - | H CF3 | ||
IId-5 | IId | - | Et | ||
IIe-1 | IIe | - | H | ||
IIe-2 | IIe | - | H CH3 | ||
IIe-3 | IIe | - | CH3 | ||
IIe-4 | IIe | - | H CF3 | ||
IIe-5 | IIe | - | Et | ||
IIf-1 | IIf | CH3 | H | ||
IIf-2 | IIf | CH3 | H CH3 | ||
IIf-3 | IIf | CH3 | CH3 | ||
IIf-4 | IIf | CF3 | H | ||
IIf-5 | IIf | CH3 | H CF3 | ||
IIf-6 | IIf | Et | H | ||
IIf-7 | IIf | Et | H CH3 | ||
IIf-8 | IIf | Et | Et | ||
IIf-9 | IIf | Ph | H | ||
IIg-1 | IIg | CH3 | H | ||
IIg-2 | IIg | CH3 | H CH3 | ||
IIg-3 | IIg | CH3 | CH3 | ||
IIg-4 | IIg | CF3 | H | ||
IIg-5 | IIg | CH3 | H CF3 | ||
IIg-6 | IIg | Et | H | ||
IIg-7 | IIg | Et | H CH3 | ||
IIg-8 | IIg | Et | Et | ||
IIh-1 | IIh | CH3 | H | ||
IIh-2 | IIh | CH3 | H CH3 | ||
IIh-3 | IIh | CH3 | CH3 | ||
IIh-4 | IIh | CF3 | H | ||
IIh-5 | IIh | CH3 | H CF3 | ||
IIh-6 | IIh | Et | H | ||
IIh-7 | IIh | Et | H CH3 | ||
IIh-8 | IIh | Et | Et | ||
IIj-1 | IIj | CH3 | H | ||
IIj-2 | IIj | CH3 | H CH3 | ||
IIj-3 | IIj | CH3 | CH3 | ||
IIj-4 | IIj | CF3 | H | ||
IIj-5 | IIj | CH3 | H CF3 | ||
IIj-6 | IIj | Et | H | ||
IIj-7 | IIj | Et | H CH3 | ||
IIj-8 | IIj | Et | Et | ||
IIj-9 | IIj | Ph | H | ||
IIk-1 | IIk | CH3 | H | ||
IIk-2 | IIk | CH3 | H CH3 | ||
IIk-3 | IIk | CH3 | CH3 | ||
IIk-4 | IIk | CF3 | H | ||
IIk-5 | IIk | CH3 | H CF3 | ||
IIk-6 | IIk | Et | H | ||
IIk-7 | IIk | Et | H CH3 | ||
IIk-8 | IIk | Et | Et | ||
IIm-1 | IIm | CH3 | H | ||
IIm-2 | IIm | CH3 | H CH3 | ||
IIm-3 | IIm | CH3 | CH3 | ||
IIm-4 | IIm | CF3 | H | ||
IIm-5 | IIm | CH3 | H CF3 | ||
IIm-6 | IIm | Et | H | ||
IIm-7 | IIm | Et | H CH3 | ||
IIm-8 | IIm | Et | Et | ||
IIn-1 | IIn | CH3 | H | ||
IIn-2 | IIn | CH3 | H CH3 | ||
IIn-3 | IIn | CH3 | CH3 | ||
IIn-4 | IIn | CF3 | H | ||
IIn-5 | IIn | CH3 | H CF3 | ||
IIn-6 | IIn | Et | H | ||
IIn-7 | IIn | Et | H CH3 | ||
