CN100393777C - 硅氧烷基树脂及用其制造的半导体的层间绝缘膜 - Google Patents
硅氧烷基树脂及用其制造的半导体的层间绝缘膜 Download PDFInfo
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- CN100393777C CN100393777C CNB2004100617351A CN200410061735A CN100393777C CN 100393777 C CN100393777 C CN 100393777C CN B2004100617351 A CNB2004100617351 A CN B2004100617351A CN 200410061735 A CN200410061735 A CN 200410061735A CN 100393777 C CN100393777 C CN 100393777C
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- siloxane
- based resin
- solvent
- monomer
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- 239000011229 interlayer Substances 0.000 title abstract description 5
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2962—Silane, silicone or siloxane in coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2995—Silane, siloxane or silicone coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
本发明公开了一种具有新型结构的硅氧烷基树脂,以及用它形成的半导体的层间绝缘膜。该硅氧烷基树脂除了具有优异的机械性能之外,还具有如此低的介电常数,以至于它们可用作半导体器件互连层之间的绝缘膜材料。
Description
按照35U.S.C.§119(a),本非临时申请要求2003年7月1日提交的韩国专利申请Kr2003-44119号的优先权,并将其内容在此引入作为参考。
技术领域
本发明主要涉及一种硅氧烷基树脂及用其制造的半导体的层间绝缘膜(interlayer insulating film)。更具体地,本发明涉及一种具有全新结构的硅氧烷基树脂,其可以用来制造半导体的层间绝缘膜。
背景技术
随着多级集成电路器件中电路密度的增加,器件的性能开始依赖于线路速率(line rate)。所以,需要通过降低器件中的绝缘膜的容量的方法来降低线路的电阻和电容。具体地,美国专利US3615272、4399266、4756977和US4999397公开了使用聚倍半硅氧烷,通过SOD(旋涂沉积)法来制造绝缘膜,该聚倍半硅氧烷具有2.5~3.1的介电常数和良好的平坦化性质。
氢化倍半硅氧烷及其制备方法在本领域是公知的。美国专利US3615272公开了制备完全缩合的可溶性氢化倍半硅氧烷树脂的方法,该方法包括通过在硫酸介质中缩合三氯甲烷硅,然后用水或硫酸的水溶液洗涤生成的树脂的步骤。美国专利US5010159也公开了合成可溶的、缩合的氢化硅树脂的方法,其包含在含有芳基磺酸水合物的水解介质中水解氢化硅烷以及使得到的树脂与中和剂接触的步骤。美国专利US6232424描述了高可溶的硅树脂组合物,具有非常好的溶液稳定性,该硅树脂组合物是通过在水及催化剂存在下,水解和缩聚四烷氧基硅烷、有机硅烷和有机三烷氧基硅烷的单体来制备的。