CN100550461C - 具有真空侧壁子的相变存储单元 - Google Patents
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Abstract
一种存储器单元包含：第一电极和第二电极构件，在衬底上相互分离；相变元件，与该第一电极和第二电极构件电性接触且连接分离两者间的空间。此相变元件包含两个区段，每一段与该电极构件中的一个接触。这两个区段在两电极之间的一个位置处相连，使得该相连位置有着小于该相变元件其余部分的横截面积。该电极、该衬底和该相变元件定义一个气室。
Description
联合研究合约的当事人
纽约国际商业机械公司、台湾旺宏国际股份有限公司及德国英飞凌技术公司(Infineon Technologies A.G.)为联合研究合约的当事人。
技术领域
本发明涉及非易失性存储器器件，特别是涉及使用相变存储元件的存储器器件。
背景技术
相变为基础的存储器材料已广泛用于读写光盘，且这些材料也逐渐使用于计算机存储器器件中。这些材料具有至少二种固相，通常为非晶固相及通常结晶固相。激光脉冲用于读写光谱，以在这二种相之间切换，并读取该材料在相变之后的光学性质，而电子脉冲则以相同的方式使用于计算机存储器器件中。
相变为基础的存储器材料，如硫属化物(Chalcogenide)及其类似的材料，也可以通过施加适合于集成电路操作的电流而改变状态。通常为非晶状态具有的特征在于比通常为结晶状态具有更高的电阻，其可以被快速感应以指示数据。该性质有利于作为非易失性存储器电路的可编程电阻材料，其可以用随机方式进行数据的读取与写入。
自非晶(amorphous)状态改变为结晶(crystalline)状态的相变通常是较低电流的操作。而自结晶状态改变为结非晶状态的相变，在此称为重置，通常是较高电流的操作，会包含一个短的高电流脉冲以融化或崩解此结晶结构，当此相变材料快速冷却后，为焠炼此相变过程，造成至少一部分的相变结构可以稳定在此非晶状态。通常希望此相变材料自结晶状态改变为结非晶状态的重置电流是越小越好。可以通过缩小单元内相变材料尺寸以及电极与此相变材料的接触面积的方式，来减小重置所需的重置电流值，所以高电流密度可以藉由较小电流通过此相变材料元件的方式来达成。
目前发展的方向之一已经朝向在集成电路结构内形成细小毛孔，和利用少量可编程电阻材料填充于此细小毛孔中。公开了朝向细小毛孔发展的专利有：Ovshinsky于1997年11月11日获准的美国专利No.5,687,112、发明名称为“Multibit Single Cell Memory ElementHaving Tapered Contact(具尖形接触窗的多位单一单元存储器单元)”的专利，Zahorik等人于1998年8月4日获准美国专利No.5,789,277、发明名称为“Method of Making Chalcogenide[sic]Memory Device(制造硫属化物[sic]存储器单元的方法)”的专利，Doan等人于2000年11月21日获准美国专利No.6,150,253，发明名称为“ControllableOvonic Phase-Change Semiconductor Memory Device and Methods ofFabricating the Same(可控制双向相变半导体存储器单元及其制造方法)”。以及Reinberg于1999年7月6日获准美国专利No.5,920,788，发明名称为“Chalcogenide Memory Cell with a Plurality ofChalcogenide Electrodes(有着许多硫属化物电极之硫属化物存储单元)”。
当使用传统的相变存储器结构时，一个特殊的热传导问题会在此传统设计中发生。通常而言，这些现有技术教导在该相变存储单元的两侧使用金属电极，且金属电极的大小相当于此相变构件的大小。如此的电极会构成热导体，金属的高导热性会很快将热带离此相变材料。因为由于发热的结果而发生相变，此热传导效应会造成需要更高的电流，才能产生所预期的相变。
