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1. 发明授权

US09130165B2 Atomic layer deposition of metal oxide materials for memory applications 有权
标题翻译：用于记忆应用的金属氧化物材料的原子层沉积
公开(公告)号：US09130165B2
公开(公告)日：2015-09-08
申请号：US14506298
申请日：2014-10-03
申请人： Intermolecular Inc. , Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Yun Wang , Tony P. Chiang , Vidyut Gopal , Imran Hashim , Dipankar Pramanik
IPC分类号： H01L47/00 , H01L45/00 , C23C16/40 , C23C16/455 , H01L21/02 , H01L27/24
CPC分类号： H01L45/145 , C23C16/40 , C23C16/45525 , H01L21/02175 , H01L21/02178 , H01L21/02181 , H01L21/02186 , H01L21/02189 , H01L21/02192 , H01L21/02194 , H01L21/022 , H01L21/0228 , H01L27/2463 , H01L45/08 , H01L45/1266 , H01L45/146 , H01L45/1608 , H01L45/1616
摘要： Embodiments of the invention generally relate to nonvolatile memory devices, such as a ReRAM cells, and methods for manufacturing such memory devices, which includes optimized, atomic layer deposition (ALD) processes for forming metal oxide film stacks. The metal oxide film stacks contain a metal oxide coupling layer disposed on a metal oxide host layer, each layer having different grain structures/sizes. The interface disposed between the metal oxide layers facilitates oxygen vacancy movement. In many examples, the interface is a misaligned grain interface containing numerous grain boundaries extending parallel to the electrode interfaces, in contrast to the grains in the bulk film extending perpendicular to the electrode interfaces. As a result, oxygen vacancies are trapped and released during switching without significant loss of vacancies. Therefore, the metal oxide film stacks have improved switching performance and reliability during memory cell applications compared to traditional hafnium oxide based stacks of previous memory cells.
摘要翻译：本发明的实施例一般涉及非易失性存储器件，例如ReRAM单元，以及用于制造这种存储器件的方法，其包括用于形成金属氧化物膜堆叠的优化的原子层沉积（ALD）工艺。金属氧化物膜堆叠包含设置在金属氧化物主体层上的金属氧化物耦合层，每个层具有不同的晶粒结构/尺寸。设置在金属氧化物层之间的界面有助于氧空位移动。在许多示例中，与垂直于电极界面延伸的体膜中的晶粒相反，界面是不对齐的晶粒界面，其包含平行于电极界面延伸的许多晶界。因此，氧空缺在切换期间被捕获和释放，而空位明显损失。因此，与以前的存储单元的传统的基于氧化铪的堆叠相比，金属氧化物膜堆叠在存储单元应用中具有改进的开关性能和可靠性。

2. 发明授权

US09087978B1 Transition metal oxide bilayers 有权
公开(公告)号：US09087978B1
公开(公告)日：2015-07-21
申请号：US14618055
申请日：2015-02-10
申请人： Intermolecular Inc. , Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Hieu Pham , Vidyut Gopal , Imran Hashim , Tim Minvielle , Yun Wang , Takeshi Yamaguchi , Hong Sheng Yang
IPC分类号： H01L29/02 , H01L45/00
CPC分类号： H01L45/08 , H01L27/2409 , H01L27/2463 , H01L45/1233 , H01L45/1253 , H01L45/145 , H01L45/146 , H01L45/147 , H01L45/16 , H01L45/1616 , H01L45/1625 , H01L45/1641
摘要： Embodiments of the invention include nonvolatile memory elements and memory devices comprising the nonvolatile memory elements. Methods for forming the nonvolatile memory elements are also disclosed. The nonvolatile memory element comprises a first electrode layer, a second electrode layer, and a plurality of layers of an oxide disposed between the first and second electrode layers. One of the oxide layers has linear resistance and substoichiometric composition, and the other oxide layer has bistable resistance and near-stoichiometric composition. Preferably, the sum of the two oxide layer thicknesses is between about 20 Å and about 100 Å, and the oxide layer with bistable resistance has a thickness between about 25% and about 75% of the total thickness. In one embodiment, the oxide layers are formed using reactive sputtering in an atmosphere with controlled flows of argon and oxygen.

