公开(公告)号：US20160133837A1

公开(公告)日：2016-05-12

申请号：US14539054

申请日：2014-11-12

Applicant: Intermolecular Inc.

Inventor： Chien-Lan Hsueh ,  Randall J. Higuchi

IPC: H01L45/00

CPC classification number: H01L45/1616 ,  C23C16/34 ,  C23C16/345 ,  C23C16/45531 ,  C23C16/45553 ,  H01L45/04 ,  H01L45/145

Abstract: Metal silicon nitride nanolaminates are formed at temperatures of 200-400 C by alternating ALD monolayers or thin CVD layers of metal nitride and silicon nitride. The silicon nitride layers are formed from a silicon halide precursor, causing nitrogen bonds to replace the halogen bonds, which is a lower-energy reaction than bonding nitrogen to elemental silicon. The silicon content, and thereby the resistivity, of the nanolaminate can be tuned by either a sub-saturation dose of the silicon halide precursor (forming ALD sub-monolayers) or by the relative number of metal nitride and silicon nitride layers. Resistivities between 1 and 500 Ω·cm, suitable for ReRAM embedded resistors, can be achieved. Some of the nanolaminates can function as combination embedded resistors and electrodes.

Abstract translation: 通过交替的ALD单层或金属氮化物和氮化硅的薄CVD层在200-400℃的温度下形成金属氮化硅纳米级氨酸盐。 氮化硅层由卤化硅前体形成，导致氮键取代卤键，这是将氮键接到元素硅上的低能反应。 可以通过次级饱和剂量的卤化硅前体（形成ALD亚单层）或相对数量的金属氮化物和氮化硅层来调节纳米材料的硅含量以及由此的电导率。 可实现适用于ReRAM嵌入式电阻器的1〜500Ω电阻率和OHgr·cm。 一些纳米材料可以作为组合嵌入式电阻器和电极。

公开(公告)号：US09246096B2

公开(公告)日：2016-01-26

申请号：US14624295

申请日：2015-02-17

Applicant: Intermolecular Inc. ,  Kabushiki Kaisha Toshiba ,  SanDisk 3D LLC

Inventor： Zhendong Hong ,  Vidyut Gopal ,  Imran Hashim ,  Randall J. Higuchi ,  Tim Minvielle ,  Hieu Pham ,  Takeshi Yamaguchi

IPC: H01L29/768 ,  H01L29/40 ,  H01L21/8222 ,  H01L21/20 ,  H01L45/00 ,  H01L27/24

CPC classification number: H01L45/146 ,  H01L27/2463 ,  H01L45/04 ,  H01L45/08 ,  H01L45/1233 ,  H01L45/1616

Abstract: 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.

公开(公告)号：US09040413B2

公开(公告)日：2015-05-26

申请号：US13714162

申请日：2012-12-13

Applicant: Intermolecular Inc. ,  Kabushiki Kaisha Toshiba ,  SanDisk 3D LLC

Inventor： Randall J. Higuchi ,  Chien-Lan Hsueh ,  Yun Wang

IPC: H01L21/44 ,  H01L45/00 ,  H01L27/24

CPC classification number: H01L45/1608 ,  H01L27/2409 ,  H01L27/2463 ,  H01L45/08 ,  H01L45/10 ,  H01L45/1233 ,  H01L45/145 ,  H01L45/146 ,  H01L45/1616

Abstract: A nonvolatile memory device contains a resistive switching memory element with improved device switching performance and lifetime by custom tailoring the average concentration of defects in the resistive switching film and methods of forming the same. The nonvolatile memory element includes a first electrode layer, a second electrode layer, and a resistive switching layer disposed between the first electrode layer and the second electrode layer. The resistive switching layer comprises a first sub-layer and a second sub-layer, wherein the first sub-layer has more defects than the first sub-layer. A method includes forming a first sub-layer on the first electrode layer by a first ALD process and forming a second sub-layer on the first sub-layer by a second ALD process, where the first sub-layer has a different amount of defects than the second sub-layer.