IIn-8 | IIn | Et | Et | ||
IIo-1 | IIo | CH3 | H | ||
IIo-2 | IIo | CH3 | H CH3 | ||
IIo-3 | IIo | CH3 | CH3 | ||
IIo-4 | IIo | CF3 | H | ||
IIo-5 | IIo | CH3 | H CF3 | ||
IIo-6 | IIo | Et | H | ||
IIo-7 | IIo | Et | H CH3 | ||
IIo-8 | IIo | Et | Et | ||
IIp-1 | IIp | CH3 | H | ||
IIp-2 | IIp | CH3 | H CH3 | ||
IIp-3 | IIp | CH3 | CH3 | ||
IIp-4 | IIp | CF3 | H | ||
IIp-5 | IIp | CH3 | H CF3 | ||
IIp-6 | IIp | Et | H | ||
IIp-7 | IIp | Et | H CH3 | ||
IIp-8 | IIp | Et | Et | ||
參考此等通式之通式(III)化合物之較佳實例在下表中給出。
Et表示乙基且Ph表示苯基。
編號 | 化學式 | R | R' |
IIIa-1 | IIIa | CH3 | H |
IIIa-2 | IIIa | CH3 | H CH3 |
IIIa-3 | IIIa | CH3 | CH3 |
IIIa-4 | IIIa | CF3 | H |
IIIa-5 | IIIa | CH3 | H CF3 |
IIIa-6 | IIIa | Et | H |
IIIa-7 | IIIa | Et | H CH3 |
IIIa-8 | IIIa | Et | Et |
IIIb-1 | IIIb | CH3 | H |
IIIb-2 | IIIb | CH3 | H CH3 |
IIIb-3 | IIIb | CH3 | CH3 |
IIIb-4 | IIIb | CF3 | H |
IIIb-5 | IIIb | CH3 | H CF3 |
IIIb-6 | IIIb | Et | H |
IIIb-7 | IIIb | Et | H CH3 |
IIIb-8 | IIIb | Et | Et |
IIIc-1 | IIIc | - | H |
IIIc-2 | IIIc | - | H CH3 |
IIIc-3 | IIIc | - | CH3 |
IIIc-4 | IIIc | - | H CF3 |
IIIc-5 | IIIc | - | Et |
IIId-1 | IIId | CH3 | H |
IIId-2 | IIId | CH3 | H CH3 |
IIId-3 | IIId | CH3 | CH3 |
IIId-4 | IIId | CF3 | H |
IIId-5 | IIId | CH3 | H CF3 |
IIId-6 | IIId | Et | H |
IIId-7 | IIId | Et | H CH3 |
IIId-8 | IIId | Et | Et |
IIId-9 | IIId | Ph | H |
IIIe-1 | IIIe | - | H |
IIIe-2 | IIIe | - | H CH3 |
IIIe-3 | IIIe | - | CH3 |
IIIe-4 | IIIe | - | H CF3 |
IIIe-5 | IIIe | - | Et |
IIIf-1 | IIIf | CH3 | H |
IIIf-2 | IIIf | CH3 | H CH3 |
IIIf-3 | IIIf | CH3 | CH3 |
IIIf-4 | IIIf | CF3 | H |
IIIf-5 | IIIf | CH3 | H CF3 |
IIIf-6 | IIIf | Et | H |
IIIf-7 | IIIf | Et | H CH3 |
IIIf-8 | IIIf | Et | Et |
IIIf-9 | IIIf | Ph | H |
IIIg-1 | IIIg | CH3 | H |
IIIg-2 | IIIg | CH3 | H CH3 |
