CN101409327A - 具有缓冲层的电阻式存储结构 - Google Patents

具有缓冲层的电阻式存储结构 Download PDF

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CN101409327A
CN101409327A CNA2008101281632A CN200810128163A CN101409327A CN 101409327 A CN101409327 A CN 101409327A CN A2008101281632 A CNA2008101281632 A CN A2008101281632A CN 200810128163 A CN200810128163 A CN 200810128163A CN 101409327 A CN101409327 A CN 101409327A
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resilient coating
memory element
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CN101409327B (zh
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简维志
张国彬
赖二琨
谢光宇
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Macronix International Co Ltd
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Abstract

本发明公开了一种存储器装置，包括第一电极与第二电极以及介于第一与第二电极间并与其电性耦接的存储元件与缓冲层。存储元件包括一种以上的金属氧化合物。缓冲层至少包括一氧化物或一氮化物。于另一实施例中，存储装置包括第一电极与第二电极以及介于第一与第二电极间并与其电性耦接的存储元件与缓冲层。缓冲层具有一小于50埃的厚度。存储装置包括一或多种金属的氧化合物。制造存储装置方法的实施例包括形成第一电极与第二电极，形成介于第一与第二电极间并与其电性耦接的存储器，该存储器包括一或多种金属的氧化合物，缓冲层包括至少一氧化物或一氮化物。

Description

具有缓冲层的电阻式存储结构
技术领域
本发明是与下列美国专利申请案相关联：「可增进数据维持性的电阻式随机存取存储结构」，申请于2006年11月16日，其申请号为11/560,723，律师档案编号MXIC 1741-1；以及「具有钨化物的电阻式存储器及其制造方法」，申请于2007年12月16日，其申请号为11/955,137，律师档案编号MXIC 1742-2。
本发明是关于存储器装置以及制造高密度存储器装置的方法，特别是关于含钨-氧化合物的数据储存材料的存储器装置。
背景技术
非易失性存储器装置包括有磁性随机存取存储器(MRAM)、铁电随机存取存储器(FRAM)，相变化随机存取存储器(PCRAM)以及其它电阻式随机存取存储器(RRAM)。由于具有结构简单、存储单元尺寸小等优点，电阻式随机存取存储器越来越受到重视。
含金属-氧化物的电阻式随机存取存储器，在施加大小适用于集成电路的电子脉冲时，其电阻可于二个以上的稳定范围间变化，而该电阻可以随机存取的方式读取或写入，进而用来表示所储存的数据。
目前有针对含氧化镍(NiO)、二氧化钛(TiO2)、二氧化铪(HfO2)与二氧化锆(ZrO2)的电阻式随机存取存储器作为存储单元中的存储材料的相关研究。此部分可见于IEEE International Electron Devices Meeting2004的IEDM Technical Digest第23.6.1～23.6.4页，由Baek等人发表的文章”Highly Scalable Non-Volatile Resistive Memory using Simple BinaryOxide Driven by Asymmetric Unipolar Voltage Pulses”。此种存储单元是利用非自我排列(non-self-aligned)的工艺形成于M-I-M的结构中，其中M代表作为电极的贵金属，而I则为氧化镍、二氧化钛、二氧化铪与二氧化锆中的任何一种。由于此种MIM结构需要使用额外的屏蔽及图案化步骤来形成贵金属电极与存储材料，故其最终形成的存储单元尺寸都很大。
