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。

公开(公告)号：US06281534B1

公开(公告)日：2001-08-28

申请号：US09170417

申请日：1998-10-13

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： H01L2976

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。

公开(公告)号：US06495878B1

公开(公告)日：2002-12-17

申请号：US09365628

申请日：1999-08-02

申请人： Shinichiro Hayashi ,  Vikram Joshi ,  Narayan Solayappan ,  Joseph D. Cuchiaro ,  Carlos A. Paz de Araujo

发明人： Shinichiro Hayashi ,  Vikram Joshi ,  Narayan Solayappan ,  Joseph D. Cuchiaro ,  Carlos A. Paz de Araujo

IPC分类号： H01L27108

CPC分类号： H01L21/02197 ,  H01L21/02205 ,  H01L21/02282 ,  H01L21/02348 ,  H01L21/31691 ,  H01L27/0629

摘要： A high dielectric constant insulator including a thin film of a metal oxide selected from the group consisting of tungsten-bronze-type oxides, pyrochlore-type oxides, and combinations of Bi2O3 with an oxide selected from the group consisting of perovskites and pyrochlore-type oxides. An embodiment contains metal oxides represented by the general stoichiometric formulas AB2O6, A2B2O7 and A2Bi2B2O10, wherein A represents A-site atoms selected from the group of metals consisting of Ba, Bi, Sr, Pb, Ca, K, Na and La; and B represents B-site atoms selected from the group of metals consisting of Ti, Zr, Ta, Hf, Mo, W and Nb. Preferably, the metal oxides are (BaxSr1−x)(TayNb1−y)2O6, where 0≦x≦1.0 and 0≦y≦1.0; (BaxSr1−x)2(TayNb1−Y)2O7, where 0≦x≦1.0 and 0≦y≦1.0; and (BaxSr1−x)2Bi2(TayNb1−y)2O10, where 0≦x≦1.0 and 0≦y≦1.0. Thin films according to the invention have a relative dielectric constant ≧40, and preferably about 100. The value of Vcc in the metal oxides of the invention is close to zero. The value of Tcc is

摘要翻译： 一种高介电常数绝缘体，包括选自钨青铜型氧化物，烧绿石型氧化物和Bi 2 O 3与选自钙钛矿和烧绿石型氧化物的氧化物的组合的金属氧化物的薄膜 。 一个实施方案包含由一般化学计量式AB2O6，A2B2O7和A2B2B2O10表示的金属氧化物，其中A表示选自由Ba，Bi，Sr，Pb，Ca，K，Na和La组成的金属组中的A位原子; B表示选自由Ti，Zr，Ta，Hf，Mo，W和Nb组成的金属组中的B位原子。 优选地，金属氧化物是（BaxSr1-x）（TayNb1-y）2O6，其中0 <= x <= 1.0且0 <= y <= 1.0; （BaxSr1-x）2（TayNb1-Y）2O7，其中0 <= x <= 1.0且0 <= y <= 1.0; 和（BaxSr1-x）2Bi2（TayNb1-y）2O10，其中0 <= x <= 1.0且0 <= y <= 1.0。 根据本发明的薄膜的相对介电常数> 40，优选约100。本发明的金属氧化物中的Vcc值接近零。 Tcc的值<1000ppm，优选<100。

公开(公告)号：US06413883B1

公开(公告)日：2002-07-02

申请号：US09243254

申请日：1999-02-03

申请人： Shinichiro Hayashi ,  Larry D. McMillan ,  Carlos A. Paz de Araujo

发明人： Shinichiro Hayashi ,  Larry D. McMillan ,  Carlos A. Paz de Araujo

IPC分类号： H01L2131

CPC分类号： C23C18/1216 ,  C23C18/1291 ,  C23C18/14 ,  H01L21/02197 ,  H01L21/02282 ,  H01L21/02348 ,  H01L21/31691

摘要： A plurality of liquids, the flow of each controlled by a volumetric flowrate controller, are mixed in a mixer to form a final precursor that is misted and then deposited on a substrate. A physical property of precursor liquid is adjusted by adjusting the volumetric flowrate controllers, so that when precursor is applied to substrate and treated, the resulting thin film of solid material has a smooth and planar surface. Typically the physical property is the viscosity of the precursor, which is selected to be relatively low, in the range of 1-2 centipoise.