IIIg-3 | IIIg | CH3 | CH3 |
IIIg-4 | IIIg | CF3 | H |
IIIg-5 | IIIg | CH3 | H CF3 |
IIIg-6 | IIIg | Et | H |
IIIg-7 | IIIg | Et | H CH3 |
IIIg-8 | IIIg | Et | Et |
IIIh-1 | IIIh | - | H |
IIIh-2 | IIIh | - | H CH3 |
IIIh-3 | IIIh | - | CH3 |
IIIh-4 | IIIh | - | H CF3 |
IIIh-5 | IIIh | - | Et |
IIIj-1 | IIIj | - | H |
IIIj-2 | IIIj | - | H CH3 |
IIIj-3 | IIIj | - | CH3 |
IIIj-4 | IIIj | - | H CF3 |
IIIj-5 | IIIj | - | Et |
IIIk-1 | IIIk | CH3 | H |
IIIk-2 | IIIk | CH3 | H CH3 |
IIIk-3 | IIIk | CH3 | CH3 |
IIIk-4 | IIIk | CF3 | H |
IIIk-5 | IIIk | CH3 | H CF3 |
IIIk-6 | IIIk | Et | H |
IIIk-7 | IIIk | Et | H CH3 |
IIIk-8 | IIIk | Et | Et |
IIIm-1 | IIIm | CH3 | H |
IIIm-2 | IIIm | CH3 | H CH3 |
IIIm-3 | IIIm | CH3 | CH3 |
IIIm-4 | IIIm | CF3 | H |
IIIm-5 | IIIm | CH3 | H CF3 |
IIIm-6 | IIIm | Et | H |
IIIm-7 | IIIm | Et | H CH3 |
IIIm-8 | IIIm | Et | Et |
IIIn-1 | IIIn | CH3 | H |
IIIn-2 | IIIn | CH3 | H CH3 |
IIIn-3 | IIIn | CH3 | CH3 |
IIIn-4 | IIIn | CF3 | H |
IIIn-5 | IIIn | CH3 | H CF3 |
IIIn-6 | IIIn | Et | H |
IIIn-7 | IIIn | Et | H CH3 |
IIIn-8 | IIIn | Et | Et |
IIIo-1 | IIIo | CH3 | H |
IIIo-2 | IIIo | CH3 | H CH3 |
IIIo-3 | IIIo | CH3 | CH3 |
IIIo-4 | IIIo | CF3 | H |
IIIo-5 | IIIo | CH3 | H CF3 |
IIIo-6 | IIIo | Et | H |
IIIo-7 | IIIo | Et | H CH3 |
IIIo-8 | IIIo | Et | Et |
IIIo-9 | IIIo | Ph | H |
IIIp-1 | IIIp | CH3 | H |
IIIp-2 | IIIp | CH3 | H CH3 |
IIIp-3 | IIIp | CH3 | CH3 |
IIIp-4 | IIIp | CF3 | H |
IIIp-5 | IIIp | CH3 | H CF3 |
IIIp-6 | IIIp | Et | H |
IIIp-7 | IIIp | Et | H CH3 |
IIIp-8 | IIIp | Et | Et |
IIIq-1 | IIIq | CH3 | H |
IIIq-2 | IIIq | CH3 | H CH3 |
IIIq-3 | IIIq | CH3 | CH3 |
IIIq-4 | IIIq | CF3 | H |
IIIq-5 | IIIq | CH3 | H CF3 |
IIIq-6 | IIIq | Et | H |
IIIq-7 | IIIq | Et | H CH3 |
IIIq-8 | IIIq | Et | Et |
