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1. 发明授权

US5962069A Process for fabricating layered superlattice materials and AB0.sub.3 type metal oxides without exposure to oxygen at high temperatures 失效
标题翻译：用于在高温下不暴露于氧气的层压超晶格材料和AB03型金属氧化物的制造方法
公开(公告)号：US5962069A
公开(公告)日：1999-10-05
申请号：US900270
申请日：1997-07-25
申请人： Gunther Schindler , Walter Hartner , Carlos Mazure , Narayan Solayappan , Vikram Joshi , Gary F. Derbenwick
发明人： Gunther Schindler , Walter Hartner , Carlos Mazure , Narayan Solayappan , Vikram Joshi , Gary F. Derbenwick
IPC分类号： C23C18/12 , H01L21/314 , H01L21/316 , B05D3/02 , H01L21/3205
CPC分类号： H01L21/31691 , C23C18/1216 , C23C18/1225 , C23C18/1275 , C23C18/1283 , C23C18/1295
摘要： A liquid precursor containing a metal is applied to a first electrode, dried in air at a first temperature of 160.degree. C. and then a second temperature of 260.degree. C., RTP baked at a temperature of 300.degree. C. in oxygen, RTP baked at a temperature of 650.degree. C. in nitrogen, and annealed at a temperature of 800.degree. C. in nitrogen to form a strontium bismuth tantalate layered superlattice material. A second electrode is deposited and then the device is patterned to form a capacitor, and a second anneal is performed at a temperature of 800.degree. C. in nitrogen. Alternatively, the second anneal may be performed in oxygen at a temperature of 600.degree. C. or less. In this manner, a high electronic quality thin film of a layered superlattice material is fabricated without a high-temperature oxygen anneal.
摘要翻译：将含有金属的液体前体施加到第一电极上，在空气中在160℃的第一温度下干燥，然后在260℃的第二温度下干燥，在氧气中在300℃下进行RTP烘焙，RTP 在氮气中在650℃下烘烤，并在氮气中在800℃的温度下退火，形成钽酸铋锶层状超晶格材料。沉积第二电极，然后将器件图案化以形成电容器，并且在氮气中在800℃的温度下进行第二次退火。或者，第二退火可以在600℃以下的温度下进行。以这种方式，在没有高温氧退火的情况下制造层状超晶格材料的高电子质量薄膜。

2. 发明授权

US06171934B2 Recovery of electronic properties in process-damaged ferroelectrics by voltage-cycling 失效
标题翻译：通过电压循环恢复工艺损坏的铁电体中的电子特性
公开(公告)号：US06171934B2
公开(公告)日：2001-01-09
申请号：US09144297
申请日：1998-08-31
申请人： Vikram Joshi , Narayan Solayappan , Walter Hartner , G{umlaut over (u)}nther Schindler
发明人： Vikram Joshi , Narayan Solayappan , Walter Hartner , G{umlaut over (u)}nther Schindler
IPC分类号： H01L21326
CPC分类号： H01L27/11502 , H01L27/11507 , H01L28/55
摘要： An integrated circuit is formed containing a metal-oxide ferroelectric thin film. An voltage-cycling recovery process is conducted to reverse the degradation of ferroelectric properties caused by hydrogen. The voltage-cycling recovery process is conducted by applying from 104 to 1011 voltage cycles with a voltage amplitude of from 1 to 15 volts. Conducting voltage-cycling at a higher temperature in the range 30-200° C. enhances recovery. Preferably the metal oxide thin film comprises layered superlattice material. Preferably the layered superlattice material comprises strontium bismuth tantalate or strontium bismuth tantalum niobate. If the integrated circuit manufacture includes a forming-gas anneal, then the voltage-cycling recovery process is performed after the forming-gas anneal. The voltage-cycling recovery process obviates oxygen-recovery annealing, and it allows continued use of conventional hydrogen-rich plasma processes and forming-gas anneals without the risk of permanent damage to the ferroelectric thin film.
摘要翻译：形成含有金属氧化物铁电体薄膜的集成电路。进行电压循环恢复处理以逆转由氢引起的铁电性能的降低。通过施加电压幅度为1至15伏特的104至1011个电压周期来执行电压循环恢复过程。在30-200℃范围内的较高温度下进行电压循环，提高了回收率。优选地，金属氧化物薄膜包括层状超晶格材料。优选地，层状超晶格材料包括钽酸铋钽铋或铌酸铋钽酸铋。如果集成电路制造包括成形气体退火，则在成形气体退火之后执行电压循环恢复过程。电压循环恢复过程避免氧回收退火，并且其允许继续使用常规富氢等离子体工艺和形成气体退火，而不会对铁电薄膜造成永久损坏的风险。