3. 发明申请

US20150179935A1 Atomic Layer Deposition of Metal Oxides for Memory Applications 有权
标题翻译：用于存储器应用的金属氧化物的原子层沉积
公开(公告)号：US20150179935A1
公开(公告)日：2015-06-25
申请号：US14624295
申请日：2015-02-17
申请人： Intermolecular Inc. , Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Zhendong Hong , Vidyut Gopal , Imran Hashim , Randall J. Higuchi , Tim Minvielle , Hieu Pham , Takeshi Yamaguchi
IPC分类号： H01L45/00
CPC分类号： H01L45/146 , H01L27/2463 , H01L45/04 , H01L45/08 , H01L45/1233 , H01L45/1616
摘要： Embodiments of the invention generally relate to nonvolatile memory devices and methods for manufacturing such memory devices. The methods for forming improved memory devices, such as a ReRAM cells, provide optimized, atomic layer deposition (ALD) processes for forming a metal oxide film stack which contains at least one hard metal oxide film (e.g., metal is completely oxidized or substantially oxidized) and at least one soft metal oxide film (e.g., metal is less oxidized than hard metal oxide). The soft metal oxide film is less electrically resistive than the hard metal oxide film since the soft metal oxide film is less oxidized or more metallic than the hard metal oxide film. In one example, the hard metal oxide film is formed by an ALD process utilizing ozone as the oxidizing agent while the soft metal oxide film is formed by another ALD process utilizing water vapor as the oxidizing agent.
摘要翻译：本发明的实施例一般涉及用于制造这种存储器件的非易失性存储器件和方法。用于形成改进的存储器件（例如ReRAM单元）的方法提供优化的原子层沉积（ALD）工艺，用于形成金属氧化物膜堆叠，其包含至少一个硬金属氧化物膜（例如，金属被完全氧化或基本上被氧化）和至少一种软金属氧化物膜（例如，金属比硬金属氧化物氧化较少）。由于软金属氧化物膜比硬金属氧化物膜氧化得更少或更金属，所以软金属氧化物膜的电阻小于硬金属氧化物膜。在一个实例中，通过利用臭氧作为氧化剂的ALD工艺形成硬质金属氧化物膜，而通过利用水蒸汽作为氧化剂的另一ALD工艺形成软金属氧化物膜。

4. 发明授权

US09001554B2 Resistive random access memory cell having three or more resistive states 有权
标题翻译：具有三个或更多个电阻状态的电阻随机存取存储单元
公开(公告)号：US09001554B2
公开(公告)日：2015-04-07
申请号：US13738061
申请日：2013-01-10
申请人： Intermolecular Inc. , Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Imran Hashim , Ryan C. Clarke , Nan Lu , Tim Minvielle , Takeshi Yamaguchi
IPC分类号： H01L45/00 , G11C13/00
CPC分类号： H01L45/146 , G11C11/56 , G11C11/5685 , G11C13/0002 , G11C13/0007 , G11C13/0064 , G11C13/0069 , G11C13/0097 , G11C2213/32 , G11C2213/71 , G11C2213/77 , H01L45/08 , H01L45/1233 , H01L45/1253
摘要： Provided are resistive random access memory (ReRAM) cells, each having three or more resistive states and being capable of storing multiple bits of data, as well as methods of fabricating and operating such ReRAM cells. Such ReRAM cells or, more specifically, their resistive switching layer have wide range of resistive states and are capable of being very conductive (e.g., about 1 kOhm) in one state and very resistive (e.g., about 1 MOhm) in another state. In some embodiments, a resistance ratio between resistive states may be between 10 and 1,000 even up to 10,000. The resistive switching layers also allow establishing stable and distinct intermediate resistive states that may be assigned different data values. These layers may be configured to switching between their resistive states using fewer programming pulses than conventional systems by using specific materials, switching pluses, and resistive state threshold.
摘要翻译：提供了电阻随机存取存储器（ReRAM）单元，每个单元具有三个或更多个电阻状态，并且能够存储多个数据位，以及制造和操作这样的ReRAM单元的方法。这样的ReRAM单元或更具体地，它们的电阻式开关层具有宽范围的电阻状态，并且在另一状态下能够在一种状态下非常导电（例如，约1kOhm），并且在另一状态下具有很强的电阻（例如约1MOhm）。在一些实施例中，电阻状态之间的电阻比可以在10和1,000之间甚至高达10,000。电阻式开关层还允许建立可分配不同数据值的稳定和不同的中间电阻状态。这些层可以被配置为使用比常规系统更少的编程脉冲在其电阻状态之间切换，通过使用特定的材料，开关和电阻状态阈值。

