CN104094430A - 具有钝化的切换层的非易失性电阻式存储器元件 - Google Patents
具有钝化的切换层的非易失性电阻式存储器元件 Download PDFInfo
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
- H10N70/8833—Binary metal oxides, e.g. TaOx
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- H10B—ELECTRONIC MEMORY DEVICES
- H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
- H10B63/80—Arrangements comprising multiple bistable or multi-stable switching components of the same type on a plane parallel to the substrate, e.g. cross-point arrays
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- H10N70/023—Formation of switching materials, e.g. deposition of layers by chemical vapor deposition, e.g. MOCVD, ALD
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Abstract
一种非易失性电阻式存储器元件具有在沉积切换层期间或之后利用例如氮等非金属掺杂剂原子进行钝化的新型可变电阻层。在可变电阻层中非金属掺杂剂原子的存在使切换层能够通过较小的切换电流来进行操作同时维持改进的数据保持特性。
Description
技术领域
本发明涉及一种非易失性电阻式存储器元件(nonvolatile resistivememory element),更具体地涉及具有钝化的切换层(passivated switchinglayer)的非易失性电阻式存储器元件以及其形成方法。
背景技术
非易失性存储器元件用在需要持久性数据存储的设备(例如数码相机和数字音乐播放器)中,以及用在计算机系统中。电可擦除可编程只读存储器(EPROM,electrically-erasable programmable read only memory)和NAND闪存是当前正在使用的非易失性存储器技术。然而,随着器件尺寸缩小,缩放(scaling)问题对传统非易失性存储器技术提出挑战。这导致了对包括电阻式切换的非易失性存储器的、替代性非易失性存储器技术的研究。
使用双稳态(即,具有不同电阻的两个稳定状态)的存储器元件来形成电阻式切换的非易失性存储器。可以通过施加适当的电压或电流而将双稳态存储器元件置于高电阻状态或低电阻状态。电压脉冲通常用于使双稳态存储器元件从一个电阻状态切换到另一电阻状态。随后,可以在存储器元件上执行无损读取操作以确定被存储在其中的数据位的值。
随着电阻式切换的存储器设备尺寸缩小,重要的是减少可靠地置位(set)、复位(reset)和/或确定设备的期望的“接通(on)”和“关断(off)”状态所必需的必要电流和电压,从而把设备的功耗、设备的电阻性发热和相邻设备之间的串扰减至最低。此外,非常希望通过这样的设备将数据可靠地保持更长时间段。
因为形成有相对较少的氧空位的双稳态存储器元件可以导致更低的操作电压和电流,所以通常期望使形成在双稳态存储器元件中的氧空位的数量最小化。然而,具有少量的氧空位的双稳态存储器元件本质上更可能遭受数据保持问题,这是因为在这样的存储器元件中即使少量的氧空位损失或迁移也可以改变存储器元件的电阻状态,从而导致数据丢失。因此,在电阻式双稳态存储器元件的设计中,在受益于具有更少的氧空位的、具有更低的操作电压和电流的构造与受益于具有更多氧空位的、具有更高的耐用性和可靠性的构造之间存在取舍。
鉴于上述情况,在本领域中需要的是具有降低的电流和电压要求以及可靠的数据保持特性的非易失性电阻式切换的存储器设备。
发明内容
