公开(公告)号：US06576568B2

公开(公告)日：2003-06-10

申请号：US09823932

申请日：2001-03-29

申请人： Robert P Mandal ,  Alexandros T Demos ,  Timothy Weidman ,  Michael P Nault ,  Nikolaos Bekiaris ,  Scott J Weigel ,  Lee A. Senecal ,  James E. MacDougall ,  Hareesh Thridandam

发明人： Robert P Mandal ,  Alexandros T Demos ,  Timothy Weidman ,  Michael P Nault ,  Nikolaos Bekiaris ,  Scott J Weigel ,  Lee A. Senecal ,  James E. MacDougall ,  Hareesh Thridandam

IPC分类号： H01L2131

CPC分类号： H01L21/02126 ,  C01B33/16 ,  H01L21/02203 ,  H01L21/02216 ,  H01L21/02282 ,  H01L21/31695 ,  Y10S438/96 ,  Y10T428/249953 ,  Y10T428/249969

摘要： A process for depositing porous silicon oxide-based films using a sol-gel approach utilizing a precursor solution formulation which includes a purified nonionic surfactant and an additive among other components, where the additive is either an ionic additive or an amine additive which forms an ionic ammonium type salt in the acidic precursor solution. Using this precursor solution formulation enables formation of a film having a dielectric constant less than 2.5, appropriate mechanical properties, and minimal levels of alkali metal impurities. In one embodiment, this is achieved by purifying the surfactant and adding ionic or amine additives such as tetraalkylammonium salts and amines to the stock precursor solution. In some embodiments, the ionic additive is a compound chosen from a group of cationic additives of the general composition [NR(CH3)3]+A−, where R is a hydrophobic ligand of chain length 1 to 24, including tetramethylammonium and cetyltrimethylammonium, and A− is an anion, which may be chosen from the group consisting essentially of formate, nitrate, oxalate, acetate, phosphate, carbonate, and hydroxide and combinations thereof. Tetramethylammonium salts, or more generally tetraalkylammonium salts, or tetraorganoammonium salts or organoamines in acidic media are added to surfactant templated porous oxide precursor formulations to increase the ionic content, replacing alkali ion impurities (sodium and potassium) removed during surfactant purification, but which are found to exhibit beneficial effects in promoting the formation of the resulting dielectric.

公开(公告)号：US06896955B2

公开(公告)日：2005-05-24

申请号：US10219164

申请日：2002-08-13

申请人： Robert P. Mandal ,  Alexandros T. Demos ,  Timothy Weidman ,  Michael P. Nault ,  Nikolaos Bekiaris ,  Scott J. Weigel ,  Lee A. Senecal ,  James E. MacDougal ,  Hareesh Thridandam

发明人： Robert P. Mandal ,  Alexandros T. Demos ,  Timothy Weidman ,  Michael P. Nault ,  Nikolaos Bekiaris ,  Scott J. Weigel ,  Lee A. Senecal ,  James E. MacDougal ,  Hareesh Thridandam

IPC分类号： B05D5/12 ,  B05D7/24 ,  C01B33/16 ,  C09D5/25 ,  C09D183/02 ,  H01L21/20 ,  H01L21/314 ,  H01L21/316 ,  H01L21/768 ,  H01L23/522 ,  B32B3/00

CPC分类号： H01L21/02126 ,  C01B33/16 ,  H01L21/02203 ,  H01L21/02216 ,  H01L21/02282 ,  H01L21/31695 ,  Y10S438/96 ,  Y10T428/249953 ,  Y10T428/249969

摘要： A process for depositing porous silicon oxide-based films using a sol-gel approach utilizing a precursor solution formulation which includes a purified nonionic surfactant and an additive among other components, where the additive is either an ionic additive or an amine additive which forms an ionic ammonium type salt in the acidic precursor solution. Using this precursor solution formulation enables formation of a film having a dielectric constant less than 2.5, appropriate mechanical properties, and minimal levels of alkali metal impurities. In one embodiment, this is achieved by purifying the surfactant and adding ionic or amine additives such as tetraalkylammonium salts and amines to the stock precursor solution. In some embodiments, the ionic additive is a compound chosen from a group of cationic additives of the general composition [NR(CH3)3]+A−, where R is a hydrophobic ligand of chain length 1 to 24, including tetramethylammonium and cetyltrimethylammonium, and A− is an anion, which may be chosen from the group consisting essentially of formate, nitrate, oxalate, acetate, phosphate, carbonate, and hydroxide and combinations thereof. Tetramethylammonium salts, or more generally tetraalkylammonium salts, or tetraorganoammonium salts or organoamines in acidic media are added to surfactant templated porous oxide precursor formulations to increase the ionic content, replacing alkali ion impurities (sodium and potassium) removed during surfactant purification, but which are found to exhibit beneficial effects in promoting the formation of the resulting dielectric.