3. 发明授权

US06322849B2 Recovery of electronic properties in hydrogen-damaged ferroelectrics by low-temperature annealing in an inert gas 失效
标题翻译：在惰性气体中通过低温退火在氢损坏的铁电体中回收电子性能
公开(公告)号：US06322849B2
公开(公告)日：2001-11-27
申请号：US09191634
申请日：1998-11-13
申请人： Vikram Joshi , Narayan Solayappan , Walter Hartner , Günther Schindler
发明人： Vikram Joshi , Narayan Solayappan , Walter Hartner , Günther Schindler
IPC分类号： B05D512
CPC分类号： H01L27/11502 , H01L27/11507 , H01L28/55
摘要： An integrated circuit is formed containing a metal-oxide ferroelectric thin film. An inert-gas recovery anneal is conducted to reverse the degradation of ferroelectric properties caused by hydrogen. The inert-gas recovery anneal is conducted in an unreactive gas atmosphere at a temperature range from 300° to 1000° C. for a time period from one minute to two hours. Preferably, the metal-oxide thin film comprises layered superlattice material. Preferably, the layered superlattice material comprises strontium bismuth tantalate or strontium bismuth tantalum niobate. If the integrated circuit manufacture includes a forming-gas anneal, then the inert-gas recovery anneal is performed after the forming-gas anneal, preferably at or near the same temperature and for the same time duration as the forming-gas anneal. The inert-gas recovery anneal obviates oxygen-recovery annealing, and it allows continued use of conventional hydrogen-rich plasma processes and forming-gas anneals without the risk of permanent damage to the ferroelectric thin film. The unreactive gas atmosphere can contain a pure unreactive gas or a mixture of unreactive gases. The unreactive gas can be any relatively unreactive gas, such as nitrogen or argon.
摘要翻译：形成含有金属氧化物铁电体薄膜的集成电路。进行惰性气体回收退火以逆转由氢引起的铁电性能的降低。惰性气体回收退火在300〜1000℃的无反应气体气氛中进行1分钟〜2小时。优选地，金属氧化物薄膜包括层状超晶格材料。优选地，层状超晶格材料包括铋铋钽酸锶或铌酸铋钽酸铋。如果集成电路制造包括成形气体退火，则惰性气体回收退火在成形气体退火之后进行，优选在与成形气体退火相同或接近相同的温度和相同的持续时间。惰性气体回收退火避免了氧回收退火，并且允许继续使用常规富氢等离子体工艺和形成气体退火，而不会对铁电薄膜造成永久性损坏的风险。非活性气体气氛可以含有纯的非反应性气体或非反应性气体的混合物。非反应性气体可以是任何相对不反应的气体，例如氮气或氩气。

4. 发明授权

US06867452B2 Interlayer oxide containing thin films for high dielectric constant application of the formula AB2O6 or AB2O7 失效
标题翻译：含有氧化物的薄膜用于高介电常数应用的AB2O6或AB2O7
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。

5. 发明授权

US06781184B2 Barrier layers for protecting metal oxides from hydrogen degradation 有权
标题翻译：用于保护金属氧化物免受氢降解的阻挡层
公开(公告)号：US06781184B2
公开(公告)日：2004-08-24
申请号：US09998469
申请日：2001-11-29
申请人： Narayan Solayappan , Jolanta Celinska , Vikram Joshi , Carlos A. Paz de Araujo , Larry D. McMillan
发明人： Narayan Solayappan , Jolanta Celinska , Vikram Joshi , Carlos A. Paz de Araujo , Larry D. McMillan
IPC分类号： H01L27108
CPC分类号： H01L28/57 , H01L23/642 , H01L2924/0002 , H01L2924/00
摘要： A hydrogen diffusion barrier in an integrated circuit is located to inhibit diffusion of hydrogen to a thin film of a metal oxide, such as a ferroelectric layered superlattice material, in an integrated circuit. The hydrogen diffusion barrier comprises at least one of the following chemical compounds: strontium tantalate, bismuth tantalate, tantalum oxide, titanium oxide, zirconium oxide and aluminum oxide. The hydrogen barrier layer is amorphous and is made by a MOCVD process at a temperature of 450° C. or less. A supplemental hydrogen barrier layer comprising a material selected from the group consisting of silicon nitride and a crystalline form of one of said hydrogen barrier layer materials is formed adjacent to said hydrogen diffusion barrier.
摘要翻译：集成电路中的氢扩散阻挡层位于集成电路中以抑制氢扩散到诸如铁电层状超晶格材料的金属氧化物的薄膜。氢扩散阻挡层包括以下化合物中的至少一种：钽酸锶，钽酸铋，氧化钽，氧化钛，氧化锆和氧化铝。氢阻挡层是无定形的，并且在450℃或更低的温度下通过MOCVD工艺制成。在与所述氢扩散阻挡层相邻的地方形成包括选自氮化硅和所述氢阻挡层材料之一的结晶形式的材料的补充氢阻挡层。

