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1. 发明授权

US6140252A Porous dielectric material with improved pore surface properties for electronics applications 失效
标题翻译：多孔电介质材料，具有改进的孔表面性能，适用于电子应用
公开(公告)号：US6140252A
公开(公告)日：2000-10-31
申请号：US72905
申请日：1998-05-05
申请人： Chih-Chen Cho , Bruce E. Gnade , Douglas M. Smith , Jin Changming , William C. Ackerman , Gregory C. Johnston
发明人： Chih-Chen Cho , Bruce E. Gnade , Douglas M. Smith , Jin Changming , William C. Ackerman , Gregory C. Johnston
IPC分类号： H01L21/768 , H01L21/316 , H01L21/469 , H01L23/522 , H01L23/532
CPC分类号： H01L23/5329 , H01L21/7682 , H01L23/5222 , H01L2221/1047 , H01L2924/0002
摘要： This invention provides an improved porous structure for semiconductor devices and a process for making the same. This process may be applied to an existing porous structure 28, which may be deposited, for example, between patterned conductors 24. The method may comprise providing a substrate comprising a microelectronic circuit and a porous silica layer, the porous silica layer having an average pore diameter between 2 and 80 nm; and heating the substrate to one or more temperatures between 100 and 490 degrees C. in a substantially halogen-free atmosphere, whereby one or more dielectric properties of the porous dielectric are improved. In some embodiments, the atmosphere comprises a phenyl-containing atmosphere, such as hexaphenyldisilazane. In some embodiments, the method further comprises cooling the substrate and exposing the substrate to a substantially halogen-free atmosphere comprising either a phenyl-containing compound, such as hexaphenyldisilazane; or a methyl-containing compound, such as hexamethyldisilazane. It has been found that a porous structure treated in such a manner generally exhibits improved dielectric properties relative to an untreated sample.
摘要翻译：本发明提供一种用于半导体器件的改进的多孔结构及其制造方法。该方法可以应用于可以例如在图案化导体24之间沉积的现有多孔结构28.该方法可以包括提供包括微电子电路和多孔二氧化硅层的基底，多孔二氧化硅层具有平均孔直径在2和80nm之间; 并在基本上无卤素的气氛中将衬底加热至100至490摄氏度之间的一个或多个温度，从而提高多孔电介质的一种或多种介电性能。在一些实施方案中，气氛包含含苯基的气氛，例如六苯基二硅氮烷。在一些实施方案中，该方法还包括冷却基底并将基底暴露于基本上无卤素的气氛中，该气氛包含含苯基的化合物，例如六苯基二硅氮烷; 或含甲基的化合物，例如六甲基二硅氮烷。已经发现，以这种方式处理的多孔结构通常相对于未处理的样品表现出改善的介电性能。

2. 发明授权

US5847443A Porous dielectric material with improved pore surface properties for electronics applications 失效
公开(公告)号：US5847443A
公开(公告)日：1998-12-08
申请号：US746689
申请日：1996-11-14
申请人： Chi-Chen Cho , Bruce E. Gnade , Douglas M. Smith , Jin Changming , William C. Ackerman , Gregory C. Johnston
发明人： Chi-Chen Cho , Bruce E. Gnade , Douglas M. Smith , Jin Changming , William C. Ackerman , Gregory C. Johnston
IPC分类号： H01L21/768 , H01L21/316 , H01L21/469 , H01L23/522 , H01L23/532 , H01L23/58
CPC分类号： H01L23/5329 , H01L21/7682 , H01L23/5222 , H01L2221/1047 , H01L2924/0002
摘要： This invention provides an improved porous structure for semiconductor devices and a process for making the same. This process may be applied to an existing porous structure 28, which may be deposited, for example, between patterned conductors 24. The method may comprise providing a substrate comprising a microelectronic circuit and a porous silica layer, the porous silica layer having an average pore diameter between 2 and 80 nm; and heating the substrate to one or more temperatures between 100 and 490 degrees C. in a substantially halogen-free atmosphere, whereby one or more dielectric properties of the porous dielectric are improved. In some embodiments, the atmosphere comprises a phenyl-containing atmosphere, such as hexaphenyldisilazane. In some embodiments, the method further comprises cooling the substrate and exposing the substrate to a substantially halogen-free atmosphere comprising either a phenyl-containing compound, such as hexaphenyldisilazane; or a methyl-containing compound, such as hexamethyldisilazane. It has been found that a porous structure treated in such a manner generally exhibits improved dielectric properties relative to an untreated sample.