IIIr-1 | IIIr | CH3 | H |
IIIr-2 | IIIr | CH3 | H CH3 |
IIIr-3 | IIIr | CH3 | CH3 |
IIIr-4 | IIIr | CF3 | H |
IIIr-5 | IIIr | CH3 | H CF3 |
IIIr-6 | IIIr | Et | H |
IIIr-7 | IIIr | Et | H CH3 |
IIIr-8 | IIIr | Et | Et |
IIIr-9 | IIIr | Ph | H |
較佳地,R在1號位不攜載氫原子,亦即R不攜載鍵結至氮或氧原子之原子的氫原子,其因此相對於鋁原子在β位。亦較佳地,R''在1號位不攜載氫原子。更佳地,R及R''兩者在1號位不攜載氫。實例為在1號位攜載兩個烷基側基之烷基,亦即1,1-二烷基烷基,諸如第三丁基、1,1-二甲基丙基;在1號位具有兩個鹵素之烷基,諸如三氟甲基、三氯甲基、1,1-二氟乙基;三烷基矽烷基,諸如三甲基矽烷基、三乙基矽烷基、二甲基-第三丁基矽烷基;芳基,尤其苯基或經烷基取代之苯基,諸如2,6-二異丙基苯基、2,4,6-三異丙基苯基。在1號位不攜載氫原子之烷基為尤其較佳的。
通式(I)、(II)或(III)化合物之分子量不超過1000 g/mol、更佳不超過800 g/mol、甚至更佳不超過600 g/mol,尤其不超過500 g/mol。
較佳地,通式(I)、(II)或(III)化合物之熔點在-80℃至125℃、較佳-60℃至80℃、甚至更佳-40℃至50℃,尤其-20℃至20℃範圍內。若通式(I)、(II)或(III)化合物熔融得到在分解溫度之前保持不變的透明液體,則其為有利的。
較佳地,通式(I)、(II)或(III)化合物之分解溫度為至少80℃,更佳至少100℃,尤其至少120℃,諸如至少150℃。通常,分解溫度不大於250℃。通式(I)、(II)或(III)化合物具有高蒸氣壓。較佳地,蒸氣壓在200℃之溫度下,更佳地在150℃下,尤其在120℃下為至少1毫巴。通常,蒸氣壓為1毫巴時之溫度為至少50℃。
用於根據本發明之方法中的通式(I)、(II)或(III)化合物係以高純度使用來達成最佳結果。高純度意謂所用之物質含有至少90 wt%、較佳至少95 wt%、更佳至少98 wt%,尤其至少99 wt%之含金屬或半金屬的化合物或通式(I)、(II)或(III)化合物。純度可藉由根據DIN 51721(Prufung fester Brennstoffe-Bestimmung des Gehaltes an Kohlenstoff und Wasserstoff-Verfahren nach Radmacher-Hoverath,2001年8月)之元素分析來測定。
使通式(I)、(II)或(III)化合物自氣態與固體基板接觸。可藉由將其加熱至高溫以使其變為氣態。在任何情況下,必須選擇低於通式(I)、(II)或(III)化合物之分解溫度的溫度。分解溫度為原始通式(I)、(II)或(III)化合物開始改變其化學結構及組成的溫度。較佳地,加熱溫度在0℃至300℃、更佳10℃至250℃、甚至更佳20℃至200℃,尤其30℃至150℃範圍內。
使通式(I)、(II)或(III)化合物變為氣態之另一方式為直接液體注入(direct liquid injection;DLI),如例如在US 2009/0 226 612 A1中所描述。在此方法中,通式(I)、(II)或(III)化合物典型地溶解於溶劑中且噴灑於載氣或真空中。若通式(I)、(II)或(III)化合物之蒸氣壓及溫度足夠高且壓力足夠低,則通式(I)、(II)或(III)化合物變為氣態。可使用各種溶劑,其限制條件為通式(I)、(II)或(III)化合物在該溶劑中展示足夠的溶解度,諸如至少1 g/l、較佳至少10 g/l、更佳至少100 g/l。此等溶劑之實例為配位溶劑,諸如四氫呋喃、二烷、二乙氧基乙烷、吡啶;或非配位溶劑,諸如己烷、庚烷、苯、甲苯或二甲苯。溶劑混合物亦為適合的。