摘要翻译： 一种使用溶胶 - 凝胶方法沉积多孔氧化硅基膜的方法，该方法使用前体溶液制剂，其包含纯化的非离子表面活性剂和其它组分中的添加剂，其中添加剂是形成离子的离子添加剂或胺添加剂 铵型盐在酸性前体溶液中。 使用这种前体溶液制剂可以形成介电常数小于2.5，适当的机械性能和最低水平的碱金属杂质的薄膜。 在一个实施方案中，这通过纯化表面活性剂并将离子或胺添加剂例如四烷基铵盐和胺添加到原料前体溶液中来实现。 在一些实施方案中，离子添加剂是选自一般组成的阳离子添加剂组合物[NR（CH 3）3） 其中R是链长1至24的疏水性配体，包括四甲基铵和十六烷基三甲基铵，并且A是一种阴离子，其可以选自下组： 基本上由甲酸盐，硝酸盐，草酸盐，乙酸盐，磷酸盐，碳酸盐和氢氧化物组成。 在表面活性剂模板化的多孔氧化物前体制剂中加入四甲基铵盐或更一般的四烷基铵盐或四官能铵盐或有机胺，以增加离子含量，代替在表面活性剂纯化过程中除去的碱离子杂质（钠和钾），但发现 以促进所形成的电介质的形成。

公开(公告)号：US07265062B2

公开(公告)日：2007-09-04

申请号：US10636517

申请日：2003-08-07

申请人： Robert P. Mandal ,  Alexandros T. Demos ,  Timothy Weidman ,  Michael P. Nault ,  Nikolaos Bekiaris ,  Scott Jeffrey Weigel ,  Lee A. Senecal ,  James E. Mac Dougall ,  Hareesh Thridandam

发明人： Robert P. Mandal ,  Alexandros T. Demos ,  Timothy Weidman ,  Michael P. Nault ,  Nikolaos Bekiaris ,  Scott Jeffrey Weigel ,  Lee A. Senecal ,  James E. Mac Dougall ,  Hareesh Thridandam

IPC分类号： H01L21/31

CPC分类号： H01L21/02126 ,  C01B33/16 ,  H01L21/02203 ,  H01L21/02216 ,  H01L21/02282 ,  H01L21/31695

摘要： A process for depositing porous silicon oxide-based films using a sol-gel approach utilizing a precursor solution formulation which includes a purified nonionic surfactant and an additive among other components, where the additive is either an ionic additive or an amine additive which forms an ionic ammonium type salt in the acidic precursor solution. Using this precursor solution formulation enables formation of a film having a dielectric constant less than 2.5, appropriate mechanical properties, and minimal levels of alkali metal impurities. In one embodiment, this is achieved by purifying the surfactant and adding ionic or amine additives such as tetraalkylammonium salts and amines to the stock precursor solution.

摘要翻译： 一种使用溶胶 - 凝胶方法沉积多孔氧化硅基膜的方法，该方法使用前体溶液制剂，其包含纯化的非离子表面活性剂和其它组分中的添加剂，其中添加剂是形成离子的离子添加剂或胺添加剂 铵型盐在酸性前体溶液中。 使用这种前体溶液制剂可以形成介电常数小于2.5，适当的机械性能和最低水平的碱金属杂质的薄膜。 在一个实施方案中，这通过纯化表面活性剂并将离子或胺添加剂例如四烷基铵盐和胺添加到原料前体溶液中来实现。

公开(公告)号：US20080145535A1

公开(公告)日：2008-06-19

申请号：US11949868

申请日：2007-12-04

申请人： Xinjian Lei ,  Hareesh Thridandam ,  Manchao Xiao ,  Heather Regina Bowen ,  Thomas Richard Gaffney

发明人： Xinjian Lei ,  Hareesh Thridandam ,  Manchao Xiao ,  Heather Regina Bowen ,  Thomas Richard Gaffney

