公开(公告)号：US20140103284A1

公开(公告)日：2014-04-17

申请号：US14136219

申请日：2013-12-20

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.

公开(公告)号：US20150179935A1

公开(公告)日：2015-06-25

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: 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：US20150179316A1

公开(公告)日：2015-06-25

申请号：US14139260

申请日：2013-12-23

Applicant: Intermolecular Inc.

Inventor： Chien-Lan Hsueh ,  Randall J. Higuchi

IPC: H01C17/08

CPC classification number: H01C17/08 ,  C23C16/308 ,  C23C16/34 ,  C23C16/45553 ,  H01L45/08 ,  H01L45/12 ,  H01L45/1233 ,  H01L45/146 ,  H01L45/16

Abstract: Provided are methods of forming nitrides at low substrate temperatures, such as less than 500° C. or even less than 400° C. The nitrides can be formed using atomic layer deposition (ALD), chemical vapor deposition (CVD), and other like techniques. The low substrate temperatures allow using various temperature sensitive precursors, such as Tetrakis(DiMethylAmino)Hafnium (i.e., TDMAHf) or TertiaryButylimido-Tris(DiEthylamino)Tantalum (i.e., TBTDET), to form nitrides of components provided by these precursors. Furthermore, the low temperatures preserve other structures present on the substrate prior to forming the nitride layers. Nitrogen-containing precursors with low dissociation energy are used in these methods. Some examples of such nitrogen-containing precursors include hydrazine (N2H4), diazene (N2H2), triazene (N3H3), triazane (N3H5), alkyl-substituted variations thereof, and salts thereof. Also provided are methods of forming oxy-nitrides using low substrate temperatures. Nitride and oxy-nitride layers formed using these methods may be used as embedded resistors in resistive switching memory (ReRAM) cells and other like applications.

Abstract translation: 提供了在低基板温度例如小于500℃或甚至低于400℃时形成氮化物的方法。氮化物可以使用原子层沉积（ALD），化学气相沉积（CVD）等形成 技术 低底物温度允许使用各种温度敏感性前体，例如四（二甲基氨基）铪（即TDMAHf）或叔丁基亚氨基 - 三（二乙基氨基）钽（即TBTDET）），以形成由这些前体提供的组分的氮化物。 此外，在形成氮化物层之前，低温保存存在于衬底上的其它结构。 在这些方法中使用具有低解离能的含氮前体。 这种含氮前体的一些实例包括肼（N 2 H 4），二氮烯（N 2 H 2），三氮烯（N 3 H 3），三氮杂萘（N 3 H 5），其烷基取代的变体及其盐。 还提供了使用低基板温度形成氧氮化物的方法。 使用这些方法形成的氮化物和氮氧化物层可以用作电阻式开关存储器（ReRAM）单元和其它类似应用中的嵌入式电阻器。

公开(公告)号：US20150176122A1

公开(公告)日：2015-06-25

申请号：US14136384

申请日：2013-12-20

Applicant: Intermolecular Inc.

Inventor： Chien-Lan Hsueh ,  Tony P. Chiang ,  Randall J. Higuchi ,  Kurt Pang

IPC: C23C16/44

CPC classification number: C23C16/44 ,  C23C16/308 ,  C23C16/34 ,  C23C16/45527 ,  Y10T428/24355

Abstract: Ternary oxides, nitrides and oxynitrides of the form (a)(b)OxNy are formed by ALD or CVD when the reaction temperature ranges of the (a) precursor and the (b) precursor do not overlap. Chemically-reacted sub-layers, e.g., (a)OxNy, are formed by reacting the lower-temperature precursor with O and/or N at a temperature within its reaction range. Physisorbed sub-layers (e.g., (b) or (b)+ligand) are formed between the chemically-reacted sub-layers by allowing the higher-temperature precursor to physically adsorb to the low-temperature surface. When the desired sub-layers are formed, the substrate is heated to a temperature at which the higher-temperature precursor reacts (optionally in the presence of more O and/or N) to form (a)(b)OxNy. Quarternary and more complex compounds can be similarly formed.

Abstract translation: （a）（a）（b）的三元氧化物，氮化物和氮氧化物当（a）前体和（b）前体的反应温度范围不重叠时，通过ALD或CVD形成OxNy。 化学反应的亚层，例如，（a）OxNy是通过在其反应范围内的温度下使低温前体与O和/或N反应形成的。 通过使高温前体物理吸附到低温表面，在化学反应的子层之间形成物理吸附的子层（例如，（b）或（b）+配体））。 当形成所需的子层时，将基底加热至较高温度前体反应的温度（任选地在更多的O和/或N的存在下）以形成（a）（b）OxNy。 可以类似地形成四元和更复杂的化合物。

公开(公告)号：US20150093876A1

公开(公告)日：2015-04-02

申请号：US14565712

申请日：2014-12-10

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

Inventor： Brian Butcher ,  Randall J. Higuchi ,  Yun Wang

IPC: H01L45/00

CPC classification number: H01L45/1616 ,  H01L27/2481 ,  H01L45/08 ,  H01L45/1233 ,  H01L45/1253 ,  H01L45/146 ,  H01L45/1641

Abstract: Provided are methods of fabricating memory cells such as resistive random access memory (ReRAM) cells. A method involves forming a first layer including two high-k dielectric materials such that one material has a higher dielectric constant than the other material. In some embodiments, hafnium oxide and titanium oxide form the first layer. The higher-k material may be present at a lower concentration. In some embodiments, a concentration ratio of these two high-k materials is between about 3 and 7. The first layer may be formed using atomic layer deposition. The first layer is then annealed in an oxygen-containing environment. The method may proceed with forming a second layer including a low-k dielectric material, such as silicon oxide, and forming an electrode. After forming the electrode, the memory cell is annealed in a nitrogen containing environment. The nitrogen anneal may be performed at a higher temperature than the oxygen anneal.

