CN103915496B - 石墨烯电子器件及其制造方法 - Google Patents

石墨烯电子器件及其制造方法 Download PDF

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CN103915496B
CN103915496B CN201310534898.6A CN201310534898A CN103915496B CN 103915496 B CN103915496 B CN 103915496B CN 201310534898 A CN201310534898 A CN 201310534898A CN 103915496 B CN103915496 B CN 103915496B
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金容诚
李昌承
李周浩
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Samsung Electronics Co Ltd
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Abstract

本公开提供一种石墨烯电子器件及其制造方法。该石墨烯电子器件包括在石墨烯层上的第一栅极结构和第二栅极结构，因此可以在一个器件中形成具有石墨烯晶体管和石墨烯二极管的特性的开关器件或存储器器件。

Description

石墨烯电子器件及其制造方法
技术领域
本公开涉及石墨烯电子器件。
背景技术
形成在硅衬底上的半导体器件已经迅速地被高度集成以具有高性能。然而，由于硅本身的特性和制造工艺上的限制，在改善半导体器件的性能上存在限制。因此，已经对下一代器件开展研究，该下一代器件可以克服具有硅衬底的传统半导体器件的限制。
在发现石墨烯（石墨单原子层）之后，石墨烯由于其优异的电性能和机械性能而正被认为是下一代材料。石墨烯是其中碳原子被连接成平面内六边形的材料，并具有对应于单原子层的非常小的厚度。因此，石墨烯导电比主要用作半导体的多晶硅快一百倍，并在理论上具有200000cm2/Vs的电子迁移率。此外，已知石墨烯可以具有为铜的电导率的一百倍的电导率，因此石墨烯被认为是电子器件的基本材料。
特别地，石墨烯是零带隙的半导体材料，因此，如果石墨烯纳米带（GNR）被制造为具有10nm或更小的沟道宽度，则由于尺寸效应而产生带隙。因此，可以制造能够在室温操作的场效应晶体管（FET）。
通常，石墨烯通过化学气相沉积（CVD）方法生长在由铜（Cu）或镍（Ni）形成的金属薄膜上，然后可以被转移到绝缘薄膜上。
发明内容
提供了包括石墨烯场效应晶体管（FET）和石墨烯二极管的石墨烯开关器件。
提供了通过将石墨烯FET和石墨烯二极管结合而形成的石墨烯存储器器件。
其他的方面将在以下的描述中部分地阐述，并将部分地从该描述而变得明显，或者可以通过实践给出的实施例而掌握。
根据本发明的方面，提供一种包括石墨烯的石墨烯电子器件，该石墨烯电子器件包括：第一导电层和半导体层，形成在中间层的第一区域上；第二导电层，形成在中间层的第二区域上；石墨烯层，形成在中间层、半导体层以及第二导电层上；以及第一栅极结构和第二栅极结构，形成在石墨烯层上。
第一栅极结构可以形成在石墨烯层上，对应于中间层的第一区域。
第二栅极结构可以形成在石墨烯层上，对应于中间层的第一区域与第二区域之间的间隔。
中间层可以形成在支撑结构上。
第一栅极结构可以包括栅极绝缘层和第一栅极。
第二栅极结构可以包括栅极绝缘层和第二栅极。
第一栅极结构可以包括铁电层和第一栅极。
第二栅极结构可以包括铁电层和第二栅极。
第一栅极结构可以包括第一隧穿氧化物层、第一浮置栅极、第一阻挡氧化物层以及第一栅极。