IPC分类号： C23C16/06

CPC分类号： C23C16/34 ,  C23C16/45553

摘要： A process to deposit metal silicon nitride on a substrate comprising: sorbing a metal amide on a heated substrate, purging away the unsorbed metal amide, contacting a silicon-containing source having one or more Si—H3 fragments with the heated substrate to react with the sorbed metal amide, wherein the silicon-containing source has one or more H3Si—NR02(R0═SiH3, R, R1 or R2, defined below) groups selected from the group consisting of one or more of: wherein R and R1 in the formulas represent aliphatic groups typically having from 2 to about 10 carbon atoms, e.g., branched alkyl, cycloalkyl with R and R1 in formula A also being combinable into a cyclic group, and R2 representing a single bond, (CH2)n, a ring, or SiH2, and purging away the unreacted silicon-containing source.

摘要翻译： 一种在衬底上沉积金属氮化硅的方法，包括：在加热的衬底上吸附金属酰胺，清除未吸附的金属酰胺，与含有一个或多个Si-H 3 N 3片段的含硅源接触 加热的底物与吸附的金属酰胺反应，其中含硅源具有一个或多个H 3 Si-NR O 2 O 2， （R 0〜S 3 H 3，R 1，R 1或R 2）定义如下）选自 由下式中的一个或多个组成：其中式中的R和R 1表示通常具有2至约10个碳原子的脂族基团，例如支链烷基，具有R和R 1的环烷基 式A中也可以组合成环状基团，R 2表示单键，（CH 2 CH 2）n， 环或SiH 2 H 2，并且清除未反应的含硅源。

公开(公告)号：US20070275166A1

公开(公告)日：2007-11-29

申请号：US11439554

申请日：2006-05-23

申请人： Hareesh Thridandam ,  Manchao Xiao ,  Xinjian Lei ,  Thomas Richard Gaffney

发明人： Hareesh Thridandam ,  Manchao Xiao ,  Xinjian Lei ,  Thomas Richard Gaffney

IPC分类号： C23C16/00

CPC分类号： H01L21/31608 ,  C23C16/402 ,  H01L21/02126 ,  H01L21/02219 ,  H01L21/02271 ,  H01L21/3145 ,  H01L21/31633

摘要： The present invention is directed to a method for depositing a silicon oxide layer on a substrate by CVD. The reaction of an organoaminosilane precursor where the alkyl group has at least two carbon atoms in the presence of an oxidizing agent allows for the formation of a silicon oxide film. The organoaminosilanes are represented by the formulas: The use of diisopropylaminosilane is the preferred precursor for the formation of the silicon oxide film.

摘要翻译： 本发明涉及通过CVD在衬底上沉积氧化硅层的方法。 在氧化剂存在下，烷基具有至少两个碳原子的有机氨基硅烷前体的反应允许形成氧化硅膜。 有机基氨基硅烷由下式表示：使用二异丙基氨基硅烷是形成氧化硅膜的优选前体。

公开(公告)号：US07678422B2

公开(公告)日：2010-03-16

申请号：US11949868

申请日：2007-12-04

申请人： Xinjian Lei ,  Hareesh Thridandam ,  Manchao Xiao ,  Heather Regina Bowen ,  Thomas Richard Gaffney

发明人： Xinjian Lei ,  Hareesh Thridandam ,  Manchao Xiao ,  Heather Regina Bowen ,  Thomas Richard Gaffney

IPC分类号： C23C16/18 ,  C23C16/30

CPC分类号： C23C16/34 ,  C23C16/45553

摘要： A process to deposit metal silicon nitride on a substrate comprising: sorbing a metal amide on a heated substrate, purging away the unsorbed metal amide, contacting a silicon-containing source having one or more Si—H3 fragments with the heated substrate to react with the sorbed metal amide, wherein the silicon-containing source has one or more H3Si—NR02 (R0═SiH3, R, R1 or R2, defined below) groups selected from the group consisting of one or more of: wherein R and R1 in the formulas represent aliphatic groups typically having from 2 to about 10 carbon atoms, e.g., branched alkyl, cycloalkyl with R and R1 in formula A also being combinable into a cyclic group, and R2 representing a single bond, (CH2)n, a ring, or SiH2, and purging away the unreacted silicon-containing source.

