CN100524881C - 用于制造柱状相变存储元件的方法 - Google Patents
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- H—ELECTRICITY
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- H10N70/011—Manufacture or treatment of multistable switching devices
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- H10N70/063—Patterning of the switching material by etching of pre-deposited switching material layers, e.g. lithography
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- H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
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- H10N70/801—Constructional details of multistable switching devices
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- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8828—Tellurides, e.g. GeSbTe
Abstract
本发明公开一种柱状相变存储元件,其包括第一与第二电极元件以及位于该两个元件之间的相变元件。第二电极材料与氯敏感相变材料被选定。第一电极元件被形成。相变材料沉积于第一电极元件之上,接着第二电极材料沉积于相变材料之上。第二电极材料与相变材料被蚀刻而不使用氯气,以形成第二电极元件与相变元件。该第二电极材料选择步骤、相变材料选择步骤以及蚀刻工艺选择步骤的实施,使得在蚀刻过程中,相变元件相对于第二电极元件并不会形成侧蚀。
Description
技术领域
本发明涉及使用存储材料(尤其是相变存储材料,包括以硫属化物为基础的材料等)的高密度存储元件,以及用于制造这种元件的方法。
背景技术
以相变为基础的存储材料被广泛地运用于读写光盘中。这些材料包括有至少两种固态相,包括如大部分为非晶态的固态相,以及大体上为晶态的固态相。激光脉冲用于读写光盘中,以在两种相中切换,并读取此种材料在相变之后的光学性质。
如硫属化物及类似材料的这种相变存储材料,可通过施加其幅度适用于集成电路中的电流,而致使晶相变化。一般而言非晶态的特征为其电阻高于晶态,此电阻值可轻易测量得到而用于作为指示。这种特性则引起使用可编程电阻材料以形成非易失性存储器电路等兴趣,此电路可用于随机存取读写。
从非晶态转变至晶态一般为低电流步骤。从晶态转变至非晶态(以下称为重置(reset))一般为高电流步骤,其包括短暂的高电流密度脉冲以融化或破坏结晶结构,其后此相变材料会快速冷却,抑制相变的过程,使得至少部份相变结构得以维持在非晶态。理想状态下,致使相变材料从晶态转变至非晶态的重置电流幅度应越低越好。欲降低重置所需的重置电流幅度,可通过减小在存储器中的相变材料元件的尺寸、以及减少电极与此相变材料的接触面积而达成,因此可针对此相变材料元件施加较小的绝对电流值而得到较高的电流密度。
此领域发展的一种方法致力于在集成电路结构上形成微小孔洞,并使用微量可编程的电阻材料填充这些微小孔洞。致力于这种微小孔洞的专利包括:于1997年11月11日公开的美国专利第5,687,112号“Multibit Single CellMemory Element Having Tapered Contact”、发明人为Ovshinky;于1998年8月4日公开的美国专利第5,789,277号“Method of Making Chalogenide[sic]Memory Device”、发明人为Zahorik等;于2000年11月21日公开的美国专利第6,150,253号“Controllable Ovonic Phase-ChangeSemiconductor Memory Device and Methods of Fabricatingthe Same”、发明人为Doan等。