目前亦有针对含有铜的氧化物(CuxO)的电阻式随机存取存储器作为存储单元中的存储材料的相关研究。此部分可见于IEEE InternationalElectron Devices Meeting 2005的IEDM Technical Digest第746～749页，由Chen等人发表的文章”Non-Volatile Resistive Switching for AdvancedMemory Applications”。其中CuxO材料是利用铜的热氧化工艺来形成，并作为存储单元的下电极，而上电极则由沉积并刻蚀而得的双层钛/钛化氮(Ti/TiN)薄膜所组成。此种结构需要使用额外的屏蔽来形成上、下电极，且所形成的存储单元尺寸都很大。此外，由于擦除过程中施加的电场会促使铜离子形成铜的氧化物，则具有含铜的下电极会使得存储单元的擦除步骤变得更复杂。同时，CuxO仅具有10倍左右的相对窄的电阻操作区间。
目前亦有针对含有铜-三氧化钨(Cu-WO3)的电阻式随机存取存储器作为存储单元中的存储材料的相关研究。此部分可见于2006年9月，第5卷第5期的IEEE Transactions on Nanotechnology的第535～544页，由Kozicki等人发表的文章”A Low-Power Nonvolatile Switching ElementBased on Copper-Tungsten Oxide Solid Electrolyte”，其中有关于钨金属制成的切换元件、含有钨-氧化物以及经光扩散的铜的电解质以及铜的上电极的相关描述。该切换元件是通过将钨-氧化物成长或沉积于钨材料上而形成，钨-氧化物上并形成有一层铜，其可透过光扩散作用而进入钨-氧化物内以形成固态电解质，而在固态电解质上则形成并图案化有一作为上电极的铜层。于施加偏压时，铜离子会由上电极处电沉积而进入固态电解质，进而使切换元件改变电阻。此外，文中并提到「当上电极缺少铜时，将无法侦测到切换活动」(见该文第539页第1栏)。据此，可知此种结构需要有一个铜的上电极，且其涉及形成固态电解质的多个工艺步骤。此外，该结构尚需要相反电性的偏压来引发铜离子的注入以程序化或擦除固态电解质。
发明内容
有鉴于此，本发明的一实施例中提供了一种存储器装置，其包括第一电极与第二电极以及介于第一电极与第二电极间并与其电性耦接的存储元件与缓冲层。存储元件包括一种以上的金属氧化合物，且在施加能量的情形下，可诱发存储元件的电阻于二个以上的稳定范围间变化。缓冲层至少包括一氧化物或一氮化物，且存储元件具有增进的数据维持性与可写入次数。于某些实施例中，缓冲层包括一小于50埃的厚度。于某些实施例中，存储元件包括一种以上的钨氧化合物(tungsten oxygen compound)。于某些实施例中，缓冲层至少包括一种下列物质：二氧化硅(SiO2)、氧化钨(WO)、氧化钛(TiO)、氧化镍(NiO)、氧化铝(AlO)、氧化铜(CuO)、氧化锆(ZrO)、氮化硅(Si3N4)、氮化钛(TiN)。于某些实施例中，存储元件至少包括一种下列物质：钨的氧化物(WOx)、氧化镍(NiO)、五氧化二铌(Nb2O5)、二氧化铜(CuO2)、五氧化二钽(Ta2O5)、三氧化二铝(Al2O3)、氧化钴(CoO)、三氧化二铁(Fe2O3)、二氧化铪(HfO2)、二氧化钛(TiO2)、钛酸锶(SrTiO3)、锆酸锶(SrZrO3)、钛酸锶钡((BaSr)TiO3)、锗钛(GeTi)、锡锰碲(SnMnTe)、锑碲(SbTe)、锰酸的钙镨化物(Pr1-xCaxMnO3)、(含银离子或亚铜离子的碲-铜/钆氧化物、锗锑)(Te-Cu/GdOx，GeSb with Ag+or Cu+)。
于另一实施例中，存储装置包括第一电极与第二电极以及介于第一与第二电极间并与其电性耦接的存储元件与缓冲层，存储装置亦包括一或多种金属的氧化合物。缓冲层具有一小于50埃的厚度。
制造存储装置方法的一实施例可以下述步骤进行。形成第一电极与第二电极，形成介于第一与第二电极间并与其电性耦接的存储器，该存储器包括一或多种金属的氧化合物，缓冲层包括至少一氧化物或一氮化物。于某些实施例中，缓冲层是介于存储元件与第一电极间并与其电性耦接。于某些实施例中，缓冲层具有一小于50埃的厚度。于某些实施例中，缓冲层具有一介于约1013至约1016欧姆-厘米间的电阻率。