一种解决此热传导效应问题的方式可见于美国专利No.6,815,704，发明名称为“Self Aligned Aire-Gap Thermal Insulationfor Nano-scale Insulated Chalcogenide Electronics(NICS)RAM(自动对准空气间隙热绝缘之纳米等级硫属化物电子式(NICE)随机存取存储器(RAM))”，其中公开了一种绝缘此存储单元的方法。此结构及其制造过程是非常复杂的，然而仍无法达到此存储器器件内的最小电流通过。
因此，必须要提供有着小尺寸以及低重置电流的存储器单元结构，此外，此结构必须解决热传导问题，且其制造方法必须符合大规模存储器器件所需的严谨工艺改变异规范。更需要提供一种结构及其制造方法，可以同时适用于同一晶片中周边电路的制造。
发明内容
本发明的一个重要目的为提供一种存储器单元，包含第一电极和第二电极构件，在衬底上相互分离。相变元件，与该第一电极和第二电极构件电性接触且连接分离两者间的空间。此相变元件包含两个区段，每一段与该电极构件中的一个接触。这两个区段在两电极之间的一个位置处相连，使得该相连位置有着小于该相变元件其余部分的横截面积。该电极、该衬底和该相变元件定义一个气室(chamber)。
附图说明
图1示出了根据本发明实施例的相变存储器器件的立体图；
图2示出了根据本发明实施例的相变存储器器件的详细剖面图；
图3示出了根据本发明图1的相变存储器器件的操作示意图；
图4a到4h示出了根据本发明的实施例的制造相变存储器器件的工艺步骤；以及
图5示出了本发明如图1的相变存储器器件。
【主要元件符号说明】
10： 存储单元
12： 衬底
13： 上方元件
14、16： 电极
20、20a、20b： 相变元件
23： 电极间的空间
24： 真空侧壁子
25： 接触区域
26： 介质填充材料
具体实施方式
以下参考附图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。本发明是由权利要求所定义的。所有本发明的实施例、特征、观点及优点等将可通过下列说明及附图获得充分了解。
如图1所示，为根据本发明的相变存储器元件10的基本布局图。如业界所熟知，相变随机存取存储(PCRAM)单元包含相变元件20，其由具有两个固态相的材料构成。优选的，此材料可以在施加适当的电流脉冲下由非晶改变至结晶且可回复至非晶。此存储单元的一般操作原则，可以参阅先前所提到的参考资料，而关于该相变材料的操作细节，则会在以下详加叙述。
以下会先描述关于此存储单元的结构以及功能，之后则会详述其工艺。此单元最好是形成在介质层或是衬底12之上，最好包含有氧化硅或是已知的替代品，如高分子材料、氮化硅或是其他介质填充材料(dielectric fill material)。在一个实施例中，此介质层包含相对较好的热绝缘以及电绝缘性质，以提供热绝缘及电绝缘之用。两个电极14和16，优选地是由耐热金属，如钨所构成，形成在此介质层之上。其它的耐热金属也可以使用，包括钛(Ti)，钼(Mo)，铝(Al)，钽(Ta)，铜(Cu)，铂(Pt)，铱(Ir)，镧(La)，镍(Ni)及钌(Ru)，以及这些金属的氧化物或是氮化物。这两个电极稍微分开，其距离大约介于30到70纳米之间，最好是50纳米。必须注意的是，自图面下方向上延伸的方向称为垂直方向，两侧延伸方向称为侧向或是水平方向，仅是为了方便说明起见。并不影响实际元件在制造或是操作时的真实走向。
相变元件20通常是在这二个电极之间包含细长条的相变材料，并桥接这二个电极。此元件的宽度大约介于10到30纳米之间，最好是20纳米，而厚度约为10纳米。介质填充材料26(参阅图4h)位于电极以及此相变元件之上。此介质填充材料最好是与衬底12的材料相同，或是选自与其类似的族群之中。此材料的导热性应该低于氧化硅，或是小于0.014J/cm*deg K*sec。这样的介质填充材料包括低介质系数材料热绝缘物质，如具硅(Si)、碳(C)、氧(O)、氟(F)及氢(H)等组合者。做为介质填充材料26的热绝缘材料例如包括SiCOH、聚亚醯胺(polyimide)、聚酰亚胺(polyimide)及氟碳聚合物。其他可作为介质填充材料的实例包括氟二氧化硅、硅氧烷(silsesquioxane)、聚亚芳香醚(polyarylene ether)、聚对二甲苯(parylene)、含氟聚合物、含氟非晶碳、金刚石类碳、多孔性二氧化硅(porous silica)、中孔性二氧化硅(mesoporous silica)、多孔性硅氧烷、多孔性聚亚酰胺、以及多孔性聚亚芳香醚。此介质填充材料填充封闭介于两电极上方的空隙，因此两个电极和两个介质层在这二个电极之间可以定义出一个真空侧壁子。
