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21. 发明授权

US06376691B1 Metal organic precursors for transparent metal oxide thin films and method of making same 失效
标题翻译：透明金属氧化物薄膜的金属有机前体及其制备方法
公开(公告)号：US06376691B1
公开(公告)日：2002-04-23
申请号：US09388044
申请日：1999-09-01
申请人： Jolanta Celinska , Carlos A. Paz de Araujo , Joseph D. Cuchiaro , Jeffrey W. Bacon , Larry D. McMillan
发明人： Jolanta Celinska , Carlos A. Paz de Araujo , Joseph D. Cuchiaro , Jeffrey W. Bacon , Larry D. McMillan
IPC分类号： C07F1900
CPC分类号： C07C53/126
摘要： A liquid precursor for forming a transparent metal oxide thin film comprises a first organic precursor compound. In one embodiment, the liquid precursor is for making a conductive thin film. In this embodiment, the liquid precursor contains a first metal from the group including tin, antimony, and indium dissolved in an organic solvent. The liquid precursor preferably comprises a second organic precursor compound containing a second metal from the same group. Also, the liquid precursor preferably comprises an organic dopant precursor compound containing a metal selected from the group including niobium, tantalum, bismuth, cerium, yttrium, titanium, zirconium, hafnium, silicon, aluminum, zinc and magnesium. Liquid precursors containing a plurality of metals have a longer shelf life. The addition of an organic dopant precursor compound containing a metal, such as niobium, tantalum or bismuth, to the liquid precursor enhances control of the conductivity of the resulting transparent conductor. In a second embodiment, a liquid precursor for forming a transparent metal oxide nonconductive thin film comprises an organic precursor compound containing a metal from the group including cerium, yttrium, titanium, zirconium, hafnium, silicon, aluminum, niobium, tantalum, and bismuth. Liquid precursors of the invention preferably comprise a metal organic precursor compound, such as an ethylhexanoate, an octanoate, or a neodecanoate, dissolved in a solvent, such as xylenes, n-octane and n-butyl acetate.
摘要翻译：用于形成透明金属氧化物薄膜的液体前体包括第一有机前体化合物。在一个实施例中，液体前体用于制造导电薄膜。在该实施方案中，液体前体含有溶解在有机溶剂中的包含锡，锑和铟的第一金属。液体前体优选包含含有来自相同基团的第二金属的第二有机前体化合物。此外，液体前体优选包含含有选自铌，钽，铋，铈，钇，钛，锆，铪，硅，铝，锌和镁的金属的有机掺杂剂前体化合物。含有多种金属的液体前体具有更长的保质期。向液体前体中添加含有诸如铌，钽或铋的金属的有机掺杂剂前体化合物增强了所得到的透明导体的导电性的控制。在第二实施方案中，用于形成透明金属氧化物非导电薄膜的液体前体包括含有包括铈，钇，钛，锆，铪，硅，铝，铌，钽和铋的金属的有机前体化合物。本发明的液体前体优选包含溶解在溶剂例如二甲苯，正辛烷和乙酸正丁酯中的金属有机前体化合物，例如乙基己酸酯，辛酸酯或新癸酸酯。

