CN108495949B - 产生薄无机膜的方法 - Google Patents
产生薄无机膜的方法 Download PDFInfo
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- CN108495949B CN108495949B CN201680070246.3A CN201680070246A CN108495949B CN 108495949 B CN108495949 B CN 108495949B CN 201680070246 A CN201680070246 A CN 201680070246A CN 108495949 B CN108495949 B CN 108495949B
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- alkenyl
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- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 239000007787 solid Substances 0.000 claims abstract description 44
- 239000003446 ligand Substances 0.000 claims abstract description 36
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- 239000000443 aerosol Substances 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 9
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 238000000231 atomic layer deposition Methods 0.000 abstract description 8
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract description 5
- -1 (hexamethyldisilylamino) tetrahydrofuran Chemical compound 0.000 description 55
- 239000010408 film Substances 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
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- 238000000354 decomposition reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 238000000921 elemental analysis Methods 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
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- 229910021529 ammonia Inorganic materials 0.000 description 5
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- 239000012528 membrane Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
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- 239000012043 crude product Substances 0.000 description 4
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
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- JAIWFUHVFMKUFA-UHFFFAOYSA-N N-propan-2-yl-1-(1H-pyrrol-2-yl)methanimine Chemical compound C(C)(C)N=CC=1NC=CC=1 JAIWFUHVFMKUFA-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