此相变元件20可以选自一组优选地包含硫属化物(Chalcogenide)材料的群组之中。硫属化物包括下列形成元素周期表上第VI族的部分的四种元素之中任意一种：氧(O)、硫(S)、硒(Se)、以及碲(Te)。硫属化物是将硫属元素与更为正电性的元素或自由基结合而得到。硫硫属化合物合金是将硫属化合物与例如过渡金属等的其它物质结合。硫属化合物合金通常包括一个以上的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个以上的复合物：锑(Sb)、镓(Ga)、铟(In)、以及银(Ag)。许多以相变为基础的存储器材料已经在技术文件中进行了描述，包括下列的合金：Ga/Sb，In/Sb，In/Se，Sb/Te，Ge/Te，Ge/Sb/Te，In/Sb/Te，Ga/Se/Te，Sn/Sb/Te，In/Sb/Ge，Ag/In/Sb/Te，Ge/Sn/Sb/Te，Ge/Sb/Se/Te及Te/Ge/Sb/S。在Ge/Sb/Te合金族群里，有许多的合金组成可以使用。组成的特征在于TeaGebSb100-(a+b)，其中a及b代表占构成元件总原子数的原子百分比。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Te浓度远低于70％，典型地低于60％，并且Te含量通常在从最低23％至最高58％的范围内，且最佳地是介于48％至58％的Te含量。Ge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％，一般为低于50％。最佳地，Ge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Sb。(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”，SPIE v.3109，pp.28-37(1997))。更一般地，过渡金属例如铬(Cr)、铁(Fe)、镍(Ni)、铌(Nb)、钯(Pd)、铂(Pt)、以及上述的混合物或合金，可与Ge/Sb/Te结合以形成相变合金，其具有可编程的电阻特性。可使用的存储器材料的特殊示例如Ovshinsky‘112专利中栏11-13所述，在此引入该示例作为参考。
在此存储器单元的活性沟道区域中，相变合金可在第一结构态与第二结构态之间按照其局部次序进行切换，其中第一结构态一般为非晶固态(amorphous solid phase)，而第二结构态一般为结晶固态(crystalline solid phase)。这些相变材料至少是双稳态(bistable)的。术语“非晶”用于指示相对较无次序的结构，其与单晶相比更加无次序性，而具有可检测的特征，例如与结晶态相比具有更高的电阻值。术语“结晶态”用于指示相对较有次序的结构，其与非晶态相比更有次序，因此包括可检测的特征，例如比非晶态更低的电阻值。典型地，相变材料可以在完全结晶态与完全非晶态之间的所有可检测的不同状态之间进行电切换。其它受到非晶态与结晶态之间的改变的影响的材料特征包括：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，或者可切换成为由两种以上固态所形成的混合物，提供从非晶态至结晶态之间的灰度级部分。此材料中的电特性也可能随之改变。