3. 发明授权

US5561318A Porous composites as a low dielectric constant material for electronics applications 失效
标题翻译：多孔复合材料作为用于电子应用的低介电常数材料
公开(公告)号：US5561318A
公开(公告)日：1996-10-01
申请号：US477029
申请日：1995-06-07
申请人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
发明人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
IPC分类号： C04B38/00 , H01L21/312 , H01L21/314 , H01L21/316 , H01L21/768 , H01L23/522 , H01L23/532 , H01L23/58
CPC分类号： H01L21/7682 , H01L21/02126 , H01L21/02203 , H01L21/02216 , H01L21/02282 , H01L21/02337 , H01L21/02343 , H01L21/02359 , H01L21/02362 , H01L21/31695 , H01L21/76835 , H01L23/5222 , H01L23/5329 , H01L21/3121 , H01L2221/1047 , H01L2924/0002
摘要： This invention provides a process for making a semiconductor device with reduced capacitance between adjacent conductors. This process can include applying and gelling one or more solutions between and over conductors 24 and drying the wet gel to create at least porous dielectric sublayers 28 and 29. By varying the composition of the solutions, gelling conditions, drying temperature, composition of the solvents in the wet gel, or a combination of these approaches, the porosity of the sublayers may be tailored individually. A non-porous dielectric layer 30 may be formed over porous layer 28, which may complete an interlayer dielectric. A novel process for creating the porous dielectric layer is disclosed, which can be completed at vacuum or ambient pressures, yet results in porosity, pore size, and shrinkage of the dielectric during drying comparable to that previously attainable only by drying gels at supercritical pressure.
摘要翻译：本发明提供一种在相邻导体之间制造具有降低的电容的半导体器件的方法。该方法可以包括在导体24之间和之上施加和凝胶化一种或多种溶液并干燥湿凝胶以产生至少多孔介电子层28和29.通过改变溶液的组成，胶凝条件，干燥温度，溶剂的组成在湿凝胶中，或这些方法的组合，子层的孔隙率可以单独定制。无孔介电层30可以形成在多孔层28之上，多孔层28可以完成层间电介质。公开了一种用于产生多孔介电层的新方法，其可以在真空或环境压力下完成，但是在干燥期间导致电介质的孔隙率，孔径和收缩相当于仅通过在超临界压力下干燥凝胶可获得的电介质层。

4. 发明授权

US5804508A Method of making a low dielectric constant material for electronics 失效
标题翻译：制造电子材料用低介电常数材料的方法
公开(公告)号：US5804508A
公开(公告)日：1998-09-08
申请号：US735758
申请日：1996-10-23
申请人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
发明人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
IPC分类号： C04B38/00 , H01L21/312 , H01L21/314 , H01L21/316 , H01L21/768 , H01L23/522 , H01L21/31
CPC分类号： H01L21/02126 , H01L21/02203 , H01L21/02216 , H01L21/02282 , H01L21/02337 , H01L21/02343 , H01L21/02359 , H01L21/02362 , H01L21/3121 , H01L21/3122 , H01L21/31695 , H01L21/76801 , H01L21/7682 , H01L21/76834 , H01L2221/1047
摘要： This invention provides a process for making a semiconductor device with reduced capacitance between adjacent conductors. This process can include applying a solution between conductors 24, and then gelling, surface modifying, and drying the solution to form an extremely porous dielectric layer 28. A non-porous dielectric layer 30 may be formed over porous layer 28, which may complete an interlayer dielectric. A novel process for creating the porous dielectric layer is disclosed, which can be completed at vacuum or ambient pressures, yet results in porosity, pore size, and shrinkage of the dielectric during drying comparable to that previously attainable only by drying gels at supercritical pressure.
摘要翻译：本发明提供一种在相邻导体之间制造具有降低的电容的半导体器件的方法。该方法可以包括在导体24之间施加溶液，然后将溶液凝胶化，表面改性和干燥以形成极其多孔的介电层28.多孔介质层30可形成在多孔层28之上，多孔层28可以完成层间电介质。公开了一种用于产生多孔介电层的新方法，其可以在真空或环境压力下完成，但是在干燥期间导致电介质的孔隙率，孔径和收缩相当于仅通过在超临界压力下干燥凝胶可获得的电介质层。

