CN114729449A - 产生含金属或含半金属的膜的方法 - Google Patents
产生含金属或含半金属的膜的方法 Download PDFInfo
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- CN114729449A CN114729449A CN202080079413.7A CN202080079413A CN114729449A CN 114729449 A CN114729449 A CN 114729449A CN 202080079413 A CN202080079413 A CN 202080079413A CN 114729449 A CN114729449 A CN 114729449A
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- 238000000034 method Methods 0.000 claims abstract description 46
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
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- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
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Classifications
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- 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]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
-
- 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
- C23C16/06—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 deposition of metallic material
- C23C16/18—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 deposition of metallic material from metallo-organic compounds
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/28—Deposition of only one other non-metal element
-
- 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
Abstract
本发明属于制备含无机金属或含无机半金属的膜的方法的领域。制备含无机金属或含无机半金属的膜的方法包括:(a)将含金属或含半金属的化合物从气态沉积至固体基材上和(b)使具有沉积的含金属或含半金属的化合物的固体基材与通式(I)或(II)化合物接触;其中Z为NR2、PR2、OR、SR、CR2、SiR2,X为H、R’或NR’2,其中至少一个X为H,n为1或2,和R和R’为烷基、链烯基、芳基或甲硅烷基。
Description
本发明属于在基材上产生含无机金属或含无机半金属的膜的方法的领域,特别是原子层沉积方法。
随着例如在半导体产业中微型化的不断发展,对在基材上无机薄膜的需求增加,而对该类膜的质量要求变得更加严格。薄金属或薄半金属的膜用于不同目的,例如阻挡层、导电特征或覆盖层。数种产生金属或半金属的膜的方法为已知的。其中一种是将成膜化合物从气态沉积在基材上。为了使金属或半金属原子在适度的温度变为气态,必须提供挥发性前体,例如通过使金属或半金属与合适配体络合。这些前体对于蒸发而言必须足够稳定,但另一方面它们需要具有足够反应性以与沉积表面反应。
EP 1 788 116 A1公开了一种由二烷基酰胺基二氢铝前体沉积铝膜的方法。然而,用该方法无法得到铝膜以外的膜。
为了将沉积的金属或半金属配合物转化为金属或半金属膜,通常必须将沉积的金属或半金属配合物暴露于还原剂。通常,氢气用于将沉积的金属或半金属配合物转化为金属或半金属膜。虽然氢气可作为一些金属的还原剂,但它通常需要等离子体活化。等离子体方法受限于较低的纵横比,并且可导致基材等离子体受损。因此,希望使用不需要任何等离子体活化的还原剂。