第二栅极结构可以包括第二隧穿氧化物层、第二浮置栅极、第二阻挡氧化物层以及第二栅极。
根据本发明的另一方面，提供一种形成石墨烯电子器件的方法，该方法包括：在衬底上形成半导体层、第一导电层以及第二导电层；通过将绝缘材料施加在衬底、半导体层、第一导电层以及第二导电层上而形成中间层；去除衬底，并在中间层、半导体层以及第二导电层上形成石墨烯层；以及在石墨烯层上形成第一栅极结构和第二栅极结构。
形成石墨烯电子器件的方法还可以包括：在形成中间层之后，在中间层上形成支撑结构。
衬底可以包括硅和硅氧化物层，衬底可以通过蚀刻硅氧化物层而去除。
衬底可以包括透明衬底，衬底可以通过激光剥离工艺而去除。
在中间层上形成催化剂层之后，石墨烯层可以通过热解方法或者化学气相沉积（CVD）方法而形成在催化剂层上。
附图说明
这些和/或其他的方面将从以下结合附图对实施例的描述而变得显然并更易于理解，附图中：
图1A是根据本发明构思的实施例的石墨烯电子器件的截面图；
图1B是图1A的石墨烯电子器件的示意性平面图；
图2是示出根据本发明构思的实施例的石墨烯电子器件的电特性的曲线图；
图3A至图3D是示出根据本发明构思的实施例的制造图1A所示的石墨烯电子器件的方法的图示；
图4是根据本发明构思的实施例的包括石墨烯的铁电存储器件的截面图；
图5是根据本发明构思的实施例的包括石墨烯的闪存器件的截面图；以及
图6是根据本发明构思的实施例的包括石墨烯的混合型存储器件的截面图。
具体实施方式
现在将详细参照实施例，附图中示出了实施例的示例，其中相同的附图标记始终指代相同的元件。在这点上，本发明的实施例可以具有不同的形式，而不应被解释为限于这里阐述的描述。因此，下面参照附图仅描述了实施例，以解释本说明书的方面。当在这里使用时，术语“和/或”包括一个或多个相关所列项目的任意和所有组合。诸如“......中的至少一个”的表述，当在一列元件之前时，修改了这些元件的整个列表而不修改列表中的各个元件。
图1A是根据本发明构思的实施例的石墨烯电子器件100的截面图。此外，图1B是根据本发明构思的实施例的石墨烯电子器件100的示意性平面图。图1A是沿图1B的线m1-m2截取的截面图。
参照图1A和图1B，根据本发明构思的实施例的石墨烯电子器件100包括：形成在支撑结构10上的中间层11、形成在中间层11的第一区域上的第一导电层12和半导体层13、以及形成在中间层11的第二区域上的第二导电层14。半导体层13和第二导电层14的上表面可以被中间层11暴露。在一个实施例中，中间层11、半导体层13和第二导电层14的上表面可以共平面。此外，石墨烯层15可以形成在中间层11、半导体层13以及第二导电层14上（也就是，形成在中间层11、半导体层13和第二导电层14的上表面上），第一和第二栅极结构可以形成在石墨烯层15上。第一栅极结构可以包括栅极绝缘层16和第一栅极17。第二栅极结构可以包括栅极绝缘层16和第二栅极18。在石墨烯层15上，第一栅极结构可以对应于中间层11的第一区域而形成，第二栅极结构可以对应于中间层11的第一区域与第二区域之间的间隔而形成。
根据本实施例的石墨烯电子器件可以形成为执行石墨烯晶体管和石墨烯二极管的功能。参照图1A，半导体层13和石墨烯层15可以是根据经由第一栅极17施加的电压而用作石墨烯可调二极管的二极管区域。此外，关于石墨烯晶体管功能，图1A中的第一导电层12和半导体层13可以是源电极、第二导电层14可以是漏电极，石墨烯层15可以是沟道区，第二栅极18可以是栅电极。
下面描述形成根据本发明构思的实施例的石墨烯电子器件中每个层的材料。
支撑结构10可以支撑形成于其上的石墨烯电子器件的每个层，并且为了加工稳定性而可以在制造工艺中形成。支撑结构10可以由各种材料形成，例如半导体衬底（诸如用作半导体器件的衬底的Si衬底）、聚合物衬底或胶带。支撑结构10可以包括对于中间层11具有高附着性的材料，如果需要，支撑结构10可以由与中间层11相同的材料形成。