摘要翻译： 将多个液体，每个由体积流量控制器控制的流量在混合器中混合以形成被雾化并随后沉积在基底上的最终前体。 通过调节体积流量控制器来调节前体液体的物理性质，使得当将前体施加到基底并进行处理时，所得到的固体材料薄膜具有平滑和平坦的表面。 通常，物理性质是前体的粘度，其被选择为相对较低，在1-2厘泊的范围内。

公开(公告)号：US6133092A

公开(公告)日：2000-10-17

申请号：US122562

申请日：1998-07-24

申请人： Shinichiro Hayashi ,  Carlos A. Paz de Araujo

发明人： Shinichiro Hayashi ,  Carlos A. Paz de Araujo

IPC分类号： C23C18/12 ,  H01L21/314 ,  H01L21/316 ,  H01L21/8246 ,  H01L27/105 ,  H01L21/8242 ,  H01L21/20

CPC分类号： H01L21/31691 ,  C23C18/1216 ,  C23C18/1295

摘要： A liquid precursor containing thallium is applied to a first electrode, RTP baked at a temperature lower than 725.degree. C., and annealed at the same temperature for a time period from one to five hours to yield a ferroelectric layered superlattice material. A second electrode is formed to form a capacitor, and a second anneal is performed at a temperature lower than 725.degree. C. If the material is strontium bismuth thallium tantalate, the precursor contains (m-1) mole-equivalents of strontium for each of (2.2-x) mole-equivalents of bismuth, x mole-equivalents of thallium, and m mole-equivalents of tantalum, where m=2 and 0.0

摘要翻译： 将包含铊的液体前体施加到第一电极，RTP在低于725℃的温度下烘烤，并在相同温度下退火1至5小时，得到铁电层状超晶格材料。 形成第二电极以形成电容器，并且在低于725℃的温度下进行第二退火。如果该材料是钽酸锶钽酸锶，则前体含有（m-1）摩尔当量的锶 （2.2-x）摩尔当量的铋，x摩尔当量的铊和m摩尔当量的钽，其中m = 2和0.0

公开(公告)号：US5972428A

公开(公告)日：1999-10-26

申请号：US611414

申请日：1996-03-05

申请人： Shinichiro Hayashi ,  Larry D. McMillan ,  Masamichi Azuma ,  Carlos A. Paz de Araujo

发明人： Shinichiro Hayashi ,  Larry D. McMillan ,  Masamichi Azuma ,  Carlos A. Paz de Araujo

IPC分类号： H01L21/314 ,  H01L21/316 ,  C23C16/00 ,  B05D1/02

CPC分类号： H01L21/31691

摘要： A liquid primer is misted, flowed into a deposition chamber and deposited on a substrate. A liquid precursor is then misted, flowed into a deposition chamber and deposited on the substrate. The primer and precursor are dried to form a solid thin film, which is then annealed to form a part of an electronic component in an integrated circuit, such as the dielectric in a memory cell. The primer is a solvent, and the precursor includes a metal carboxylate, a metal alkoxide, or a metal alkoxycarboxylate in a precursor solvent. Preferably, the primer and the precursor solvent are the same solvent, such as 2-methoxyethanol, xylenes, or n-butyl acetate.

摘要翻译： 液体底漆被雾化，流入沉积室并沉积在基底上。 然后液体前体被雾化，流入沉积室并沉积在基底上。 将底漆和前体干燥以形成固体薄膜，然后将其退火以形成集成电路中的电子部件的一部分，例如存储单元中的电介质。 引物是溶剂，前体在前体溶剂中包括金属羧酸盐，金属醇盐或烷氧基羧酸金属盐。 优选地，底漆和前体溶剂是相同的溶剂，例如2-甲氧基乙醇，二甲苯或乙酸正丁酯。

公开(公告)号：US06383555B1

公开(公告)日：2002-05-07

申请号：US09615373

申请日：2000-07-13

申请人： Shinichiro Hayashi ,  Larry D. McMillan ,  Carlos A. Paz de Araujo

发明人： Shinichiro Hayashi ,  Larry D. McMillan ,  Carlos A. Paz de Araujo

IPC分类号： B05D512

CPC分类号： H01L21/31691 ,  B05D1/00 ,  B05D1/60 ,  B05D3/0493 ,  B05D3/062 ,  B05D3/065 ,  C23C8/10 ,  C23C16/4412 ,  C23C16/4486 ,  C23C16/45561 ,  C23C16/4558 ,  C23C16/46 ,  C23C16/482 ,  C23C16/52 ,  C23C18/12 ,  C23C18/1216 ,  C23C18/1287 ,  C23C18/1291 ,  C23C18/14 ,  C23C26/02 ,  C30B7/00 ,  C30B7/005 ,  C30B29/68 ,  H01L21/02197 ,  H01L21/02282 ,  H01L21/02348 ,  H01L27/11502 ,  H01L28/55 ,  H01L28/56 ,  H01L28/60 ,  H01L41/314 ,  H05K3/105 ,  Y10S427/101

摘要： A substrate is located within a deposition chamber, the substrate defining a substrate plane. A liquid precursor is misted by ultrasonic or venturi apparatus, to produce a colloidal mist. The mist is generated, allowed to settle in a buffer chamber, filtered through a system up to 0.01 micron, and flowed into the deposition chamber between the substrate and barrier plate to deposit a liquid layer on the substrate. The liquid is dried to form a thin film of solid material on the substrate, which is then incorporated into an electrical component of an integrated circuit.