5. 发明授权

US08987697B2 Transition metal oxide bilayers 有权
标题翻译：过渡金属氧化物双层
公开(公告)号：US08987697B2
公开(公告)日：2015-03-24
申请号：US14252285
申请日：2014-04-14
申请人： Intermolecular Inc. , Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Hieu Pham , Vidyut Gopal , Imran Hashim , Tim Minvielle , Yun Wang , Takeshi Yamaguchi , Hong Sheng Yang
IPC分类号： H01L29/02 , H01L45/00 , H01L27/24
CPC分类号： H01L45/08 , H01L27/2409 , H01L27/2463 , H01L45/1233 , H01L45/1253 , H01L45/145 , H01L45/146 , H01L45/147 , H01L45/16 , H01L45/1616 , H01L45/1625 , H01L45/1641
摘要： Embodiments of the invention include nonvolatile memory elements and memory devices comprising the nonvolatile memory elements. Methods for forming the nonvolatile memory elements are also disclosed. The nonvolatile memory element comprises a first electrode layer, a second electrode layer, and a plurality of layers of an oxide disposed between the first and second electrode layers. One of the oxide layers has linear resistance and substoichiometric composition, and the other oxide layer has bistable resistance and near-stoichiometric composition. Preferably, the sum of the two oxide layer thicknesses is between about 20 Å and about 100 Å, and the oxide layer with bistable resistance has a thickness between about 25% and about 75% of the total thickness. In one embodiment, the oxide layers are formed using reactive sputtering in an atmosphere with controlled flows of argon and oxygen.
摘要翻译：本发明的实施例包括非易失性存储器元件和包括非易失性存储元件的存储器件。还公开了形成非易失性存储元件的方法。非易失性存储元件包括第一电极层，第二电极层和设置在第一和第二电极层之间的多个氧化物层。氧化物层中的一个具有线性电阻和亚化学计量组成，另一个氧化物层具有双稳态电阻和近化学计量组成。优选地，两个氧化物层厚度的总和在约和之间，并且具有双稳态电阻的氧化物层具有在总厚度的约25％至约75％之间的厚度。在一个实施例中，氧化物层在具有受控的氩气和氧气的气氛中使用反应溅射形成。

6. 发明申请

US20140374240A1 MULTIFUNCTIONAL ELECTRODE 有权
标题翻译：多功能电极
公开(公告)号：US20140374240A1
公开(公告)日：2014-12-25
申请号：US14479565
申请日：2014-09-08
申请人： INTERMOLECULAR INC. , KABUSHIKI KAISHA TOSHIBA , SANDISK 3D LLC
发明人： Hieu Pham , Vidyut Gopal , Imran Hashim , Tim Minvielle , Dipankar Pramanik , Yun Wang , Takeshi Yamaguchi , Hong Sheng Yang
IPC分类号： C23C14/34 , C23C14/06
CPC分类号： C23C14/345 , C23C14/0042 , C23C14/0641 , C23C14/083 , C23C14/225 , H01L27/2409 , H01L27/2463 , H01L45/08 , H01L45/12 , H01L45/1233 , H01L45/1266 , H01L45/145 , H01L45/146 , H01L45/16 , H01L45/1608 , H01L45/1616 , H01L45/1625
摘要： A nonvolatile memory element is disclosed comprising a first electrode, a near-stoichiometric metal oxide memory layer having bistable resistance, and a second electrode in contact with the near-stoichiometric metal oxide memory layer. At least one electrode is a resistive electrode comprising a sub-stoichiometric transition metal nitride or oxynitride, and has a resistivity between 0.1 and 10Ω cm. The resistive electrode provides the functionality of an embedded current-limiting resistor and also serves as a source and sink of oxygen vacancies for setting and resetting the resistance state of the metal oxide layer. Novel fabrication methods for the second electrode are also disclosed.
摘要翻译：公开了一种非易失性存储元件，其包括第一电极，具有双稳态电阻的近化学计量的金属氧化物存储层和与近化学计量的金属氧化物存储层接触的第二电极。至少一个电极是包含亚化学计量的过渡金属氮化物或氮氧化物的电阻电极，并且电阻率在0.1和10Ω之间; 厘米。电阻电极提供嵌入式限流电阻器的功能，并且还用作用于设置和复位金属氧化物层的电阻状态的氧空位的源极和吸收器。还公开了用于第二电极的新颖制造方法。