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- 238000005229 chemical vapour deposition Methods 0.000 description 3
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- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
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- 102100038239 Protein Churchill Human genes 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000168 pyrrolyl group Chemical group 0.000 description 1
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- 238000002310 reflectometry Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 239000002002 slurry Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000004587 thienothienyl group Chemical group S1C(=CC2=C1C=CS2)* 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明属于在基材上产生薄无机膜的方法,特别是原子层沉积法的领域。本发明涉及一种包括使通式(I)化合物变为气态或气溶胶状态并使气态或气溶胶状态的通式(I)化合物沉积在固体基材上的方法,其中M为Mn、Ni或Co,X为与M配位的配体,n为0、1或2,R1、R2为烷基、链烯基、芳基或甲硅烷基,m为1、2或3,R3、R4和R5为烷基、链烯基、芳基、烷氧基或芳氧基,且p为1、2或3。
Description
本发明属于在基材上产生薄无机膜的方法,特别是原子层沉积法的领域。
对基材上的薄无机膜的需求随着持续小型化,例如在半导体工业中持续小型化而增加,同时对该类膜的质量要求变得更严格。薄无机膜用于不同目的,例如阻挡层、介电质、导电特征、封盖或精细结构的分离。已知数种产生薄无机膜的方法。其中之一将气态成膜化合物沉积在基材上。为了使金属原子在中等温度下变为气态,必须例如通过金属与合适配体的络合来提供挥发性前体。在将络合的金属沉积至基材后,需要除去这些配体。
US 2014/0255606 A1公开了用于膜沉积的双(六甲基二甲硅烷基氨基)四氢呋喃钴。然而,该配合物在蒸发之后不够稳定,且不能得到具有足以用于某些应用的质量的膜。
Bryan等在Inorganic Chemistry,第52卷(2013),第12152-12160页中公开了六甲基二甲硅烷基氨基三甲基膦基钴。然而,该化合物并未用于成膜方法。
本发明的目的为提供一种在经济可行的条件下用于在固体基材上产生具有高质量且再现性的含Mn、Ni和/或Co的膜的方法。希望该方法可在含Mn、Ni或Co的前体在其与固体基材接触前尽可能少分解下操作。同时希望提供使前体在沉积于固体基材后容易分解的方法。还旨在提供一种使用含Mn、Ni或Co的前体的方法,其可容易地改性并仍保持稳定,以使前体的性能符合特定需求。
这些目的通过包括使通式(I)化合物变为气态或气溶胶状态并将气态或气溶胶状态的通式(I)化合物沉积在固体基材的方法实现,其中:
M为Mn、Ni或Co,
X为与M配位的配体,
n为0、1或2,
R1、R2为烷基、链烯基、芳基或甲硅烷基,
m为1、2或3,
R3、R4和R5为烷基、链烯基、芳基、烷氧基或芳氧基,且
p为1、2或3。
本发明进一步涉及通式(I)化合物在固体基材上的成膜方法中的用途,其中
M为Mn、Ni或Co,
X为与M配位的配体,
n为0、1或2,
R1、R2为烷基、链烯基、芳基或甲硅烷基,
m为1、2或3,
R3、R4和R5为烷基、链烯基、芳基、烷氧基或芳氧基,且
p为1、2或3。
本发明进一步涉及一种通式(I)化合物,其中
M为Mn、Ni或Co,
X为与M配位的配体,
n为0、1或2,
R1、R2为烷基、链烯基、芳基或甲硅烷基,
m为1、2或3,
R3、R4和R5为烷基、链烯基、芳基、烷氧基或芳氧基,且
p为1、2或3,
其中R3、R4和R5中的一个不同于其它两个,或者所有R3、R4和R5彼此不同。