美国专利US6000339描述了有助于改进对氧等离子体的抵抗、物理性质以及涂层膜的厚度的二氧化硅基的化合物,可以在水和催化剂存在下,使选自烷氧基硅烷、含氟烷氧基硅烷和烷基烷氧基硅烷的单体与钛或锆-醇盐化合物反应而获得。美国专利US5853808描述了有助于形成富SiO2陶瓷涂层的硅氧烷和倍半硅氧烷聚合物,该聚合物可以通过水解和缩聚具有有β-取代的烷基的有机硅烷来制备。同时,EP0997497A1公开了包含单、二、三、四烷氧基硅烷的烷氧基硅烷和三烷氧基硅烷二聚物某种结合的水解和缩聚,可以提供用于绝缘膜的树脂材料。
发明内容
本发明的特征在于制造具有优越的机械性能和非常低的介电常数(verylow dielectric constant)的硅氧烷基树脂,和使用该硅氧烷基树脂形成低介电绝缘膜。
一方面,本发明涉及了一种硅氧烷基树脂,其通过在有机溶剂中及,在酸或碱催化剂和水存在下,水解和缩合下面式1的具有放射结构(radialstructure)的硅烷基单体和选自下面式2~4中的至少一种单体来制备:
式1
Si[(CH2)kSiY1Y2Y3]4
其中,
k是1到10的整数;
Y1、Y2和Y3独立地为C1-C3烷基,C1-C10烷氧基、或卤素原子,条件是它们中至少有一个是可以水解的;
式2
其中,
R1是C1-C3烷基或C6-C15芳基;
X1、X2和X3独立地为氢原子、C1-C3烷基、C1-C10烷氧基、或卤素原子,条件是它们中至少有一个是可以水解的;
m是0-10的整数;以及
p是3-8的整数;
式3
其中,
R2是C1-C3烷基或C6-C15芳基;
X4是氢原子或C1-C10烷氧基;
Y1是氢原子、C1-C3烷基或C1-C10烷氧基;以及
n是0-10的整数;
式4
R3SiX5X6X7
其中,
R3是C1-C3烷基或C6-C15芳基;
X5、X6和X7独立地为氢原子、C1-C3烷基、C1-C10烷氧基或卤素原子,条件是它们中至少有一个是可以水解的。
另一方面,本发明还涉及制备半导体的层间绝缘膜的方法,该方法包括下列步骤:通过将硅氧烷基树脂溶解在有机溶剂中,提供树脂溶液;用该树脂溶液涂布硅片;热固化得到的涂层膜。
本发明的再一方面涉及使用上述的硅氧烷基树脂制造的层间绝缘膜。
优选实施方式
下文中,将在实施例中详细解释本发明。
本发明是通过缩合式1的放射(radial)硅烷基单体和选自式2-4的化合物中的至少一种化合物,来制备高溶解性的硅氧烷基树脂。
该硅氧烷基树脂具有3.0或更低的介电常数,所以它很适合于低介电的涂层膜。
而且,本发明还提供了通过用含有上述硅氧烷基树脂的溶液涂布硅片,该硅氧烷基树脂在有机溶剂中,并热固化得到的涂层膜,而制备绝缘膜的方法。
同时,根据本发明,将成孔剂(porogen)和本发明的硅氧烷基树脂结合使用将进一步降低最终的绝缘膜的介电常数至2.5或更低。
式1
Si[(CH2)kSiY1Y2Y3]4
其中,
k是1到10的整数;
Y1、Y2和Y3独立地为C1-C3烷基,C1-C10烷氧基或卤素原子,条件是它们中至少有一个是可以水解的。
式2
其中,
R1是C1-C3烷基或C6-C15芳基;
X1、X2和X3独立地为氢原子、C1-C3烷基、C1-C10烷氧基或卤素原子,条件是它们中至少有一个是可以水解的;
m是0-10的整数;以及
p是3-8的整数。
式3
其中,
R2是C1-C3烷基或C6-C15芳基;
X4是氢原子或C1-C10烷氧基;
Y1是氢原子、C1-C3烷基或C1-C10烷氧基;以及
n是0-10的整数。
式4
R3SiX5X6X7
其中,
R3是C1-C3烷基或C6-C15芳基;
X5、X6和X7独立地为氢原子、C1-C3烷基、C1-C10烷氧基或卤素原子,条件是它们中至少有一个是可以水解的。在制备这种硅氧烷基树脂时,以摩尔比为1∶99-99∶1混合式1单体和选自式2-4表示的化合物中的单体。