在以非常小的尺寸制造这些装置、以及欲满足生产大尺寸存储装置时所需求的严格工艺参数时,则会遭遇到问题。优选地提供一种存储单元(memory cell)结构,其具有小尺寸以及低重置电流,以及用于制造这种结构的方法
发明内容
本发明的第一目的,有关于一种用于制造柱状相变存储元件的方法,此相变存储元件包括第一与第二电极元件、以及位于此二电极元件之间的相变元件。氯敏感相变材料被选定。第一电极元件被形成。此相变材料沉积于第一电极元件之上,且第二电极材料沉积于相变材料之上。不使用氯气的蚀刻工艺被选定。第二电极材料与相变材料根据所选定的蚀刻工艺而被蚀刻,以分别形成第二电极元件与相变元件,进而生成柱状相变存储元件。第二电极材料沉积步骤、相变材料选择步骤、以及蚀刻工艺选择步骤实施以使得在蚀刻步骤中,相变元件相对于第二电极元件并不形成侧蚀。
本发明的第二目的,是提供一种用于制造柱状相变存储元件的方法,此存储元件包括第一与第二电极元件、以及位于这两个电极元件之间的相变元件。选择第一与第二电极材料。选择氯敏感相变材料。形成第一电极元件,此第一电极元件包括了第一电极材料。相变材料沉积于第一电极元件上,接着第二电极材料沉积于相变材料之上。在第二电极材料上形成蚀刻掩模,并将其修剪。选择第一蚀刻工艺,此工艺并不使用氯气。利用第一蚀刻工艺而蚀刻第二电极材料与相变材料中未经修剪的掩模所覆盖的部分,以分别形成初步第二电极元件与初步相变元件,同时再次在初步相变元件之上沉积第一与第二电极材料中的至少一种,以生成初步柱状相变存储元件。选择第二蚀刻工艺,此工艺并不使用氯气。利用第二蚀刻工艺而蚀刻此初步柱状相变存储元件,以移除再次沉积且经蚀刻的材料,以形成第二电极元件与相变元件,生成柱状相变存储元件。本方法的实施使得在初步柱状相变存储元件蚀刻步骤中,相变元件相对于第二电极元件并不会形成侧蚀。
在某些实施例中,第一电极元件形成步骤的实施,可以利用钨、多晶硅,与氮化钛之中的至少一种作为第一电极元件。第二电极材料沉积步骤可包括选择钨、多晶硅的至少一种。相变材料选择步骤可包括选定Ge2Sb2Te5作为相变材料。第二蚀刻工艺选择步骤可包括等离子体蚀刻步骤。
在此描述的用于形成相变栅极以用于相变随机存取存储器(PCRAM)元件中的方法,可用于制造其它元件的微小相变栅极、电桥或类似结构。
以下详细说明本发明的结构与方法。本发明内容说明章节目的并非在于定义本发明。本发明由权力要求书所定义。凡是本发明的实施例、特征、目的及优点等将可通过下列说明的权利要求及附图获得充分了解。
附图说明
图1-7示出用于制造柱状相变存储元件的方法;
图1示出用于制造存储单元存取层的最后步骤;
图2示出在图1的结构上沉积相变材料层与第二电极层的结果;
图3示出形成于图2的结构上的光刻掩模;
图4示出修剪图3的光刻掩模的结果;
图5示出图4以后的结构经过蚀刻的结果;
图6示出从图5的结构中移除经修剪的光刻掩模的结果,生成柱状相变电极结构;
图7示出替代方法,其中图4的结构被蚀刻以生成初步柱状相变电极结构,其具有覆盖于初步相变元件之上的一层再次沉积的电极材料,之后则使用等离子体增强化学蚀刻,以生成图6的结构。
具体实施方式
接下来针对本发明的叙述,典型地参考至特定结构的实施例与方法。必须注意的是,以下叙述并非用于限制本发明于所揭露的特定实施例与方法中,且本发明可利用其它特征、元件、方法与实施例而实施。在各实施例中的相似元件,会以相似的标号指定。
请参照图1-7以了解本发明用于制造柱状相变存储元件的方法。请参见图1,存储单元存取层20形成于基板22之上。存取层20典型地包括了存取晶体管(未示出);其它类型的存取元件也可被使用。存取层20包括了第一、第二、以及第三栓塞28,30,32,其均位于介质薄膜层34之中。作用为第一电极元件的第一、第二与第三栓塞28,30,32,典型地由钨、多晶硅或氮化钛所构成。存储单元存取层20具有上表面36。