于某些实施例中，一第二缓冲层乃形成于存储元件与第二电极之间并与其电性耦接，且第二缓冲层包括至少一氧化物或一氮化物。
本发明可增进电阻式存储结构的效能，包括数据维持性与可写入次数。
本发明的结构与方法将于文后详细描述，且发明内容所述的并非用以限定本发明，本发明的范围应由权利要求范围来限定。举凡本发明的特征、目的及优点等将可透过下列说明所附图式、实施方式及权利要求范围获得充分了解。
附图说明
图1为本发明第一实施例的电阻式存储结构的简化剖面图，其包括一介于下电极与存储单元间的缓冲层。
图2为本发明第二实施例的电阻式存储结构的简化剖面图，其包括一介于上电极与存储单元间的缓冲层。
图3为本发明第三实施例的电阻式存储结构的简化剖面图，其包括一介于下电极与存储单元间的缓冲层以及一介于上电极与存储单元间的缓冲层。
图4为不包括缓冲层的电阻式存储结构其电阻率与维持时间的关系图。
图5为本发明一实施例的电阻式存储结构其电阻率与维持时间的关系图，由此可看出本发明一实施例具有增进的数据维持性。
图6为不包括缓冲层的电阻式存储结构其电阻率与写入次数的关系图。
图7为本发明一实施例的电阻式存储结构其电阻率与写入次数的关系图，由此可看出本发明一实施例具有增进的可写入次数。
图8为本发明一实施例的电阻式存储结构其电阻率与读取干扰的关系图，此可看出本发明一实施例不论是在开启或关闭的状态，均具有绝佳的读取干扰特性。
图9为包括电阻式存储结构的集成电路方块图。
【主要元件符号说明】
10      电阻式存储结构
11      衬底
12      堆栈
14      介电层
16      下电极
18、19  缓冲层
20  存储元件层
22  上电极
24  存储单元区域
26  存储元件
110 一集成电路
112 存储器阵列
114 字线译码器
116 字线
118 位线译码器
120 位线
122 总线
124 感应放大器与数据输入结构
126 总线
128 数据输入线
130 其它电路
132 数据输出线
134 控制器
136 偏压调整供应电压与电流源
具体实施方式
以下说明请配合参考图1至图9以了解本发明各实施例。应注意的是，本发明并不仅限于所揭露的实施例，且本发明可以其它特征、元件、方法与实施方式来实施。于图式中，相同元件是使用相同编号来代表。
图1为本发明第一实施例的电阻式存储结构10的简化剖面图，结构10包括一上方形成有铝铜(AlCu)堆栈12的衬底11，而堆栈12上则形成有一介电层14，其通常是二氧化硅。下电极16是由堆栈12处延伸通过整个介电层14，且下电极16为一导电元件。举例来说，下电极16可以是存取晶体管的漏极端或是二极管的一端。缓冲层18可利用顺流式等离子体、等离子体溅射或反应性溅射等方式形成于介电层14与下电极16之上，且缓冲层18包括一小于50埃的厚度。采用缓冲层18的优点将于文后详述。缓冲层18至少包括一氧化物或一氮化物，举例来说，缓冲层18可包括至少一种下列的物质：二氧化硅、氧化钨、氧化钛、氧化镍、氧化铝、氧化铜、氧化锆、氮化硅以及氮化钛。缓冲层18的电阻率较佳是介于1013至1016欧姆-厘米间，且其厚度较佳是小于5纳米(即50埃)。缓冲层18可利用如物理气相沉积法或化学气相沉积法的方法来形成。
厚度在50至1000埃间的存储元件层20是沉积于缓冲层18上。存储元件层20包括一种以上的金属-氧化合物，特别是包括钨-氧化合物WxOy，像是一种以上的三氧化钨(WO3)、五氧化二钨(W2O5)、二氧化钨(WO2)。于某些实施例中，像是以等离子体氧化或热氧化的方式来形成存储元件层20时，可能会有多种不同的钨-氧化合物产生。于一实施例中，存储元件层20包括了三氧化钨/五氧化二钨/二氧化钨，且其厚度为140埃左右。上电极22是形成于存储元件层20上，而下电极16与上电极22通常是如钨或铝铜的金属。此外，下电极16与上电极22排列的部分则于其间定义了存储单元区域24。存储元件层20位于存储单元区域24的部份组成了与下电极16以及上电极22电性耦接的存储元件26。存储元件26可包括至少一种下列物质：钨的氧化物、氧化镍、五氧化二铌、二氧化铜、五氧化二钽、三氧化二铝、氧化钴、三氧化二铁、二氧化铪、二氧化钛、钛酸锶、锆酸锶、钛酸锶钡、锗钛、锡锰碲、锑碲、锰酸的钙镨化物(Pr1-xCaxMnO3)、(含银离子或亚铜离子的碲-铜/钆氧化物、锗锑)。