用于制备本发明的硅氧烷基树脂的优选的酸或碱催化剂可以列举但不限于:盐酸、硝酸、苯磺酸、草酸、甲酸、氢氧化钾、氢氧化钠、三乙胺、碳酸氢钠和吡啶。使用该催化剂,使得催化剂与单体的摩尔比为0.000001∶1-10∶1。
在本发明的硅氧烷基树脂的制备中,相对于1摩尔的单体,水的用量为1-1000摩尔,使得水与单体的摩尔比为1∶1-1000∶1。
在本发明的硅氧烷基树脂的制备中,使用的有机溶剂的非限定性实例包括脂肪族烃溶剂,如己烷;芳烃溶剂,如苯甲醚、1,3,5-三甲基苯和二甲苯;酮类溶剂如甲基异丁基酮、1-甲基-2-吡咯烷酮(pyrrolidinone)、环己酮和丙酮;醚类溶剂如四氢呋喃和异丙醚;乙酸酯类溶剂如乙酸乙酯、乙酸丁酯和丙二醇甲基醚乙酸酯;醇类溶剂如异丙醇和丁醇;酰胺类溶剂如二甲基乙酰胺和二甲基甲酰胺;硅类溶剂及其混合物。
根据本发明,在0-200℃,优选50-110℃下,进行水解和缩聚反应0.1-100小时,优选5-48小时。
这样制备的硅氧烷基树脂的Mw为3000-300,000。在所有端基中Si-OR含量超过5摩尔%。
本发明还提供了使用本发明的硅氧烷基树脂形成用于半导体器件的层间绝缘膜的方法。该绝缘膜具有低于3.0的低介电性质,而且显示出卓越的机械性能和耐热性能。根据本发明,这种绝缘膜是通过用含有本发明的硅氧烷基树脂的溶液涂布硅片,该硅氧烷基树脂溶在有机溶剂中,并热固化得到的涂层膜而获得的。也就是说,将溶解在有机溶剂中的本发明的硅氧烷基树脂涂布到基材上。然后,通过简单常温干燥,或在接下来的热固化步骤的开始,通过使基材处于真空条件或在200℃或更低温度下适度加热,蒸发有机溶剂,使得树脂涂层膜可以沉积在基材的表面上。由此,通过在150~600℃,优选200~450℃加热基材1~150分钟,使树脂涂层膜固化,以便获得不溶、无裂纹膜。如在此使用的,“无裂纹膜”指没有任何使用光学显微镜,在放大率1000X下可以观察到裂纹的膜。如在此使用的,“不溶膜”指基本不溶于被描述用于溶解本发明的硅氧烷基树脂的任何溶剂的膜。
根据本发明,成孔剂(porogen)与本发明的硅氧烷基树脂结合使用,可以进一步降低最终绝缘膜的介电常数至2.50或更低。如在此使用的,“成孔剂”指产生孔的(pore-generating)任何化合物。在使用成孔剂的情况下,需要加热树脂膜至成孔剂的分解温度上的附加步骤,使得成孔剂可以分解。
用于本发明的成孔剂可以是本领域众所周知的任何产生孔的化合物,其非限定性实例为环糊精、聚己内酯,及其衍生物。基于硅氧烷基树脂的固体含量,以1~70重量%的含量混合成孔剂。
溶解硅氧烷基树脂或成孔剂,来提供液态涂布组合物的溶剂的非限定性实例优选为:脂肪族烃溶剂,如己烷;芳烃溶剂,如苯甲醚、1,3,5-三甲苯和二甲苯;酮类溶剂如甲基异丁基酮、1-甲基-2-吡咯烷酮、环己酮和丙酮;醚类溶剂如四氢呋喃和异丙醚;乙酸酯类溶剂如乙酸乙酯、乙酸丁酯和丙二醇甲基醚乙酸酯;醇类溶剂如异丙醇、丁醇;酰胺类溶剂如二甲基乙酰胺、二甲基甲酰胺;硅类溶剂及其混合物。
在液体涂布组合物的制备中,包含硅氧烷基树脂和成孔剂的固体成分优选为全部组合物的5-70重量%。而有机溶剂的用量应足以将包含硅氧烷基树脂和成孔剂的固体成分均匀涂布到晶片(wafter)的表面。有机溶剂的用量应该为液体涂布组合物的20-99.9重量%,优选为70-95重量%。如果在液体涂布组合物中有机溶剂的含量低于20重量%,那么就会有部分的硅氧烷基树脂没有被溶解。相反,如果有机溶剂的含量高于99.9重量%,最终树脂膜的厚度将薄至1000或更薄。
在本发明中,可以使用本领域中公知的各种涂布方法,将由此获得的液态涂布组合物涂布到硅片上。可用于本发明的涂布方法的非限定性实例包括:旋涂、浸涂、喷涂、流涂(flow coating)和丝网印刷,同时最优选旋涂。