可替代地,通式(I)、(II)或(III)化合物可藉由直接液體蒸發(direct liquid evaporation;DLE)變為氣態,如例如藉由J. Yang等人(Journal of Materials Chemistry,2015)所描述。在此方法中,將通式(I)、(II)或(III)化合物與溶劑(例如烴,諸如十四烷)混合,且在低於溶劑之沸點下加熱。藉由蒸發溶劑,使通式(I)、(II)或(III)化合物變為氣態。此方法具有表面上無微粒污染物形成之優勢。
較佳地在減壓下使通式(I)、(II)或(III)化合物變為氣態。以此方式,可通常在較低加熱溫度下進行該方法,從而減少通式(I)、(II)或(III)化合物之分解。亦有可能使用加壓來將呈氣態之通式(I)、(II)或(III)化合物推向固體基板。通常,出於此目的,惰性氣體(諸如氮氣或氬氣)用作載氣。較佳地,壓力為10巴至10-7
毫巴,更佳為1巴至10-3
毫巴,尤其為1毫巴至0.01毫巴,諸如0.1毫巴。
典型地,通式(I)、(II)或(III)化合物在該方法中充當還原劑。根據本發明,在使含金屬或半金屬的化合物與通式(I)、(II)或(III)化合物接觸之前,將其自氣態沉積至固體基板上。含金屬或半金屬的化合物通常經還原成金屬、金屬氮化物、金屬碳化物、金屬碳氮化物、金屬合金、金屬間化合物或其混合物。在本發明之上下文中,金屬膜為具有高電導率(通常至少104
S/m,較佳至少105
S/m,尤其至少106
S/m)之含金屬或半金屬的膜。
通式(I)、(II)或(III)化合物與具有經沉積之含金屬或半金屬的化合物的固體基板之表面形成永久結合的低傾向性。因此,含金屬或半金屬的膜幾乎不會被通式(I)、(II)或(III)化合物之反應副產物污染。較佳地,含金屬或半金屬的膜含有總共小於5重量%,更佳小於1 wt%,尤其小於0.5 wt%,諸如小於0.2 wt%之氮。
含金屬或半金屬的化合物含有至少一種金屬或半金屬原子。金屬包括Li、Be、Na、Mg、Al、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Rb、Sr、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、In、Sn、Cs、Ba、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Hf、Ta、W、Re、Os、Ir、Pt、Au、Hg、Tl、Bi。半金屬包括B、Si、Ge、As、Sb、Se、Te。較佳地,含金屬或半金屬的化合物含有比Cu更具電正性,更佳比Ni更具電正性之金屬或半金屬。特定言之,含金屬或半金屬的化合物含有Ti、Ta、Mn、Mo、W、Ge、Ga、As、In、Sb、Te、Al或Si。超過一種含金屬或半金屬的化合物有可能同時或連續地沉積於表面上。若超過一種含金屬或半金屬的化合物沉積於固體基板上,則有可能所有含金屬或半金屬的化合物含有相同金屬或半金屬或不同金屬或半金屬,較佳其含有不同金屬或半金屬。
可變為氣態之任何含金屬或半金屬的化合物均為適合的。此等化合物包括金屬或半金屬烷,諸如二甲基鋅、三甲基鋁;金屬烷氧基化物,諸如四甲氧基矽、四異丙氧基鋯或四異丙氧基鈦;環戊二烯基金屬或半金屬錯合物,如五甲基環戊二烯基-三甲氧基鈦或二(乙基環戊二烯基)錳;金屬或半金屬碳烯,諸如參(新戊基)新亞戊基鉭或氯化雙亞咪唑啶基釕;金屬或半金屬鹵化物,諸如三氯化鋁、五氯化鉭、四氯化鈦、五氯化鉬、四氯化鍺、三氯化鎵、三氯化砷或六氯化鎢;一氧化碳錯合物,如六羰基鉻或四羰基鎳;胺錯合物,諸如雙(第三丁亞胺基)雙(二甲胺基)鉬、雙(第三丁亞胺基)雙(二甲胺基)鎢或肆(二甲胺基)鈦;二酮錯合物,諸如參(乙醯丙酮根)鋁或雙(2,2,6,6-四甲基-3,5-庚二酮基)錳。金屬或半金屬鹵化物,尤其氯化鋁、溴化鋁及碘化鋁為較佳的。較佳地,含金屬或半金屬的化合物之分子量為至多1000 g/mol,更佳至多800 g/mol,尤其至多600 g/mol,諸如至多500 g/mol。
該方法較佳地以原子層沉積(atomic layer deposition;ALD)法形式進行,其包含以下工序:
(a)將含金屬或半金屬的化合物自氣態沉積至固體基板上,及