于操作过程中，施加至下电极16以及上电极22的电压会在二者间形成流经存储元件26的电流，并诱发存储元件26的电阻产生可程序化的变化，而电阻的变化则可用来表示储存在存储元件26中的数据。于某些实施例中，存储元件26可储存二个位或以上的数据。
图2为本发明第二实施例的电阻式存储结构10的简化剖面图，其与图1类似但不包括缓冲层18，而是包括介于存储元件26以及上电极22间的缓冲层19。图3为本发明第三实施例的电阻式存储结构10的简化剖面图，其则包括一介于下电极16与存储元件26间的缓冲层18以及一介于上电极22与存储元件26间的缓冲层19。
电阻式存储结构10可利用传统的后段工艺钨栓塞工艺方式来制作，且可利用单一屏蔽来形成缓冲层19与上电极22。
通过缓冲层18、缓冲层19或同时采用二者，可增进电阻式存储结构10的效能，而此部份是配合图4至图8予以说明。其中，图5、图7、图8的结果是以图1的结构进行分析而得，而测试的结构具有以下特性：下电极16是由钨组成，且其平均直径约为200纳米；上电极22是由铝组成，且其平均宽度约为500纳米；存储元件层20是由钨的氧化物所组成，且其厚度约为140埃；缓冲层18是由二氧化硅组成，且其厚度约为2纳米。图4、图6中所显示的结果是是以一种与测试的结构大致相同，但不包括任何缓冲层的电阻式存储结构(文后称为传统电阻式存储结构)进行分析所得。
图4为传统电阻式存储结构于开启与关闭状态的电阻率与维持时间关系图，由图4可看出，电阻率随着时间(以对数刻度表示)的增加相对快速，特别是在开启状态下最为明显。相较之下，图5中以电阻率与维持时间所描绘的直线则几乎是平坦的，由此可看出本发明大大地改善了传统电阻式存储结构的效能。
图6为传统电阻式存储结构其电阻率与写入次数的关系图，由图6可看出不论是在开启或关闭状态，电阻率均随着时间大幅增加。相较之下，图7中以电阻率与写入次数所描绘的直线，不论是在开启或关闭状态均相对平坦，由此可看出本发明的电阻式存储结构10在写入次数上，大大地改善了传统电阻式存储结构10的效能。
图8为电阻式存储结构10其电阻率与读取干扰的关系图，其中可看出结构10的电阻率不论是在开启或关闭的状态，均具有绝佳的读取干扰特性(读取干扰是指存储元件26因读取状态而造成的电阻增减)。
图9为一集成电路110的简化方块图，其包括了具有电阻式存储结构10的存储器阵列112。具有读取、设定与重设模式的字线译码器114是与多条沿着存储器阵列112排列的字线116彼此耦接并电性相连。位线(栏)译码器118是与多条沿着阵列中的栏排列的位线120电性相连，以读取、设定与重设阵列112中的存储元件26。地址是透过总线122提供至字线译码器及驱动器114与位线译码器118。于方块124中，包括读取、设定与重设模式所需的电压及/或电流源的感应放大器与数据输入结构是通过数据总线126耦接至位线译码器118。通过数据输入线128，数据是由集成电路110上的输入/输出端或由集成电路110内部或外部的其它数据源传送至方块124中的数据输入结构。集成电路110还可以包括其它电路130，像是一般用途的处理器、特殊用途的应用电路或是可提供阵列112所支持的系统单芯片功能的模块或其组合。数据透过数据输出线132由方块124的感应放大器传送至集成电路110上的输入/输出端或其它集成电路110内部或外部的数据目的地。
于本实施例中，控制器134是以偏压调整状态机构为例，其是控制偏压调整供应电压与电流源136，如读取、程序化、擦除、擦除验证以及程序化验证电压及/或电流。此外，控制器134可利用技术领域中已知的特殊用途逻辑电路来实作。于其它实施方式中，控制器134可包括一般用途的处理器以执行计算机程序来控制元件的操作，而该处理器可以实作于相同的集成电路上。于另外的实施方式中，控制器134可利用特殊用途逻辑电路与一般用途的处理器的组合来实作。
一种钨-氧化合物WxOy的形成方法是利用物理气相沉积法溅射或磁控溅射法，在1至100毫托耳的压力下配合使用反应性气体如氩气、氮气、氧气及/或氦气等。沉积通常于室温下进行，宽高比1～5的准直器可用来提升填充的效能。此外，也可以使用数十到数百伏特的直流偏压来提升填充效能，而直流偏压可与准直器同步使用。
于沉积后，可选择性地在真空、氮气或混合有氧气/氮气的环境下进行退火处理，藉以提升金属氧化物的氧分布情形。退火处理的温度可介于400至600℃，而处理时间则少于2小时。
