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CN1550048B - 非易失性可调电阻器件和可编程存储单元的制造 - Google Patents

非易失性可调电阻器件和可编程存储单元的制造 Download PDF

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CN1550048B
CN1550048B CN028170202A CN02817020A CN1550048B CN 1550048 B CN1550048 B CN 1550048B CN 028170202 A CN028170202 A CN 028170202A CN 02817020 A CN02817020 A CN 02817020A CN 1550048 B CN1550048 B CN 1550048B
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K·A·坎贝尔
J·T·穆尔
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Abstract

在衬底(12)上形成第一导电电极材料(16)。在其上形成含硫族化物材料(22)。该硫族化物材料包括AxSey，A优选的是Ge和Si。在该硫族化物材料上形成含银层(24)。照射银以有效断开在含银层和硫族化物材料的界面处的硫族化物材料的硫族化物键，并且将至少一些银扩散进入该硫族化物材料。在该照射之后，将该硫族化物材料外表面暴露于含碘的流体以有效降低在该暴露之前的硫族化物材料外表面的粗糙度。在该暴露之后，在该硫族化物材料上淀积第二导电电极材料(26)，其连续并且至少完全覆盖在硫族化物材料上，将该第二导电电极材料形成为该器件的电极。

Description

非易失性可调电阻器件和可编程存储单元的制造
技术领域
本发明涉及形成非易失性可调电阻器件的方法和形成存储电路的可编程存储单元的方法。
背景技术
半导体制造向着将单个电子元件制作越来越小的方向努力，导致更为密集的集成电路。一种集成电路包括以二进制数据形式存储信息的存储电路。制造这种电路使得数据是易失性或非易失性的。易失性存储器件导致断开电源时数据丢失。当电源断开时非易失性存储电路断开仍能保留存入的数据。
本发明主要致力于对在Kozicki等的美国专利号为5,761,115；5,896,312；5,914,893和6,084,796公开的存储电路的设计和操作的改进，这些专利源于1996年5月30日提交的序列号为08/652,706的美国专利申请，公开了有关可编程的金属化单元。这种单元包括其间容纳有绝缘电介质材料的反向电极。电介质材料中的容纳物是快离子导体材料。这种材料的电阻可以在高绝缘和高导电状态之间变化。在其常规高电阻状态下，为了执行写操作，电压电位施加于其中某一电极，同时另一电极保持在零电压或接地。施加了电压的电极起到阳极的作用，同时保持零电压或接地的电极起到阴极的作用。快速离子导电材料的特性是在一定的施加电压下进行结构的变化。随着这一电压的施加，导电枝状结晶或丝极在电极之间延伸，顶电极和底电极的有效互连使得它们电短路。
这种情况一旦发生，枝状结晶的生长停止，并且当移除电压电势时保留枝状结晶。这就可以有效导致电极之间的大部分快离子导体材料的电阻降低1000倍。通过反向阳极和阴极之间的电压电位可以将这种材料恢复到高电阻状态，借此丝极消失。再次，当去除反向电压时，保持了高电阻状态。因此，这种器件可以起到例如存储电路的可编程存储单元的作用。