相变材料可通过施加电脉冲而从一种相态切换至另一种相态。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，其一般称为重置脉冲。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结晶态，其一般称为编程脉冲。在较短、较大幅度脉冲中的能量足够大，因此足以破坏结晶结构的结合键，同时其足够短，因此可以防止原子再次排列成结晶态。适合脉冲的状况可以依照经验法则判断，不需要过多的实验，就能找出适用于特定的相变材料及元件结构的条件。在本文的后续部分，此相变材料称为GST，同时应该理解的是，也可以使用其它类型的相变材料。用于实施在此所述的计算机存储器的材料为Ge2Sb2Te5。
其他可编程电阻存储器材料也可以使用于本发明的其他实施例中，包括掺杂N2的GST，GexSbb，或其它以不同结晶态之间的转换来决定电阻的物质；PrxCayMnO3，PrSrMnO，ZrOx或其它使用电脉冲来改变电阻状态的物质；TCNQ、PCBM、TCNQ-PCBM、Cu-TCN、Ag-TCNQ、C60-TCNQ、以其它物质掺杂的TCNQ、或包括用电脉冲控制的双稳定或多稳定电阻态的任何其它高分子材料。
参阅图2，为本发明的存储单元的一个更详细的图示，显示出此相变元件实际上包含两个区段20a和20b，每一段有着圆形端点。这两区段在真空侧壁子24上方相连，造成接触区域横截面积小于相变元件其他区域横截面积。关于此元件的形成，将会于底下的叙述厘清此点。
参阅图3，显示了本发明存储单元的操作。在图中显示，自电极14流出的操作电流，箭头标示为I，跟着箭头进入此相变元件20a和20b，最后自电极16流出。必须注意的是，电流的方向仅是为了例示而任意选取的，在实际操作时也可以是相反的方向。
如图中所示，在此二相变元件中的电场和电流密度，相较于此二相变元件相遇的接触区域25而言是较低的。接触区域中相对较小的横截面积会产生比相变元件其他区域高的电流和电场密度。其结果是，接触区域内会产生比相变元件其他区域更多的热量，而且相变仅会在此接触区域内发生(如图中的深色区域)。
除此之外，此真空侧壁子24的低导热性会减少热量自接触区域内传导出去，有效地增加此相变材料单位面积内所产生的热量。此接触区域的热绝缘特性可以使存储单元的设计需要比传统方式更小的电流，如此也可以减少存储单元本身的尺寸。
根据本发明实施例中如何制造相变存储器器件的制作流程图，自图3开始显示。为了简明起见，图示中仅显示此相变元件及其相关特征，并没有显示图1中的电极及其相关结构。可以明了的是，电极结构与相变结构两者结合构成本发明实施例的一部份，本领域技术人员都能够轻易明了如何将本发明所教示的特征运用于传统的工艺与技术之中。
根据本发明实施例中的如何制造如图1所示的相变存储器器件的制作流程图，显示于图4a到4h。第一步骤，如图4a所示，是从提供衬底开始的，其优选地由介质材料形成，诸如二氧化硅，正如先前所描述的材料。此衬底然后被初始图案化及蚀刻，优选地是使用业界熟知的光刻技术，以减少整体的厚度，仅保留如图4b所示的衬底中央部份的上方元件13。
此两个电极元件会在下两个步骤所形成。图4c显示沉积电极材料15(如上所述)于衬底上的结果，其厚度大于衬底中央部份的上方元件13。此电极材料然后被平坦化，最好是使用化学机械研磨(chemical-mechanical polishing，CMP)技术，直到厚度可以使得衬底中央部份的上方元件13的上半部裸露出来为止，如图4d所示。此蚀刻形成两个电极14和16。
使用选择性蚀刻工艺来除去上方元件13的物质，仅留下电极间空间23，如图4e所示。在此，假设此介质物质是氧化硅，则最好是使用湿蚀刻工艺，最好是缓冲氢氟酸(buffered HF)。替代的方法是，干蚀刻，如氟化物为基础的等离子蚀刻，也可以在此使用。必须理解的是，不同的物质必须使用不同的蚀刻配方。此步骤的结果是在衬底上产生两个分离的电极14和16，其中间是电极间空间23。
图4f显示此相变元件20的沉积，以形成此存储单元10。此沉积最好是利用溅镀工艺。如此可以形成较小横截面积的中央部份，如图4g所示的近视图，其中，沉积正在进行中。如业界人士所熟知，溅镀工艺将产生如图中所示的表面边缘弯曲。额外生长的物质会造成自两边开始沉积，直到最后两边在缝隙中央上方接触为止。新沉积的物质会与原先已沉积的物质接合，所以此物质会造成自两边开始沉积，直到两边在缝隙中央上方接触，如图中所示。这两边的接触会造成电极间空间23的封闭，因此定义出真空侧壁子24。最后，此相变元件20裁剪至合适的尺寸，令其不会超越电极的宽度，且额外的介质填充材料26被沉积，如图4h所示。此物质封闭此真空侧壁子24，使得此元件保持在其间保持真空。