摘要翻译： 衬底位于沉积室内，衬底限定衬底平面。 液体前体被超声波或文氏管装置迷雾，产生胶体雾。 产生雾，允许沉淀在缓冲室中，通过高达0.01微米的系统过滤，并流入基板和阻挡板之间的沉积室，以在基板上沉积液体层。 将液体干燥以在基板上形成固体材料的薄膜，然后将其并入集成电路的电气部件中。

公开(公告)号：US5965219A

公开(公告)日：1999-10-12

申请号：US591341

申请日：1996-01-25

申请人： Shinichiro Hayashi ,  Larry D. McMillan ,  Carlos A. Paz de Araujo

发明人： Shinichiro Hayashi ,  Larry D. McMillan ,  Carlos A. Paz de Araujo

IPC分类号： B05D1/00 ,  B05D3/04 ,  B05D3/06 ,  B05D7/24 ,  C23C8/10 ,  C23C16/44 ,  C23C16/448 ,  C23C16/455 ,  C23C16/46 ,  C23C16/48 ,  C23C16/52 ,  C23C18/12 ,  C23C18/14 ,  C23C26/02 ,  C30B7/00 ,  H01L21/02 ,  H01L21/314 ,  H01L21/316 ,  H01L27/115 ,  H01L41/24 ,  H05K3/10 ,  C23C8/00

CPC分类号： C23C18/1216 ,  B05D1/00 ,  B05D1/60 ,  B05D3/0493 ,  B05D3/062 ,  B05D3/065 ,  C23C16/4412 ,  C23C16/448 ,  C23C16/4486 ,  C23C16/45561 ,  C23C16/4558 ,  C23C16/46 ,  C23C16/482 ,  C23C16/52 ,  C23C18/14 ,  C23C26/02 ,  C23C8/10 ,  C30B29/68 ,  C30B7/00 ,  C30B7/005 ,  H01L21/31691 ,  H01L27/11502 ,  H01L28/56 ,  H01L28/60 ,  H01L41/317 ,  H01L28/55 ,  H01L41/1871 ,  H05K3/105

摘要： UV radiation is applied to a substrate in a deposition chamber to desorb water and other contaminates from it. A liquid precursor is misted, flowed into the deposition chamber and deposited on a substrate while UV radiation is applied to the mist. The film of liquid on the substrate is dried and annealed on the substrate while the UV radiation is applied to form a solid thin film of a metal oxide. The thin film is then incorporated into an electronic device of an integrated circuit fabricated on the substrate. The application of UV radiation to both the mist during deposition and the thin film after deposition significantly increases the quality of the resulting integrated circuits. The process has been found to be particularly excellent for making BST, strontium bismuth tantalate, and strontium bismuth niobate.

摘要翻译： 将UV辐射施加到沉积室中的基底以从其中解吸水和其它污染物。 液体前体被雾化，流入沉积室并沉积在基底上，同时将紫外线辐射施加于雾。 将衬底上的液体膜干燥并在衬底上退火，同时施加UV辐射以形成金属氧化物的固体薄膜。 然后将薄膜并入到在衬底上制造的集成电路的电子器件中。 在沉积期间将UV辐射施加到雾和沉积后的薄膜显着增加了所得到的集成电路的质量。 已经发现该方法对于制备BST，钽酸锶锶和铌酸铋锶特别优异。

公开(公告)号：US5843516A

公开(公告)日：1998-12-01

申请号：US714774

申请日：1996-09-16

申请人： Gary F. Derbenwick ,  Larry D. McMillan ,  Narayan Solayappan ,  Michael C. Scott ,  Carlos A. Paz de Araujo ,  Shinichiro Hayashi

发明人： Gary F. Derbenwick ,  Larry D. McMillan ,  Narayan Solayappan ,  Michael C. Scott ,  Carlos A. Paz de Araujo ,  Shinichiro Hayashi