Abstract translation: 非易失性存储器件包含电阻式开关存储器元件，通过定制电阻式开关膜中的平均缺陷浓度及其形成方法，具有改进的器件切换性能和寿命。 非易失性存储元件包括设置在第一电极层和第二电极层之间的第一电极层，第二电极层和电阻开关层。 电阻开关层包括第一子层和第二子层，其中第一子层具有比第一子层更多的缺陷。 一种方法包括通过第一ALD工艺在第一电极层上形成第一子层，并通过第二ALD工艺在第一子层上形成第二子层，其中第一子层具有不同的缺陷量 比第二个子层。

公开(公告)号：US09018068B2

公开(公告)日：2015-04-28

申请号：US13869800

申请日：2013-04-24

Applicant: Intermolecular Inc.

Inventor： Randall J. Higuchi ,  Chien-Lan Hsueh ,  Yun Wang

IPC: H01L45/00 ,  H01L27/24 ,  H01L21/02

CPC classification number: H01L27/2463 ,  H01L21/0228 ,  H01L45/04 ,  H01L45/1233 ,  H01L45/145 ,  H01L45/1616

Abstract: A nonvolatile resistive memory element includes a novel switching layer and methods of forming the same. The switching layer includes a material having bistable resistance properties and formed by bonding silicon to oxygen or nitrogen. The switching layer may include at least one of SiOx, SiOxNy, or SiNx. Advantageously, the SiOx, SiOxNy, and SiNx generally remain amorphous after thermal anneal processes are used to form the devices, such as ReRAM devices.

Abstract translation: 非易失性电阻性存储元件包括新型开关层及其形成方法。 开关层包括具有双稳电阻性质并通过将硅键合到氧或氮而形成的材料。 开关层可以包括SiO x，SiO x N y或SiN x中的至少一种。 有利地，在使用热退火工艺来形成诸如ReRAM器件的器件之后，SiO x，SiO x N y和SiN x通常保持非晶态。

公开(公告)号：US09006696B2

公开(公告)日：2015-04-14

申请号：US14480025

申请日：2014-09-08

Applicant: Intermolecular Inc. ,  Kabushiki Kaisha Toshiba ,  SanDisk 3D LLC

Inventor： Mihir Tendulkar ,  Randall J. Higuchi ,  Chien-Lan Hsueh

IPC: H01L45/00 ,  H01L27/24

CPC classification number: H01L45/165 ,  H01L27/2409 ,  H01L45/08 ,  H01L45/1233 ,  H01L45/1266 ,  H01L45/146 ,  H01L45/147 ,  H01L45/1616 ,  H01L45/1625

Abstract: Provided are resistive random access memory (ReRAM) cells and methods of fabricating thereof. A ReRAM cell includes an embedded resistor and resistive switching layer connected in series. The embedded resistor prevents excessive electrical currents through the resistive switching layer, especially when the resistive switching layer is switched into its low resistive state, thereby preventing over-programming. The embedded resistor includes aluminum, nitrogen, and one or more additional metals (other than aluminum). The concentration of each component is controlled to achieve desired resistivity and stability of the embedded resistor. In some embodiments, the resistivity ranges from 0.1 Ohm-centimeter to 40 Ohm-centimeter and remains substantially constant while applying an electrical field of up 8 mega-Volts/centimeter to the embedded resistor. The embedded resistor may be made from an amorphous material, and the material is operable to remain amorphous even when subjected to typical annealing conditions.

Abstract translation: 提供了电阻随机存取存储器（ReRAM）单元及其制造方法。 ReRAM单元包括串联连接的嵌入式电阻和电阻开关层。 嵌入式电阻器阻止通过电阻开关层的过多电流，特别是当电阻式开关层切换到其低电阻状态时，从而防止过度编程。 嵌入式电阻器包括铝，氮和一种或多种另外的金属（除铝以外）。 控制每个组分的浓度以实现嵌入式电阻器的期望的电阻率和稳定性。 在一些实施例中，电阻率范围为0.1欧姆至40欧姆厘米，并且在施加高达8兆伏特/厘米的电场到嵌入式电阻器时保持基本恒定。 嵌入式电阻器可以由非晶材料制成，并且即使经受典型的退火条件，该材料也可操作以保持非晶态。

公开(公告)号：US09065040B2

公开(公告)日：2015-06-23

申请号：US14510390

申请日：2014-10-09

Applicant: Intermolecular Inc. ,  Kabushiki Kaisha Toshiba ,  SanDisk 3D LLC

Inventor： Chien-Lan Hsueh ,  Vidyut Gopal ,  Randall J. Higuchi ,  Takeshi Yamaguchi