WO 2019/201 692 A1公开了一种使用双环氢化铝化合物作为还原剂沉积金属膜的方法。虽然该还原剂通常产生良好的结果,对一些苛刻的应用而言,要求较高蒸气压、稳定性和/或还原电位。
因此,本发明的目的为提供一种制备膜中具有较少杂质的含无机金属或含无机半金属的膜的方法。方法材料应容易处理;特别地,应在尽可能少分解下使它们蒸发。此外,方法材料在方法条件下于沉积表面不应分解,但同时应具有足够的反应性以参与表面反应。所有反应副产物应挥发,以避免膜污染。此外,应可以调整方法,使得方法材料中的金属或半金属原子挥发或并入膜内。而且,该方法应是通用的,所以其可用于产生宽范围的不同金属(包括正电金属或半金属膜)。
这些目的通过制备含无机金属或含无机半金属的膜的方法实现,该方法包括:
(a)将含金属或含半金属的化合物从气态沉积至固体基材上,和
(b)使具有沉积的含金属或含半金属的化合物的固体基材与通式(I)或(II)化合物接触:
其中Z为NR2、PR2、OR、SR、CR2、SiR2,
X为H、R’或NR’2,其中至少一个X为H,
n为1或2,和
R和R’为烷基、链烯基、芳基或甲硅烷基。
本发明进一步涉及通式(I)或(II)化合物作为气相沉积方法中的还原剂的用途。
本发明的优选实施方案可见于说明书和权利要求书中。不同实施方案的组合落入本发明范围内。
根据本发明的方法适合用于制备含无机金属或含无机半金属的膜。在本发明的上下文中,无机是指含有至少5重量%,优选至少10重量%,更优选至少20重量%,特别是至少30重量%的至少一种金属或半金属的材料。无机膜通常仅以碳化物相的形式含有碳,所述碳化物相包括混合的碳化物相如氮化物碳化物相。无机膜中不是碳化物相的一部分的碳的碳含量优选小于5重量%,更优选小于1重量%,特别是小于0.2重量%。含无机金属或含无机半金属的膜的优选实例为金属或半金属氮化物膜、金属或半金属碳化物膜、金属或半金属碳氮化物膜、金属或半金属合金膜、金属间化合物膜或含有其混合物的膜。
通过根据本发明的方法制备的膜含有金属或半金属。膜含有一种金属或半金属或超过一种金属和/或半金属是可能的。金属包括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。半金属包括B、Si、Ge、As、Sb、Se、Te。优选地,金属或半金属具有每个氧原子的氧化物形成能,其比Ni具有更高的放热性。特别地,金属或半金属为Ti、Ta、Mn、Mo、W、Ge、Ga、As、In、Sb、Te、Al或Si。
固体基材可为任何固体材料。这些包括例如金属、半金属、氧化物、氮化物和聚合物。基材也可能为不同材料的混合物。金属的实例为铝、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、二氧化钛和氧化锌。氮化物的实例为氮化硅、氮化铝、氮化钛和氮化镓。聚合物的实例为聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)和聚酰胺。
固体基材可具有任何形状。这些包括薄板、膜、纤维、各种尺寸的颗粒和具有沟槽或其它凹痕的基材。固体基材可具有任何尺寸。如果固体基材具有颗粒形状,则颗粒尺寸可在100nm以下至数厘米的范围,优选为1μm至1mm。为了避免在将含金属或含半金属的化合物沉积在颗粒或纤维上时,颗粒或纤维彼此粘附,优选使其保持移动。这例如可以通过搅拌、转鼓或流化床技术而实现。
根据本发明的方法包括(a)将含金属或含半金属的化合物从气态沉积至固体基材上。含金属或含半金属的化合物含有至少一种金属或半金属原子。金属包括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。半金属包括B、Si、Ge、As、Sb、Se、Te。优选地,金属或半金属具有每个氧原子的氧化物形成能,其具有比Ni更高的放热性。特别地,含金属或含半金属的化合物含有Ti、Ta、Mn、Mo、W、Ge、Ga、As、In、Sb、Te、Al或Si。超过一种含金属或含半金属的化合物同时地或连续地沉积在表面上是可能的。如果超过一种含金属或含半金属的化合物沉积在固体基材上,则含金属或含半金属的化合物含有相同金属或半金属或不同的是可能的,优选其含有不同的金属或半金属。