7. 发明授权

US08906736B1 Multifunctional electrode 有权
标题翻译：多功能电极
公开(公告)号：US08906736B1
公开(公告)日：2014-12-09
申请号：US14479565
申请日：2014-09-08
申请人： Intermolecular Inc. , Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Hieu Pham , Vidyut Gopal , Imran Hashim , Tim Minvielle , Dipankar Pramanik , Yun Wang , Takeshi Yamaguchi , Hong Sheng Yang
IPC分类号： H01L29/02
CPC分类号： C23C14/345 , C23C14/0042 , C23C14/0641 , C23C14/083 , C23C14/225 , H01L27/2409 , H01L27/2463 , H01L45/08 , H01L45/12 , H01L45/1233 , H01L45/1266 , H01L45/145 , H01L45/146 , H01L45/16 , H01L45/1608 , H01L45/1616 , H01L45/1625
摘要： A nonvolatile memory element is disclosed comprising a first electrode, a near-stoichiometric metal oxide memory layer having bistable resistance, and a second electrode in contact with the near-stoichiometric metal oxide memory layer. At least one electrode is a resistive electrode comprising a sub-stoichiometric transition metal nitride or oxynitride, and has a resistivity between 0.1 and 10 Ωcm. The resistive electrode provides the functionality of an embedded current-limiting resistor and also serves as a source and sink of oxygen vacancies for setting and resetting the resistance state of the metal oxide layer. Novel fabrication methods for the second electrode are also disclosed.
摘要翻译：公开了一种非易失性存储元件，其包括第一电极，具有双稳态电阻的近化学计量的金属氧化物存储层以及与近化学计量的金属氧化物存储层接触的第二电极。至少一个电极是包含亚化学计量的过渡金属氮化物或氧氮化物的电阻电极，并且电阻率在0.1和10Ω之间。电阻电极提供嵌入式限流电阻器的功能，并且还用作用于设置和复位金属氧化物层的电阻状态的氧空位的源极和吸收器。还公开了用于第二电极的新颖制造方法。

8. 发明授权

US08859328B2 Multifunctional electrode 有权
公开(公告)号：US08859328B2
公开(公告)日：2014-10-14
申请号：US14254155
申请日：2014-04-16
申请人： Intermolecular Inc. , Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Hieu Pham , Vidyut Gopal , Imran Hashim , Tim Minvielle , Dipankar Pramanik , Yun Wang , Takeshi Yamaguchi , Hong Sheng Yang
IPC分类号： H01L29/02 , H01L45/00
CPC分类号： C23C14/345 , C23C14/0042 , C23C14/0641 , C23C14/083 , C23C14/225 , H01L27/2409 , H01L27/2463 , H01L45/08 , H01L45/12 , H01L45/1233 , H01L45/1266 , H01L45/145 , H01L45/146 , H01L45/16 , H01L45/1608 , H01L45/1616 , H01L45/1625
摘要： A nonvolatile memory element is disclosed comprising a first electrode, a near-stoichiometric metal oxide memory layer having bistable resistance, and a second electrode in contact with the near-stoichiometric metal oxide memory layer. At least one electrode is a resistive electrode comprising a sub-stoichiometric transition metal nitride or oxynitride, and has a resistivity between 0.1 and 10 Ωcm. The resistive electrode provides the functionality of an embedded current-limiting resistor and also serves as a source and sink of oxygen vacancies for setting and resetting the resistance state of the metal oxide layer. Novel fabrication methods for the second electrode are also disclosed.