6. 发明授权

US06541279B2 Method for forming an integrated circuit 有权
标题翻译：集成电路形成方法
公开(公告)号：US06541279B2
公开(公告)日：2003-04-01
申请号：US09798310
申请日：2001-03-02
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： H01L2100
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(TayNby−1)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（TayNby-1）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.本发明金属氧化物中的Vcc值接近零。 Tcc的值<1000ppm，优选<100。

7. 发明授权

US07187079B2 Stacked memory cell having diffusion barriers 有权
标题翻译：具有扩散阻挡层的堆积式存储单元
公开(公告)号：US07187079B2
公开(公告)日：2007-03-06
申请号：US10666381
申请日：2003-09-19
申请人： Vikram Joshi , Narayan Solayappan , Carlos A. Paz de Araujo , Larry D. McMillan
发明人： Vikram Joshi , Narayan Solayappan , Carlos A. Paz de Araujo , Larry D. McMillan
IPC分类号： H01L23/48
CPC分类号： H01L27/11502 , C30B29/32 , C30B29/68 , H01L23/642 , H01L27/11507 , H01L28/55 , H01L2924/0002 , H01L2924/00
摘要： A nonconductive hydrogen barrier layer is deposited on a substrate and completely covers the surface area over a memory capacitor and a MOSFET switch of an integrated circuit memory cell. A portion of an insulator layer adjacent to the bottom electrode of a memory capacitor is removed by etching to form a moat region. A nonconductive oxygen barrier layer is deposited to cover the sidewall and bottom of the moat. The nonconductive oxygen barrier layer and a conductive diffusion barrier beneath the capacitor together provide a substantially continuous diffusion barrier between the capacitor and a switch. Also, the nonconductive hydrogen barrier layer, the nonconductive oxygen barrier, and the conductive diffusion barrier substantially completely envelop the capacitor, in particular a ferroelectric thin film in the capacitor.
摘要翻译：非导电氢阻挡层沉积在基板上并完全覆盖集成电路存储单元的存储电容器和MOSFET开关上的表面积。通过蚀刻去除与存储电容器的底部电极相邻的绝缘体层的一部分，以形成护城河区域。沉积非导电氧阻隔层以覆盖护城河的侧壁和底部。电容器下面的非导电氧阻挡层和导电扩散阻挡层一起在电容器和开关之间提供基本上连续的扩散阻挡层。此外，非导电氢阻挡层，非导电氧阻挡层和导电扩散阻挡层基本上完全包围电容器，特别是电容器中的铁电薄膜。

8. 发明授权

US07064374B2 Barrier layers for protecting metal oxides from hydrogen degradation 有权
公开(公告)号：US07064374B2
公开(公告)日：2006-06-20
申请号：US10872895
申请日：2004-06-21
申请人： Narayan Solayappan , Jolanta Celinska , Vikram Joshi , Carlos A. Paz de Araujo , Larry D. McMillan
发明人： Narayan Solayappan , Jolanta Celinska , Vikram Joshi , Carlos A. Paz de Araujo , Larry D. McMillan
IPC分类号： H01L27/108
CPC分类号： H01L28/57 , H01L23/642 , H01L2924/0002 , H01L2924/00
摘要： A hydrogen diffusion barrier in an integrated circuit is located to inhibit diffusion of hydrogen to a thin film of a metal oxide, such as a ferroelectric layered superlattice material, in an integrated circuit. The hydrogen diffusion barrier comprises at least one of the following chemical compounds: strontium tantalate, bismuth tantalate, tantalum oxide, titanium oxide, zirconium oxide and aluminum oxide. The hydrogen barrier layer is amorphous and is made by a MOCVD process at a temperature of 450° C. or less. A supplemental hydrogen barrier layer comprising a material selected from the group consisting of silicon nitride and a crystalline form of one of said hydrogen barrier layer materials is formed adjacent to said hydrogen diffusion barrier.