本发明的优选实施方案可见于说明书和权利要求书。不同实施方案的组合落入本发明范围内。
在通式(I)化合物中,R1和R2为烷基、链烯基、芳基或甲硅烷基,优选烷基或甲硅烷基,特别是甲硅烷基。R1和R2可彼此相同或不同。观测到与具有相同分子量且其中R1和R2相同的通式(I)化合物相比,如果R1和R2彼此不同,则通式(I)化合物的蒸气压较低。R1和R2可彼此连接,使得它们形成包含它们所连接的氮原子的环。如果至少一个R1和R2为链烯基或芳基,则该环可含有一个或多个双键。指数m可为1、2或3,优选2。如果m大于1,例如超过一个胺配体NR1R2存在于式(I)化合物中,则在不同胺配体中的相应R1和R2可彼此独立地彼此相同或不同,它们优选相同。
在通式(I)化合物中,R3、R4和R5是烷基、链烯基、芳基、烷氧基或芳氧基,优选烷基。R3、R4和R5可相同;或R3、R4和R5中的两个相同,且其余不同;或者所有R3、R4和R5彼此不同,优选R3、R4和R5中的两个相同,且第三个不同于其他两个;或者所有R3、R4和R5彼此不同;特别是R3、R4和R5中的两个相同,且第三个不同于其他两个。发现在这种情况下,与具有相同分子量且其中R3、R4和R5相同的通式(I)化合物相比,通式(I)化合物的蒸气压较低。R3、R4和R5可彼此连接,使得它们会形成包含它们所连接的磷原子的环。如果形成环的R3、R4和R5中有至少一个为链烯基或芳基,则该环可含有一个或多个双键。指数p可为1、2或3,优选1或2,特别是1。如果n大于1,例如超过一个膦配体PR3R4R5存在于通式(I)化合物中,则不同膦配体中的相应R3、R4和R5可彼此独立地彼此相同或不同,它们优选相同。更优选地,不同膦配体中的相应R3、R4和R5相同,且同时,R3、R4和R5中的一个不同于其它两个。
烷基可为线性或支化的。线性烷基的实例为甲基、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。支化烷基的实例为异丙基、异丁基、仲丁基、叔丁基、2-甲基-戊基、2-乙基-己基、环丙基、环己基、二氢茚基、降冰片烷基。优选地,该烷基为C1-C8烷基,更优选C1-C6烷基,特别是C1-C4烷基,如甲基、乙基、异丙基或叔丁基。烷基可例如被卤素如F、Cl、Br和I,特别是F;羟基;醚基团;或胺如二烷基胺取代。
链烯基含有至少一个碳-碳双键。该双键可包括使链烯基与该分子的其余部分结合的碳原子,或可将其放置在更远离链烯基与该分子的其余部分结合的位置上,优选放置在更远离链烯基与该分子的其余部分结合的位置上。链烯基可为线性或支化的。线性链烯基(其中双键包括使链烯基与该分子的其余部分结合的碳原子)的实例包括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。线性链烯基(其中双键放置在更远离链烯基与该分子的其余部分结合的位置上)的实例包括1-正丙烯-3-基、2-丁烯-1-基、1-丁烯-3-基、1-丁烯-4-基和1-己烯-6-基。支化链烯基(其中双键包括使链烯基与该分子的其余部分结合的碳原子)的实例包括1-丙烯-2-基、1-正丁烯-2-基、2-丁烯-2-基、环戊烯-1-基、环己烯-1-基。支化链烯基(其中双键放置在更远离链烯基与该分子的其余部分结合的位置上)的实例包括2-甲基-1-丁烯-4-基、环戊烯-3-基、环己烯-3-基。具有大于一个双键的链烯基的实例包括1,3-丁二烯-1-基、1,3-丁二烯-2-基和环戊二烯-5-基。
芳基包括芳族烃如苯基、萘基、蒽基和菲基,以及杂芳族基团如吡咯基、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。还可为这些基团中的几种或这些基团的组合,例如联苯基、噻吩基苯基或呋喃基噻吩基。芳基可例如被卤素如氟、氯、溴、碘;拟卤素如氰化物、氰酸酯和硫代氰酸酯;醇;烷基链或烷氧基链取代。优选芳族烃,更优选苯基。
甲硅烷基为通常具有3个取代基的硅原子。优选地,甲硅烷基具有式SiY3,其中Y为氢、烷基、链烯基、芳基或甲硅烷基。可能的是所有3个Y相同;或两个Y相同,且其余Y不同;或者所有3个Y彼此不同。两个Y一起还可形成含Si原子的环。烷基和芳基如上所述。甲硅烷基的实例包括SiH3、甲基甲硅烷基、三甲基甲硅烷基、三乙基甲硅烷基、三正丙基甲硅烷基、三异丙基甲硅烷基、三环己基甲硅烷基、二甲基叔丁基甲硅烷基、二甲基环己基甲硅烷基、甲基二异丙基甲硅烷基、三苯基甲硅烷基、苯基甲硅烷基、二甲基苯基甲硅烷基和五甲基二甲硅烷基。
烷氧基为经由氧原子连接至残余分子的烷基。芳氧基为经由氧原子连接至残余分子上的芳基。