下文中,参考下面的实施例,可以更清楚地理解本发明。应该理解,下面的实施例并不被解释为以任何方式限制本发明的范围。
实施例1:单体的合成
实施例1-1:单体(A)的合成
单体(A)
Si[CH2CH2SiCH3(OCH3)2]4
将73.384毫摩尔(10.0克)四乙烯基硅烷和0.2克的铂(0)-1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷的络合物(二甲苯中的溶液)引入烧瓶中,用300毫升的四氢呋喃稀释。然后,烧瓶冷却到-78℃,缓慢加入322.888毫摩尔(37.145克)的二氯甲基硅烷,然后反应温度逐步的回升到室温,反应在室温下继续进行40个小时,然后在0.1托的减压下将反应混合物中的挥发材料除去。向反应混合物中加入100毫升的己烷并且搅拌一个小时,然后用硅藻土过滤,得到无色澄清的溶液。然后在0.1托的减压下从得到的溶液中除去己烷,得到由下面分子式表示的液态化合物:
Si[CH2CH2SiCH3Cl2]4
16.778毫摩尔(10.0克)的上述液体化合物用500毫升的四氢呋喃稀释,向其中加入150.999毫摩尔(15.28克)的三乙胺。然后,将反应温度冷却到-78℃,向反应溶液中缓慢的加入150.999毫摩尔(4.83克)的甲醇,然后反应温度逐渐回升到室温。反应在室温下继续进行15小时,然后用硅藻土过滤,然后在大约0.1托的减压下,将挥发材料从滤出液中蒸出。
将所得溶液中加入100毫升的己烷并搅拌1小时,然后用硅藻土过滤。将搅拌溶液过滤得到的滤出液置于减压下除去己烷,得到单体(A)的无色液体。溶解在CDCl3的单体(A)的NMR分析的结果如下:
1H NMR(300MHz)数据;δ0.09(s,12H,4×-CH3),
0.48-0.54(m,16H,4×-CH2CH2-),
3.53(s,24H,4×-[OCH3]2)
实施例1-2:单体(B)的合成
单体(B)
29.014毫摩尔(10.0克)的2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷和0.164克的铂(O)-1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷的络合物(二甲苯中的溶液)引入烧瓶中,用300毫升的二***稀释。然后,烧瓶冷却到-78℃,缓慢的加入127.66毫摩尔(17.29克)的三氯硅烷,随后反应温度逐步的回升到室温。反应在室温下继续进行40个小时,然后在0.1托的减压下从反应混合物中除去挥发材料。所得溶液中加入100毫升的己烷并且搅拌1小时,然后用硅藻土过滤。在0.1托的减压下,将搅拌溶液过滤得到的滤出液减压除去其中的己烷,得到由下式代表的液体化合物:
11.28毫摩尔(10.0克)上述液态化合物用500毫升的四氢呋喃稀释,向其中加入136.71毫摩尔(13.83克)的三乙胺。然后,将反应温度降到-78℃,向反应溶液中缓慢加入136.71毫摩尔(4.38克)的甲醇,随后反应温度逐步的回升到室温。反应在室温下继续进行15个小时,用硅藻土过滤反应溶液,然后在0.1托左右的减压下从滤出液中除去挥发材料。向剩下的滤出液中加入100毫升的己烷并且搅拌1小时,然后用硅藻土过滤。向得到的滤出液中再加入5克活性炭,继续搅拌10小时,然后用硅藻土过滤。然后,减压下从滤出液中除去己烷,得到单体(B)的无色液体。溶解在CDCl3的单体(B)的NMR分析结果如下:
1H NMR(300MHz)数据;δ0.09(s,12H,4×-CH3),
0.52-0.64(m,16H,4×-CH2CH2-),
3.58(s,36H,4×-[OCH3]3)
实施例1-3:硅氧烷基单体(C)的合成
单体(C)