(b)使具有所沉積之含金屬或半金屬的化合物之固體基板與通式(I)、(II)或(III)化合物接觸。較佳地,包含(a)及(b)之工序進行至少兩次、更佳至少五次、甚至更佳至少10次,尤其至少50次。通常,包含(a)及(b)之工序進行不超過1000次。
通常,較佳的為每次將固體基板暴露於呈氣態之含金屬或半金屬的化合物或通式(I)、(II)或(III)化合物時用惰性氣體吹掃基板及其周圍設備。惰性氣體之較佳實例為氮氣及氬氣。吹掃可耗時1秒至1分鐘、較佳5秒至30秒、更佳10秒至25秒,尤其15秒至20秒。
較佳地,基板之溫度比將含金屬或半金屬的化合物變為氣態時之溫度高5℃至40℃,例如20℃。較佳地,基板之溫度為室溫至400℃,更佳100℃至300℃,諸如150℃至220℃。
較佳地,在將含金屬或半金屬的化合物沉積於固體基板上之後及在使具有所沉積之含金屬或半金屬的化合物之固體基板與通式(I)、(II)或(III)化合物接觸之前,使具有所沉積之含金屬或半金屬的化合物之固體基板與呈氣相之酸接觸。在不受理論束縛之情況下,咸信含金屬或半金屬的化合物之配位體之質子化有助於其分解及還原。適合的酸包括鹽酸及羧酸,較佳地羧酸,諸如甲酸、乙酸、丙酸、丁酸或三氟乙酸,尤其甲酸。
可替代地,有可能自通式(I)、(II)或(III)化合物沉積鋁。在此情況下,例如因為固體基板之表面上存在諸如OH基團之反應基或固體基板之溫度足夠高,故通式(I)、(II)或(III)化合物吸附至固體基板之表面。較佳地,所吸附之通式(I)、(II)或(III)化合物經分解。
分解可以各種方式實現。固體基板之溫度可升高至高於分解溫度。在此情況下,該方法為化學氣相沉積(chemical vapor deposition;CVD)方法。典型地,將固體基板加熱至300℃至1000℃範圍內,較佳350℃至600℃範圍內之溫度。
此外,有可能將所沉積之通式(I)、(II)或(III)化合物暴露於:電漿,如氧電漿、氫電漿、氨電漿或氮電漿;氧化劑,如氧氣、自由基氧、臭氧、氧化亞氮(N2
O)、氧化氮(NO)、二氧化氮(NO2
)或過氧化氫;氨或氨衍生物,例如第三丁胺、異丙胺、二甲胺、甲基乙基胺或二乙胺;肼或肼衍生物,如N,N-二甲基肼;溶劑,如水、烷烴或四氯化碳;或硼化合物,如甲硼烷。選擇取決於所需層之化學結構。對於氧化鋁,較佳使用氧化劑、電漿或水,尤其氧氣、水、氧電漿或臭氧。對於鋁,氮化物、氨、肼、肼衍生物、氮電漿或氨電漿為較佳的。對於硼化鋁,硼化合物為較佳的。對於碳化鋁,烷烴或四氯化碳為較佳的。
對於碳氮化鋁(aluminum carbide nitride),包括烷烴、四氯化碳、氨及/或肼之混合物為較佳的。
該方法較佳地以原子層沉積(ALD)方法形式進行,其包含以下工序:
(c)使固體基板與通式(I)、(II)或(III)化合物接觸,及
(d)分解所吸附之通式(I)、(II)或(III)化合物。較佳地,包含(c)及(d)之工序進行至少兩次、更佳至少五次、甚至更佳至少10次,尤其至少50次。通常,包含(c)及(d)之工序進行不超過1000次。
在此情況下,基板之溫度較佳地為比含金屬或半金屬的化合物變為氣態時之溫度高5℃至40℃,例如20℃。較佳地,基板之溫度為室溫至400℃,更佳100℃至300℃,諸如150℃至220℃。
若根據本發明之方法中之基板之溫度保持低於含金屬或半金屬的化合物之分解溫度,則典型地,將單層沉積於固體基板上。一旦含金屬或半金屬的化合物之分子沉積於固體基板上,則其頂部上之進一步沉積通常變得不大可能。因此,含金屬或半金屬的化合物於固體基板上之沉積較佳地表示自限性方法步驟。自限性沉積法步驟之典型層厚度為0.01 nm至1 nm、較佳為0.02 nm至0.5 nm、更佳為0.03 nm至0.4 nm,尤其為0.05 nm至0.2 nm。層厚度典型地藉由如PAS 1022 DE(Referenzverfahren zur Bestimmung von optischen und dielektrischen Materialeigenschaften sowie der Schichtdicke dunner Schichten mittels Ellipsometrie;2004年2月)中所描述之橢圓偏振法量測。