22. 发明授权

US5811847A PSZT for integrated circuit applications 失效
标题翻译： PSZT用于集成电路应用
公开(公告)号：US5811847A
公开(公告)日：1998-09-22
申请号：US672421
申请日：1996-06-28
申请人： Vikram Joshi , Joseph D. Cuchiaro , Carlos A. Paz de Araujo , Larry D. McMillan
发明人： Vikram Joshi , Joseph D. Cuchiaro , Carlos A. Paz de Araujo , Larry D. McMillan
IPC分类号： H01L21/02 , H01L27/115 , H01L27/108
CPC分类号： H01L27/11502 , H01L28/55
摘要： An integrated circuit memory, MMIC, or other device including a dielectric comprising lead-tin zirconium-titanium oxide (PSZT). The proportion of tin ranges from 30% to 50% of the total amount of tin, zirconium and titanium. The dielectric is formed by applying a first liquid precursor having 10% excess lead to a substrate and heating it to form a first PSZT thin film, applying a second liquid precursor having 5% excess lead to the first thin film and heating to form a second thin film, then applying the first liquid precursor and heating to form a third thin film, and annealing the three thin films together to form a PSZT dielectric layer.
摘要翻译：集成电路存储器，MMIC或包括包含铅 - 锡锆 - 氧化钛（PSZT）的电介质的其它器件。锡的比例范围为锡，锆和钛的总量的30％至50％。通过将具有10％过量的铅的第一液体前体施加到基底上并加热以形成第一PSZT薄膜，将具有5％多余铅的第二液体前体施加到第一薄膜上并加热形成第二个薄膜，然后施加第一液体前体并加热以形成第三薄膜，并将三个薄膜退火在一起以形成PSZT介电层。

23. 发明授权

US5723171A Integrated circuit electrode structure and process for fabricating same 失效
标题翻译：集成电路电极结构及其制造方法
公开(公告)号：US5723171A
公开(公告)日：1998-03-03
申请号：US772606
申请日：1996-12-23
申请人： Joseph D. Cuchiaro , Larry D. McMillan , Carlos A. Paz de Araujo
发明人： Joseph D. Cuchiaro , Larry D. McMillan , Carlos A. Paz de Araujo
IPC分类号： H01L23/52 , C23C16/44 , C23C16/448 , C23C16/455 , C23C16/46 , C23C16/48 , C23C16/52 , C23C18/12 , C23C18/14 , H01L21/02 , H01L21/314 , H01L21/316 , H01L21/3205 , H01L21/822 , H01L21/8242 , H01L27/04 , H01L27/10 , H01L27/108 , H01L27/115 , B05D5/06
CPC分类号： H01L27/11502 , C23C16/4412 , C23C16/448 , C23C16/45561 , C23C16/4558 , C23C16/46 , C23C16/482 , C23C16/52 , C23C18/1216 , C23C18/1245 , C23C18/1295 , C23C18/14 , H01L21/31691 , H01L28/56 , H01L28/60 , H01L28/65 , H01L28/55
摘要： An electrode for a ferroelectric electronic device is formed on an SiO.sub.2 isolation layer by depositing an adhesion layer, such as titanium, between about 25 .ANG. and 500 .ANG. thick, then a layer of a nobel metal, such as platinum, that is at least 10 times thicker than the adhesion layer. The electrode is then annealed at a temperature higher than the minimum oxide eutectic temperature of the adhesion layer. The electrode is moved into the annealing furnace at a ramp rate such that it reaches its anneal temperature in five minutes or less. The relative thinness of the adhesion layer and the quick ramp up of the anneal causes all the titanium to be tied up in the oxide before it can diffuse through the platinum, and prevents the formation of rutile phases of the titanium and defects such as voids and hillocks in the platinum, which can destabilize the electrode.
摘要翻译：用于铁电电子器件的电极通过在约25至500厚之间沉积诸如钛之类的粘合层，然后将诸如铂的诺贝尔金属层，至少为10埃，形成在SiO 2隔离层上比粘合层厚。然后将电极在高于粘附层的最小氧化物共晶温度的温度下退火。电极以升高速度移动到退火炉中，使其在5分钟或更短时间内达到其退火温度。粘合层的相对薄度和退火的快速上升导致所有的钛在氧化物中被扩散通过铂之前被束缚在其中，并且防止了钛的金红石相的形成以及诸如空隙和缺陷的缺陷白金中的小丘，可能会使电极不稳定。