IPC: H01L21/00 ,  H01L21/16 ,  H01L29/06 ,  H01L47/02 ,  H01L45/00 ,  H01L27/24

CPC classification number: H01L45/085 ,  H01L27/2481 ,  H01L45/08 ,  H01L45/1233 ,  H01L45/1253 ,  H01L45/145 ,  H01L45/146 ,  H01L45/1616

Abstract: A method of fabricating a resistive random access memory (ReRAM) cell may include forming a set of nanolaminate structures over an electrode, such that each structure includes at least one first element oxide layer and at least one second element oxide layer. The overall set is operable as a resistive switching layer in a ReRAM cell. In this set, an average atomic ratio of the first element to the second element is different in at least two nanolaminate structures. This ratio may be less in nanolaminate structures that are closer to electrodes than in the middle nanolaminate structures. Alternatively, this ratio may increase from one end of the set to another. The first element may be less electronegative than the second elements. The first element may be hafnium, while the second element may be one of zirconium, aluminum, titanium, tantalum, or silicon.

Abstract translation: 制造电阻随机存取存储器（ReRAM）单元的方法可以包括在电极上形成一组纳米级氨基酸结构，使得每个结构包括至少一个第一元件氧化物层和至少一个第二元件氧化物层。 整个集合可用作ReRAM单元中的电阻式开关层。 在该组中，第一元素与第二元素的平均原子比在至少两个纳米层间结构中不同。 在比中间的Nanolaminate结构中更接近于电极的纳米酸盐结构中，该比例可能更小。 或者，该比率可以从集合的一端增加到另一端。 第一元素可能比第二元素具有更少的电负性。 第一元素可以是铪，而第二元素可以是锆，铝，钛，钽或硅中的一种。

公开(公告)号：US20150060753A1

公开(公告)日：2015-03-05

申请号：US14510390

申请日：2014-10-09

Applicant: Intermolecular Inc. ,  Kabushiki Kaisha Toshiba ,  SanDisk 3D LLC

Inventor： Chien-Lan Hsueh ,  Vidyut Gopal ,  Randall J. Higuchi ,  Takeshi Yamaguchi

IPC: H01L45/00

CPC classification number: H01L45/085 ,  H01L27/2481 ,  H01L45/08 ,  H01L45/1233 ,  H01L45/1253 ,  H01L45/145 ,  H01L45/146 ,  H01L45/1616

Abstract: A method of fabricating a resistive random access memory (ReRAM) cell may include forming a set of nanolaminate structures over an electrode, such that each structure includes at least one first element oxide layer and at least one second element oxide layer. The overall set is operable as a resistive switching layer in a ReRAM cell. In this set, an average atomic ratio of the first element to the second element is different in at least two nanolaminate structures. This ratio may be less in nanolaminate structures that are closer to electrodes than in the middle nanolaminate structures. Alternatively, this ratio may increase from one end of the set to another. The first element may be less electronegative than the second elements. The first element may be hafnium, while the second element may be one of zirconium, aluminum, titanium, tantalum, or silicon.

Abstract translation: 制造电阻随机存取存储器（ReRAM）单元的方法可以包括在电极上形成一组纳米级氨基酸结构，使得每个结构包括至少一个第一元件氧化物层和至少一个第二元件氧化物层。 整个集合可用作ReRAM单元中的电阻式开关层。 在该组中，第一元素与第二元素的平均原子比在至少两个纳米层间结构中不同。 在比中间的Nanolaminate结构中更接近于电极的纳米酸盐结构中，该比例可能更小。 或者，该比率可以从集合的一端增加到另一端。 第一元素可能比第二元素具有更少的电负性。 第一元素可以是铪，而第二元素可以是锆，铝，钛，钽或硅中的一种。

公开(公告)号：US20140363920A1

公开(公告)日：2014-12-11

申请号：US14466695

申请日：2014-08-22

Applicant: Intermolecular Inc. ,  Kabushiki Kaisha Toshiba ,  SanDisk 3D LLC

Inventor： Zhendong Hong ,  Vidyut Gopal ,  Imran Hashim ,  Randall J. Higuchi ,  Tim Minvielle ,  Hieu Pham ,  Takeshi Yamaguchi

IPC: H01L45/00

CPC classification number: H01L45/146 ,  H01L27/2463 ,  H01L45/04 ,  H01L45/08 ,  H01L45/1233 ,  H01L45/1616

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US20140357046A1

公开(公告)日：2014-12-04

申请号：US14464171

申请日：2014-08-20

Applicant: Intermolecular Inc.