5. 发明授权

US5494858A Method for forming porous composites as a low dielectric constant layer with varying porosity distribution electronics applications 失效
标题翻译：用于形成多孔复合材料作为具有不同孔隙分布电子应用的低介电常数层的方法
公开(公告)号：US5494858A
公开(公告)日：1996-02-27
申请号：US255157
申请日：1994-06-07
申请人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
发明人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
IPC分类号： C04B38/00 , H01L21/312 , H01L21/314 , H01L21/316 , H01L21/768 , H01L23/522 , H01L23/532 , H01L21/469
CPC分类号： H01L21/7682 , H01L21/02126 , H01L21/02203 , H01L21/02216 , H01L21/02282 , H01L21/02337 , H01L21/02343 , H01L21/02359 , H01L21/02362 , H01L21/31695 , H01L21/76835 , H01L23/5222 , H01L23/5329 , H01L21/3121 , H01L2221/1047 , H01L2924/0002
摘要： This invention provides a process for making a semiconductor device with reduced capacitance between adjacent conductors. This process can include applying and gelling one or more solutions between and over conductors 24 and drying the wet gel to create at least porous dielectric sublayers 28 and 29. By varying the composition of the solutions, gelling conditions, drying temperature, composition of the solvents in the wet gel, or a combination of these approaches, the porosity of the sublayers may be tailored individually. A non-porous dielectric layer 30 may be formed over porous layer 28, which may complete an interlayer dielectric. A novel process for creating the porous dielectric layer is disclosed, which can be completed at vacuum or ambient pressures, yet results in porosity, pore size, and shrinkage of the dielectric during drying comparable to that previously attainable only by drying gels at supercritical pressure.
摘要翻译：本发明提供一种在相邻导体之间制造具有降低的电容的半导体器件的方法。该方法可以包括在导体24之间和之上施加和凝胶化一种或多种溶液并干燥湿凝胶以产生至少多孔介电子层28和29.通过改变溶液的组成，胶凝条件，干燥温度，溶剂的组成在湿凝胶中，或这些方法的组合，子层的孔隙率可以单独定制。无孔介电层30可以形成在多孔层28之上，多孔层28可以完成层间电介质。公开了一种用于产生多孔介电层的新方法，其可以在真空或环境压力下完成，但是在干燥期间导致电介质的孔隙率，孔径和收缩相当于仅通过在超临界压力下干燥凝胶可获得的电介质层。