图2示出了相变存储材料沉积于上表面36之上的结果,以生成相变材料层40,此相变材料如Ge2Sb2Te5等。相变材料层的厚度优选为约20至120纳米,典型地为约80纳米。第二电极层42沉积于层40之上。第二电极层典型地由钨或多晶硅所构成,且优选地其厚度为约40至100纳米,典型地为约80纳米。相变材料与其它用于形成电极的材料的选择,将在以下详述。
图3示出了生成大致位于栓塞28,30,32的中央的光刻掩模46的结果。光刻掩模46典型地具有横向尺寸48,其大致与所使用的光刻工艺的最小光刻特征尺寸相同。为了减小光刻掩模46的横向尺寸48,进行掩模修剪工艺,此工艺的结果生成了如图4所示的经修剪光刻掩模50。因此,经修剪光刻掩模50的横向尺寸52小于用于生成光刻掩模46的工艺的最小光刻特征尺寸。在实施例中,横向尺寸48优选为约40至100纳米,且典型地为约60纳米,而横向尺寸52优选地为约10至80纳米,且典型地为约40纳米。
图5示出了蚀刻第二电极层42以及相变材料层40、并部分蚀刻介质薄膜层34与栓塞28,30,32的结果。图6示出了后续将经修剪光刻掩模50移除,以留下相变元件56于第一电极元件58与第二电极元件54之间的结果。相变元件56的尺寸通过最小化相变材料层40的厚度以及使用经修剪光刻掩模50而被最小化,以减少所需要的重置电流。
在公知的蚀刻步骤中,相变元件56可能被侧蚀,进而削弱了图6中所示的柱状相变元件结构60。为了避免此种情形,则特别选定第二电极材料、相变材料、以及蚀刻工艺,使得在蚀刻过程中,相变元件56相对于第二电极元件54并不会被侧蚀。在某些实施例中,第一电极元件58以及第二电极元件54的选择,可以被蚀刻而不使用氯气。在某些实施例中,第一电极元件58利用钨、多晶硅、与氮化钛的至少一种而形成;第二电极元件54利用钨与多晶硅的至少一种而形成;相变元件56使用Ge2Sb2Te5做为相变材料而形成;以及蚀刻不使用氯气而实施。无氯蚀刻化合物包括了CF4/CHF3/Ar/O2。其它电极材料、相变材料以及蚀刻化合物也可被使用。当相变元件56由GST所构成时,虽然无氯蚀刻是重要的,但仍可使用其它相变材料以避免使用氯气。在GST以外,其它氯敏感相变材料也可使用,并使用无氯蚀刻化合物以防止相变元件的侧蚀。
本发明的另一实施例同样进行了图1-4的步骤,但不进行如图5所示的蚀刻步骤,而是进行蚀刻步骤以蚀刻(1)经修剪光刻掩模52以及未被此掩模所覆盖的(2)第二电极层42以及相变材料层40。假设第二电极层42包括了钨与多晶硅的至少一种,且相变材料层40包括了Ge2Sb2Te5,则适合的蚀刻化合物为CF4/CHF3/Ar/O2。此蚀刻步骤形成了初步柱状相变存储元件结构64,如图7所示。结构64包括了初步第二电极元件66以及初步相变元件68、其上则沉积有电极材料70。亦即,从栓塞28,30,32所形成的第一与第二电极材料的至少一种以及第二电极层42,重新沉积于初步相变元件68之上,并典型地沉积于初步第二电极元件66之上。此再次沉积的电极材料70有助于防止初步相变元件68的侧蚀。之后,实施使用如CF4或CHF3的等离子体增强化学蚀刻步骤,以过度蚀刻图7的结构64,以移除再次沉积的电极材料70、并同时部分蚀刻栓塞28,30,32与介质薄膜层34,进而生成图6的结构。
存储材料元件56的实施例包括相变为基础的存储材料,包括硫属化物材料与其它材料。硫属化物包括下列四元素的任一种:氧(O)、硫(S)、硒(Se)、以及碲(Te),形成元素周期表上第VI族的部分。硫属化物包括将硫属元素与更为正电性的元素或自由基结合而得。硫属化合物合金包括将硫属化合物与其它物质如过渡金属等结合。硫属化合物合金通常包括一种以上选自元素周期表第六栏的元素,例如锗(Ge)以及锡(Sn)。通常,硫属化合物合金包括下列元素中一种以上的复合物:锑(Sb)、镓(Ga)、铟(In)、以及银(Ag)。许多以相变为基础的存储材料已经被描述于技术文件中,包括下列合金:镓/锑、铟/锑、铟/硒、锑/碲、锗/碲、锗/锑/碲、铟/锑/碲、镓/硒/碲、锡/锑/碲、铟/锑/锗、银/铟/锑/碲、锗/锡/锑/碲、锗/锑/硒/碲、以及碲/锗/锑/硫。在锗/锑/碲合金家族中,可以尝试大范围的合金成分。此成分可以下列特征式表示:TeaGebSb100-(a+b)。