本发明的实施例提出了一种具有新型可变电阻层的非易失性电阻式存储器元件及其形成方法。在切换层的沉积期间或之后,利用非金属掺杂剂原子对新型可变电阻层进行钝化,使得切换层需要较小的切换电流并且具有改进的数据保持特性。适合于用作非金属掺杂剂原子的元素包括氮(N)、氟(F)和氯(Cl)。
根据本发明的一种实施例,形成非易失性存储器元件的方法包括如下步骤:形成可变电阻层,该可变电阻层包括在第一电极层上方的金属氧化物,其中可变电阻层包括高达3原子百分比的非金属掺杂剂原子;以及形成第二电极层,使得可变电阻层设置在第一电极层与第二电极层之间。
根据本发明的另一实施例,非易失性存储器元件包括在衬底上形成的第一电极层、第二电极层、以及可变电阻层,所述可变电阻层包括设置在第一电极层与第二电极层之间的金属氧化物,其中可变电阻层的至少一部分包括高达3原子百分比的掺杂剂原子。
附图说明
所以,通过参考附图可以得到上面简要阐述的能够详细理解本发明的实施例的上述特征的方式、本发明的实施例的更具体描述。然而,应该注意,附图仅例示了本发明的典型实施例,因此不应该被认为是对本发明范围的限制,这是因为本发明可以允许其他等效实施例。
图1是根据本发明的实施例配置的存储器设备的存储器阵列的透视图。
图2A是根据本发明的实施例配置的存储器设备的示意性横截面视图。
图2B示意性地例示了根据本发明的实施例的配置成使得电流正向流过存储器设备的存储器设备。
图3给出了根据本发明的实施例的存储器元件的一个实施例的双极切换曲线的电流与电压的双对数坐标图(log-log plot)。
图4是根据本发明的实施例的由包括新型可变电阻层的一系列沉积层形成的存储器设备的示意性横截面视图。
图5给出了根据本发明的一个实施例的在用于形成存储器设备的处理序列中的方法步骤的流程图。
为了清楚起见,在适用的地方,使用相同的附图标记指代附图中共有的相同元件。预期到的是,在没有进一步声明的情况下,一个实施例的特征可以结合到其他实施例中。
具体实施方式
用作非易失性电阻式存储器元件的切换层的材料通常需要具有双稳态特性,并且理想地能够以较低的切换电流来操作同时具有延长的数据保持特性。本发明的实施例提出了一种具有满足这些要求的新型可变电阻层的非易失性存储器元件。新型可变电阻层包括金属氧化物,该金属氧化物包含高达3原子百分比的阴离子非金属掺杂剂原子。
图1是根据本发明的实施例配置的存储器设备200的存储器阵列100的透视图。存储器阵列100可以是更大的存储器设备或其他集成电路结构(例如片上系统型设备,system-on-a-chip type device)的一部分。存储器阵列100可以形成为大容量非易失性存储器集成电路的一部分,其可以用在例如数码相机、移动电话、手持计算机以及音乐播放器等各种电子设备中。为了清楚起见,存储阵列100例示为单层存储器阵列结构。然而,也可以以垂直方式堆叠存储器阵列,例如存储器阵列100,以制造多层存储器阵列结构。
每个存储器设备200均包括非易失性电阻切换存储器设备,例如,电阻式随机存取存储器(ReRAM,resistive random access memory)设备。存储器设备200包括可以由一个或更多个材料层114形成的新型存储器元件112。材料层114包括新型可变电阻层,该新型可变电阻层包含金属氮化物、金属氧化物-氮化物或其组合,并且在下面结合图4进行描述。在一些实施例中,存储器设备200还包括电流导引器件,在下面结合图2A和图2B对其进行描述。
读取和写入电路(未示出)利用电极102和电极118连接至存储器设备200。电极102和电极118,有时称为“位线”和“字线”,用于读取数据或者将数据写入存储器设备200中的存储器元件112中。可以利用电极102和电极118的合适组合来寻址各个的存储器设备200或者存储器设备200的组。
图2A是根据本发明的实施例配置的存储器设备200的示意图。存储器设备200包括存储器元件112,并且在一些实施例中还包括电流导引器件216,存储器元件112和电流导引器件216均布置在电极102与电极118之间。在一个实施例中,电流导引器件216包括设置在电极102与存储器元件112之间或者设置在电极118与存储器元件112之间的插入电元件,例如p-n结二极管、p-i-n二极管、晶体管或其他类似器件。在一些实施例中,电流导引器件216可以包括两个或更多个半导体材料层,例如,两个或更多个掺杂的硅层,该半导体材料层配置成允许或禁止电流在不同方向流过存储器元件112。此外,读取和写入电路150经由如所示的电极102和电极118耦接至存储器设备200。读取和写入电路150配置成感测存储器设备200的电阻状态并且设置存储器设备200的电阻状态。