根据本发明,通式(I)化合物中的配体X可为与M配位的任何配体。指数n可为0、1或2,优选0或1,特别是0。如果n是2,即通式(I)化合物含有两个X,则两个X可彼此相同或不同,它们优选相同。任何或所有的X可在M的任何配体球中,例如在内配体球中、在外配体球中或者仅仅松散地与M结合。优选地,X位于M的内配体球中。据信如果所有配体X位于M的内配体球中,则通式(I)化合物的挥发性高,使得可使它变为气态或气溶胶状态而不分解。
本发明通式(I)化合物中的配体X包括以下的阴离子:卤素如氟、氯、溴或碘,拟卤素如氰化物、异氰化物、氰酸酯、异氰酸酯、硫代氰酸酯、异硫氰酸酯或叠氮化物。其它合适的配体X为烷基阴离子如甲基、乙基、丁基或新戊基阴离子以及含硅的烷基,例如三甲基甲硅烷基甲基。另一可能的配体X为氢化物(hydride)、一氧化氮(NO)和一氧化碳(CO)。
此外,X可以是通过中性或阴离子氮原子(例如通过与M配位之前脱质子化)与M配位的配体。优选地,X为通过至少两个中性或阴离子氮原子配位的配体。这些包括脒类(例如乙脒或N,N'-双异丙基乙脒)、胍类(如胍)、氨基亚胺(如2-N-叔丁基氨基-2-甲基丙醛-N-叔丁基亚胺)、二亚胺类(如乙二醛-N,N'-双异丙基二亚胺、乙二醛-N,N'-双叔丁基二亚胺或2,4-戊二酮二亚胺)、二酮亚胺类(如N,N'-2,4-戊二酮亚胺酯)和亚氨基吡咯,包括吡咯-2-甲醛烷基亚胺如吡咯-2-甲醛乙基亚胺、吡咯-2-甲醛异丙基亚胺或吡咯-2-甲醛叔丁基亚胺以及吡咯-2,5-二甲醛烷基二亚胺如吡咯-2,5-二甲醛叔丁基二亚胺。
X还可为其中氧原子与M配位的配体。实例为烷醇化物、四氢呋喃、乙酰丙酮化物或1,1,1,5,5,5-五氟乙酰丙酮。X的其它合适实例包括与M配位的氮和氧原子,包括二甲基氨基异丙醇、甲酰胺、乙酰胺、2,4-戊二酮-N-烷基亚胺如2,4-戊二酮-N-异丙基亚胺。
X还可为用π键与M配位的不饱和烃。它们可为脂族或芳族的。不饱和烃包括烯烃如乙烯、丙烯、异丁烯、环己烯、环辛烯、环辛二烯和苯乙烯和炔如乙炔、丙炔、2-丁炔。X还可为不饱和阴离子烃,其可经由阴离子和不饱和键进行配位,例如经由烯丙基、2-甲基烯丙基或1,3-双(三甲基甲硅烷基)烯丙基。经由π键与M配位的芳族X包括环戊二烯阴离子和其衍生物;苯和其衍生物如甲苯或二甲苯。
优选地,配体X为经由氮与M配位的配体,或者X为脂族烃、烷醇化物、腈、溴、CO或NO。特别优选的配体X为甲基、乙基、丙基、新戊基、三甲基甲硅烷基甲基、烯丙基、2-甲基烯丙基、1,3-双(三甲基甲硅烷基)烯丙基、2-N-叔丁基氨基-2-甲基丙醛-N-叔丁基亚胺、N,N'-双异丙基乙脒、乙二醛-N,N'-双叔丁基二亚胺、乙二醛-N,N'-双异丙基二亚胺、吡咯-2-甲醛异丙基亚胺或吡咯-2-甲醛叔丁基亚胺、甲醇化物、乙醇化物、CO、NO、腈、溴、乙烯、环辛烯、环辛二烯或2-丁炔,特别是2-甲基烯丙基、N,N'-双异丙基乙脒、乙二醛-N,N'-双叔丁基二亚胺、吡咯-2-甲醛异丙基亚胺、CO和NO。
金属M为Mn、Ni或Co,即锰、镍或钴,优选Ni或Co,特别是Co。金属M可处于各种氧化态,例如0、+1、+2、+3或+4。优选地,X和n的选择使得通式(I)化合物为电中性的。
优选通式(I)化合物的分子量可为至多1000g/mol,更优选至多800g/mol,特别是至多600g/mol。
在下表中给出通式(I)化合物的一些优选实例。
COD表示1,5-环辛二烯,DPMA表示N,N-二异丙基-2-甲基脒酯,TMS-Me表示三甲基甲硅烷基甲基,HMG表示六甲基胍酯,TAMPTI表示2-(N-叔丁基氨基)-2-甲基丙醛-N-叔丁基亚胺,PCII表示吡咯-2-甲醛异丙基亚胺,TMS表示三甲基甲硅烷基,TMP表示2,2,6,6-四甲基哌啶,BTMSA表示1,3-双(三甲基甲硅烷基)烯丙基。
本发明方法中所用的通式(I)化合物优选以高纯度使用,以实现最佳结果。高纯度是指所用物质含有至少90wt%通式(I)化合物,优选至少95wt%通式(I)化合物,更优选至少98wt%通式(I)化合物,特别是至少99wt%通式(I)化合物。可通过根据DIN 51721(Prüfungfester Brennstoffe-Bestimmung des Gehaltes an Kohlenstoff undWasserstoff-Verfahren nach Radmacher-Hoverath,2001年8月)的元素分析来确定纯度。
在本发明方法中,使通式(I)化合物变为气态或气溶胶状态。这可通过将通式(I)化合物加热至高温来实现。在任何情况下,必须选择低于通式(I)化合物的分解温度的温度。优选地,加热温度为稍微高于室温至300℃,更优选30℃至250℃,甚至更优选40℃至200℃,特别是50℃至150℃。