一位研究员描述了最有用的合金为,在沉积材料中所包含的平均碲浓度远低于70%,典型地低于60%,并在一般型态合金中的碲含量范围从最低23%至最高58%,且最佳介于48%至58%的碲含量。锗的浓度高于约5%,且其在材料中的平均范围从最低8%至最高30%,一般低于50%。最佳地,锗的浓度范围介于8%至40%。在此成分中所剩下的主要成分则为锑。上述百分比为原子百分比,其为所有组成元件总和为100%。(Ovshinky‘112专利,栏10~11)由另一研究者所评估的特殊合金包括Ge2Sb2Te5、GeSb2Te4、以及GeSb4Te7。(Noboru Yamada,”Potential of Ge-Sb-Te Phase-changeOptical Disks for High-Data-Rate Recording”,SPIEv.3109,pp.28-37(1997))更一般地,过渡金属如铬(Cr)、铁(Fe)、镍(Ni)、铌(Nb)、钯(Pd)、铂(Pt)、以及上述的混合物或合金,可与锗/锑/碲结合以形成相变合金其包括有可编程的电阻性质。可使用的存储材料的特殊范例,如Ovshinsky‘112专利中栏11-13所述,其范例在此列入参考。
相变材料能在此单元主动通道区域内依其位置顺序在材料为一般非晶状态的第一结构状态与为一般结晶固体状态的第二结构状态之间切换。这些材料至少为双稳定态。此术语“非晶”用于指相对较无次序的结构,其较之单晶更无次序性,而带有可检测的特征如较之晶态更高的电阻值。此术语“晶态”用于指相对较有次序的结构,其较之非晶态更有次序,因此包括有可检测的特征例如比非晶态更低的电阻值。典型地,相变材料可电切换至完全晶态与完全非晶态之间所有可检测的不同状态。其它受到非晶态与晶态的改变而影响的材料特性中包括,原子次序、自由电子密度以及活化能。此材料可切换成为不同的固态、或可切换成为由两种以上固态所形成的混合物,提供从非晶态至晶态之间的灰度部分。此材料中的电性质也可能随之改变。
相变材料可通过施加电脉冲而从一种相态切换至另一相态。先前观察指出,较短、较大幅度的脉冲倾向于将相变材料的相态改变成大体为非晶态。较长、较低幅度的脉冲倾向于将相变材料的相态改变成大体为晶态。在较短、较大幅度脉冲中的能量够大,因此足以破坏结晶结构的键,同时够短因此可以防止原子再次排列成晶态。在没有不适当实验的情形下,可决定特别适用于特定相变合金的适当脉冲量变曲线。在本文中所描述的一种适用于RRAM元件中的材料,为Ge2Sb2Te5,通常称为GST。其它类型的相变材料也可被使用。
上述有关于本发明的描述,参照至相变材料。然而也可使用其它类型的存储材料,有时称为可编程材料。如本发明中所使用的,存储材料为其电气性质(如电阻等)可以通过施加能量而改变的材料;上述的改变可以为阶梯式改变、或连续改变、或二者的组合。可用于本发明其它实施例中的其它可编程的存储材料包括,掺杂N2的GST、GexSby、或其它以不同晶态转换来决定电阻的物质;PrxCayMnO3、PrSrMnO、ZrOx、TiOx、NiOx、WOx、经掺杂的SrTiO3或其它利用电脉冲以改变电阻状态的材料;或其它使用电脉冲以改变电阻状态的物质;TCNQ(7,7,8,8-tetracyanoquino dimethane)、PCBM(methanofullerene 6,6-phenyl C61-butyric acid methylester)、TCNQ-PCBM、Cu-TCNQ、Ag-TCNQ、C60-TCNQ、以其它物质掺杂的TCNQ、或任何其它聚合物材料其包括有以电脉冲而控制的双稳定或多稳定电阻态。可编程电阻存储材料的其它范例,包括GeSbTe、GeSb、NiO、Nb-SrTiO3、Ag-GeTe、PrCaMnO、ZnO、Nb2O5、Cr-SrTiO3。
接下来则简单叙述一种电阻存储材料。
硫属化物材料
GexSbyTez
x:y:z=2:2:5
其它成分为x:0~5;y:0~5;z:0~10
以氮、硅、钛或其它元件掺杂的GeSbTe也可被使用。
形成方法:利用PVD溅射或磁控溅射方式,其反应气体为氩气、氮气、及/或氦气、压力为1mTorr至100mTorr。此沉积步骤一般于室温下进行。长宽比为1~5的准直器(collimater)可用于改良其填入表现。为了改善其填入表现,也可使用数十至数百伏特的直流偏压。另一方面,同时合并使用直流偏压以及准直器也是可行的。