6. 发明授权

US5470802A Method of making a semiconductor device using a low dielectric constant material 失效
标题翻译：使用低介电常数材料制造半导体器件的方法
公开(公告)号：US5470802A
公开(公告)日：1995-11-28
申请号：US247195
申请日：1994-05-20
申请人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
发明人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
IPC分类号： C04B38/00 , H01L21/312 , H01L21/314 , H01L21/316 , H01L21/768 , H01L23/522 , H01L21/02
CPC分类号： H01L21/02126 , H01L21/02203 , H01L21/02216 , H01L21/02282 , H01L21/02337 , H01L21/02343 , H01L21/02359 , H01L21/02362 , H01L21/3121 , H01L21/3122 , H01L21/31695 , H01L21/76801 , H01L21/7682 , H01L21/76834 , H01L2221/1047
摘要： This invention provides a process for making a semiconductor device with reduced capacitance between adjacent conductors. This process can include applying a solution between conductors 24, and then gelling, surface modifying, and drying the solution to form an extremely porous dielectric layer 28. A non-porous dielectric layer 30 may be formed over porous layer 28, which may complete an interlayer dielectric. A novel process for creating the porous dielectric layer is disclosed, which can be completed at vacuum or ambient pressures, yet results in porosity, pore size, and shrinkage of the dielectric during drying comparable to that previously attainable only by drying gels at supercritical pressure.
摘要翻译：本发明提供一种在相邻导体之间制造具有降低的电容的半导体器件的方法。该方法可以包括在导体24之间施加溶液，然后将溶液凝胶化，表面改性和干燥以形成极其多孔的介电层28.多孔介质层30可形成在多孔层28之上，多孔层28可以完成层间电介质。公开了一种用于产生多孔介电层的新方法，其可以在真空或环境压力下完成，但是在干燥期间导致电介质的孔隙率，孔径和收缩相当于仅通过在超临界压力下干燥凝胶可获得的电介质层。

7. 发明授权

US5750415A Low dielectric constant layers via immiscible sol-gel processing 失效
标题翻译：低介电常数层通过不混溶溶胶 - 凝胶加工
公开(公告)号：US5750415A
公开(公告)日：1998-05-12
申请号：US250747
申请日：1994-05-27
申请人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
发明人： Bruce E. Gnade , Chih-Chen Cho , Douglas M. Smith
IPC分类号： H01L21/314 , H01L21/316 , H01L21/768 , H01L23/522 , H01L23/532 , H01L21/44
CPC分类号： H01L21/02126 , H01L21/02203 , H01L21/02282 , H01L21/02304 , H01L21/02362 , H01L21/31695 , H01L21/76801 , H01L21/7682 , H01L23/5222 , H01L23/5329 , H01L21/76834 , H01L2924/0002
摘要： A method for forming air gaps 22 between metal leads 16 of a semiconductor device. A metal layer is deposited on a substrate 12. The metal layer is etched to form metal leads 16, exposing portions of the substrate 12. A disposable liquid 18 is deposited on the metal leads 16 and the exposed portions of substrate 12, and a top portion of the disposable liquid 18 is removed to lower the disposable liquid 18 to at least the tops of the leads 16. A porous silica precursor film 20 is deposited on the disposable liquid 18 and over the tops of the leads 16. The porous silica precursor film 20 is gelled to form a low-porosity silica film 24. The disposable liquid 18 is removed through the low-porosity silica film 24 to form air gaps 22 between metal leads 16 beneath the low-porosity silica film 24. The air gaps 22 have a low dielectric constant and result in reduced capacitance between the metal leads and decreased power consumption.
摘要翻译：一种用于在半导体器件的金属引线16之间形成气隙22的方法。金属层沉积在基底12上。金属层被蚀刻以形成金属引线16，暴露基底12的部分。一次性液体18沉积在金属引线16和基底12的暴露部分上，顶部去除一次性液体18的一部分以将一次性液体18降低到至少引线16的顶部。多孔二氧化硅前体膜20沉积在一次性液体18上并在引线16的顶部上。多孔二氧化硅前体膜20凝胶化以形成低孔隙率二氧化硅膜24.一次性液体18通过低孔隙率二氧化硅膜24去除，以在低孔隙率二氧化硅膜24下面的金属引线16之间形成气隙22。气隙22 具有低介电常数，并且导致金属引线之间的电容降低并降低功耗。