使通式(I)化合物变为气态或气溶胶状态的另一种方法是直接液体注射(DLI),例如如US 2009/02226612 A1中所述。在该方法中,通常将通式(I)化合物溶于溶剂中,并以载流气体或在真空中将其喷雾。取决于通式(I)化合物的蒸气压、温度和压力,使通式(I)化合物变为气态或气溶胶态。可以使用各种溶剂,条件是通式(I)化合物在该溶剂中显示出足够的溶解度,如至少1g/l,优选至少10g/l,更优选至少100g/l。这些溶剂的实例为配位溶剂,例如四氢呋喃、二烷、二乙氧基乙烷、吡啶,或者非配位溶剂,例如己烷、庚烷、苯、甲苯或二甲苯。溶剂混合物也是合适的。包含通式(I)化合物的气溶胶应包含非常细的液滴或固体颗粒。优选地,该液滴或固体颗粒具有不大于500nm,更优选不大于100nm的重量平均直径。可通过如ISO 22412:2008中所述的动态光散射来测定液滴或固体颗粒的重量平均直径。还可能的是通式(I)化合物的一部分为气态,且其余为气溶胶状态,例如由于通式(I)化合物的有限蒸气压,导致气溶胶状态的通式(I)化合物的部分蒸发。
作为替换,可通过如J.Yang等(Journal of Materials Chemistry C,2015年)所述的直接液体蒸发(DLE)使含金属化合物变为气态。在该方法中,将含金属化合物或还原剂与溶剂如烃如十四烷进行混合,并在溶剂的沸点以下加热。通过溶剂的蒸发,使含金属化合物或还原剂变为气态。该方法具有在表面上不形成颗粒状污染物的优点。
优选使通式(I)化合物在减压下变为气态或气溶胶状态。通过这种方式,该方法通常可在较低的加热温度下进行,导致通式(I)化合物的分解减少。
还可使用加压来使气态或气溶胶状态的通式(I)化合物推向固体基材。通常为此使用惰性气体如氮气或氩气作为载气。压力优选为10巴至10-7毫巴,更优选1巴至10-3毫巴,特别是1至0.01毫巴,如0.1毫巴。
在本发明方法中,将气态或气溶胶状态的通式(I)化合物沉积至固体基材上。固体基材可以是任何固体材料。它们包括例如金属、半金属、氧化物、氮化物和聚合物。基材也可是不同材料的混合物,金属的实例为钽、钨、钴、镍、铂、钌、钯、锰、铝、钢、锌和铜。半金属的实例为硅、锗和砷化镓。氧化物的实例为二氧化硅、二氧化钛、氧化锆和氧化锌。氮化物的实例为氮化硅、氮化铝、氮化钛、氮化钽和氮化镓。聚合物的实例为聚对苯二甲酸乙二酯(PET)、聚亚乙基萘二甲酸(PEN)和聚酰胺。
固体基材可具有任何形状。这些包括片材、膜、纤维、各种尺寸的颗粒,以及具有沟槽或其它凹陷的基材。固体基材可具有任何尺寸。如果固体基材具有颗粒形状,则颗粒的尺寸可为低于100nm至几厘米,优选1μm至1mm。为了避免在使通式(I)化合物沉积于其上的同时颗粒或纤维彼此粘附,优选使它们维持移动。这可例如通过搅拌、通过转鼓或通过流化床技术实现。
如果基材与通式(I)化合物接触,则发生沉积。通常可用两种不同的方式进行沉积过程:将基材在通式(I)化合物的分解温度以上或以下加热。如果将基材在通式(I)化合物的分解温度以上加热,则只要更多气态或气溶胶状态的通式(I)化合物到达固体基材的表面,通式(I)化合物就会在固体基材的表面上连续分解。该方法通常称为化学气相沉积(CVD)。通常,因为有机材料由金属M释放出,所以在固体基材上形成均质组合物如金属氧化物或氮化物的无机层。通常将该固体基材加热至300-1000℃,优选350-600℃。
作为替换,基材处处于低于通式(I)化合物的分解温度。通常,固体基材的温度等于或低于使通式(I)化合物变为气态或气溶胶状态的温度,其通常为室温或仅略高于室温。优选地,基材的温度比使通式(I)化合物变为气态或气溶胶状态之处低至少30℃。优选地,基材的温度为室温至400℃,更优选100-300℃,如150-220℃。
在固体基材上的通式(I)化合物的沉积是物理吸附或化学吸附方法。优选地,通式(I)化合物化学吸附至固体基材上。可通过将具有所述基材表面的石英晶体的石英微量天平暴露于气态或气溶胶状态的通式(I)化合物确定通式(I)化合物是否化学吸附至固体基材上。通过石英晶体的固有频率记录质量增加。在石英晶体所放置的室抽空后,质量不应降低至初始质量,但如果进行化学吸附,则会大约残留残余通式(I)化合物的单层。在通式(I)化合物化学吸附至固体基材的大多数情况下,由于键在基材上形成,M的X射线光电子光谱(XPS)信号(ISO 13424,EN-Surface chemical analysis-X-ray photoelectronspectroscopy-Reporting of results of thin-film analysis,2013年10月)变化。