而另一种钨-氧化合物WxOy的形成方法则是利用高温氧化系统进行氧化，像是使用氧化炉或快速热脉冲(RTP)系统。其是于温度200至700℃间，在纯氧气或混合有氮气/氧气、数毫托耳至1大气压的环境下进行，而处理时间可从数分钟至数小时。另一种氧化方法则是等离子体氧化，其中钨的表面是在1至100毫托耳的压力下，于纯氧、混合有氩气/氧气或混合有氩气/氮气/氧气的环境下，以射频或直流电衍生的等离子体进行氧化。氧化时间可由数秒至数分钟，氧化温度则可由室温至300℃，端视等离子体氧化的程度而定。
虽然本发明是已参照实施例来加以描述，然本发明创作并未受限于其详细描述内容。替换方式及修改样式是已于先前描述中所建议，且其它替换方式及修改样式将为熟习此项技艺之人士所思及。特别是，所有具有实质上相同于本发明的构件结合而达成与本发明实质上相同结果者，皆不脱离本发明的精神范畴。因此，所有此等替换方式及修改样式是意欲落在本发明于随附权利要求范围及其均等物所界定的范畴之中。举例来说，在缓冲层与存储元件及/或电极之间可采用材料的过渡层或保护层。
前述所提及的专利、专利申请案以及各文献均纳入本案作为参考。

Claims (31)

1、一种存储器装置，其特征在于，包括：
一第一电极与一第二电极；以及
一存储元件与一缓冲层，介于该第一电极与该第二电极之间，并与该第一电极以及该第二电极电性耦接，该存储元件包括一种或以上的金属氧化合物，以及
该缓冲层至少包括一氧化物或一氮化物之一。
2、根据权利要求1所述的存储器装置，其特征在于，该缓冲层是介于该存储元件与该第一电极之间，并与该存储元件以及该第一电极电性耦接。
3、根据权利要求1所述的存储器装置，其特征在于，该缓冲层包括一小于50埃的厚度。
4、根据权利要求1所述的存储器装置，其特征在于，该缓冲层包括一介于1013至1016欧姆-厘米间的电阻率。
5、根据权利要求2所述的存储器装置，其特征在于，更包括一第二缓冲层，该第二缓冲层是介于该存储元件与该第二电极之间，并与该存储元件以及该第二电极电性耦接，且该第二缓冲层至少包括一氧化物或一氮化物之一。
6、根据权利要求5所述的存储器装置，其特征在于，该第二缓冲层包括一小于50埃的厚度。
7、根据权利要求1所述的存储器装置，其特征在于，该存储元件介于该第一电极与该第二电极之间的厚度是介于50至1000埃。
8、根据权利要求1所述的存储器装置，其特征在于，该存储元件至少包括一种下列物质：钨的氧化物WOx、氧化镍NiO、五氧化二铌Nb2O5、二氧化铜CuO2、五氧化二钽Ta2O5、三氧化二铝Al2O3、氧化钴CoO、三氧化二铁Fe2O3、二氧化铪HfO2、二氧化钛TiO2、钛酸锶SrTiO3、锆酸锶SrZrO3、钛酸锶钡(BaSr)TiO3、锗钛GeTi、锡锰碲SnMnTe、锑碲SbTe、锰酸的钙镨化物Pr1-xCaxMnO3、含银离子或亚铜离子的碲-铜/钆氧化物或锗锑Te-Cu/GdOX，GeSb with Ag+or Cu+。
9、根据权利要求1所述的存储器装置，其特征在于，该缓冲层至少包括一种下列物质：氧化钨WO、氧化钛TiO、氧化镍NiO、氧化铝AlO、氧化铜CuO、氧化锆ZrO、氮化硅Si3N4、氮化钛TiN。
10、根据权利要求1所述的存储器装置，其特征在于，该缓冲层包括二氧化硅SiO2。
11、一种存储器装置，其特征在于，包括：
一第一电极与一第二电极；以及
一存储元件与一缓冲层，介于该第一电极与该第二电极之间，并与该第一电极以及该第二电极电性耦接，该存储元件包括一种或以上的金属氧化合物，以及
该缓冲层包括一小于50埃的厚度。
12、根据权利要求11所述的存储器装置，其特征在于，该缓冲层是介于该存储元件与该第一电极之间，并与该存储元件以及该第一电极电性耦接。
13、根据权利要求11所述的存储器装置，其特征在于，该存储元件至少包括一种下列物质：钨的氧化物WOx、氧化镍NiO、五氧化二铌Nb2O5、二氧化铜CuO2、五氧化二钽Ta2O5、三氧化二铝Al2O3、氧化钴CoO、三氧化二铁Fe2O3、二氧化铪HfO2、二氧化钛TiO2、钛酸锶SrTiO3、锆酸锶SrZrO3、钛酸锶钡(BaSr)TiO3、锗钛GeTi、锡锰碲SnMnTe、锑碲SbTe、锰酸的钙镨化物Pr1-xCaxMnO3、含银离子或亚铜离子的碲-铜/钆氧化物或锗锑Te-Cu/GdOX，GeSb with Ag+or Cu+。
14、根据权利要求11所述的存储器装置，其特征在于，该缓冲层包括一介于1013至1016欧姆-厘米间的电阻率。