8. 发明授权

US06380105B1 Low volatility solvent-based method for forming thin film nanoporous aerogels on semiconductor substrates 有权
标题翻译：在半导体衬底上形成薄膜纳米多孔气凝胶的低挥发性溶剂型方法
公开(公告)号：US06380105B1
公开(公告)日：2002-04-30
申请号：US09324370
申请日：1999-06-02
申请人： Douglas M. Smith , Gregory P. Johnston , William C. Ackerman , Richard A. Stoltz , Alok Maskara , Teresa Ramos , Shin-Puu Jeng , Bruce E. Gnade
发明人： Douglas M. Smith , Gregory P. Johnston , William C. Ackerman , Richard A. Stoltz , Alok Maskara , Teresa Ramos , Shin-Puu Jeng , Bruce E. Gnade
IPC分类号： H01L2131
CPC分类号： H01L21/31695 , B01J13/0091 , H01L21/02203 , H01L21/02214 , H01L21/02282 , H01L21/3105
摘要： This invention has enabled a new, simple thin film nanoporous dielectric fabrication method. In general, this invention uses glycerol, or another low volatility compound, as a solvent. This new method allows thin film aerogels/low density xerogels to be made without supercritical drying, freeze drying, or a surface modification step before drying. Thus, this invention allows production of nanoporous dielectrics at room temperature and atmospheric pressure, without a separate surface modification step. Although this new method allows fabrication of aerogels without substantial pore collapse during drying, there may be some permanent shrinkage during aging and/or drying. This invention allows controlled porosity thin film nanoporous aerogels to be deposited, gelled, aged, and dried without atmospheric controls. In another aspect, this invention allows controlled porosity thin film nanoporous aerogels to be deposited, gelled, rapidly aged at an elevated temperature, and dried with only passive atmospheric controls, such as limiting the volume of the aging chamber.
摘要翻译：本发明实现了一种新的，简单的薄膜纳米多孔电介质制造方法。通常，本发明使用甘油或另一种低挥发性化合物作为溶剂。这种新方法允许在干燥之前不进行超临界干燥，冷冻干燥或表面改性步骤制备薄膜气凝胶/低密度干凝胶。因此，本发明允许在室温和大气压下制备纳米多孔电介质，而无需单独的表面改性步骤。虽然这种新方法允许在干燥期间制造气凝胶而没有实质的孔隙塌陷，但在老化和/或干燥期间可能存在一些永久收缩。本发明允许控制孔隙率薄膜纳米多孔气凝胶沉积，凝胶化，老化和干燥而无需大气控制。另一方面，本发明允许受控孔隙率的薄膜纳米多孔气凝胶沉积，凝胶化，在升高的温度下快速老化，并且仅用无源大气控制干燥，例如限制老化室的体积。

9. 发明授权

US6130152A Aerogel thin film formation from multi-solvent systems 失效
标题翻译：从多溶剂系统形成气凝胶薄膜
公开(公告)号：US6130152A
公开(公告)日：2000-10-10
申请号：US746679
申请日：1996-11-14
申请人： Douglas M. Smith , Gregory P. Johnston , William C. Ackerman , Shin-Puu Jeng , Bruce E. Gnade
发明人： Douglas M. Smith , Gregory P. Johnston , William C. Ackerman , Shin-Puu Jeng , Bruce E. Gnade
IPC分类号： B01F3/12 , C01B33/14 , C01B33/145 , C01B33/155 , C01B33/158 , H01L21/312 , H01L21/316 , H01L21/768
CPC分类号： C01B33/158 , C01B33/145 , C01B33/155 , H01L21/02126 , H01L21/02216 , H01L21/02282 , H01L21/3122 , H01L21/7682 , H01L21/31695
摘要： This invention pertains generally to precursors and deposition methods suited to aerogel thin film fabrication. An aerogel precursor sol which contains an oligomerized metal alkoxide (such as TEOS), a high vapor pressure solvent (such as ethanol) and a low vapor pressure solvent (such as water and 1-butanol) is disclosed. By a method according to the present invention, such a precursor sol is applied as a thin film to a semiconductor wafer, and the high vapor pressure solvent is allowed to evaporate while evaporation of the low vapor pressure solvent is limited, preferably by controlling the atmosphere adjacent to the wafer. The reduced sol is then allowed to gel at a concentration determined by the ratio of metal.alkoxide to low vapor pressure solvent. One advantage of the present invention is that it provides a stable, spinnable sol for setting film thickness and providing good planarity and gap fill for patterned wafers. In addition, however, the reduced sol may be gelled rapidly from a known sol concentration keyed to the desired final density of the aerogel thin film and largely independent of film thickness and spin conditions.
摘要翻译：本发明一般涉及适用于气凝胶薄膜制造的前体和沉积方法。公开了含有低聚金属醇盐（如TEOS），高蒸气压溶剂（如乙醇）和低蒸气压溶剂（如水和1-丁醇））的气凝胶前体溶胶。通过根据本发明的方法，将这种前体溶胶作为薄膜施加到半导体晶片，并且在蒸发低蒸气压溶剂的同时，优选通过控制气氛，使高蒸气压溶剂蒸发邻近晶片。然后将还原的溶胶以由金属醇盐与低蒸气压溶剂的比例确定的浓度凝胶化。本发明的一个优点是提供了一种稳定的可纺丝溶胶，用于设定膜厚度并为图案化晶片提供良好的平面度和间隙填充。然而，此外，还原的溶胶可以从已知的溶胶浓度快速凝胶化，所述溶胶浓度与气凝胶薄膜的所需最终密度密切相关，并且在很大程度上与膜厚度和旋转条件无关。