电极之间容纳的优选可调电阻材料一般优选包含具有金属离子扩散其中的硫族化物材料。具体的例子是其间具有银离子扩散的硒化锗。在硒化锗材料中提供银离子的本方法是初始地化学汽相淀积其间没有任何银离子容纳的硒化锗玻璃。此后例如通过溅射、物理汽相淀积或其它技术将银薄层淀积在玻璃上。示例性的厚度是200
Figure S02817020220070612D000022
或更少。优选的是用波长小于500nm的电磁能照射银层。淀积的银层的薄特性能够使得这种能量穿过银层到达银层/玻璃界面，以有效断开硫族化物材料的硫族化物键。这能形成Ag2Se，这可以有效地用银掺杂玻璃。施加的能量和覆盖的银最终导致银迁移至玻璃层中，以便得到银在整个层中典型的均匀分布。
取决于硒化锗的化学计量比，银在硒化锗中的饱和度明显是在最大值为34原子百分比或更小。然而，用于单元制作的优选的现有技术制作的浓度小于该最大值；在原子百分比为34的最大值的情况下，实例性的浓度为大约27原子百分比。
当银在硫族化物材料中达到理想浓度后，接着淀积顶部电极材料(一般是银)。但是，当掺杂/扩散至硫族化物材料中的银接近最大或饱和时，发现在表面形成有一些Ag2Se并且保留在表面，这与扩散进入玻璃不同。进而，表面的Ag2Se一般以半圆结节或突起的形态在任意位置出现，大小为至20微米。遗憾的是，当随后淀积一般的银电极材料时，趋向于在早先的突起上堆积。这将对穿过顶部电极材料的掺杂的锗玻璃造成空隙，借此银掺杂的硒化锗玻璃被部分暴露。遗憾的是，一般用于构图顶部电极的某些光显影溶液(也就是四甲基氢氧化铵)将腐蚀暴露的玻璃。
希望克服或至少减少这些问题。尽管本发明主要致力于克服上述问题，但不限于此。本领域技术人员可以在与上述问题无关的其它方面理解本发明的适用范围，本发明仅由所附权利要求书的文字表述和根据等效的相应解释来限定。
发明内容
本发明包括形成存储电路的可编程存储单元和非易失性可调电阻器件的方法。在一种实施步骤中，形成非易失性可调电阻器件的方法包括在衬底上形成第一导电电极材料。含硫族化物材料形成在第一导电电极材料上。硫族化物材料包含AxSey，其中“A”包含选自周期表的13族、14族、15族或17族的至少一种元素。在硫族化物材料上形成含银层。有效地照射银以断开在含银层和硫族化物材料的界面处的硫族化物材料的硫族化物键，并且将至少一些银扩散进入硫族化物材料，形成硫族化物材料的外部表面。照射之后，硫族化物材料的外部表面暴露于含碘的流体，以便有效降低暴露之前硫族化物材料外部表面的粗糙度。在该暴露后，在硫族化物材料上淀积第二导电电极材料，该第二导电电极材料连续并且至少完全覆盖在该硫族化物材料上，将第二导电电极材料形成为器件的电极。
考虑和公开了其它实施步骤和方式。
附图说明
下面参考附图描述本发明的优选实施例。
图1是根据本发明的一方面，在工艺中的半导体晶片片段的示意性剖面图。
图2是图1所示晶片片段在图1之后的工艺步骤的视图。
图3是图1所示晶片片段在图2之后的工艺步骤的视图。
图4是图1所示晶片片段在图3之后的工艺步骤的视图。
图5是图1所示晶片片段在图4之后的工艺步骤的视图。
图6是图1所示晶片片段在图5之后的工艺步骤的视图。
具体实施方式
参照图1，示出了形成非易失性可调电阻器件的一个优选实施例的衬底10。仅作为实例，这种实例性的器件包括可编程金属化单元和上面提到的专利的可编程光学元件，进一步仅作为实例，这些器件包括可编程电容元件、可编程电阻元件、集成电路的可编程反熔丝和存储电路的可编程存储单元。在此引入上述专利作为参考。本发明考虑任何现有的非易失性可调电阻器件的制造工艺和结构以及正在开发的这种器件。在本文的上下文中，术语“半导体衬底”或“半导电衬底”定义为任何包含半导体材料的结构，包括但不限于体半导体材料诸如半导体晶片(单独的或其上包含其它材料的组合)以及半导体材料层(单独的或包含其它材料的组合)。术语“衬底”指任何支持结构，包括但不限于上述描述的半导体衬底。同时本文的上下文中，如果没有额外指明，术语“层”包含单层和多层。此外，技术人员可以理解“可调电阻器件”包括除电阻特性变化之外其他特性也变化的器件。例如，仅作为实例，除了电阻之外，器件的电容和/或电感也可以改变。