249.208毫摩尔(10.0克)的1,3-二氯四甲基二硅氧烷引入烧瓶中,用500毫升的四氢呋喃稀释。随后将烧瓶冷却到-78℃,加入108.212毫摩尔(10.95克)的三乙胺。然后,向烧瓶中缓慢的加入107.990毫摩尔(3.46克)甲醇,随后反应温度逐步的回升到室温。反应在室温下继续进行15个小时,将反应溶液用硅藻土过滤。然后在0.1托左右的减压下从滤出液中除去挥发材料。在剩下的滤出液中加入100毫升己烷,并且搅拌1小时,然后用硅藻土过滤。在减压下,从滤出液中除去己烷,得到无色液体。通过该液体的简单蒸馏得到无色液态单体(C)。溶解在CDCl3的单体(C)的NMR分析的结果如下:
1H NMR(300MHz)数据;δ0.068(s,12H,4×-CH3),
3.45(s,6H,2×-OCH3)
实施例1-4:硅氧烷基单体(D)的合成
单体(D)
单体(D)的合成和实施例1-2中的方式相同,只是1,3-二氯四甲基二硅氧烷被1,5-二氯六甲基三硅氧烷代替。
由此制备并溶解在CDCl3的单体(D)的NMR分析结果如下:
1H NMR(300MHz)数据;δ0.068(s,18H,6×-CH3),
3.45(s,6H,2×-OCH3)
实施例1-5:硅氧烷基单体(E)的合成
单体(E)
单体(E)的合成和实施例1-2中的方式相同,只是1,3-二氯四甲基二硅氧烷被1,7-二氯八甲基四硅氧烷代替。
由此制备并溶解在CDCl3的单体(D)的NMR分析的结果如下:
1H NMR(300MHz)数据;δ0.068(s,24H,8x-CH3),
3.45(s,6H,2x-OCH3)
实施例1-6:硅氧烷基单体(F)
单体(F)
使用从Sigma.Aldrich Co.,USA公司购买的单体(F)。
实施例1-7:硅氧烷基单体(G)
单体(G)
CH3Si(OCH3)3
使用从Sigma.Aldrich Co.,USA公司购买的单体(G)。
实施例2:硅氧烷树脂的合成
将具有与有机基团相连的放射结构的硅氧烷基单体(A)和单体(B)~(G)中的至少一种单体放入烧瓶中,用四氢呋喃来稀释,四氢呋喃量为烧瓶中单体总量的15倍。随后将烧瓶冷却到-78℃。在-78℃,向烧瓶中加入预定量的盐酸(HCl)和水,随后反应温度逐步的回升到70℃。在70℃下反应继续进行20小时。反应完全后将反应混合物移入分液漏斗,然后加入与前面稀释单体使用的四氢呋喃等量的二***和四氢呋喃。然后,进行三次洗涤,每次用达到分液漏斗中的总溶液量的1/10的水。洗涤之后,从剩余的溶液中蒸去挥发材料,得到白色粉末状的聚合物。将粉末完全溶解于少量丙酮中形成澄清的溶液,该溶液通过0.2微米的注射式过滤器(syringe filter)进行过滤以除去杂质,得到澄清的滤液。然后缓慢加入去离子水。结果形成白色粉状物质,将将该物质从液相(丙酮和水的混合溶液)分离,并且在0~20℃温度下和大约0.1托的减压下干燥10小时,形成分级的(fractionated)硅氧烷基树脂。
表1
实施例3:成分分析
如下所述,对实施例2中得到的各个硅氧烷基树脂进行了Si-OH、Si-OCH3、Si-CH3含量的分析。结果如下:
表2
硅氧烷树脂 | Si-OH(%) | Si-OCH<sub>3</sub>(%) | Si-CH<sub>3</sub>(%) |
(a) | 33.9 | 2.1 | 64.0 |
(b) | 39.2 | 1.3 | 59.5 |
(c) | 35.7 | 0.8 | 63.5 |
(d) | 24.9 | 1.5 | 73.6 |
(e) | 27.1 | 1.0 | 71.9 |
(f) | 27.5 | 1.0 | 71.5 |
(g) | 25.9 | 0.9 | 73.2 |
(h) | 27.7 | 6.6 | 65.7 |
(i) | 21.5 | 5.1 | 73.4 |