图2B示意性地例示了根据本发明的实施例的配置成使得电流正向(“I+”)流过存储器设备200的存储器设备200。然而,由于电流导引器件216的设计,还可以通过向电极102和电极118施加反向偏压使得较小的电流反向流过设备。
在读取操作期间,读取和写入电路150利用在存储器阵列100中适当选择的电极102和电极118在电阻切换存储器元件112两端施加读取电压VREAD,例如,+0.5伏(V)。然后,读取和写入电路150感测由此产生的穿过存储器设备200的电流。相对较高的“接通”电流值(ION)表示存储器元件112处于其低电阻状态,相对较低的“关断”电流值(IOFF)表示存储器元件112处于其高电阻状态。根据其历史,以这种方式被寻址的具体存储器元件112可以处于高电阻状态(HRS,high resistance state)或低电阻状态(LRS,low resistance state)中的任一状态。因此存储器元件112的电阻确定了什么数字数据被存储在存储器元件112中。例如,如果存储器元件112处于高电阻状态,可以说存储器元件112包含逻辑零(即,“0”位),另一方面,如果存储器元件112处于低电阻状态,可以说存储器元件112包含逻辑1(即,“1”位)。
在写入操作期间,可以通过由读取和写入电路150向电极102和电极118的合适组合施加合适的写入信号来改变在存储器阵列100中的具体存储器元件112的电阻状态。在一些实施例中,为了实现这样的改变,使用双极切换,其中相反极性的“置位”和“复位”电压用于使已选择的存储器元件112的电阻在高电阻状态和低电阻状态之间改变。图3给出了存储器元件112的一个实施例的双极切换曲线252的电流(I)与电压(V)的双对数坐标图251,因此例示了用于置位和复位存储器元件112的内容的典型阈值。例如,存储器元件112开始可处于高电阻状态(例如,存储逻辑“零”)。为了在存储器元件112中存储逻辑“1”,将存储器元件112置于其低电阻状态。这可以通过利用读取和写入电路150以将“置位”电压VSET(例如,-2V至-4V)施加在电极102和电极118两端使得“置位”电流ISET流动穿过存储器元件112来实现。在一个实施例中,将负VSET电压施加于存储器元件112,以使存储器元件112切换至其低电阻状态。在该区域中,存储器元件112被改变,使得在去除“置位”电压VSET之后,存储器元件112以低电阻状态为特征。相反,为了在存储器元件112中存储逻辑“零”,可以通过将正“复位”电压VRESET(例如,+2V至+5V)施加在存储器元件112两端而使存储器元件再次置于其高电阻状态,使得“复位”电流IRESET流动穿过存储器元件112。当读取和写入电路150将VRESET施加于存储器元件112时,存储器元件112进入其高电阻状态。当从存储器元件112去除了“复位”电压VRESET时,在施加读取电压VREAD时,存储器元件112再次以高电阻为特征。虽然本文中存储器元件112的讨论主要是提供双极切换的示例,但是在不脱离本文中所描述的发明的范围内的情况下,存储器元件112的一些实施例可以使用单极切换,其中“置位”和“复位”电压具有相同的极性。
为了配备可用的存储器元件112,通常在电极102和电极118两端施加形成电压VFORM至少一次以“老化测试(burn-in)”存储器阵列100中的每个存储器设备200。据认为,通常显著大于VRESET和VSET电压的形成电压VFORM的施加引起在设备的制造过程期间在可变电阻层206(图4中例示)内形成的缺陷在该层的不同区域内移动、排列和/或聚集,使得可变电阻层206在存储器元件的整个寿命内在“接通”和“关断”电阻状态之间一致且可靠地切换。在一个实施例中,形成电压VFORM在VRESET或VSET电压的约1倍至约5倍之间。在一个示例中,形成电压在VRESET或VSET电压的约1.4倍至约2.5倍之间。在一个示例中,形成电压在约3伏至约7伏之间。然而,应当注意,在某些情况下,期望形成一种存储器元件112,使得根本不需要施加形成电压来确保该设备在其整个寿命内如所期望的执行。