24. 发明授权

US5614018A Integrated circuit capacitors and process for making the same 失效
标题翻译：集成电路电容器和制造相同的工艺
公开(公告)号：US5614018A
公开(公告)日：1997-03-25
申请号：US273592
申请日：1994-07-11
申请人： Masamichi Azuma , Carlos A. Paz De Araujo , Michael C. Scott , Joseph D. Cuchiaro
发明人： Masamichi Azuma , Carlos A. Paz De Araujo , Michael C. Scott , Joseph D. Cuchiaro
IPC分类号： C23C16/44 , C23C16/448 , C23C16/455 , C23C16/46 , C23C16/48 , C23C16/52 , C23C18/12 , C23C18/14 , C30B7/00 , H01C7/10 , H01L21/02 , H01L21/314 , H01L21/316 , H01L21/8242 , H01L27/108 , H01L27/115 , C30B9/08
CPC分类号： H01L27/11502 , C04B35/4682 , C04B35/6264 , C23C16/4412 , C23C16/448 , C23C16/4486 , C23C16/45561 , C23C16/4558 , C23C16/46 , C23C16/482 , C23C16/52 , C23C18/1216 , C23C18/1275 , C23C18/1295 , C23C18/14 , C30B29/68 , C30B7/00 , H01C7/1013 , H01L21/314 , H01L21/31691 , H01L27/10805 , H01L28/56 , H01L28/60 , C04B2235/3213 , C04B2235/3224 , C04B2235/3227 , C04B2235/3229 , C04B2235/3243 , C04B2235/3268 , C04B2235/441 , C04B2235/449 , C04B2235/72 , H01L28/55
摘要： A xylene exchange is performed on a stock solution of BST of greater then 99.999% purity dissolved in methoxyethanol, and a carboxylate of a dopant metal, such as magnesium 2-ethylhexanoate is added to form a precursor. The precursor is spun on a first electrode, dried at 400.degree. C. for 2 minutes, then annealed at 750.degree. C. to 800.degree. C. for about an hour to form a layer of accurately doped BST. A second electrode is deposited, patterned, and annealed at between 750.degree. C. to 800.degree. C. for about 30 minutes. Excellent leakage current results if the dopant is magnesium of about 5% molarity. For other dopants, such as Mg, Nb, Y, Bi, and Sn the preferred dopant range is 0.2% to 0.3% molarity. The magnesium-doped material is used as a buffer layer between the electrodes and BST dielectric of an undoped BST capacitor.
摘要翻译：对溶解在甲氧基乙醇中的纯度为99.999％的BST的原液进行二甲苯交换，加入2-乙基己酸镁等掺杂剂金属的羧酸盐，形成前体。将前体在第一电极上旋转，在400℃下干燥2分钟，然后在750℃至800℃退火约1小时以形成精确掺杂的BST层。在750℃至800℃下沉积，图案化和退火第二电极约30分钟。如果掺杂剂为约5％摩尔浓度的镁，则会产生优异的漏电流。对于其它掺杂剂如Mg，Nb，Y，Bi和Sn，优选的掺杂剂范围为0.2％至0.3％摩尔浓度。掺杂镁的材料用作未掺杂的BST电容器的电极和BST电介质之间的缓冲层。