衬底10包含体单晶半导体材料12，例如硅，具有形成于其上的绝缘电介质层14，例如二氧化硅。第一电极材料16形成在电介质层14上。仅作为实例，结合制作的优选器件类型，优选材料包括在上述Kozicki等人的专利中描述的任何材料。电介质层18形成在第一电极材料16上。优选的实例是氮化硅。
电介质层18到达第一电极材料16而形成开口20。开口中填充硫族化物材料22至第一厚度，本实例中厚度由电介质层18的厚度基本限定。仅作为实例，实例性的第一厚度的范围在
Figure S02817020220070612D000031
至含硫族化物材料包含AxSey，其中“A”包含选自周期表的13族(B、Al、Ga、In，T1)、14族(C、Si、Ge、Sn，Pb)、15族(N、P、As、Sb，Bi)或17族(F、Cl、Br、I，At)的至少一种元素。仅作为实例，“A”的优选元素是Ge和Si。在衬底10上形成硫族化物材料22的优选方法的实例是通过化学汽相淀积完全来填充开口20，然后进行平坦化工艺，例如化学机械抛光。硫族化物材料22优选形成为非晶形的，并且在完成后的器件中保持非晶形。
在硫族化物材料22上形成含银层24至第二厚度。含银层24优选主要(大多数)为银元素，可以由或基本上由银元素组成。在一优选实施例中，第二厚度至少是第一厚度的30％。
参照图2，有效地照射含银层24以便断开在含银层24和硫族化物材料22的界面处的硫族化物材料22的硫族化物键，并且将至少一些银扩散进入硫族化物材料22。图2中，硫族化物材料22被标明为标记硫族化物材料23，并且在图中加上小点以表示其中容纳的金属离子。优选的照射包括具有波长约为164-904nm的光化辐射照射，更具体的例子是辐射曝光范围在404-408nm之间。更具体的例子是泛光灯UV暴露工具，在室温和室压下的含氧环境中，在4.5毫瓦/cm2能量下操作15分钟。直接容纳于硫族化物材料22上的所有含银层24可能扩散或仅部分扩散入硫族化物材料中。还选择适当薄的含银层24的厚度，可以使得碰撞电磁辐射基本上透过含银层24至该材料与硫族化物材料22的界面。示例的优选厚度为小于或等于200
Figure S02817020220070612D000041
br/>此外，作为硫族化物材料22的线性厚度百分比的含银层24的表观线性厚度有效导致硫族化物材料内的近似相同的原子百分比的金属掺入。无论如何，这导致了硫族化物材料23具有外部表面25。
在仅一个实施例中，外部表面25的特征在于，至少在部分外部表面形成Ag2Se，在一个实施例中有效地照射以在硫族化物材料22/23上形成不连续的Ag2Se的层27。更为优选的是，有效地照射以使Ag2Se下的硫族化物材料保持基本非晶的状态。甚至更为优选的是，有效地照射以将含硫族化物材料掺杂到在多个可调电阻状态的最小状态下平均至少为30原子百分比的银。此外，通过任何其它现有的或正在开发的方法，本发明考虑在含硫族化物材料上形成Ag2Se例如不连续的Ag2Se层的其它方法。