摘要翻译： 一种在衬底上沉积金属氮化硅的方法，包括：在加热的衬底上吸附金属酰胺，清除未吸附的金属酰胺，将具有一个或多个Si-H 3片段的含硅源与被加热的衬底接触，与 吸附的金属酰胺，其中所述含硅源具有一个或多个选自下列中的一个或多个的一个或多个的R 3 Si-NRO 2（R 0 = SiH 3，R 1，R 2或R 2，定义如下）：其中式中的R和R 1 代表通常具有2至约10个碳原子的脂族基团，例如支链烷基，具有式R中R和R 1的环烷基也可结合成环状基团，并且R 2表示单键，（CH 2）n，环或 SiH2，并且清除未反应的含硅源。

公开(公告)号：US20080207007A1

公开(公告)日：2008-08-28

申请号：US12030186

申请日：2008-02-12

申请人： Hareesh Thridandam ,  Manchao Xiao ,  Xinjian Lei ,  Thomas Richard Gaffney ,  Eugene Joseph Karwacki

发明人： Hareesh Thridandam ,  Manchao Xiao ,  Xinjian Lei ,  Thomas Richard Gaffney ,  Eugene Joseph Karwacki

IPC分类号： H01L21/31

CPC分类号： H01L21/0228 ,  C23C16/30 ,  C23C16/308 ,  C23C16/345 ,  C23C16/401 ,  C23C16/452 ,  C23C16/45542 ,  C23C16/45553 ,  H01L21/0214 ,  H01L21/02167 ,  H01L21/0217 ,  H01L21/02274 ,  H01L21/3141 ,  H01L21/3144 ,  H01L21/3145 ,  H01L21/3185

摘要： The present invention is a process of plasma enhanced cyclic chemical vapor deposition of silicon nitride, silicon carbonitride, silicon oxynitride, silicon carboxynitride, and carbon doped silicon oxide from alkylaminosilanes having Si—H3, preferably of the formula (R1R2N)SiH3 wherein R1 and R2 are selected independently from C2 to C10 and a nitrogen or oxygen source, preferably ammonia or oxygen has been developed to provide films with improved properties such as etching rate, hydrogen concentrations, and stess as compared to films from thermal chemical vapor deposition.

摘要翻译： 本发明是由具有Si-H 3 3烷基氨基硅烷的氮化硅，碳氮化硅，氮氧化硅，氮氧化硅和碳掺杂的氧化硅等离子体增强的循环化学气相沉积的方法，优选式 （R 1，R 2，N 2）其中R 1和R 2各自独立地选自氢， 独立于C 2至C 10，并且已经开发了氮或氧源，优选氨或氧，以提供具有改进性质的膜，例如蚀刻速率，氢浓度 ，与热化学气相沉积的薄膜相比。

公开(公告)号：US07582574B2

公开(公告)日：2009-09-01

申请号：US11747019

申请日：2007-05-10

申请人： Robert Daniel Clark ,  Hareesh Thridandam ,  Kirk Scott Cuthill ,  Arthur Kenneth Hochberg

发明人： Robert Daniel Clark ,  Hareesh Thridandam ,  Kirk Scott Cuthill ,  Arthur Kenneth Hochberg

IPC分类号： H01L21/31 ,  H01L21/469

CPC分类号： C23C16/401

摘要： A method for forming a metal silicate as a high k dielectric in an electronic device, comprising the steps of: providing diethylsilane to a reaction zone; concurrently providing a source of oxygen to the reaction zone; concurrently providing a metal precursor to the reaction zone; reacting the diethylsilane, source of oxygen and metal precursor by chemical vapor deposition to form a metal silicate on a substrate comprising the electronic device. The metal is preferably hafnium, zirconium or mixtures thereof. The dielectric constant of the metal silicate film can be tuned based upon the relative atomic concentration of metal, silicon, and oxygen in the film.