人们认为,存储器元件112的电阻状态的变化可能是“陷阱调解(trap-mediated)”(即,电阻状态的改变是归因于在存储器设备200被反向偏置时存储器元件112的可变电阻层中的陷阱或缺陷的重新分配或填充)。当可变电阻层包括金属氧化物(有时称为主体氧化物(host oxide))时,一般认为这些缺陷或陷阱是在可变电阻层的沉积和/或最初的“老化测试”(或“形成”)期间形成的氧空位。通过使金属/氧比率大于在可变电阻层中精确化学计量(exact stoichiometry)的金属/氧比率,很可能在可变电阻层中产生这样的氧空位。氧空位还可以通过在使金属氧化物键断裂之后经由电学方法或化学方法将氧原子从其原子位置转移而形成。一种可能的化学方法是将氮原子引入可变电阻层的金属氧化物材料中。在这种情况下,为了维持电中性,均带有一个负电荷的两个氮原子产生带有净电荷“+2”的一个氧空位。可变电阻层的电阻在很大程度上通过在可变电阻层中形成的这种氧空位的总数量和这种空位将电子传输通过可变电阻层的能力来确定。
用于切换可变电阻层所需的切换电流(即,“置位”电流ISET和“复位”电流IRESET)与包含在可变电阻层中的空位的数量之间的关系通过公式1进行量化:
(1) Iswitch=α*Nvac
其中,Iswitch=在期望的VSET和VRESET下通过可变电阻层的切换电流;α=表示当在可变电阻层两端施加VSET或VRESET时可变电阻层中的氧空位传输电子的平均能力的因子;以及NVAC=可变电阻层中氧空位的数量。电子传输因子α和空位的数量NVAC可以根据可变电阻层的具体材料以及可变电阻层形成的方式而改变。应该注意,可变电阻层的切换电流ISWITCH与可变电阻层的电阻成反比,结果随着可变电阻层的电阻增大,切换电流ISWITCH按比例减小。因此,具体可变电阻层(例如氧化铪(HfOx)层)的电阻值可以通过改变电子传输因子α和/或空位数量NVAC来进行调整。
减小可变电阻层中的空位的数量NVAC将增加可变电阻层的电阻,从而有利地减小了切换电流ISWITCH。然而,在包含可变电阻层的存储器元件的整个寿命内,形成有相对较小数量的空位NVAC的可变电阻层本质上更可能遭受数据保持问题。这是因为在将数据存储在存储器元件中时出现的空位数量NVAC的小变化能够使可变电阻层的电阻产生不期望的大变化。当这样的电阻变化足够大时,可变电阻层的电阻状态改变,导致数据的丢失。这种特征在公式2中量化:
其中,R=处于具体电阻状态的可变电阻层的电阻;△R=响应于可变电阻层中氧空位的数量的变化△NVAC的可变电阻层的电阻R的变化;NVAC=可变电阻层中存在的氧空位的数量;以及△NVAC=在数据存储在可变电阻层中的时间段期间在可变电阻层中氧空位NVAC的数量的变化。公式2表明如果氧空位的数量NVAC相对较小,例如,5或10,则空位数量的变化△NVAC会相对较小,例如,1至5,并且还产生大的电阻变化△R。这是因为变化△R与变化△NVAC和氧空位的数量NVAC之比成正比。公式2与以下观察相符:该观察指明已知的具有低切换电流ISWITCH的非易失性电阻切换存储器设备存在数据保持问题。
本发明的实施例设想了在切换层的沉积期间或之后利用非金属掺杂剂原子进行钝化的可变电阻层,使得切换层通过较小的切换电流来进行操作,并且该切换层具有改进的数据保持特性。根据是否分别取代金属或氧离子,非金属掺杂剂原子可以是阳离子或阴离子中的任一种。按照公式1,掺杂剂原子的优选类型为同时地增加在可变电阻层中形成的氧空位的数量NVAC并且降低可变电阻层的电子传输因子α的那些类型。以这样的方式,切换电流ISWITCH可以维持在期望的值,而不使氧空位NVAC的数量降低至不期望的低值。相反,氧空位的数量NVAC可以显著增加,从而改进了可变电阻层的数据保持特性。
具体地,适当的非金属掺杂剂原子要么降低切换层中的带正电荷的氧空位的形成能量要么增加将氧原子从其原子位置移走的可能性,从而增加在形成过程期间产生的带电空位的数量。因此,对于相同的形成电压VFORM,在形成过程期间在可变电阻层中产生更大数量的带电空位(即,氧空位的数量NVAC)。同时,非金属掺杂剂原子使可变电阻层中存在的氧空位钝化,从而减少了可变电阻层中的电子传输,也就是说,减少了公式1中的电子传输因子α的值。