10. 发明授权

US06437007B1 Aerogel thin film formation from multi-solvent systems 有权
标题翻译：从多溶剂系统形成气凝胶薄膜
公开(公告)号：US06437007B1
公开(公告)日：2002-08-20
申请号：US09549289
申请日：2000-04-14
申请人： Douglas M. Smith , Gregory P. Johnston , William C. Ackerman , Shin-Puu Jeng , Bruce E. Gnade
发明人： Douglas M. Smith , Gregory P. Johnston , William C. Ackerman , Shin-Puu Jeng , Bruce E. Gnade
IPC分类号： B01F312
CPC分类号： C01B33/158 , C01B33/145 , C01B33/155 , H01L21/02126 , H01L21/02216 , H01L21/02282 , H01L21/3122 , H01L21/31695 , H01L21/7682 , H01L2221/1047
摘要： This invention pertains generally to precursors and deposition methods suited to aerogel thin film fabrication. An aerogel precursor sol which contains an oligomerized metal alkoxide (such as TEOS), a high vapor pressure solvent (such as ethanol) and a low vapor pressure solvent (such as water and 1-butanol) is disclosed. By a method according to the present invention, such a precursor sol is applied as a thin film to a semiconductor wafer, and the high vapor pressure solvent is allowed to evaporate while evaporation of the low vapor pressure solvent is limited, preferably by controlling the atmosphere adjacent to the wafer. The reduced sol is then allowed to gel at a concentration determined by the ratio of metal alkoxide to low vapor pressure solvent. One advantage of the present invention is that it provides a stable, spinnable sol for setting film thickness and providing good planarity and gap fill for patterned wafers. In addition, however, the reduced sol may be gelled rapidly from a known sol concentration keyed to the desired final density of the aerogel thin film and largely independent of film thickness and spin conditions.
摘要翻译：本发明一般涉及适用于气凝胶薄膜制造的前体和沉积方法。公开了含有低聚金属醇盐（如TEOS），高蒸气压溶剂（如乙醇）和低蒸气压溶剂（如水和1-丁醇））的气凝胶前体溶胶。通过根据本发明的方法，将这种前体溶胶作为薄膜施加到半导体晶片，并且在蒸发低蒸气压溶剂的同时，优选通过控制气氛，使高蒸气压溶剂蒸发邻近晶片。然后将还原的溶胶以由金属醇盐与低蒸气压溶剂的比例确定的浓度凝胶化。本发明的一个优点是提供了一种稳定的可纺丝溶胶，用于设定膜厚度并为图案化晶片提供良好的平面度和间隙填充。然而，此外，还原的溶胶可以从已知的溶胶浓度快速凝胶化，所述溶胶浓度与气凝胶薄膜的所需最终密度密切相关，并且在很大程度上与膜厚度和旋转条件无关。

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