15、根据权利要求11所述的存储器装置，其特征在于，更包括一第二缓冲层，该第二缓冲层是介于该存储元件与该第二电极之间，并与该存储元件以及该第二电极电性耦接，且该第二缓冲层至少包括一氧化物或一氮化物之一。
16、根据权利要求15所述的存储器装置，其特征在于，该第二缓冲层包括一小于50埃的厚度。
17、根据权利要求11所述的存储器装置，其特征在于，该存储元件介于该第一电极与该第二电极之间的厚度是介于50至1000埃。
18、根据权利要求11所述的存储器装置，其特征在于，该缓冲层至少包括一种下列物质：氧化钨WO、氧化钛TiO、氧化镍NiO、氧化铝AlO、氧化铜CuO、氧化锆ZrO、氮化硅Si3N4、氮化钛TiN。
19、根据权利要求11所述的存储器装置，其特征在于，该缓冲层包括二氧化硅SiO2。
20、一种制造一存储器装置的方法，其特征在于，包括：
形成一第一电极与一第二电极；以及
形成一存储元件与一缓冲层，该存储元件与该缓冲层是介于该第一电极以及该第二电极之间，并与该第一电极以及该第二电极电性耦接，该存储元件包括一种或以上的金属氧化合物，以及
该缓冲层至少包括一氧化物或一氮化物之一。
21、根据权利要求20所述的方法，其特征在于，该缓冲层是以顺流式等离子体、等离子体溅射或反应性溅射的方式形成。
22、根据权利要求20所述的方法，其特征在于，该存储元件是以等离子体氧化或热氧化的方式形成。
23、根据权利要求20所述的方法，其特征在于，该缓冲层是介于该存储元件与该第一电极之间，并与该存储元件以及该第一电极电性耦接。
24、根据权利要求20所述的方法，其特征在于，该缓冲层包括一小于50埃的厚度。
25、根据权利要求20所述的方法，其特征在于，该缓冲层包括一介于1013至1016欧姆-厘米间的电阻率。
26、根据权利要求23所述的方法，其特征在于，更包括形成一第二缓冲层，该第二缓冲层是介于该存储元件与该第二电极之间，并与该存储元件以及该第二电极电性耦接，且该第二缓冲层至少包括一氧化物或一氮化物之一。
27、根据权利要求26所述的方法，其特征在于，该第二缓冲层包括一小于50埃的厚度。
28、根据权利要求20所述的方法，其特征在于，该存储元件介于该第一电极与该第二电极之间的厚度是介于50至1000埃。
29、根据权利要求20所述的方法，其特征在于，该存储元件至少包括一种下列物质：钨的氧化物WOx、氧化镍NiO、五氧化二铌Nb2O5、二氧化铜CuO2、五氧化二钽Ta2O5、三氧化二铝Al2O3、氧化钴CoO、三氧化二铁Fe2O3、二氧化铪HfO2、二氧化钛TiO2、钛酸锶SrTiO3、锆酸锶SrZrO3、钛酸锶钡(BaSr)TiO3、锗钛GeTi、锡锰碲SnMnTe、锑碲SbTe、锰酸的钙镨化物Pr1-xCaxMnO3、含银离子或亚铜离子的碲-铜/钆氧化物或锗锑(Te-Cu/GdOX，GeSb with Ag+or Cu+)。
30、根据权利要求20所述的方法，其特征在于，该缓冲层至少包括一种下列物质：氧化钨WO、氧化钛TiO、氧化镍NiO、氧化铝AlO、氧化铜CuO、氧化锆ZrO、氮化硅Si3N4、氮化钛TiN。
31、根据权利要求20所述的方法，其特征在于，该缓冲层包括二氧化硅SiO2。
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US10720578B2 (en) 2016-04-29 2020-07-21 The Institute of Microelectronics of Chinese Academy of Sciences Self-gating resistive storage device having resistance transition layer in vertical trench in stacked structure of insulating dielectric layers and electrodes

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US20100276658A1 (en) 2010-11-04
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US7777215B2 (en) 2010-08-17
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