中间层11可以由聚合物材料或者具有绝缘特性的材料形成。中间层11可以是在形成石墨烯电子器件100期间保护石墨烯层15以及第一导电层12和第二导电层14的保护层。第一导电层12、第二导电层14、第一栅极17以及第二栅极18由导电材料形成，该导电材料可以包括金属、金属合金、导电金属氧化物或导电聚合物。
半导体层13可以由半导体材料形成，例如包括硅（Si）、非晶硅（a-Si）、ZnO、GaInZnOx、HfInZnOx、GaN、GaAs或AlGaAs的材料，并可以形成为具有单层结构或多层结构。此外，半导体层13可以包括用杂质掺杂的层，例如a-Si/n型Si结构。栅极绝缘层16可以由形成于半导体器件中的绝缘材料形成，例如硅氧化物、硅氮化物、铝氧化物、铪氧化物、锌氧化物或者镁氧化物。
石墨烯层15可以通过各种方法来形成。例如，为了形成石墨烯层15，首先形成包括Ni、Cu、Co、Pt或Ru的催化剂层，石墨烯层15可以通过热解方法或者化学气相沉积（CVD）方法形成在催化剂层上。
图2是示意地示出根据本发明构思的实施例的石墨烯电子器件100的电特性的曲线图。
参照图2，在没有将电压施加至第一栅极17和第二栅极18（Vg1=0，Vg2=0）的状态下，根据经由第一导电层12和第二导电层14施加的电压的电流遵循曲线1。
此外，在没有将电压施加至第一栅极17（Vg1=0）并且将电压施加至第二栅极18（Vg2>0）时，电流根据曲线2的晶体管特性而增大。另一方面，在将电压施加至第一栅极17（Vg1>0）并且没有将电压施加至第二栅极18（Vg2=0）时，导通电压由于可调二极管特性而增大，如曲线3所示。如果将电压施加至第一栅极17和第二栅极18两者（Vg1>0，Vg2>0），电流和导通电压都根据晶体管特性和可调二极管特性而增大，如曲线4所示。
在下文，参照图3A至图3D描述根据本发明构思的实施例的制造石墨烯电子器件的方法。图3A至图3D是示出根据本发明构思的实施例的制造图1A所示的石墨烯电子器件100的方法的图示。
参照图3A，半导体层32、第一导电层33以及第二导电层34形成在衬底30和31上。衬底30和31可以由各种衬底材料形成，例如可以包括其上形成硅氧化物层31的硅衬底30、玻璃衬底、SiC衬底或者GaN衬底。半导体材料层形成在衬底30和31上并被图案化以形成半导体层32，导电材料层被形成和图案化以形成第一导电层33和第二导电层34。
参照图3B，绝缘材料施加在衬底30和31、半导体层32、第一导电层33和第二导电层34上以形成中间层35。中间层35可以由绝缘材料诸如聚合物、硅氧化物或者硅氮化物形成。在形成中间层35之后，支撑结构36形成在中间层35上。支撑结构36被形成以在后续工艺中支撑器件，并可以被选择性省略。
参照图3C，衬底30和31被去除。衬底30和31可以以不同方式去除，例如，如果衬底30和31包括硅/硅氧化物，则硅氧化物可以被蚀刻而去除。此外，衬底的界面区域可以通过在激光剥离（LLO）工艺中照射激光而分开。在此情况下，衬底30和31可以在诸如SiO:H、SiN:H、a-Si:H、AlO、ZnO、MgO或GaN的材料通过等离子体增强CVD（PECVD）方法形成在诸如玻璃的透明衬底上的状态下使用。当照射激光以分离如上所述形成的衬底时，在透明衬底的界面处产生气体，使得透明衬底可以被分离。然后，石墨烯层37形成在衬底30和31从其分离的部分上。
参照图3D，栅极绝缘层38形成在石墨烯层37上，然后导电材料被施加在栅极绝缘层38上并被图案化以形成第一栅极39a和第二栅极39b。
根据本发明构思的实施例的石墨烯电子器件可以根据在石墨烯层上形成的栅极结构而用于形成各种电子器件。