如果使本发明方法中的基材的温度维持低于通式(I)化合物的分解温度,则通常在固体基材上沉积单层。在将通式(I)分子沉积在固体基材后,则在其顶部的进一步沉积通常会变得不太可能。因此,在固体基材上沉积通式(I)化合物优选为自限制工艺步骤。自限制沉积工艺步骤的典型层厚度为0.01-1nm,优选0.02-0.5nm,更优选0.03-0.4nm,特别是0.05-0.2nm。通常通过如PAS 1022DE(Referenzverfahren zur Bestimmung vonoptischen und dielektrischen Materialeigenschaften sichie der SchichtdickedünnerSchichten mittels Ellipsometrie,2004年2月)所述的椭圆偏振法来测量层厚。
通常希望形成比刚刚所述的层更厚的层。为了在本发明方法中实现这一点,优选通过除去所有配体来分解经沉积的通式(I)化合物,此后沉积其他通式(I)化合物。该序列优选进行至少2次,更优选至少10次,特别是至少50次。在本发明的上下文中,除去所有配体是指除去经沉积的通式(I)化合物中的配体总重量的至少95wt%,优选至少98wt%,特别是至少99wt%。可用各种方式进行分解。可将固体基材的温度升高至分解温度以上。
此外,可将经沉积的通式(I)化合物暴露于等离子体如氧等离子体或氢等离子体,氧化剂如氧、氧自由基、臭氧、一氧化二氮(N2O)、一氧化氮(NO)、二氧化物(NO2)或过氧化氢,还原剂如氢、醇、肼或羟胺或溶剂如水。优选使用氧化剂、等离子体或水以获得金属氧化物层。优选暴露于水、氧等离子体或臭氧。特别优选暴露于水。如果需要元素态金属层,优选使用还原剂。优选的实例为氢、氢自由基、氢等离子体、氨、氨自由基、氨等离子体,氨的衍生物如叔丁胺、异丙胺、二甲胺、甲基乙胺或二乙胺,肼或肼的衍生物如N,N-二甲基肼,硅烷、二硅烷、三硅烷、环五硅烷、环六硅烷、二甲基硅烷、二乙基硅烷或三甲硅烷基胺,更优选氢、氢自由基、氢等离子体、氨、氨自由基、氨等离子体、肼、N,N-二甲基肼和硅烷,特别是氢。还原剂可以直接引起经沉积的通式(I)化合物的分解,或者可在通过不同试剂如水分解经沉积的通式(I)化合物后施用该还原剂。对于金属氮化物层,优选使用氨或肼。通常,观测所生成膜的短分解时间和高纯度。
包括自限制工艺步骤和随后的自限制反应的沉积方法通常是指原子层沉积(ALD)。等效表述为分子层沉积(MLD)或原子层外延(ALE)。因此,本发明方法优选为ALD方法。ALD方法由George详细描述(Chemical Reviews 110(2010),111-131)。
本发明方法的一个特别优点为通式(I)化合物是非常多用途的,所以可以在宽范围内改变工艺参数。因此,本发明方法包括CVD方法以及ALD方法。
取决于以ALD方法进行的本发明方法的序列数,产生各种厚度的膜。优选地,在固体基材上沉积通式(I)化合物以及分解经沉积的通式(I)化合物的序列进行至少两次。可重复该序列许多次,例如10-500次,如50或100次。通常,不重复该序列1000次以上。理想地,膜的厚度与所进行的序列数成比例。然而,实际上从前30-50个序列的比例中观测到某些偏差。假设固体基材的表面结构的不规则性造成了该不成比例。
本发明方法的一个序列可进行几毫秒至几分钟,优选0.1秒至1分钟,特别是1-10秒。固体基材(其处在比通式(I)化合物的分解温度低的温度下)暴露于通式(I)化合物中越久,就形成越多缺陷较少的平整膜。
R3、R4和R5中的一个不同于其它两个或者所有R3、R4和R5彼此不同的通式(I)化合物特别适用于本发明方法,因此,本发明进一步涉及通式(I)化合物,其中R3、R4和R5中的一个不同于其它两个,或者所有R3、R4和R5彼此不同。通式(I)化合物的变量的定义和优选实施方案如上述方法中所述。
本发明方法产生薄膜。膜可以是仅仅一个经沉积的分子式(I)化合物单层、几个连续沉积和分解的通式(I)化合物层或者几个不同的层,其中通过使用通式(I)化合物来产生膜中的至少一个层。膜可包含缺陷如孔。然而,这些缺陷通常构成膜所覆盖的表面积的小于一半。该膜优选为无机膜。为了产生无机膜,必须如上所述由膜除去所有有机配体。更优选地,该膜为元素态金属膜。膜可以具有0.1nm至1μm或更高的厚度,其取决于如上所述的成膜方法。优选地,该膜具有0.5-50nm的厚度。该膜优选具有非常均匀的膜厚度,这是指在基材的不同位置上的膜厚度变化非常小,通常小于10%,优选小于5%。此外,该膜优选为基材表面上的保形膜。用来确定膜厚度和均匀性的合适方法为XPS或椭圆偏振法。
可将本发明方法所得的膜用于电子元件中。电子元件可具有各种尺寸的结构特征,例如10nm至100μm,如100nm或1μm。形成电子元件的膜的方法特别适用于非常精细的结构。因此,优选尺寸小于1μm的电子元件。电子元件的实例为场效晶体管(FET)、太阳能电池、发光二极管、传感器或电容器。在光学器件如发光二极管或光传感器中,本发明的膜用于提高反射光的层的反射率。传感器的实例为氧传感器,例如如果制备金属氧化物膜,则膜可用作氧导体。在使用金属氧化物半导体的场效晶体管(MOS-FET)中,膜可用作介电层或扩散阻挡层。还可用膜来制造半导体层,其中在固体基材上沉积元素态的镍–硅。