图4是根据本发明的实施例的由包括新型可变电阻层206的一系列沉积层形成的存储器设备200的示意性横截面图。在图4例示的实施例中,存储器设备200在衬底201(例如,硅衬底或SOI衬底)的表面部分之上形成,或者与衬底201(例如,硅衬底或SOI衬底)的表面部分集成在一起并且设置在衬底201(例如,硅衬底或SOI衬底)的表面部分之上。应该注意,关于本发明的实施例,本文中所使用的相对的方向术语仅用于描述的目的,并且不限制本发明的范围。具体地,方向术语,例如“在…之上(over)”、“在…上方(above)”、“在…下方(under)”等是在以下假设下使用:在其上形成实施例的衬底201为“底部”元件,因此衬底201是在其上形成本发明的“下方”元件。
在图4中例示的实施例中,存储器设备200包括设置在电极102与电极118之间的存储器元件112。存储器元件112是包括可变电阻层206的非易失性电阻式存储器元件。在另一实施例中,存储器设备200还包括可选的中间电极和置于电极118与可变电阻层206之间的可选的电流导引器件216。
电极102和电极118是由具有期望功函数的导电材料形成,该期望功函数调整成适合(tailor)构成可变电阻层206的材料的带隙。在一些配置中,电极102和电极118由不同材料形成,使得电极102和电极118具有相差为期望值(例如,0.1eV、0.5eV、1.0eV等)的功函数。例如,在一个实施例中,电极102包括TiN,其具有4.5eV至4.6eV的功函数,而电极118可以是n型多晶硅,其具有约4.1eV至4.15eV的功函数。适合用于电极102和/或电极118的其他电极材料包括p型多晶硅(4.9eV至5.3eV)、n型多晶硅、过渡金属、过渡金属合金、过渡金属氮化物、过渡金属碳化物、钨(4.5eV至4.6eV)、氮化钽(4.7eV至4.8eV)、氧化钼(约5.1eV)、氮化钼(4.0eV至5.0eV)、铱(4.6eV至5.3eV)、氧化铱(约4.2eV)、钌(约4.7eV)和氧化钌(约5.0eV)。其他潜在的电极材料包括钛/铝合金(4.1eV至4.3eV)、镍(约5.0eV)、氮化钨(约4.3eV至5.0eV)、氧化钨(5.5eV至5.7eV)、铝(4.2eV至4.3eV)、掺杂有铜或硅的铝(4.1eV至4.4eV)、铜(约4.5eV)、碳化铪(4.8eV至4.9eV)、氮化铪(4.7eV至4.8eV)、氮化铌(约4.95eV)、碳化钽(约5.1eV)、钽硅氮化物(约4.4eV)、钛(4.1eV至4.4eV)、碳化钒(约5.15eV)、氮化钒(约5.15eV)和氮化锆(约4.6eV)。在一些实施例中,电极102是从材料的组中选择的元素所形成的金属、金属合金、金属氮化物或金属碳化物,该材料的组包括钛(Ti)、钨(W)、钽(Ta)、钴(Co)、钼(Mo)、镍(Ni)、钒(V)、铪(Hf)、铝(Al)、铜(Cu)、铂(Pt)、钯(Pd)、铱(Ir)、钌(Ru)和其组合。在一个示例中,电极102包括从掺杂有硅的铝(AlSi)或钛/铝合金(TixAly)的组中选择的金属合金。
可变电阻层206包括可以在两种或更多种稳定的电阻状态之间进行切换的介电材料。在一些实施例中,可变电阻层206具有在约与约之间的厚度,并且包含一种或更多种过渡金属的氧化物,该过渡金属包括但不限于铪(Hf)、锆(Zr)、钛(Ti)、钽(Ta)、铝(Al)、镧(La)、钇(Y)、镝(Dy)和镱(Yb)。此外,高达3原子百分比的可变电阻层206包含阴离子非金属掺杂剂原子。用于可变电阻层206的合适的掺杂剂原子是在被引入可变电阻层206中之后甚至在存储器设备200的形成和集成期间产生的升高的温度(例如,450℃至900℃)时仍基本保持不变的阴离子非金属掺杂剂原子。
在一个实施例中,使用氮(N)作为非金属掺杂剂原子。氮是已被证实通过钝化栅氧化物中的氧空位来减少高介电常数栅氧化物(例如氧化铪(HfOx))中的漏电流的掺杂剂。在这样的应用中,氮掺杂剂增加氧化铪层的固定电荷也是已知的。本领域中的技术人员应该理解的是,虽然在互补金属氧化物半导体(CMOS,complimentary metal oxide semiconductor)晶体管的栅氧化物中固定电荷是极不合需要的,但是增加可变电阻层206中的固定电荷是改进存储器设备200的数据保持的有益特征。在其他实施例中,使用氟(F)和/或氯(Cl)作为非金属掺杂剂原子。