9. 发明申请

US20140084237A1 DEFECT GRADIENT TO BOOST NONVOLATILE MEMORY PERFORMANCE 有权
标题翻译：缺陷增强非易失性存储器性能
公开(公告)号：US20140084237A1
公开(公告)日：2014-03-27
申请号：US14075036
申请日：2013-11-08
申请人： Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Yun Wang , Tony Chiang , Imran Hashim
IPC分类号： H01L45/00
CPC分类号： H01L45/122 , H01L27/2463 , H01L45/08 , H01L45/146 , H01L45/1608
摘要： Embodiments of the present invention generally relate to a resistive switching nonvolatile memory element that is formed in a resistive switching memory device that may be used in a memory array to store digital data. The memory element is generally constructed as a metal-insulator-metal stack. The resistive switching portion of the memory element includes a getter and/or a defect portion. In general, the getter portion is an area of the memory element that is used to help form, during the resistive switching memory device's fabrication process, a region of the resistive switching layer that has a greater number of vacancies or defects compared to the remainder of resistive switching layer. The defect portion is an area of the memory element that has a greater number of vacancies or defects compared to the remainder of the resistive switching layer, and is formed during the resistive switching memory device's fabrication process.
摘要翻译：本发明的实施例一般涉及一种电阻式开关非易失性存储元件，其形成在电阻式开关存储器件中，其可用于存储阵列中以存储数字数据。存储元件通常构造为金属 - 绝缘体 - 金属叠层。存储元件的电阻性切换部分包括吸气剂和/或缺陷部分。通常，吸气剂部分是存储元件的区域，其用于帮助在电阻式开关存储器件的制造过程期间形成与其余部分相比具有更大数量的空位或缺陷的电阻式开关层的区域电阻式开关层。缺陷部分是与电阻开关层的其余部分相比具有更大数量的空位或缺陷的存储元件的区域，并且在电阻式开关存储器件的制造工艺期间形成。

10. 发明授权

US09006026B2 Atomic layer deposition of metal oxides for memory applications 有权
标题翻译：用于记忆应用的金属氧化物的原子层沉积
公开(公告)号：US09006026B2
公开(公告)日：2015-04-14
申请号：US14466695
申请日：2014-08-22
申请人： Intermolecular Inc. , Kabushiki Kaisha Toshiba , SanDisk 3D LLC
发明人： Zhendong Hong , Vidyut Gopal , Imran Hashim , Randall J. Higuchi , Tim Minvielle , Hieu Pham , Takeshi Yamaguchi
IPC分类号： H01L21/00 , H01L21/8222 , H01L45/00 , H01L27/24
CPC分类号： H01L45/146 , H01L27/2463 , H01L45/04 , H01L45/08 , H01L45/1233 , H01L45/1616
摘要： Embodiments of the invention generally relate to nonvolatile memory devices and methods for manufacturing such memory devices. The methods for forming improved memory devices, such as a ReRAM cells, provide optimized, atomic layer deposition (ALD) processes for forming a metal oxide film stack which contains at least one hard metal oxide film (e.g., metal is completely oxidized or substantially oxidized) and at least one soft metal oxide film (e.g., metal is less oxidized than hard metal oxide). The soft metal oxide film is less electrically resistive than the hard metal oxide film since the soft metal oxide film is less oxidized or more metallic than the hard metal oxide film. In one example, the hard metal oxide film is formed by an ALD process utilizing ozone as the oxidizing agent while the soft metal oxide film is formed by another ALD process utilizing water vapor as the oxidizing agent.
摘要翻译：本发明的实施例一般涉及用于制造这种存储器件的非易失性存储器件和方法。用于形成改进的存储器件（例如ReRAM单元）的方法提供优化的原子层沉积（ALD）工艺，用于形成金属氧化物膜堆叠，其包含至少一个硬金属氧化物膜（例如，金属被完全氧化或基本上被氧化）和至少一种软金属氧化物膜（例如，金属比硬金属氧化物氧化较少）。由于软金属氧化物膜比硬金属氧化物膜氧化得更少或更金属，所以软金属氧化物膜的电阻小于硬金属氧化物膜。在一个实例中，通过利用臭氧作为氧化剂的ALD工艺形成硬质金属氧化物膜，而通过利用水蒸汽作为氧化剂的另一ALD工艺形成软金属氧化物膜。

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