25. 发明授权

US06372286B1 Barium strontium titanate integrated circuit capacitors and process for making the same 失效
标题翻译：钛酸钡锶集成电路电容器及其制造方法
公开(公告)号：US06372286B1
公开(公告)日：2002-04-16
申请号：US08277035
申请日：1994-07-19
申请人： Masamichi Azuma , Michael C. Scott , Carlos A. Paz de Araujo , Joseph D. Cuchiaro
发明人： Masamichi Azuma , Michael C. Scott , Carlos A. Paz de Araujo , Joseph D. Cuchiaro
IPC分类号： B05D512
CPC分类号： C04B35/4682 , C04B35/6264 , C04B2235/3213 , C04B2235/3224 , C04B2235/3227 , C04B2235/3229 , C04B2235/3243 , C04B2235/3268 , C04B2235/441 , C04B2235/449 , C04B2235/72 , C23C16/4412 , C23C16/448 , C23C16/4486 , C23C16/45561 , C23C16/4558 , C23C16/46 , C23C16/482 , C23C16/52 , C23C18/1216 , C23C18/1275 , C23C18/14 , C30B7/00 , C30B29/68 , H01C7/1013 , H01L21/314 , H01L21/31691 , H01L27/10805 , H01L27/11502 , H01L28/55 , H01L28/56 , H01L28/60
摘要： Integrated circuit capacitors in which the capacitor dielectric is a thin film of BST having a grain size smaller than 2000 Å. Typical gain sizes are 40 nanometers and less. The BST is formed by deposition of a liquid precursor by a spin-on process. The original liquid precursor includes an alkoxycarboxylate dissolved in 2-methoxyethanol and an xylene exchange is preformed just prior to spinning. The precursor is dried in air at a temperature of about 400° C. and then furnace annealed in oxygen at a temperature of between 675° C. and 850° C.
摘要翻译：集成电路电容器，其中电容器电介质是具有小于2000埃的晶粒尺寸的BST薄膜。典型的增益尺寸为40纳米以下。 BST通过旋涂工艺沉积液体前体而形成。原始液体前体包括溶解在2-甲氧基乙醇中的烷氧基羧酸酯，并且在旋转之前预先形成二甲苯交换。前体在空气中在约400℃的温度下干燥，然后在675℃至850℃的温度下在氧气中进行炉退火。

26. 发明授权

US06447838B1 Integrated circuit capacitors with barrier layer and process for making the same 失效
标题翻译：具有阻挡层的集成电路电容器及其制造方法
公开(公告)号：US06447838B1
公开(公告)日：2002-09-10
申请号：US08543827
申请日：1995-10-16
申请人： Masamichi Azuma , Eiji Fujii , Yasuhiro Uemoto , Shinichiro Hayashi , Toru Nasu , Yoshihiro Shimada , Akihiro Matsuda , Tatsuo Otsuki , Michael C. Scott , Joseph D. Cuchiaro , Carlos A. Paz de Araujo
发明人： Masamichi Azuma , Eiji Fujii , Yasuhiro Uemoto , Shinichiro Hayashi , Toru Nasu , Yoshihiro Shimada , Akihiro Matsuda , Tatsuo Otsuki , Michael C. Scott , Joseph D. Cuchiaro , Carlos A. Paz de Araujo
IPC分类号： B05D512
CPC分类号： H01L28/75 , H01L21/28568 , H01L28/55 , H01L28/65 , Y10T29/42
摘要： A Ti/TiN adhesion/barrier layer is formed on a substrate and annealed. The anneal step is performed at a temperature within a good morphology range of 100° C. above a base barrier anneal temperature that depends on the thickness of said barrier layer. The base barrier anneal temperature is about 700° C. for a barrier thickness of about 1000 Å and about 800° C. for a barrier thickness of about 3000 Å. The barrier layer is 800 Å thick or thicker. A first electrode is formed, followed by a BST dielectric layer and a second electrode. A bottom electrode structure in which a barrier layer of TiN is sandwiched between two layers of platinum is also disclosed. The process and structures also produce good results with other capacitor dielectrics, including ferroelectrics such as strontium bismuth tantalate.
摘要翻译：在基板上形成Ti / TiN粘合/阻挡层并退火。退火步骤在取决于所述阻挡层的厚度的基本阻挡退火温度之上的100℃的良好形态范围内进行。对于约3000的屏障厚度，对于约1000和约800℃的阻挡层厚度，基底阻挡退火温度为约700℃。阻挡层厚度为800或更厚。形成第一电极，随后是BST介电层和第二电极。还公开了其中TiN阻挡层夹在两层铂之间的底部电极结构。该工艺和结构也与其他电容器电介质（包括铁电锶钽酸锶）等产生良好的结果。