参照图3，照射之后，硫族化物材料外部表面25暴露于含碘的流体以有效降低在暴露以前硫族化物材料外部表面25的粗糙度。在一个优选实施例中，这种暴露对于Ag2Se有效腐蚀掉至少部分Ag2Se，更优选的是有效腐蚀掉至少大部分Ag2Se，最优选的是有效腐蚀掉基本上所有的Ag2Se，如图3所示。在一实例性实施例中，认为粗糙度的降低不依赖于Ag2Se的形成和去除。而且在一实例性实施例中，腐蚀掉至少部分Ag2Se被认为对表面粗糙度没有影响。
一种优选的含碘的流体是液体，例如碘化物溶液如碘化钾溶液。优选实例的碘化钾溶液是每1升20％至50％体积比的碘化钾溶液中包含5-30克的I2。在蒸汽中暴露，当然也考虑例如在环境温度和压力条件，或者增大或减小环境温度和/或压力条件下的液体溶液。一个具体的实例是在每1升30％碘化钾溶液包含20克I2的碘化钾溶液中浸渍衬底。
参照图4，在暴露之后，在硫族化物材料23上淀积第二导电电极层26。在优选实施例中，这种第二导电电极材料连续并且至少完全覆盖在硫族化物材料23上。第二电极层26的实例性的优选厚度范围是至
Figure S02817020220070612D000052
第一和第二导电电极材料可以是同种材料或不同材料。仅作为实例，优选的顶部和底部电极材料包括银、钨、铂、镍、碳、铬、钼、铝、锰、铜、钴、钯、钒、钛、它们的合金以及包含其中一种或多种元素的化合物。按照优选可编程金属化的单元的实施例，其中“A”是Ge，第一电极材料16和层26的至少一种构成银。在层26的形成过程中将有部分银扩散至硫族化物材料23中。
参照图5，层26被图形化为电极30。典型的和优选的是使用光刻技术构图以产生电极30。这只是提供一个形成在操作上接近硫族化物材料的第二电极材料的优选实例。在一优选实施例中，这导致了非易失性可调电阻器件的形成，该非易失性可调电阻器件制作成存储电路的可编程存储单元。
参照图6，最后在器件上形成一层或多层电介质层32。当然，也可以配置插入导电层和半导体层，形成所描述器件外部的其它线路和器件。

Claims (51)

1.一种形成非易失性可调电阻器件的方法，包含：
在衬底上形成第一导电电极材料；
在该第一导电电极材料上形成含硫族化物材料，该硫族化物材料包括选自周期表的13族、14族、15族或17族的至少一种元素的硒化物；
在硫族化物材料上形成含银层；
照射银以断开在含银层和硫族化物材料的界面处的硫族化物材料的硫族化物键，并且将至少一些银扩散进入该硫族化物材料，并且形成硫族化物材料的外表面；
在该照射之后，将硫族化物材料的外表面暴露于含碘的流体以降低暴露之前的硫族化物材料外部表面的粗糙度；以及
在该暴露之后，在硫族化物材料上淀积第二导电电极材料，其连续并且至少完全覆盖在硫族化物材料上，将第二导电电极材料形成为该器件的电极。
2.如权利要求1所述的方法，其中含碘的流体是液体。
3.如权利要求1所述的方法，其中含碘的流体是碘化物溶液。
4.如权利要求1所述的方法，其中含碘的流体是碘化钾溶液。
5.如权利要求4所述的方法，其中该碘化钾溶液在每1升20％至50％体积比的碘化钾溶液中含有5至30克I2。
6.如权利要求1所述的方法，其中含银层主要是元素银。
7.如权利要求1所述的方法，其中该照射形成Ag2Se作为至少部分外表面，该腐蚀腐蚀掉至少一些Ag2Se并且由此对所述粗糙度的降低起至少部分作用。
8.如权利要求1所述的方法，其中所述至少一种元素包含Ge。
9.如权利要求1所述的方法，其包括将器件形成为存储电路的可编程存储单元。
10.如权利要求1所述的方法，其中第一和第二导电电极材料是不同的。
11.一种形成非易失性可调电阻器件的方法，包含：
在衬底上形成第一导电电极材料；
在第一导电电极材料上形成含硫族化物材料，该硫族化物材料包括选自周期表的13族、14族、15族或17族的至少一种元素的硒化物；
在形成含硫族化物材料之后，在含硫族化物材料上形成Ag2Se；