可以选择性地在真空中或氮气环境中进行沉积后退火处理,以改良硫属化物材料的结晶状态。此退火处理的温度典型地介于100℃至400℃,而退火时间则少于30分钟。
硫属化物材料的厚度随着单元结构的设计而定。一般而言,硫属化物的厚度大于8nm的可以具有相变特性,使得此材料展现至少双稳定的电阻态。
其它有关相变随机存取存储元件的制造、元件材料、使用与操作等信息,请参见美国专利申请第11/155,067,其申请日为2005/6/17,其发明名称为“Thin Film Fuse PhaseChange Ram And Manufacturing Method”。
上述叙述中可能使用到之上、之下、顶、底、覆盖、底下等词汇。这些词汇用于协助读者更了解本发明,而非用于限制本发明。
虽然本发明已参照优选实施例来加以描述,将为我们所了解的是,本发明并未受限于其详细描述内容。替换方式及修改样式已于先前描述中所建议,并且其它替换方式及修改样式将为本领域技术人员所想到。特别是,根据本发明的结构与方法,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的都不脱离本发明的精神范围。因此,所有这种替换方式及修改样式将落在本发明在所附权利要求书及其等同物所界定的范围之中。任何在前文中提及的专利申请以及公开文本,均列为本申请的参考。
Claims (10)
1、一种用于制造柱状相变存储元件的方法,所述相变存储元件包括第一与第二电极元件,以及位于所述两个电极元件之间的相变元件,所述方法包括:
选择氯敏感相变材料;
形成第一电极元件;
在所述第一电极元件上沉积所述相变材料;
在所述相变材料上沉积第二电极材料;
选择不使用氯气的蚀刻工艺;
根据所选定的蚀刻工艺而蚀刻所述第二电极材料与所述相变材料,以分别形成第二电极元件与相变元件,进而生成柱状相变存储元件;以及
通过实施所述第二电极材料沉积步骤、所述相变材料选择步骤以及所述蚀刻工艺选择步骤,能够使得在所述蚀刻步骤中所述相变元件相对于所述第二电极元件并不会形成侧蚀。
2、如权利要求1所述的方法,其中所述第一电极元件形成步骤的实施,利用下列组群中的至少一种做为所述第一电极元件:钨、多晶硅以及氮化钛。
3、如权利要求1所述的方法,其中所述第二电极材料沉积步骤包括选择钨与多晶硅的至少一种做为所述第二电极材料。
4、如权利要求1所述的方法,其中所述相变材料选择步骤包括选择Ge2Sb2Te5做为所述相变材料。
5、如权利要求1所述的方法,还包括选择第一电极材料作为所述第一电极元件的步骤,且其中所述第一与第二电极材料的选择使得所述蚀刻步骤不需要使用氯气。
6、一种用于制造柱状相变存储元件的方法,所述相变存储元件包括第一与第二电极元件以及位于两个所述电极元件之间的相变元件,所述方法包括:
选择第一电极材料;
选择第二电极材料;
选择氯敏感相变材料;
形成第一电极元件,所述第一电极元件包括所述第一电极材料;
在所述第一电极元件上沉积所述相变材料;
在所述相变材料上沉积所述第二电极材料;
在所述第二电极材料上形成蚀刻掩模;
修剪所述蚀刻掩模以生成经修剪的蚀刻掩模;
选择第一蚀刻工艺,其不使用氯气;
根据所述第一蚀刻工艺而蚀刻所述第二电极材料与所述相变材料未被所述经修剪蚀刻掩模所遮蔽的部分,以分别形成初步第二电极元件以及初步相变材料,并在所述初步第二电极元件上再次沉积所述第一与第二电极材料的至少一种,以生成初步柱状相变存储元件;
选择第二蚀刻工艺,其不使用氯气;
根据所述第二蚀刻工艺而蚀刻所述初步柱状相变存储元件,以移除再次沉积的材料,从而形成第二电极元件与相变元件,进而生成柱状相变存储元件;以及
所述方法的实施使得在所述初步柱状相变存储元件的蚀刻步骤中,所述相变元件相对于所述第二电极并不会形成侧蚀。
7、如权利要求6所述的方法,其中所述第一电极材料选择步骤包括选择下列组群的至少一种:钨、多晶硅以及氮化钛。
8、如权利要求6所述的方法,其中所述第二电极材料选择步骤包括选择钨与多晶硅的至少一种。
9、如权利要求6所述的方法,其中所述相变材料选择步骤包括选择Ge2Sb2Te5作为所述相变材料。
10、如权利要求6所述的方法,其中所述第二蚀刻工艺选择步骤包括等离子体蚀刻步骤。
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