IPC分类号： C23C18/12 ,  H01L21/314 ,  H01L21/316 ,  B05D5/12

CPC分类号： H01L21/31691 ,  C23C18/1216 ,  C23C18/1225

摘要： A precursor liquid comprising several metal 2-ethylhexanoates, such as strontium, tantalum and bismuth 2-ethylhexanoates, in a xylenes/methyl ethyl ketone solvent is prepared, a substrate is placed within a vacuum deposition chamber, a small amount of hexamethyl-disilazane is added to the precursor liquid is misted, and the mist is flowed into the deposition chamber while maintaining the chamber at ambient temperature to deposit a layer of the precursor liquid on the substrate. The liquid is dried, baked, and annealed to form a thin film of a layered superlattice material, such as strontium bismuth tantalate, on the substrate. Then an integrated circuit is completed to include at least a portion of the layered superlattice material film in a component of the integrated circuit.

摘要翻译： 制备在二甲苯/甲基乙基酮溶剂中包含若干金属2-乙基己酸酯如锶，钽和铋2-乙基己酸酯的前体液体，将基材置于真空沉积室内，少量六甲基二硅氮烷 加入到前体液体中，雾气流入沉积室，同时将室保持在环境温度，以将一层前体液体沉积在基底上。 将液体干燥，烘烤和退火，以在基底上形成层状超晶格材料（例如钽酸锶锶）的薄膜。 然后，完成集成电路以将集成电路的部件中的至少一部分分层超晶格材料膜包括在内。

公开(公告)号：US06867452B2

公开(公告)日：2005-03-15

申请号：US10278581

申请日：2002-10-23

申请人： Shinichiro Hayashi ,  Vikram Joshi ,  Narayan Solayappan ,  Joseph D. Cuchiaro ,  Carlos A. Paz de Araujo

发明人： Shinichiro Hayashi ,  Vikram Joshi ,  Narayan Solayappan ,  Joseph D. Cuchiaro ,  Carlos A. Paz de Araujo

IPC分类号： H01L21/314 ,  H01L21/316 ,  H01L27/06 ,  H01L29/76 ,  H01L29/94 ,  H01L31/062 ,  H01L31/113 ,  H01L31/119

CPC分类号： H01L21/02197 ,  H01L21/02205 ,  H01L21/02282 ,  H01L21/02348 ,  H01L21/31691 ,  H01L27/0629

摘要： A high dielectric constant insulator including a thin film of a metal oxide selected from the group consisting of tungsten-bronze-type oxides, pyrochlore-type oxides, and combinations of Bi2O3 with an oxide selected from the group consisting of perovskites and pyrochlore-type oxides. An embodiment contains metal oxides represented by the general stoichiometric formulas AB2O6, A2B2O7 and A2Bi2B2O10, wherein A represents A-site atoms selected from the group of metals consisting of Ba, Bi, Sr, Pb, Ca, K, Na and La; and B represents B-site atoms selected from the group of metals consisting of Ti, Zr, Ta, Hf, Mo, W and Nb. Preferably, the metal oxides are (BaxSr1−x)(TayNb1−y)2O6, where 0≦y≦1.0 and 0≦y≦1.0; (BaxSr1−x)2(TayNb1−y)2O7, where 0≦x≦1.0 and 0≦y≦1.0; and (BaxSr1−x)2Bi2(TayNb1−y)2O10, where 0≦x≦1.0 and 0≦y≦1.0. Thin films according to the invention have a relative dielectric constant ≧40, and preferably about 100. The value of Vcc in the metal oxides of the invention is close to zero. The value of Tcc is

摘要翻译： 一种高介电常数绝缘体，包括选自钨青铜型氧化物，烧绿石型氧化物和Bi 2 O 3与选自钙钛矿和烧绿石型氧化物的氧化物的组合的金属氧化物的薄膜 。 一个实施方案包含由一般化学计量式AB2O6，A2B2O7和A2B2B2O10表示的金属氧化物，其中A表示选自由Ba，Bi，Sr，Pb，Ca，K，Na和La组成的金属组中的A位原子; B表示选自由Ti，Zr，Ta，Hf，Mo，W和Nb组成的金属组中的B位原子。 优选地，金属氧化物是（BaxSr1-x）（TayNb1-y）2O6，其中0 <= y <= 1.0且0 <= Y＆LE; 1.0; （BAxSr1-x）2（TayNb1-y）2O7，其中0 <= x <= 1.0且0 <= y <= 1.0; AND（BAxSr1-x）2Bi2（TayNb1-y）2O10，其中0 <= x <= 1.0且0 <= y <= 1.0。 根据本发明的薄膜的相对介电常数> 40，优选约100。本发明的金属氧化物中的Vcc值接近零。 Tcc的值<1000ppm，优选<100。