Abstract translation: 提供制造诸如电阻随机存取存储器（ReRAM）单元的存储单元的方法。 一种方法包括形成包括两个高k介电材料的第一层，使得一种材料具有比其它材料更高的介电常数。 在一些实施方案中，氧化铪和氧化钛形成第一层。 较高k的材料可以以更低的浓度存在。 在一些实施方案中，这两种高k材料的浓度比在约3和7之间。第一层可以使用原子层沉积形成。 然后将第一层在含氧环境中退火。 该方法可以继续形成包括低k介电材料（例如氧化硅）的第二层，并形成电极。 在形成电极之后，在含氮环境中对存储单元进行退火。 氮退火可以在比氧退火更高的温度下进行。

公开(公告)号：US08883557B1

公开(公告)日：2014-11-11

申请号：US14016775

申请日：2013-09-03

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 ,  H01L29/02 ,  H01L47/00 ,  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：US08835890B2

公开(公告)日：2014-09-16

申请号：US14136219

申请日：2013-12-20

Applicant: Intermolecular Inc.

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

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

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：US20140166956A1

公开(公告)日：2014-06-19

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: H01L45/00

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：US09425394B2

公开(公告)日：2016-08-23

申请号：US14565712

申请日：2014-12-10

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

Inventor： Brian Butcher ,  Randall J. Higuchi ,  Yun Wang

IPC: H01L45/00 ,  H01L27/24

CPC classification number: H01L45/1616 ,  H01L27/2481 ,  H01L45/08 ,  H01L45/1233 ,  H01L45/1253 ,  H01L45/146 ,  H01L45/1641

Abstract: Provided are methods of fabricating memory cells such as resistive random access memory (ReRAM) cells. A method involves forming a first layer including two high-k dielectric materials such that one material has a higher dielectric constant than the other material. In some embodiments, hafnium oxide and titanium oxide form the first layer. The higher-k material may be present at a lower concentration. In some embodiments, a concentration ratio of these two high-k materials is between about 3 and 7. The first layer may be formed using atomic layer deposition. The first layer is then annealed in an oxygen-containing environment. The method may proceed with forming a second layer including a low-k dielectric material, such as silicon oxide, and forming an electrode. After forming the electrode, the memory cell is annealed in a nitrogen containing environment. The nitrogen anneal may be performed at a higher temperature than the oxygen anneal.

Abstract translation: 提供制造诸如电阻随机存取存储器（ReRAM）单元的存储单元的方法。 一种方法包括形成包括两个高k介电材料的第一层，使得一种材料具有比其它材料更高的介电常数。 在一些实施方案中，氧化铪和氧化钛形成第一层。 较高k的材料可以以更低的浓度存在。 在一些实施方案中，这两种高k材料的浓度比在约3和7之间。第一层可以使用原子层沉积形成。 然后将第一层在含氧环境中退火。 该方法可以继续形成包括低k介电材料（例如氧化硅）的第二层，并形成电极。 在形成电极之后，在含氮环境中对存储单元进行退火。 氮退火可以在比氧退火更高的温度下进行。

公开(公告)号：US09276203B2

公开(公告)日：2016-03-01

申请号：US13721406

申请日：2012-12-20

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

Inventor： Chien-Lan Hsueh ,  Randall J. Higuchi ,  Tim Minvielle ,  Jinhong Tong ,  Yun Wang ,  Takeshi Yamaguchi

IPC: H01L29/00 ,  H01L47/00 ,  H01L29/02 ,  H01L29/04 ,  H01L29/06 ,  H01L47/02 ,  H01L45/00 ,  H01L27/24

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

Abstract: Provided are resistive random access memory (ReRAM) cells having switching layers that include hafnium, aluminum, oxygen, and nitrogen. The composition of such layers is designed to achieve desirable performance characteristics, such as low current leakage as well as low and consistent switching currents. In some embodiments, the concentration of nitrogen in a switching layer is between about 1 and 20 atomic percent or, more specifically, between about 2 and 5 atomic percent. Addition of nitrogen helps to control concentration and distribution of defects in the switching layer. Also, nitrogen as well as a combination of two metals helps with maintaining this layer in an amorphous state. Excessive amounts of nitrogen reduce defects in the layer such that switching characteristics may be completely lost. The switching layer may be deposited using various techniques, such as sputtering or atomic layer deposition (ALD).

Abstract translation: 提供了具有包括铪，铝，氧和氮的开关层的电阻随机存取存储器（ReRAM）单元。 这些层的组成被设计成实现期望的性能特性，例如低电流泄漏以及低和一致的开关电流。 在一些实施方案中，开关层中氮的浓度在约1至20原子百分比之间，或更具体地在约2至5原子百分比之间。 添加氮有助于控制开关层缺陷的浓度和分布。 此外，氮气以及两种金属的组合有助于将该层保持在非晶状态。 过量的氮减少了层中的缺陷，使得开关特性可能完全丧失。 可以使用诸如溅射或原子层沉积（ALD）的各种技术来沉积切换层。