理想地,可变电阻层206的大部分或全部的氧空位通过掺杂剂原子进行钝化。因此,可变电阻层206中的期望的最小掺杂剂原子浓度等于或大于估计的空位浓度,该空位浓度可以在每立方厘米5.0×10e16至5.0×10e19个空位的范围内。在使用氮原子作为非金属掺杂剂原子的实施例中,需要2个氮原子来钝化单个氧空位,并且期望的最小掺杂剂原子浓度等于或大于估计的空位浓度的两倍。因为,在一些实施例中,引入可变电阻层206中的掺杂剂原子的很大一部分可能与氧空位不相符并且不成对,所以引入可变电阻层206中的掺杂剂原子的浓度大于可变电阻层206中估计的空位浓度。在这样的实施例中,非金属掺杂剂原子的浓度可以高达3原子百分比,以确保可变电阻层206中存在的大部分或全部的氧空位通过掺杂剂原子进行钝化。然而,大于约3原子百分比的掺杂剂原子浓度通常不合需要;在这样高的浓度下,掺杂剂原子以与半导体中的p型掺杂剂相同的方式作用,并且增加了可变电阻层206的电导率。如上面所提及的,向可变电阻层206添加掺杂剂原子的目的是实现相反的效果,即降低电导率,因此掺杂剂原子的浓度优选地不大于约3原子百分比。
应该注意,可变电阻层206中仅仅存在掺杂剂原子不一定如期望的使氧空位钝化。通常,掺杂剂原子排列在可变电阻层206内部而不是作为用于形成可变电阻层206的化合物的一部分。因此,可以有效地钝化氧空位的掺杂剂原子位于可变电阻层206的空隙位置(interstitial location)和/或取代位置(substitutional location)中。例如,可变电阻层206中以任意浓度存在的氮化物形式的氮不增加氧空位的数量NVAC或减小电子传输因子α。因此,将掺杂剂原子引入可变电阻层206中的方式确定了这样的原子是否有效地钝化氧空位。在一些实施例中,在可变电阻层206的沉积期间将掺杂剂原子引入可变电阻层206中。在其他实施例中,在可变电阻层206的沉积之后的处理步骤中将掺杂剂原子引入可变电阻层206中。
图5给出了根据本发明的实施例的用于形成存储器设备200的处理序列500中方法步骤的流程图。尽管该方法步骤是结合图4中的存储器设备200进行描述的,但是本领域的技术人员将理解的是,利用处理序列500形成其他电阻切换存储器设备也在本发明的范围内。
如所示,方法500从步骤502开始,在步骤502中,在衬底201上形成电极118。在一个实施例中,电极118为使用常规CVD多晶硅沉积技术在衬底201上形成的高掺杂的多晶硅层。在一个实施例中,电极118包括多晶硅,并且厚度在约至约之间。
在步骤504中,在电极118上或之上形成可变电阻层206。在一些实施例中,如图4所示,在电极118上形成可变电阻层206。在其他实施例中,在电极118上所形成的一个或更多个中间层上形成可变电阻层206。利用一种或更多种沉积工艺形成可变电阻层206,使得可变电阻层206包括用作空位钝化掺杂剂原子的一种或更多种化学元素。本发明的实施例包括沉积可变电阻层206的各种方法,并且部分地取决于可变电阻层206的具体成分和包含在其中的具体掺杂剂原子。
在一些实施例中,在可变电阻层206的沉积之后的处理步骤中将掺杂剂原子掺入到可变电阻层206中。在这样的实施例中,例如,使用反应性物理气相沉积(PVD,physical vapor deposition)工艺来沉积可变电阻层206以形成期望的金属氧化物层。在反应性PVD中,氧与溅射的金属(例如,铪)反应以沉积期望的金属氧化物膜(例如,氧化铪)。在随后的处理步骤中,将期望的掺杂剂原子(例如,氮)引入到所沉积的金属氧化物膜中。例如,在这样的一个实施例中,在氧或氧-氩气氛中通过反应性PVD来沉积氧化铪层,并且利用在氨(NH3)气氛中的热处理、去耦等离子体氮化(DPN,decoupled plasma nitridization)或氮离子注入将氮原子引入所沉积的氧化铪膜中。在这样的另一实施例中,可以使用本领域中已知的在技术上可行的任何其他金属氧化物沉积方法来沉积用于在步骤504中形成可变电阻层206的金属氧化物膜,所述方法包括化学气相沉积(CVD,chemical vapor deposition)、原子层沉积(ALD,atomic layerdeposition)等。