优选的电子元件是晶体管。优选地,膜在晶体管中用作扩散阻挡层、接触、衬垫或覆盖层。锰或钴的扩散阻挡层特别可用于避免铜触点扩散至介电质,其通常用作自形成的铜阻挡层。如果晶体管由硅制成,则可在沉积镍或钴并加热之后,一些硅扩散至镍而形成例如NiSi或CoSi2。
附图简述
图1-4描述了实施例中的化合物的热重分析数据。
实施例
实施例1(对比例)
将NaN(SiMe3)2(7.34g,40.0mmol)在THF(40mL,-36℃)中的冷却溶液滴加至CoCl2(2.60g,20.0mmol)在THF(20mL,-36℃)中的冷却浆料中。观测到由蓝色至绿色的颜色变化。在室温下搅拌1小时后,在真空下除去所有挥发性物质。用戊烷(3×30mL)萃取深绿色固体,并滤过P3玻璃料。除去溶剂得到绿色晶体状的C-0(7.01g,77.5%)。双重升华(40℃/1mtorr)20小时分别获得分析纯样品。通过在-36℃下缓慢蒸发戊烷溶液获得用于X射线结晶解析的晶体。
1H-NMR(300MHz,C6D6):(ppm)=162.6(br,4H,CH2CH2O或CH2CH2O),97.0(br,4H,CH2CH2O或CH2CH2O),16.4(br,36H,SiMe3)。
元素分析:C16H44CoN2OSi4计算值:C,42.53;H,9.82;N,6.20。实测值:C,42.05;H,10.58;N,6.20。
C-0在102℃下具有1毫巴的蒸气压。在升华后,在蒸发处可观测到金属残余物。图1显示包括微分热重法(DTA)的热重量(TG)分析。在300℃下的残余质量为5.1%,最大DTA出现在159℃下。
实施例2
将溶于冷Et2O(2mL,-36℃)中的PMe3(0.25mL,2.42mmol)滴加至C-0(1.0g,2.21mmol)在Et2O(3mL,-36℃)中的冷却溶液中。未观测到颜色变化。在室温下搅拌16小时得到蓝绿色溶液。在真空下除去溶剂得到作为粗产物的C-1(966mg)。升华(75℃/1mtorr)14小时得到蓝绿色固体的分析级纯样品(608mg,60%)。通过在-36℃下缓慢蒸发戊烷溶液获得用于X射线结晶解析的晶体。
1H-NMR(300MHz,C6D6):(ppm)=168.8(br,9H,PMe3),24.2(br,36H,SiMe3)。
元素分析:C15H45CoN2PSi4计算值:C,39.53;H,9.95;N,6.15。实测值:C,39.04;H,10.43;N,5.97。
C-1在138℃下具有1毫巴的蒸气压。在升华后,未在蒸发处观测到残余物。图2显示TG和DTA。在300℃下的残余质量为14.1%,最大DTA出现在193℃下。
实施例3
将溶于冷Et2O(2mL,-36℃)中的P(i-Pr)3(0.35mL,1.77mmol)滴加至C-0(800mg,1.77mmol)在Et2O(3mL,-36℃)中的冷却溶液中。在室温下搅拌3天得到绿色溶液。在真空下除去溶剂得到作为粗产物的3。升华(80℃/1mtorr)17小时得到亮绿色固体的分析级纯样品(714mg,75%)。通过在-36℃下缓慢蒸发戊烷溶液得到用于X射线结晶解析的晶体。
1H-NMR(300MHz,C6D6):(ppm)=175.5(br,P(CH(CH3)2)3),31.7(br,18H,P(CH(CH3)2)3),19.6(br,36H,SiMe3)。
元素分析:C21H57CoN2PSi4计算值:C,46.71;H,10.64;N,5.19。实测值:C,46.01;H,11.72;N,5.08。
C-2在133℃下具有1毫巴的蒸气压。在升华后,未在蒸发处观测到残余物。图3显示TG和DTA。在300℃下的残余质量为14.3%,最大DTA出现在191℃下。
实施例4
将溶于冷Et2O(2mL,-36℃)中的PMe2t-Bu(0.25mL,1.80mmol)滴加至C-0(813mg,1.80mmol)在Et2O(3mL,-36℃)中的冷却溶液中。在室温下搅拌17小时得到绿色溶液。除去溶剂得到作为粗产物的C-3。升华(60℃/1mtorr)22小时得到绿色固体的分析级纯样品(545mg,51%)。通过在-36℃下缓慢蒸发戊烷溶液得到用于X射线结晶解析的晶体。
1H-NMR(300MHz,C6D6):(ppm)=152.1(br,6H,PMe2t-Bu),54.6(br,9H,PMe2t-Bu),21.8(br,36H,SiMe3)。