可以变成气态的任何含金属或含半金属的化合物是合适的。这些化合物包括金属或半金属烷基,例如二甲基锌、三甲基铝;金属烷氧基化物,例如四甲氧基硅、四异丙氧基锆或四异丙氧基钛;金属或半金属环戊二烯基配合物如五甲基环戊二烯基-三甲氧基钛或二(乙基环戊二烯基)锰;金属或半金属碳烯,例如三(新戊基)亚新戊基钽或双亚咪唑烷基钌氯化物;金属或半金属卤化物,例如三氯化铝、五氯化钽、四氯化钛、五氯化钼、四氯化锗、三氯化镓、三氯化砷或六氯化钨;一氧化碳配合物如六羰基铬或四羰基镍;胺配合物,例如双(叔丁基亚氨基)双(二甲基酰胺基)钼、双(叔丁基亚氨基)双(二甲基酰胺基)钨或四(二甲基酰胺基)钛;二酮酸盐配合物,例如三(乙酰丙酮根合)铝或双(2,2,6,6-四甲基-3,5-庚二酮根合)锰。优选金属或半金属卤化物,特别是氯化铝、溴化铝和碘化铝。优选含金属或含半金属的化合物的分子量为至多1000g/mol,更优选至多800g/mol,特别是至多600g/mol,例如至多500g/mol。
如果根据本发明的方法中基材温度保持在低于含金属或含半金属的化合物的分解温度,则通常在固体基材上沉积单层。一旦含金属或含半金属的化合物的分子沉积在固体基材上,通常在其顶部的进一步沉积变得较不有利的。因此,含金属或含半金属的化合物在固体基材上的沉积优选代表自限制性方法步骤。自限制性沉积方法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。层厚度通常通过PAS1022DE(Referenzverfahren zur Bestimmung von optischen und dielektrischenMaterialeigenschaften sowie der Schichtdicke dünner Schichten mittelsEllipsometrie;2004年2月)所述的椭圆偏振法测量。
根据本发明的方法包括(b)使具有沉积的含金属或含半金属的化合物的固体基材与通式(I)或(II)化合物接触。Z为NR2、PR2、OR、SR、CR2、SiR2,优选NR2、PR2、OR、SR,特别是NR2或PR2。Z可全部相同或彼此不同,优选它们相同。X为H、R’或NR’2,其中至少一个X为H,优选各Al原子的至少一个X为H,特别是所有的X为H、或各Al原子的一个X为H且其它X为NR’2或R’。在本发明的上下文中,H包括氢的所有同位素,特别是1H和2H。后者还称为氘D。取决于Z,指数n可为1或2。通常,如果Z为NR2、PR2、OR、SR,则n为2,且如果Z为CR2、SiR2,则n为1。
通式(I)或(II)化合物中的R和R’为烷基、链烯基、芳基或甲硅烷基,优选烷基或甲硅烷基,特别是甲基、乙基、异丙基、仲丁基、叔丁基、三甲基甲硅烷基。R和R’可相同或彼此不同,优选地,所有R相同,优选所有R’相同,特别是所有R和R’相同。两个R可一起形成环,优选3-8员环,特别是5或6员环。
烷基可为直链或支化的。直链烷基的实例为甲基、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、新戊基、2-乙基-己基、环丙基、环己基、二氢茚基、降冰片烷基。优选地,烷基为C1-C8烷基,更优选C1-C6烷基,特别是C1-C4烷基,例如甲基、乙基、异丙基或叔丁基。
链烯基含有至少一个碳-碳双键。双键可包括R或R’键合于分子的其余部分所用的碳原子,或其可位于较远离R或R’键合于分子的其余部分的位置。链烯基可为直链或支化的。直链链烯基(其中双键包括R或R’键合于分子的其余部分所用的碳原子)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。直链链烯基(其中双键位于较远离R或R’键合至分子的其余部分的位置)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、1-己烯-6-基。支化链烯基(其中双键包括R或R’键合于分子的其余部分所用的碳原子)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(其中双键位于较远离R或R’键合于分子的其余部分的位置)的实例包括2-甲基-1-丁烯-4-基、环戊烯-3-基、环己烯-3-基。具有超过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、环戊二烯-5-基。
芳基包括芳族烃如苯基、萘基、蒽基、菲基和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。数种这些基团或这些基团的组合也是可能的,如联苯、噻吩并苯基或呋喃基噻吩基。芳基可例如经卤素(如氟、氯、溴、碘);经拟卤素(如氰化物、氰酸酯、硫氰酸酯);经醇;经烷基链或烷氧基链取代。优选芳族烃,更优选为苯基。