27. 发明授权

US06285048B1 Barium strontium titanate integrated circuit capacitors and process for making the same 失效
标题翻译：钛酸钡锶集成电路电容器及其制造方法
公开(公告)号：US06285048B1
公开(公告)日：2001-09-04
申请号：US08165082
申请日：1993-12-10
申请人： Masamichi Azuma , Michael C. Scott , Carlos A. Paz de Araujo , Joseph D. Cuchiaro
发明人： Masamichi Azuma , Michael C. Scott , Carlos A. Paz de Araujo , Joseph D. Cuchiaro
IPC分类号： H01L31072
CPC分类号： C04B35/4682 , C04B35/6264 , C04B2235/3213 , C04B2235/3224 , C04B2235/3227 , C04B2235/3229 , C04B2235/3243 , C04B2235/3268 , C04B2235/441 , C04B2235/449 , C04B2235/72 , C23C16/4412 , C23C16/448 , C23C16/4486 , C23C16/45561 , C23C16/4558 , C23C16/46 , C23C16/482 , C23C16/52 , C23C18/1216 , C23C18/1275 , C23C18/14 , C30B7/00 , C30B29/68 , H01C7/1013 , H01L21/314 , H01L21/31691 , H01L27/10805 , H01L27/11502 , H01L28/55 , H01L28/56 , H01L28/60
摘要： Integrated circuit capacitors in which the capacitor dielectric is a thin film of BST having a grain size smaller than 2000 Å. Typical gain sizes are 40 nanometers and less. The BST is formed by deposition of a liquid precursor by a spin-on process. The original liquid precursor includes an alkoxycarboxylate dissolved in 2-methoxyethanol and an xylene exchange is preformed just prior to spinning. The precursor is dried in air at a temperature of about 400° C. and then furnace annealed in oxygen at a temperature of between 675° C. and 850° C.
摘要翻译：集成电路电容器，其中电容器电介质是具有小于2000埃的晶粒尺寸的BST薄膜。典型的增益尺寸为40纳米以下。 BST通过旋涂工艺沉积液体前体而形成。原始液体前体包括溶解在2-甲氧基乙醇中的烷氧基羧酸酯，并且在旋转之前预先形成二甲苯交换。前体在空气中在约400℃的温度下干燥，然后在675℃至850℃的温度下在氧气中进行炉退火。

28. 发明授权

US06358758B2 Low imprint ferroelectric material for long retention memory and method of making the same 有权
标题翻译：用于长保留记忆的低压刻铁电材料和制造相同的方法
公开(公告)号：US06358758B2
公开(公告)日：2002-03-19
申请号：US09860386
申请日：2001-05-19
申请人： Koji Arita , Shinichiro Hayashi , Joseph D. Cuchiaro , Carlos A. Paz de Araujo
发明人： Koji Arita , Shinichiro Hayashi , Joseph D. Cuchiaro , Carlos A. Paz de Araujo
IPC分类号： H01L2100
CPC分类号： H01L21/31691 , H01L27/10852
摘要： A liquid precursor for forming a thin film of ferroelectric metal oxide in an integrated circuit contains metal oxides in excess of the stoichiometrically balanced amount. When the precursor comprises strontium, bismuth, tantalum and niobium for forming strontium bismuth tantalum niobate, the precursor contains excess amounts of at least one of tantalum and niobium. Capacitors containing thin films of layered superlattice material made from a precursor containing excess tantalum and niobium show good polarizability and low percentage imprint after 1010 negative polarization switching pulses at 75° C., and after 109 negative polarization switching pulses at 125° C.
摘要翻译：用于在集成电路中形成铁电体金属氧化物薄膜的液体前体包含超过化学计量平衡量的金属氧化物。当前体包含用于形成铌酸铋钽酸铋的锶，铋，钽和铌时，前体含有过量的钽和铌中的至少一种。含有由含有过量的钽和铌的前体制成的层状超晶格材料的薄膜的电容器在75℃下在1010个负极化开关脉冲之后和在125℃的109个负极化开关脉冲之后显示出良好的极化率和低百分比印记。