照射Ag2Se，在照射之后，将Ag2Se暴露于含碘流体，以腐蚀掉至少一些Ag2Se；以及
在该暴露之后，在硫族化物材料上淀积第二导电电极材料，将该第二导电电极材料形成为该器件的电极。
12.一种形成非易失性可调电阻器件的方法，包含：
在衬底上形成第一导电电极材料；
在该第一导电电极材料上形成含硫族化物材料，该硫族化物材料包括选自周期表的13族、14族、15族或17族的至少一种元素的硒化物；
在形成含硫族化物材料后，在含硫族化物材料上形成Ag2Se；
在照射之后，将Ag2Se暴露于含碘的流体以腐蚀掉至少部分Ag2Se；以及
在该暴露之后，在硫族化物材料上淀积第二导电电极材料，并将第二导电电极材料形成为该器件的电极。
13.如权利要求11所述的方法，包括将所述器件形成为存储电路的可编程存储单元。
14.如权利要求12所述的方法，其中所述至少一种元素包含Ge。
15.如权利要求12所述的方法，包括将非易失性可调电阻器件形成为存储电路的可编程存储单元。
16.如权利要求12所述的方法，其中含碘的流体是液体。
17.如权利要求12所述的方法，其中含碘的流体是碘化物溶液。
18.如权利要求12所述的方法，其中含碘的流体是碘化钾溶液。
19.如权利要求18所述的方法，其中该碘化钾溶液在每1升20％至50％体积比的碘化钾溶液中含有5至30克I2。
20.一种形成非易失性可调电阻器件的方法，包含：
在衬底上形成第一导电电极材料；
在第一导电电极材料上形成含硫族化物材料，该硫族化物材料包括选自周期表的13族、14族、15族或17族的至少一种元素的硒化物；
在形成含硫族化物材料之后，在含硫族化物材料上形成不连续的Ag2Se层；
照射Ag2Se，在照射之后，将Ag2Se暴露于含碘流体，以腐蚀掉至少一些Ag2Se；以及
在该暴露之后，在硫族化物材料上淀积第二导电电极材料，该第二导电电极材料连续并且至少完全覆盖在该硫族化物材料上，将该第二导电电极材料形成为该器件的电极。
21.如权利要求12所述的方法，其中该暴露腐蚀掉全部的Ag2Se。
22.一种形成非易失性可调电阻器件的方法，包含：
在衬底上形成第一导电电极材料；
在该第一导电电极材料上形成含硫族化物材料，该硫族化物材料包括选自周期表的13族、14族、15族或17族的至少一种元素的硒化物；
在形成含硫族化物材料后，在含硫族化物材料上形成不连续的Ag2Se层；
在照射之后，将Ag2Se暴露于含碘的流体以刻蚀掉至少一些Ag2Se；以及
在该暴露之后，在硫族化物材料上淀积第二导电电极材料，该第二导电电极材料连续并且至少完全覆盖在硫族化物材料上，并将第二导电电极材料形成为该器件的电极。
23.如权利要求22所述的方法，其中含碘的流体是液体。
24.如权利要求22所述的方法，其中含碘的流体是碘化物溶液。
25.如权利要求22所述的方法，其中含碘的流体是碘化钾溶液。
26.如权利要求25所述的方法，其中该碘化钾溶液在每1升20％至50％体积比的碘化钾溶液中含有5至30克I2。
27.如权利要求22所述的方法，其中在多个可调电阻状态中的最低状态将含硫族化物材料掺杂到至少30原子％的Ag。
28.如权利要求22所述的方法，其中该暴露腐蚀掉全部Ag2Se。
29.一种形成存储电路的可编程存储单元的方法，包含：
在衬底上形成第一导电电极材料；
在第一导电电极材料上形成非晶的含硫族化物材料，该硫族化物材料包括选自周期表的13族、14族、15族或17族的至少一种元素的硒化物；
在含硫族化物材料上形成含银层；
照射银以断开在含银层和硫族化物材料的界面处的硫族化物材料的硫族化物键，并且将至少一些银扩散进入该硫族化物材料，该照射在含硫族化物材料上形成不连续的Ag2Se层，该照射将Ag2Se之下的硫族化物材料保持为非晶态，该照射将含硫族化物材料掺杂到在多个可变电阻状态中的最低状态中的平均至少30原子％的银；