甲硅烷基为典型地具有三个取代基的硅原子。优选地,甲硅烷基具有式SiE3,其中E彼此独立地为氢、烷基、芳基或甲硅烷基。可能所有三个E相同,或两个E相同且其余E不同,或所有三个E彼此不同,优选所有E相同。烷基和芳基如上文所描述。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、五甲基二甲硅烷基。
优选地,通式(I)化合物为以下通式中的一个。
通式(I)化合物的就这些通式而言的优选实例给于下表中。
Me代表甲基,Et代表乙基,-(CH2)2-代表由两个R形成的亚乙基,-(CH2)4-代表由两个R形成的亚丁基。
一些通式(I)化合物的合成描述于例如E.Ashby等,Inorganic Chemistry,第10卷(1971),893-899页或I.Krossing等,Zeitschrift fürNaturforschung B,第63卷(2008),1045-1051页。
优选地,通式(II)化合物为以下通式中的一个。
通式(II)化合物就这些通式而言的优选实例给于下表中。
Me代表甲基,Et代表乙基,-(CH2)2-代表由两个R形成的亚乙基,-(CH2)4-代表由两个R形成的亚丁基。
一些通式(II)化合物的合成描述于例如K.Ouzounis等,Zeitschrift fuerAnorganische und Allgemeine Chemie,第504卷(1983),第67-76页或A.Storr等,Journalof the Chemical Society,Dalton Transactions:Inorganic Chemistry(1972-1999),1972,第326-330页。
优选地,R在1-位不具有氢原子,即R不具有键合于与氮或氧原子键合的原子上的氢原子,其因此相对于铝原子处于β-位。还优选地,R’在1-位不具有氢原子。更优选地,R和R’在1-位均不具有氢原子。实例为在1-位具有两个烷基侧基的烷基,即1,1-二烷基烷基,例如叔丁基、1,1-二甲基丙基;在1-位具有两个卤素的烷基,例如三氟甲基、三氯甲基、1,1-二氟乙基;三烷基甲硅烷基,例如三甲基甲硅烷基、三乙基甲硅烷基、二甲基-叔丁基甲硅烷基;芳基,特别是苯基或烷基取代的苯基,例如2,6-二异丙基苯基、2,4,6-三异丙基苯基。在1-位不具有氢原子的烷基为特别优选的。
通式(I)或(II)化合物优选具有不大于1000g/mol,更优选不大于800g/mol,甚至更优选不大于600g/mol,特别是不大于500g/mol的分子量。
优选地,通式(I)或(II)化合物具有-80至125℃,优选-60至80℃,甚至更优选-40至50℃,特别是-20至20℃的熔点。有利的是通式(I)或(II)化合物熔化而获得澄清液体,该液体在分解温度前维持不变。
优选地,通式(I)或(II)化合物具有至少80℃,更优选至少100℃,特别是至少120℃,例如至少150℃的分解温度。通常,分解温度不大于250℃。通式(I)或(II)化合物具有高蒸气压。优选地,蒸气压在200℃,更优选150℃,特别是120℃的温度下为至少1毫巴。通常,蒸气压为1毫巴时的温度为至少50℃。
根据本发明的方法中所用通式(I)或(II)化合物在高纯度下使用以获得最佳结果。高纯度意指所用物质含有至少90重量%,优选至少95重量%,更优选至少98重量%,特别是至少99重量%含金属或含半金属的化合物或通式(I)或(II)化合物。纯度可根据DIN51721通过元素分析测定(Prüfung fester Brennstoffe-Bestimmung des Gehaltes anKohlenstoff und Wasserstoff-Verfahren nach Radmacher-Hoverath,2001年8月)。
使通式(I)或(II)化合物从气态与固体基材接触。例如可通过将其加热至高温而变成气态。在任何情况下必须选择通式(I)或(II)化合物的分解温度以下的温度。分解温度为通式(I)或(II)原始化合物开始改变其化学结构和组成的温度。优选地,加热温度在0℃至300℃,更优选在10℃至250℃,甚至更优选在20℃至200℃,特别是在30℃至150℃范围内。