必须明了的是，这些图示仅是显示了理想的情形。图5则是比较符合现实的状况，其显示了电极14和16的边缘不是垂直向上的，而是在蚀刻上方元件13以形成真空侧壁子24时，会有一侧削的情况发生。此外，也会在溅镀时残留一些相变元件在真空侧壁子的底部，但是这些少量的相变元件并不会影响到此元件的操作。
虽然已经参考优选实施例对本发明进行了描述，但是应该理解的是，本发明并非限制于所述内容。先前描述中已经建议了可替换方案及修改方式，并且其它可替换方案及修改方式是本领域技术人员能够想到的。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组合从而实现与本发明实质上相同的结果的技术都不脱离本发明的精神范畴。因此，所有这些可替换方案及修改方式都会落在本发明的附带的权利要求以及等价物所界定的范围中。
Claims (8)
1、一种存储器单元，包含：
第一电极构件和第二电极构件，其在衬底上相互分离；
相变元件，其与所述第一电极构件和第二电极构件电性接触且连接分离两者间的空间，其中：
所述相变元件包含两个区段，每一段与所述第一电极构件和第二电极构件中的一个接触，并在所述两个电极之间的一个位置处相连，使得所述相连位置有着小于所述相变元件其余部分的横截面积；以及
所述第一电极构件和第二电极构件、所述衬底和所述相变元件定义一个气室。
2、如权利要求1所述的存储器单元，其中，所述相变元件包含锗(Ge)、锑(Sb)、鍗(Te)的组合。
3、如权利要求1所述的存储器单元，其中，所述相变元件包括二种或二种以上选自下列族群中的材料的组合：锗(Ge)、锑(Sb)、鍗(Te)、硒(Se)、铟(In)、钛(Ti)、镓(Ga)、铋(Bi)、锡(Sn)、铜(Cu)、钯(Pd)、铅(Pb)、银(Ag)、硫(S)及金(Au)。
4、如权利要求1所述的存储器单元，还包括介质填充材料，其与所述第一电极构件和第二电极构件接触且环绕所述相变元件，还封闭由所述第一电极构件和第二电极构件与所述相变元件所定义的所述气室。
5、一种制造存储器单元的方法，所述方法包含：
提供衬底；
在所述衬底上形成两个电极，所述两个电极由这两个电极之间的空间所分离；
在所述两个电极之上形成相变存储元件，包含下列步骤：
开始，在所述两个电极之上沉积相变材料，使得所述相变材料向所述电极间的空间延伸；以及
继续所述沉积直到沉积在所述两个电极上的所述材料在所述电极间的空间互相连接而定义真空侧壁子。
6、如权利要求5所述的方法，其中，所述相变存储元件包含锗(Ge)、锑(Sb)、鍗(Te)的组合。
7、如权利要求5所述的方法，其中，所述相变存储元件包括二种或二种以上选自下列族群中的材料的组合：锗(Ge)、锑(Sb)、鍗(Te)、硒(Se)、铟(In)、钛(Ti)、镓(Ga)、铋(Bi)、锡(Sn)、铜(Cu)、钯(Pd)、铅(Pb)、银(Ag)、硫(S)及金(Au)。
8、如权利要求5所述的方法，还包括在由所述电极与所述相变存储元件形成的结构之上沉积介质填充材料层。
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2006
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2007
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| US7928421B2 (en) | 2011-04-19 |
| CN101060161A (zh) | 2007-10-24 |
| US20070246699A1 (en) | 2007-10-25 |
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