摘要翻译： 一种在电子器件中形成作为高k电介质的金属硅酸盐的方法，包括以下步骤：向反应区提供二乙基硅烷; 同时向反应区提供氧源; 同时向反应区提供金属前体; 通过化学气相沉积使二乙基硅烷，氧源和金属前体反应，在包含电子器件的基片上形成金属硅酸盐。 金属优选为铪，锆或其混合物。 可以基于膜中金属，硅和氧的相对原子浓度来调节金属硅酸盐膜的介电常数。

公开(公告)号：US20060182885A1

公开(公告)日：2006-08-17

申请号：US11057446

申请日：2005-02-14

申请人： Xinjian Lei ,  Hareesh Thridandam ,  Kirk Cuthill ,  Arthur Hochberg

发明人： Xinjian Lei ,  Hareesh Thridandam ,  Kirk Cuthill ,  Arthur Hochberg

IPC分类号： C23C16/00

CPC分类号： H01L21/0228 ,  C23C16/34 ,  C23C16/345 ,  C23C16/45531 ,  C23C16/45553 ,  H01L21/02142 ,  H01L21/0215 ,  H01L21/02153 ,  H01L21/02205 ,  H01L21/02216 ,  H01L21/02219 ,  H01L21/0234 ,  H01L21/28562 ,  H01L21/28568 ,  H01L21/318

摘要： This invention relates to an improved process for producing ternary metal silicon nitride films by the cyclic deposition of the precursors. The improvement resides in the use of a metal amide and a silicon source having both NH and SiH functionality as the precursors leading to the formation of such metal-SiN films. The precursors are applied sequentially via cyclic deposition onto the surface of a substrate. Exemplary silicon sources are monoalkylamino silanes and hydrazinosilanes represented by the formulas: (R1NH)nSiR2mH4-n-m (n=1,2; m=0,1,2; n+m=

摘要翻译： 本发明涉及通过循环沉积前体制备三元金属氮化硅膜的改进方法。 改进在于使用具有NH和SiH官能团的金属酰胺和硅源作为导致形成这种金属SiN膜的前体。 通过循环沉积顺序地将前体施加到衬底的表面上。 示例性硅源是由下式表示的单烷基氨基硅烷和肼基吡啶：<？in-line-formula description =“In-line formula”end =“lead”？>（R 1） （n = 1,2; m = 0,1,2; n + 1）n + m = <3）; <？in-line-formula description =“In-line Formulas”end =“tail”？> <？in-line-formula description =“In-line Formulas”end =“lead”？> and <？in-line -formulae description =“In-line Formulas”end =“tail”？> <？in-line-formula description =“In-line Formulas”end =“lead”？>（R <3> （2）N-NH（x-1）2（x） 1,2; y = 0,1,2; x + y = <3）<？in-line-formula description =“In-line Formulas”end =“tail”？>其中在上式R < 1-4是相同或不同的并且独立地选自烷基，乙烯基，烯丙基，苯基，环烷基，氟代烷基，甲硅烷基烷基。

公开(公告)号：US07064224B1

公开(公告)日：2006-06-20

申请号：US11051140

申请日：2005-02-04

申请人： Xinjian Lei ,  Manchao Xiao ,  Hareesh Thridandam ,  Kirk Scott Cuthill

发明人： Xinjian Lei ,  Manchao Xiao ,  Hareesh Thridandam ,  Kirk Scott Cuthill

IPC分类号： C07F7/10 ,  H01L21/44 ,  C23C16/00

CPC分类号： C07F15/065 ,  C07F7/10 ,  C07F15/025 ,  C07F15/045 ,  C23C16/18

摘要： This invention is related to organometallic precursors and deposition processes for fabricating conformal metal containing films on substrates such as silicon, metal nitrides and other metal layers.The organometallic precursors are N,N′-alkyl-1,1-alkylsilylamino metal complexes represented by the formula: wherein M is a metal selected from Group VIIb, VIII, IX and X, and specific examples include cobalt, iron, nickel, manganese, ruthenium, zinc, copper, palladium, platinum, iridium, rhenium, osmium, and the R1-5 can be same or different selected from hydrogen, alkyl, alkoxy, fluoroalkyl and alkoxy, cycloaliphatic, and aryl.

摘要翻译： 本发明涉及用于在诸如硅，金属氮化物和其它金属层的衬底上制造含适形金属膜的有机金属前体和沉积工艺。 有机金属前体是由下式表示的N，N'-烷基-1,1-烷基甲硅烷基氨基金属络合物：其中M是选自VIIb，VIII，IX和X族的金属，具体实例包括钴，铁，镍，锰 ，钌，锌，铜，钯，铂，铱，铼，锇和R 1-5可以相同或不同，选自氢，烷基，烷氧基，氟烷基和烷氧基，脂环族和 芳基。