9. 发明授权

US06831313B2 Ferroelectric composite material, method of making same and memory utilizing same 失效
标题翻译：铁电复合材料，制造方法和利用其的记忆
公开(公告)号：US06831313B2
公开(公告)日：2004-12-14
申请号：US10332481
申请日：2003-07-22
申请人： Kiyoshi Uchiyama , Carlos A. Paz de Araujo , Vikram Joshi , Narayan Solayappan , Jolanta Celinska , Larry D. McMillan
发明人： Kiyoshi Uchiyama , Carlos A. Paz de Araujo , Vikram Joshi , Narayan Solayappan , Jolanta Celinska , Larry D. McMillan
IPC分类号： H01L2972
CPC分类号： H01L27/11502 , H01L21/02197 , H01L21/02282 , H01L21/28291 , H01L21/31691 , H01L27/11507 , H01L28/55 , H01L29/516 , H01L29/6684 , H01L29/78391
摘要： A ferroelectric memory (436) includes a plurality of memory cells (73, 82, 100) each containing a ferroelectric thin film (15) including a microscopically composite material having a ferroelectric component (18) and a dielectric component (19), the dielectric component being a different chemical compound than the ferroelectric component. The dielectric component is preferably a fluxor, i.e., a material having a higher crystallization velocity than the ferroelectric component. The addition of the fluxor permits a ferroelectric thin film to be crystallized at a temperature of between 400° C. and 550° C.
摘要翻译：铁电存储器（436）包括多个存储单元（73,82,100），每个存储单元包含具有铁电元件（18）和电介质元件（19）的显微复合材料的铁电薄膜（15），所述电介质组分是与铁电体组分不同的化合物。电介质成分优选为磁通量，即具有比铁电体成分高的结晶速度的材料。添加磁通管允许铁电薄膜在400℃和550℃之间的温度下结晶。

10. 发明授权

US06582972B1 Low temperature oxidizing method of making a layered superlattice material 有权
标题翻译：制作层状超晶格材料的低温氧化法
公开(公告)号：US06582972B1
公开(公告)日：2003-06-24
申请号：US09544697
申请日：2000-04-07
申请人： Vikram Joshi , Jolanta Celinska , Narayan Solayappan , Larry D. McMillan , Carlos A. Paz de Araujo , Koji Arita
发明人： Vikram Joshi , Jolanta Celinska , Narayan Solayappan , Larry D. McMillan , Carlos A. Paz de Araujo , Koji Arita
IPC分类号： H01G2100
CPC分类号： H01L27/11502 , C30B7/00 , C30B7/005 , C30B29/68 , H01L21/31691
摘要： A thin film of precursor for forming a layered superlattice material is applied to an integrated circuit substrate, then a strong oxidizing agent is applied at low temperature in a range of from 100° C. to 300° C. to the precursor thin film, thereby forming a metal oxide thin film. The strong oxidizing agent may be liquid or gaseous. An example of a liquid strong oxidizing agent is hydrogen peroxide. An example of a gaseous strong oxidizing agent is ozone. The metal oxide thin film is crystallized by annealing at elevated temperature in a range of from 500° C. to 700° C., preferably not exceeding 650° C., for a time period in a range of from 30 minutes to two hours. Annealing is conducted in an oxygen-containing atmosphere, preferably including water vapor. Treatment by ultraviolet (UV) radiation may precede annealing. RTP in a range of from 500° C. to 700° C. may precede annealing.
摘要翻译：将用于形成层状超晶格材料的前体薄膜施加到集成电路基板上，然后在100℃至300℃的低温下向前体薄膜施加强氧化剂，由此形成金属氧化物薄膜。强氧化剂可以是液体或气体。液体强氧化剂的实例是过氧化氢。气态强氧化剂的实例是臭氧。金属氧化物薄膜通过在500℃至700℃，优选不超过650℃的范围内的升高温度退火30分钟至2小时的时间段而结晶。退火在含氧气氛中进行，优选包括水蒸气。紫外线（UV）辐射处理可能退火之前。可以在退火之前从500℃到700℃的范围内的RTP。

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