具有通式(I)、(II)或(III)化合物或含金屬或半金屬的化合物之基板之暴露可耗時數毫秒至若干分鐘,較佳0.1秒至1分鐘,尤其1秒至10秒。處於低於通式(I)、(II)或(III)化合物或含金屬或半金屬的化合物之分解溫度的溫度下之固體基板暴露於通式(I)、(II)或(III)化合物或含金屬或半金屬的化合物時間愈長,形成具有愈少缺陷之膜愈規則。
根據本發明之方法之特定優勢為通式(I)、(II)或(III)化合物完全通用,因此方法參數可在廣泛範圍內變化。因此,根據本發明之方法包括CVD方法以及ALD方法兩者。
根據本發明之方法得到含金屬或半金屬的無機膜。膜可為金屬之僅一個單層或更厚,諸如0.1 nm至1 μm,較佳0.5 nm至50 nm。膜可含有如孔洞之缺陷。然而,此等缺陷通常佔小於由膜覆蓋之表面積之一半。膜較佳具有極均勻之膜厚度,此意謂在基板上之不同位置的膜厚度變化極小,通常小於10%,較佳小於5%。此外,膜較佳為基板表面上之保形膜。測定膜厚度及均勻性之適合的方法為XPS或橢圓偏振法。
藉由根據本發明之方法獲得之膜可用於電子元件中。電子元件可具有各種尺寸,例如1 nm至100 μm,例如10 nm、14 nm或22 nm之結構特徵。形成用於電子元件之膜的方法尤其較適用於極精密結構。因此,具有低於1 μm之尺寸的電子元件為較佳的。電子元件之實例為場效電晶體(field-effect transistor;FET)、太陽能電池、發光二極體、感測器或電容器。在諸如發光二極體或感光器之光學裝置中,藉由根據本發明之方法所獲得之膜用以提高反射光之層的折射率。
較佳電子元件為電晶體。較佳地,膜充當電晶體中之化學障壁金屬層。化學障壁金屬層為降低鄰近層之擴散同時維持電連接性之材料。
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Claims (15)
- 如請求項1之方法,其中R為甲基、乙基、異丙基、第二丁基、第三丁基、三甲基矽烷基。
- 如請求項1或2之方法,其中R在1號位不含氫原子。
- 如請求項1至3中任一項之方法,其中n為1或2。
- 如請求項1至4中任一項之方法,其中該通式(I)、(II)或(III)化合物之熔點為-80℃至125℃。
- 如請求項1至5中任一項之方法,其中該含金屬或半金屬的化合物含有Ti、Ta、Mn、Mo、W、Ge、Ga、As、In、Sb、Te、Al或Si。
- 如請求項1至6中任一項之方法,其中該含金屬或半金屬的化合物為金屬或半金屬鹵化物。
- 如請求項1至7中任一項之方法,其中該含金屬或半金屬的無機膜含有金屬、金屬氮化物、金屬碳化物、金屬碳氮化物、金屬合金、金屬間化合物或其混合物。
- 如請求項1至8中任一項之方法,其中包含(a)及(b)之工序進行至少兩次。
- 如請求項1至9中任一項之方法,其中該方法為原子層沉積法。
- 如請求項1至10中任一項之方法,其中該通式(I)、(II)或(III)化合物之分子量不超過600 g/mol。
- 如請求項1至11中任一項之方法,其中該通式(I)、(II)或(III)化合物之蒸氣壓在200℃之溫度下為至少1毫巴。
- 如請求項1至12中任一項之方法,其中該含金屬或半金屬的無機膜含有小於5重量%之氮。
- 一種通式(I)、(II)或(III)化合物之用途,其用作氣相沉積法中之還原劑。
- 如請求項14之用途,其中該氣相沉積方法為原子層沉積法。
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US20220298637A1 (en) | 2022-09-22 |
KR20220158672A (ko) | 2022-12-01 |
WO2020244988A1 (en) | 2020-12-10 |
SG11202113376YA (en) | 2021-12-30 |
CN113906158A (zh) | 2022-01-07 |
JP2022536111A (ja) | 2022-08-12 |
IL288576A (en) | 2022-02-01 |
EP3980577A1 (en) | 2022-04-13 |
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