另一种使通式(I)或(II)化合物变为气态的方法为例如在US 2009/0 226612A1中所述的直接液体喷射(DLI)。在该方法中,通式(I)或(II)化合物典型地溶解于溶剂中且喷洒在载气或真空中。如果通式(I)或(II)化合物的蒸气压力和温度足够高且压力足够低,使通式(I)或(II)化合物变为气态。可使用各种溶剂,条件为通式(I)或(II)化合物在该溶剂中显示足够的溶解度,例如至少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、二噁烷、二乙氧基乙烷、吡啶或非配位溶剂,例如己烷、庚烷、苯、甲苯或二甲苯。溶剂混合物也是合适的。
作为替换,可通过如例如由J.Yang等(Journal of Materials Chemistry,2015)所述的直接液体蒸发(DLE)使通式(I)或(II)化合物变为气态。在该方法中,使通式(I)或(II)化合物与溶剂(例如烃如十四烷)混合,且在溶剂的沸点以下加热。通过蒸发溶剂,使通式(I)或(II)化合物变为气态。该方法具有在表面上无颗粒污染物形成的优势。
优选在减压下使通式(I)或(II)化合物变为气态。以该方式,该方法可通常在较低加热温度下进行,导致通式(I)或(II)化合物分解减少。还可使用加压以将呈气态的通式(I)或(II)化合物推向固体基材。通常,出于该目的,惰性气体(例如氮气或氩气)用作载气。优选地,压力为10巴至10-7毫巴,更优选1巴至10-3毫巴,特别是1-0.01毫巴,例如0.1毫巴。
具有通式(I)或(II)化合物或含金属或含半金属的化合物的基材的暴露可能需要数毫秒至数分钟,优选0.1秒至1分钟,特别是1-10秒。固体基材在通式(I)或(II)化合物或含金属或含半金属的化合物的分解温度以下的温度下暴露于通式(I)或(II)化合物或含金属或含半金属的化合物越长,则形成缺陷越少的更规则膜。
优选地,通式(I)或(II)化合物在该方法中作为还原剂起作用。在该情况下,在使其与通式(I)或(II)化合物接触前,使含金属或含半金属的化合物从气态沉积在固体基材上。通常将含金属或含半金属的化合物还原成金属、金属氮化物、金属碳化物、金属碳氮化物、金属合金、金属间化合物或其混合物,其中金属或半金属在还原后具有比以前较低的氧化态。在本发明的上下文中,金属膜为具有高电导率的含金属或含半金属的膜,通常为至少104S/m,优选至少105S/m,特别是至少106S/m。
通式(I)或(II)化合物与具有沉积的含金属或含半金属的化合物的固体基材表面形成永久结合的倾向低。因此,含金属或含半金属的膜具有来自并入通式(I)或(II)化合物的反应副产物的杂质含量。优选地,含金属或含半金属的膜总共含有小于5重量%,更优选小于1重量%,特别是小于0.5重量%,例如小于0.2重量%氮。
根据本发明的方法的特定优势为通式(I)或(II)化合物极具通用性,因此方法参数可在宽范围中变化。因此,根据本发明的方法包括CVD方法以和ALD方法二者。
优选地,包括(a)和(b)的序列进行至少2次,更优选至少5次,甚至更优选至少10次,特别是至少50次。通常,包括(a)和(b)的序列进行不超过1000次。
通常,每次当固体基材暴露于气态形成的含金属或含半金属的化合物或通式(I)或(II)化合物时,优选用惰性气体吹扫基材和其周围的设备。惰性气体的优选实例为氮气和氩气。吹扫可进行1秒至1分钟,优选5-30秒,更优选10-25秒,特别是15-20秒。
优选地,基材温度比使含金属或含半金属的化合物变成气态处高5-40℃,例如20℃。优选地,基材温度为室温至400℃,更优选100-300℃,例如150-220℃。
优选地,在将含金属或含半金属的化合物沉积在固体基材上后且在使具有沉积的含金属或含半金属的化合物的固体基材与通式(I)或(II)化合物接触前,使具有沉积的含金属或含半金属的化合物的固体基材与气相中的酸接触。不受理论的束缚,据信含金属或半金属化合物的配体的质子化有助于其分解和还原。合适的酸包括盐酸和羧酸,优选羧酸,例如甲酸、乙酸、丙酸、丁酸或三氟乙酸,特别是甲酸。
根据本发明的方法得到含无机金属或含无机半金属的膜。膜可仅为一个金属单层或可更厚,例如0.1nm至1μm,优选0.5-50nm。膜可含有缺陷如孔。然而,这些缺陷通常构成低于一半由膜覆盖的表面积。膜优选具有非常均匀的膜厚度,其意指在基材上的不同位置处的膜厚度变化极小,通常小于10%,优选小于5%。此外,膜优选为基材表面上的保形膜。测定膜厚度和均匀性的合适的方法为XPS或椭圆偏振法。