元素分析:C18H51CoN2PSi4计算值:C,43.42;H,10.33;N,5.63。实测值:C,41.00;H,9.94;N,5.85。
实施例5
将溶于冷Et2O(5mL,-36℃)中的Pi-Pr2t-Bu(0.28mL,1.30mmol)滴加至C-0(587mg,1.30mmol)在Et2O(3mL,-36℃)中的冷却溶液中。在室温下搅拌23小时得到绿色溶液。在真空下除去溶剂得到作为绿色油状物的C-4。在真空下干燥9小时得到绿色固体作为粗产物。升华(60℃/1mtorr)22小时得到绿色固体的分析级纯样品(320mg,44%)。通过在室温下缓慢蒸发戊烷溶液得到用于X射线结晶解析的晶体。
1H-NMR(300MHz,C6D6):(ppm)=120.8(br,P(CH(CH3)2)t-Bu),31.0(br,6H,P(CHCH3CH3)t-Bu或P(CHCH3CH3)t-Bu),27.5(br,9HP(CH(CH3)2)t-Bu),22.4(br,6H,P(CHCH3CH3)t-Bu或P(CHCH3CH3)t-Bu),16.5(br,36H,SiMe3)。
元素分析:C22H59CoN2PSi4计算值:C,46.70;H,10.96;N,4.80。实测值:C,47.70;H,10.74;N,5.06。
C-4在100℃下具有1毫巴的蒸气压。在升华后,未在蒸发处观测到残余物。图4显示TG和DTA。在300℃下的残余质量为3.3%,最大DTA出现在159℃下。
Claims (25)
2.根据权利要求1的方法,其中R3、R4和R5中的两个相同且第三个不同于其他两个,或者所有R3、R4和R5彼此不同。
3.根据权利要求1的方法,其中n为0,m为2和p为1。
4.根据权利要求2的方法,其中n为0,m为2和p为1。
5.根据权利要求1的方法,其中R1和R2为甲硅烷基。
6.根据权利要求2的方法,其中R1和R2为甲硅烷基。
7.根据权利要求3的方法,其中R1和R2为甲硅烷基。
8.根据权利要求4的方法,其中R1和R2为甲硅烷基。
9.根据权利要求1-8中任一项的方法,其中R3、R4和R5为甲基、乙基、异丙基或叔丁基。
10.根据权利要求1-8中任一项的方法,其中M为Co。
11.根据权利要求9的方法,其中M为Co。
12.根据权利要求1-8中任一项的方法,其中使通式(I)化合物化学吸附至固体基材的表面。
13.根据权利要求11的方法,其中使通式(I)化合物化学吸附至固体基材的表面。
14.根据权利要求1-8中任一项的方法,其中通过除去所有配体来分解经沉积的通式(I)化合物。
15.根据权利要求13的方法,其中通过除去所有配体来分解经沉积的通式(I)化合物。
16.根据权利要求14的方法,其中将经沉积的通式(I)化合物暴露于还原剂。
17.根据权利要求15的方法,其中将经沉积的通式(I)化合物暴露于还原剂。
18.根据权利要求14的方法,其中在固体基材上沉积通式(I)化合物以及分解经沉积的通式(I)化合物的序列进行至少两次。
19.根据权利要求15-17中任一项的方法,其中在固体基材上沉积通式(I)化合物以及分解经沉积的通式(I)化合物的序列进行至少两次。
22.根据权利要求21的化合物,其中M为Co,n为0,m为2和p为1。
23.根据权利要求21或22的化合物,其中R1和R2为甲硅烷基。
24.根据权利要求21或22的化合物,其中R3、R4和R5为甲基、乙基、异丙基或叔丁基。
25.根据权利要求23的化合物,其中R3、R4和R5为甲基、乙基、异丙基或叔丁基。
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JP2019500495A (ja) | 2019-01-10 |
TW201736632A (zh) | 2017-10-16 |
WO2017093283A1 (en) | 2017-06-08 |
IL259154A (en) | 2018-06-28 |
KR20180089466A (ko) | 2018-08-08 |
IL259154B (en) | 2022-01-01 |
EP3384063B1 (en) | 2019-09-18 |
SG11201803553UA (en) | 2018-06-28 |
EP3384063A1 (en) | 2018-10-10 |
US10669297B2 (en) | 2020-06-02 |
CN108495949A (zh) | 2018-09-04 |
TWI745318B (zh) | 2021-11-11 |
US20180346501A1 (en) | 2018-12-06 |
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