Inventor： Chien-Lan Hsueh ,  Randall J. Higuchi ,  Mihir Tendulkar

IPC: H01L45/00

CPC classification number: 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

Abstract: Provided are resistive random access memory (ReRAM) cells and methods of fabricating thereof. A ReRAM cell includes an embedded resistor and a resistive switching layer connected in series with this resistor. The resistor is configured to prevent over-programming of the cell by limiting electrical currents through the resistive switching layer. Unlike the resistive switching layer, which changes its resistance in order to store data, the embedded resistor maintains a substantially constant resistance during operation of the cell. The embedded resistor is formed from tantalum nitride and silicon nitride. The atomic ratio of tantalum and silicon may be specifically selected to yield resistors with desired densities and resistivities as well as ability to remain amorphous when subjected to various annealing conditions. The embedded resistor may also function as a diffusion barrier layer and prevent migration of components between one of the electrodes and the resistive switching layer.

Abstract translation: 提供了电阻随机存取存储器（ReRAM）单元及其制造方法。 ReRAM单元包括与该电阻器串联连接的嵌入式电阻器和电阻开关层。 电阻器被配置为通过限制通过电阻式开关层的电流来防止电池的过度编程。 与电阻开关层不同，为了存储数据而改变其电阻，嵌入式电阻器在电池工作期间保持基本恒定的电阻。 嵌入式电阻器由氮化钽和氮化硅形成。 可以特别地选择钽和硅的原子比以产生具有所需密度和电阻率的电阻器以及当经受各种退火条件时保持非晶体的能力。 嵌入式电阻器还可以用作扩散阻挡层并且防止元件在电极和电阻开关层中的一个之间的迁移。

公开(公告)号：US08853661B1

公开(公告)日：2014-10-07

申请号：US13835256

申请日：2013-03-15

Applicant: Intermolecular Inc. ,  Kabushiki Kaisha Toshiba ,  SanDisk 3D LLC

Inventor： Mihir Tendulkar ,  Randall J. Higuchi ,  Chien-Lan Hsueh

IPC: H01L29/02 ,  H01L47/00 ,  H01L27/24 ,  H01L45/00

CPC classification number: H01L45/165 ,  H01L27/2409 ,  H01L45/08 ,  H01L45/1233 ,  H01L45/1266 ,  H01L45/146 ,  H01L45/147 ,  H01L45/1616 ,  H01L45/1625

Abstract: Provided are resistive random access memory (ReRAM) cells and methods of fabricating thereof. A ReRAM cell includes an embedded resistor and resistive switching layer connected in series. The embedded resistor prevents excessive electrical currents through the resistive switching layer, especially when the resistive switching layer is switched into its low resistive state, thereby preventing over-programming. The embedded resistor includes aluminum, nitrogen, and one or more additional metals (other than aluminum). The concentration of each component is controlled to achieve desired resistivity and stability of the embedded resistor. In some embodiments, the resistivity ranges from 0.1 Ohm-centimeter to 40 Ohm-centimeter and remains substantially constant while applying an electrical field of up 8 mega-Volts/centimeter to the embedded resistor. The embedded resistor may be made from an amorphous material, and the material is operable to remain amorphous even when subjected to typical annealing conditions.

Abstract translation: 提供了电阻随机存取存储器（ReRAM）单元及其制造方法。 ReRAM单元包括串联连接的嵌入式电阻和电阻开关层。 嵌入式电阻器阻止通过电阻开关层的过多电流，特别是当电阻式开关层切换到其低电阻状态时，从而防止过度编程。 嵌入式电阻器包括铝，氮和一种或多种另外的金属（除铝以外）。 控制每个组分的浓度以实现嵌入式电阻器的期望的电阻率和稳定性。 在一些实施例中，电阻率范围为0.1欧姆至40欧姆厘米，并且在施加高达8兆伏特/厘米的电场到嵌入式电阻器时保持基本恒定。 嵌入式电阻器可以由非晶材料制成，并且即使经受典型的退火条件，该材料也可操作以保持非晶态。