在该照射之后，将Ag2Se暴露于含碘流体，以腐蚀掉至少大部分Ag2Se；以及
在该暴露之后，在硫族化物材料上淀积第二导电电极材料，该第二导电电极材料连续并且至少完全覆盖在该硫族化物材料上，将第二导电电极材料形成为该器件的电极。
30.如权利要求29所述的方法，其中含碘的流体是液体。
31.如权利要求29所述的方法，其中含碘的流体是碘化物溶液。
32.如权利要求29所述的方法，其中含碘的流体是碘化钾溶液。
33.如权利要求32所述的方法，其中该碘化钾溶液在每1升20％至50％体积比的碘化钾溶液中含有5至30克I2。
34.一种形成非易失性可调电阻结构的方法，包括：
形成硫族化物玻璃层；
在硫族化物玻璃层上形成含金属层；
照射所述含金属层以断开含金属层和硫族化物玻璃层界面处硫族化物玻璃层的硫族化物键，以使含金属层的至少一部分金属扩散进入硫族化物玻璃层；以及
在所述照射步骤之后，将硫族化物玻璃层外表面暴露于含碘的流体，其中所述含碘流体去除已被照射的所述外表面的至少一部分。
35.如权利要求34所述的方法，其中含碘的流体是液体。
36.如权利要求34所述的方法，其中含碘的流体是含碘化物溶液。
37.如权利要求34所述的方法，其中含碘的流体是碘化钾溶液。
38.如权利要求37所述的方法，其中该碘化钾溶液在每升20％至50％体积比的碘化钾溶液中含有5至30克I2。
39.如权利要求34所述的方法，其中所述照射形成Ag2Se作为外表面的至少一部分，所述腐蚀腐蚀掉至少一些Ag2Se。
40.如权利要求34所述的方法，其中含金属层是含银层。
41.如权利要求40所述的方法，其中含银层主要是元素银。
42.一种形成非易失性可调电阻结构的方法，包括：
在半导体衬底上形成第一导电层；
在所述第一导电层上形成硫族化物玻璃层；
在所述硫族化物玻璃层上形成含金属层；
照射所述含金属层以断开含金属层和硫族化物玻璃层界面处硫族化物玻璃层的硫族化物键以建立外表面；
通过用含碘流体进行腐蚀去除所述外表面的至少一部分；以及
在所述去除所述外表面的至少一部分的步骤之后，在所述去除动作之后剩余的外表面的至少一部分上形成第二导电层。
43.如权利要求42所述的方法，其中含碘的流体是液体。
44.如权利要求42所述的方法，其中含碘的流体是含碘化物溶液。
45.如权利要求42所述的方法，其中含碘的流体是碘化钾溶液。
46.如权利要求45所述的方法，其中该碘化钾溶液在每升20％至50％体积比的碘化钾溶液中含有5至30克I2。
47.如权利要求42所述的方法，其中所述照射形成Ag2Se作为外表面的至少一部分，所述腐蚀腐蚀掉至少一些Ag2Se。
48.如权利要求42所述的方法，其中含金属层是含银层。
49.如权利要求48所述的方法，其中含银层主要是元素银。
50.如权利要求42所述的方法，其中所述第一导电层和第二导电层是电极。
51.一种形成非易失性可调电阻结构的方法，包括：
在半导体衬底上形成第一导电层；
在所述第一导电层上形成硫族化物玻璃层；
在所述硫族化物玻璃层上形成含金属层；
照射所述含金属层以断开含金属层和硫族化物玻璃层界面处硫族化物玻璃层的硫族化物键以建立外表面，所述照射步骤形成Ag2Se作为外表面的至少一部分；
通过用含碘流体进行腐蚀去除所述外表面的至少一部分，所述腐蚀腐蚀掉至少一些Ag2Se；以及
在所述去除所述外表面的至少一部分的步骤之后，在所述去除动作之后剩余的外表面的至少一部分上形成第二导电层。
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