(j) | 24.9 | 4.5 | 70.6 |
(k) | 24.3 | 2.7 | 73.0 |
注:使用核磁共振分析仪(Bruker Co.)分析Si-OH、Si-OCH3、Si-CH3含量,并使用如下的公式计算:
Si-OH(%)=(Si-OH)面积÷[(Si-OH)面积+(Si-OCH3)面积/3+(Si-CH3)面积/3]×100,
Si-OCH3(%)=(Si-OCH3)面积/3÷[(Si-OH)面积+(Si-OCH3)面积/3+(Si-CH3)面积/3]×100,
Si-CH3(%)=(Si-CH3)面积/3÷[(Si-OH)面积+(Si-OCH3)面积/3+(Si-CH3)面积/3]×100。
实施例4:薄膜厚度和折射率的测量
实施例2中得到的硅氧烷基树脂及其与七(2,3,6-三-O-甲氧基)-β-环糊精的混合物分别溶解于丙二醇甲醚乙酸酯(PGMEA),使得获得的液态涂布组合物中固体的最终浓度为25重量%。然后,涂布组合物各自在硅片上旋涂30秒,保持旋转速度3000rpm。在氮气氛下,在热盘上(hot plate)相继软烘焙(在100℃下1分钟,在250℃下又1分种),以便充分蒸发有机溶剂。之后,温度以3℃/分钟的速度,在真空条件下升高到420℃,在此温度下,使涂层膜固化1小时,得到试验片。
如此制备的试验片各自分析膜厚和折射率。分别用剖面测量仪(profiler)和棱镜偶合器(prism coupler)在每个试样片的5个不同点上测量膜厚和折射率。平均厚度和折射率连同其均匀性一起在表3示出。
表3
实施例5:介电常数的测量
掺杂硼的P型硅片用3000的热氧化硅膜涂布,接着使用金属蒸发器相继沉积100的钛层、2000的铝层和100的钛层。按照上面实施例4中相同的方式,在这些晶片各自的表面形成树脂膜。接着,在树脂膜上通过硬质掩膜(hard mask)沉积1mm直径的环电极,其包含100厚的钛层和5000厚的铝层,从而提供具有MIM(金属-绝缘体-金属)结构的试验片。利用具有精密控制器(Micromanipulator)6200探针(probe)的精密电感电容电阻测定计(PRECISION LCR METER)(HP4284A)平台在100kHz测量如此获得的试验片的电容。从下面的方程计算每个测试膜的介电常数,其中“d”值使用椭率计(ellipsometer)获得:
k=C×d/εo×A
其中:
k:介电常数
C:电容
εo:真空中的介电常数
d:低介电膜的厚度
A:电极的接触面积
计算的介电常数在表4中示出:
表4
实施例6:硬度和模量的测量
使用Nanoindenter II(MIS Co.)测量上面实施例4制备的试验片的硬度和弹性模量。对每个试验片的树脂膜形成凹陷,直至凹口深度达到总厚度的10%。此时,为保证可实现该测量,每个试验片凹陷6点,测量平均硬度和模量。结果见表5:
表5
虽然已经为了解释的目的公开了本发明的优选实施方式,本领域普通技术人员应该理解不同的改进、增加和代替是可能的,而不脱离本发明附属权利要求所要求的范围和实质。
Claims (18)
1.一种硅氧烷基树脂,其通过在有机溶剂中,在酸或碱催化剂和水存在下,水解和缩合下面式1的具有放射结构的硅烷基单体和选自下面式2~4中的至少一种单体来制备:
式1
Si[(CH2)kSiY1Y2Y3]4
其中:
k是1到10的整数;
Y1、Y2和Y3独立地为C1-C3烷基,C1-C10烷氧基或卤素原子,条件是它们中至少有一个是可以水解的;
式2
其中:
R1是C1-C3烷基或C6-C15芳基;
X1、X2和X3独立地为氢原子、C1-C3烷基、C1-C10烷氧基或卤素原子,条件是它们中至少有一个是可以水解的;
m是0-10的整数;以及
p是3-8的整数;
式3
其中:
R2是C1-C3烷基或C6-C15芳基;