通过根据本发明的方法获得的膜可用于电子元件中。电子元件可具有各种尺寸的结构特征,例如1nm至100μm,例如10nm、14nm或22nm。形成用于电子元件的膜的方法特别适用于非常精细的结构。因此,优选尺寸在1μm以下的电子元件。电子元件的实例为场效晶体管(FET)、电荷捕获存储单元、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感光器中,通过根据本发明的方法获得的膜用于提高反射光的层的折射率。
优选的电子元件为晶体管。优选地,膜作为晶体管中的化学阻挡金属起作用。化学阻挡金属为在保持电连接性的同时减少相邻层扩散的材料。
实施例
实施例1
使用作为含半金属的化合物的GeBr4和化合物IIa-1进行原子层沉积方法。这些化合物各自包含在不锈钢圆筒中,并连接至具有1英寸直径沉积面积和5sccm的Ar(5N)载气流的错流ALD反应器。基本压力为约50Pa。将GeBr4加热至55℃且将化合物IIa-1加热至75℃。进行100次ALD循环,每次循环包括100ms GeBr4暴露、第一次7.9秒吹扫、100ms化合物IIa-1暴露和第二7.9秒吹扫的序列,并通过原位石英结晶微量天平(QCM)进行监测。在160-200℃的反应器温度下,观测到平均QCM频率变化为-1Hz/周期,显示稳定质量增长,并且存在与温度无关的增长率的ALD窗。GeBr4暴露导致质量增加,而通过随后用化合物IIa-1暴露而质量降低,显示化合物IIa-1与通过GeBr4暴露产生的表面的特定反应性,但没有化合物IIa-1沉积。
实施例2
使用与实施例1相同的设备、化合物和ALD循环。将具有原生氧化物表面或100nm热氧化物表面的空白硅晶片基材置于反应器中并保持在160℃的温度下。进行如实施例1所述的1000次ALD循环并在从反应器移除基材后对其分析。将通过椭圆偏振法测定约14nm厚度的层沉积在原生氧化物晶片基材上。根据AFM分析,发现沉积在热氧化物基材上的类似ALD层的均方根粗糙度为2nm
实施例3
使用与实施例1相同的设备。使用作为含半金属的化合物的GeCl4和化合物IIa-1。GeCl4包含在不锈钢圆筒中并在ALD方法中保持在0℃下。进行100次ALD循环,每次循环包括20ms GeCl4暴露、7.98秒吹扫、100ms化合物IIa-1暴露和7.9秒吹扫的序列,并通过原位石英结晶微量天平(QCM)监控。在140℃的反应器温度下,平均QCM频率变化为-0.4Hz/循环,显示稳定质量增加。GeCl4暴露导致质量增加,而通过随后通过化合物IIa-1暴露而质量降低,显示化合物IIa-1与通过GeCl4暴露产生表面的特定反应性,但没有化合物IIa-1沉积。
Claims (10)
2.根据权利要求1所述的方法,其中R为甲基、乙基、异丙基、仲丁基、叔丁基、三甲基甲硅烷基。
3.根据权利要求1或2所述的方法,其中各Al原子的至少一个X为H。
4.根据权利要求1-3中任一项所述的方法,其中Z为NR2、PR2、OR或SR。
5.根据权利要求1-4中任一项所述的方法,其中含金属或含半金属的化合物含有Ti、Ta、Mn、Mo、W、Ge、Ga、As、In、Sb、Te、Al或Si。
6.根据权利要求1-5中任一项所述的方法,其中含金属或含半金属的化合物为金属或半金属卤化物。
7.根据权利要求1-6中任一项所述的方法,其中含有(a)和(b)的序列进行至少两次。
8.根据权利要求1-7中任一项所述的方法,其中通式(I)或(II)化合物具有不大于600g/mol的分子量。
9.根据权利要求1-8中任一项所述的方法,其中通式(I)或(II)化合物在200℃的温度下具有至少1毫巴的蒸气压。
10.通式(I)或(II)化合物作为气相沉积方法中的还原剂的用途。
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CN101029384A (zh) * | 2005-11-16 | 2007-09-05 | 罗门哈斯公司 | 二烷基氨基二氢化铝化合物的薄膜汽相淀积法 |
CN107406981A (zh) * | 2015-03-12 | 2017-11-28 | 巴斯夫欧洲公司 | 产生薄无机膜的方法 |
WO2017093265A1 (en) * | 2015-11-30 | 2017-06-08 | Basf Se | Process for the generation of metallic films |
CN109844172A (zh) * | 2016-10-13 | 2019-06-04 | 巴斯夫欧洲公司 | 生产含金属膜的方法 |
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