在一些实施例中,在可变电阻层206的沉积期间将掺杂剂原子引入到可变电阻层206中。在这样的一个实施例中,利用反应性PVD工艺来沉积可变电阻层206,以形成掺杂有期望浓度的掺杂剂原子的期望金属氧化物层。在这样的实施例中,在沉积工艺期间,将低浓度的掺杂剂原子引入氧气氛下,使得期望浓度的掺杂剂原子被引入PVD金属氧化物膜中。例如,在一个实施例,在包含痕量浓度的氮(例如1原子百分比的氮)的氧气氛中经由反应性PVD来沉积氧化铪层。当氧化铪膜被沉积时,在氧气氛中的痕量氮原子被引入到氧化铪膜中,从而避免了需要附加的处理步骤来将掺杂剂原子引入到可变电阻层206中。
在步骤506中,在可变电阻层206上方形成电极102。用于形成电极102的合适的材料在上面结合图4进行了描述。在一些实施例中,如图4所示,在可变电阻层206上直接形成电极102,并且在其他实施例中,在存储器元件112的一个或更多个中间层上的可变电阻层206的上方形成电极102。根据用于形成电极102的具体材料,可以利用任何技术上可行的沉积工艺(如PVD、CVD、ALD或其他类似工艺)来形成电极102。在一个实施例中,电极102的厚度在约与1μm之间。
在步骤508中,例如,通过退火工艺对所形成的存储器设备200进行热处理。退火工艺的温度和持续时间由存储器设备200的配置以及存储器设备200中所包含的材料的来决定。例如,在一些实施例中,退火工艺发生在高于约450℃的温度下。在另一实施例中,退火处理发生在高于约600℃的温度下。在又一实施例中,退火工艺发生在高于约1000℃的温度下。退火工艺的持续时间也可以根据存储器设备200的配置而变化很大(例如,在约30秒至20分钟之间变化)。另外,真空退火、氧退火、利用气体混合物(如氢/氩混合物)的退火以及本领域中已知的其他退火工艺落在本发明的范围之内。同样地,可以在不超出本发明的范围的条件下对存储器设备200执行多个热处理步骤。例如,可以在方法500的多个步骤期间或之后执行热处理。
虽然在本文中就用于形成存储器阵列的电阻切换存储器元件来描述了本发明的实施例,但是在不脱离本文描述的本发明的基本范围的情况下本发明的实施例可以应用于其他电阻式存储器设备。
总之,本发明的实施例提供了一种具有利用非金属掺杂剂原子进行钝化的新型可变电阻层的非易失性电阻式存储器元件及其形成方法。非金属掺杂剂原子降低了切换层中的带正电荷的氧空位的形成能,从而有利地增加了在存储器元件的形成过程期间产生的带电空位的数量。此外,掺杂剂原子使氧空位钝化,从而降低了钝化的氧空位的载流能力并且增加了可变电阻层的电阻。因此,新型可变电阻层可以通过较小的切换电流来进行操作,同时具有改进的数据保持特性。
虽然前述内容涉及本发明的实施例,但是可以在不脱离本发明的基本范围的条件下设计出本发明的其他和另外的实施例,并且本发明的范围由所附的权利要求来确定。
Claims (17)
1.一种形成非易失性存储器元件的方法,包括:
形成第一层,所述第一层能够作为可变电阻层操作并且包括在第二层上方的金属氧化物,所述第二层能够作为电极层操作,其中,所述第一层包括高达3原子百分比的非金属掺杂剂原子;以及
形成能够作为电极层操作的第三层,使得所述第一层设置在所述第二层与所述第三层之间。
2.根据权利要求1所述的方法,其中,所述形成第一层包括:
沉积所述金属氧化物;以及
将所述非金属掺杂剂原子引入所述金属氧化物中。
3.根据权利要求2所述的方法,其中,沉积所述金属氧化物与将所述非金属掺杂剂原子引入所述金属氧化物中同时执行。
4.根据权利要求2所述的方法,其中,沉积所述金属氧化物包括执行反应性物理气相沉积工艺或原子层沉积工艺。
5.根据权利要求4所述的方法,其中,所述非金属掺杂剂原子包括氮(N)原子,以及将所述非金属掺杂剂原子引入所述金属氧化物中包括在所述反应性物理气相沉积工艺中纳入氮气。
6.根据权利要求2所述的方法,其中,所述非金属掺杂剂原子包括氮原子。
7.根据权利要求6所述的方法,其中,将所述非金属掺杂剂原子引入所述金属氧化物中包括从以下组中选择的至少一种工艺,所述组包括在氨(NH3)气氛中的热处理工艺、去耦等离子体氮化工艺或离子注入工艺。
8.根据权利要求1所述的方法,其中,所述非金属掺杂剂原子包括从以下组中选择的至少一种化学元素,所述组包括氮、氯(Cl)和氟(F)。
9.根据权利要求1所述的方法,其中,所述金属氧化物包括从以下组中选择的至少一种化学元素,所述组包括铪(Hf)、锆(Zr)、钛(Ti)、钽(Ta)、铝(Al)、镧(La)、钇(Y)、镝(Dy)和镱(Yb)。