X4是氢原子或C1-C10烷氧基;
Y1是氢原子、C1-C3烷基或C1-C10烷氧基;以及
n是0-10的整数;
式4
R3SiX5X6X7
其中:
R3是C1-C3烷基或C6-C15芳基;
X5、X6和X7独立地为氢原子、C1-C3烷基、C1-C10烷氧基或卤素原子,条件是它们中至少有一个是可以水解的。
2.根据权利要求1的硅氧烷基树脂,其中所述具有式1结构的单体和所述选自式2~4中的单体的摩尔比为1∶99-99∶1。
3.根据权利要求1的硅氧烷基树脂,其中所述催化剂为盐酸、硝酸、苯磺酸、草酸、甲酸、氢氧化钾、氢氧化钠、三乙胺、碳酸氢钠或吡啶。
4.根据权利要求1的硅氧烷基树脂,其中所述单体和催化剂的摩尔比为1∶0.000001-1∶10。
5.根据权利要求1的硅氧烷基树脂,其中所述单体和水的摩尔比为1∶1-1∶1000。
6.根据权利要求1的硅氧烷基树脂,其中所述水解和缩聚反应在0~200℃的温度下进行0.1~100小时。
7.根据权利要求1的硅氧烷基树脂,其中所述有机溶剂为脂肪族烃溶剂、芳烃溶剂、酮类溶剂、醚类溶剂、乙酸酯类溶剂、醇类溶剂、酰胺类溶剂、硅类溶剂或其混合物。
8.根据权利要求1的硅氧烷基树脂,其中所述树脂的重均分子量为3000~300,000。
9.一种制备半导体的层间绝缘膜的方法,该方法包括下列步骤:
通过将权利要求1的硅氧烷基树脂溶解在有机溶剂中,提供液态涂布组合物;
通过用该液态涂布组合物涂布硅片,形成涂层膜;
热固化该涂层膜。
10.根据权利要求9的方法,其中所述硅氧烷基树脂和成孔剂混合,使得硅氧烷基树脂和成孔剂的重量比为99∶1-30∶70。
11.根据权利要求10的方法,其中所述成孔剂为环糊精、聚己内酯或其衍生物。
12.根据权利要求9所述的方法,其中所述有机溶剂为脂肪族烃溶剂、芳烃溶剂、酮类溶剂、醚类溶剂、乙酸酯类溶剂、醇类溶剂、酰胺类溶剂、硅类溶剂或其混和物。
13.根据权利要求9的方法,其中固体成分的重量比率为全部组合物的5~70重量%,所述固体成分包含所述硅氧烷基树脂和成孔剂。
14.根据权利要求9的方法,其中所述液态涂布组合物旋涂于硅片上。
15.根据权利要求9的方法,其中所述热固化在150~600℃下进行1~150分钟。
16.一种半导体的层间绝缘膜,其包含权利要求1的硅氧烷基树脂。
17.根据权利要求16的半导体的层间绝缘薄膜,其中通过使用成孔剂形成贯穿于所述绝缘膜的微孔。
18.根据权利要求17的半导体的层间绝缘薄膜,其中所述成孔剂为环糊精、聚己内酯或其衍生物。
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DE602004001097D1 (de) | 2006-07-20 |
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US20060264595A1 (en) | 2006-11-23 |
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US7071540B2 (en) | 2006-07-04 |
US7294584B2 (en) | 2007-11-13 |
DE602004001097T2 (de) | 2007-01-18 |
JP2005023318A (ja) | 2005-01-27 |
US20050003681A1 (en) | 2005-01-06 |
EP1493773A1 (en) | 2005-01-05 |
KR100507967B1 (ko) | 2005-08-10 |
EP1493773B1 (en) | 2006-06-07 |
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