29. 发明授权

US06225656B1 Ferroelectric integrated circuit with protective layer incorporating oxygen and method for fabricating same 有权
标题翻译：含有保护层的铁电集成电路和氧气的制造方法
公开(公告)号：US06225656B1
公开(公告)日：2001-05-01
申请号：US09204033
申请日：1998-12-01
申请人： Joseph D. Cuchiaro , Akira Furuya , Carlos A. Paz de Araujo , Yoichi Miyasaka
发明人： Joseph D. Cuchiaro , Akira Furuya , Carlos A. Paz de Araujo , Yoichi Miyasaka
IPC分类号： H01L2972
CPC分类号： H01L27/11502 , H01L27/11507 , H01L28/55 , H01L28/56 , H01L2924/0002 , H01L2924/00
摘要： A protective layer in a ferroelectric integrated circuit contains small amounts of oxygen to protect ferroelectric oxide material against hydrogen degradation during the fabrication process. Typically, the protective layer is a hydrogen diffusion barrier layer formed to cover a thin film of ferroelectric oxide material. In one method, a small amount of oxygen is included in the sputter atmosphere during deposition of a hydrogen diffusion barrier or a metallized wiring layer. The oxygen forms oxides that inhibit diffusion of hydrogen towards the ferroelectric oxide material. The oxygen forms a concentration gradient so that the oxygen concentration in the interior of the protective layer is zero, and the oxygen concentration near the surfaces of the layer is about two weight percent.
摘要翻译：铁电集成电路中的保护层含有少量的氧以保护铁电氧化物材料在制造过程中抵抗氢降解。通常，保护层是形成为覆盖铁电氧化物材料的薄膜的氢扩散阻挡层。在一种方法中，在沉积氢扩散阻挡层或金属化布线层期间，溅射气氛中包含少量的氧。氧形成抑制氢向铁电氧化物材料扩散的氧化物。氧形成浓度梯度，使得保护层内部的氧浓度为零，并且层表面附近的氧浓度为约2重量％。

30. 发明授权

US06570202B2 Ferroelectric integrated circuit having low sensitivity to hydrogen exposure and method for fabricating same 有权
标题翻译：对氢曝露具有低灵敏度的铁电集成电路及其制造方法
公开(公告)号：US06570202B2
公开(公告)日：2003-05-27
申请号：US09779391
申请日：2001-02-07
申请人： Joseph D. Cuchiaro , Akira Furuya , Carlos A. Paz de Araujo , Yoichi Miyasaka
发明人： Joseph D. Cuchiaro , Akira Furuya , Carlos A. Paz de Araujo , Yoichi Miyasaka
IPC分类号： H01L2976
CPC分类号： H01L27/11502 , H01L27/11585 , H01L27/1159 , H01L28/55 , H01L28/75
摘要： A hydrogen barrier layer is formed above a ferroelectric thin film in an integrated circuit. The hydrogen barrier layer is directly over a protected segment of the ferroelectric thin film, while a sacrificial segment of the ferroelectric thin film extends laterally beyond the edges of the hydrogen barrier layer. The sacrificial segment absorbs hydrogen so that it cannot diffuse laterally into the protected segment of the ferroelectric thin film. After it absorbs hydrogen, the sacrificial segment is etched away to allow electrical connection to circuit layers below it. The ferroelectric thin film preferably comprises a layered superlattice compound. Excess bismuth or niobium added to the standard precursor solution of a strontium bismuth tantalum niobate compound helps to reduce hydrogen degradation of the ferroelectric properties.
摘要翻译：在集成电路中的铁电薄膜的上方形成氢阻挡层。氢阻挡层直接在铁电薄膜的受保护部分之上，而铁电薄膜的牺牲段横向延伸超过氢阻挡层的边缘。牺牲段吸收氢，使得其不能横向扩散到铁电薄膜的受保护段中。在吸收氢之后，牺牲段被蚀刻掉以允许电连接到其下方的电路层。铁电薄膜优选包含层状超晶格化合物。添加到铌酸铋钽酸锶化合物的标准前体溶液中的过量铋或铌有助于降低铁电性能的氢降解。

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