10.根据权利要求1所述的方法,其中,所述第一层的厚度在约 至之间。
11.一种非易失性存储器元件,包括:
第一层,所述第一层能够作为电极层操作并且形成在衬底之上;
第二层,所述第二层能够作为电极层操作;以及
第三层,所述第三层能够作为可变电阻层操作并且包括设置在所述第一层与所述第二层之间的金属氧化物,其中,所述第三层的至少一部分包括高达3原子百分比的非金属掺杂剂原子。
12.根据权利要求11所述的非易失性存储器元件,其中,所述金属氧化物包括从以下组中选择的至少一种化学元素,所述组包括铪、锆、钛、钽、铝、镧、钇、镝和镱。
13.根据权利要求11所述的非易失性存储器元件,其中,所述非金属掺杂剂原子包括从以下组中选择的至少一种化学元素,所述组包括氮、氯和氟。
14.根据权利要求11所述的非易失性存储器元件,其中,所述金属氧化物通过反应性物理气相沉积工艺进行沉积。
15.根据权利要求11所述的非易失性存储器元件,其中,所述非金属掺杂剂原子包括氮原子。
16.根据权利要求11所述的非易失性存储器元件,其中,所述非金属掺杂剂原子通过在氨气氛中的热处理工艺、去耦等离子体氮化工艺或离子注入工艺中的至少一种工艺来引入所述金属氧化物中。
17.根据权利要求15所述的非易失性存储器元件,其中,所述非金属掺杂剂原子通过在沉积所述金属氧化物的反应性物理气相沉积工艺中纳入氮气来引入所述金属氧化物中。
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2011
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2012
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- 2012-11-21 CN CN201280059555.2A patent/CN104094430A/zh active Pending
- 2012-11-21 WO PCT/US2012/066398 patent/WO2013081945A1/en active Application Filing
- 2012-11-21 KR KR1020147018409A patent/KR20140121393A/ko not_active Application Discontinuation
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2013
- 2013-12-18 US US14/133,107 patent/US20140103280A1/en not_active Abandoned
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107134457A (zh) * | 2016-02-29 | 2017-09-05 | 东芝存储器株式会社 | 半导体存储装置及其制造方法 |
CN107134457B (zh) * | 2016-02-29 | 2020-12-08 | 东芝存储器株式会社 | 半导体存储装置及其制造方法 |
CN109196654A (zh) * | 2016-05-25 | 2019-01-11 | 美光科技公司 | 铁电装置及形成铁电装置的方法 |
CN109196654B (zh) * | 2016-05-25 | 2022-09-30 | 美光科技公司 | 铁电装置及形成铁电装置的方法 |
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KR20140121393A (ko) | 2014-10-15 |
EP2791986A1 (en) | 2014-10-22 |
EP2791986A4 (en) | 2015-07-01 |
US20140103280A1 (en) | 2014-04-17 |
US20130140512A1 (en) | 2013-06-06 |
WO2013081945A1 (en) | 2013-06-06 |
US8637413B2 (en) | 2014-01-28 |
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