图4是根据本发明构思的实施例的包括石墨烯的铁电随机存取存储器（FRAM）器件的截面图。参照图4，中间层41形成在支撑结构40上，第一导电层42和半导体层43形成在中间层41的第一区域上，第二导电层44形成在中间层41的第二区域上。石墨烯层45可以形成在中间层41、半导体层43和第二导电层44上，第一和第二栅极结构可以形成在石墨烯层45上。第一栅极结构可以包括铁电层46和第一栅极48。此外，第二栅极结构可以包括铁电层47和第二栅极49。这里，在石墨烯层45上，第一栅极结构可以对应于中间层41的第一区域形成，第二栅极结构可以对应于中间层41的第一区域与第二区域之间的间隔而形成。铁电层46和47可以由诸如锆钛酸铅（PZT）、BaTiO3或聚偏二氟乙烯（PVDF）的铁电材料形成。根据具有图4所示的结构的存储器器件，可以实现2位/单元的存储器器件。
图5是根据本发明构思的实施例的包括石墨烯的闪存器件的截面图。
参照图5，闪存器件可以包括形成在支撑结构50上的中间层51、形成在中间层51的第一区域上的第一导电层52和半导体层53、以及形成在中间层51的第二区域上的第二导电层54。石墨烯层55可以形成在中间层51、半导体层53和第二导电层54上，第一栅极结构和第二栅极结构可以形成在石墨烯层55上。在石墨烯层55上，第一栅极结构可以对应于中间层51的第一区域而形成，第二栅极结构可以对应于中间层51的第一区域与第二区域之间的间隔而形成。第一栅极结构可以包括第一隧穿氧化物层561、第一浮置栅极562、第一阻挡氧化物层563以及第一栅极564。此外，第二栅极结构可以包括第二隧穿氧化物层571、第二浮置栅极572、第二阻挡氧化物层573以及第二栅极574。根据图5所示的存储器器件的结构，可以实现2位/单元的闪存器件。
图6是根据本发明构思的实施例的包括石墨烯的混合型存储器器件的截面图。
参照图6，混合型存储器器件可以包括形成在支撑结构60上的中间层61、形成在中间层61的第一区域上的第一导电层62和半导体层63、以及形成在中间层61的第二区域上的第二导电层64。石墨烯层65可以形成在中间层61、半导体层63和第二导电层64上，第一栅极结构和第二栅极结构可以形成在石墨烯层65上。在石墨烯层65上，第一栅极结构可以对应于中间层61的第一区域而形成，第二栅极结构可以对应于中间层61的第一区域与第二区域之间的间隔而形成。第一栅极结构可以包括隧穿氧化物层661、浮置栅极662、阻挡氧化物层663以及第一栅极664。此外，第二栅极结构可以包括铁电层671和第二栅极672。在图6所示的存储器器件中，第一栅极结构是闪存区域，第二栅极结构是铁电存储器区域。然而，第一栅极结构可以形成为包括铁电层和栅极的铁电存储器区域，第二栅极结构可以形成为闪存区域。
根据本发明构思的实施例，可以形成通过使用石墨烯而具有改善的电特性的石墨烯电子器件。此外，可以形成具有石墨烯晶体管和石墨烯二极管两者的特性的开关器件。另外，可以形成具有石墨烯晶体管和石墨烯二极管两者的特性的存储器器件。
应当理解，这里描述的示例性实施例应当仅以描述性的含义来考虑，而不是为了限制的目的。每个实施例中的特征或方面的描述应当通常被认为可用于其他实施例中的其他类似特征或方面。
本申请要求于2013年1月8在韩国知识产权局提交的韩国专利申请No.10-2013-0002223的权益，其公开通过引用整体结合于此。

Claims (15)

1.一种石墨烯电子器件，包括石墨烯，所述石墨烯电子器件包括：
第一导电层和半导体层，形成在中间层的第一区域上，其中所述半导体层位于所述第一导电层上；
第二导电层，形成在所述中间层的第二区域上，所述第二区域与所述第一区域间隔开；
石墨烯层，形成在所述中间层、所述半导体层以及所述第二导电层上；以及
第一栅极结构和第二栅极结构，形成在所述石墨烯层上，
其中所述石墨烯层设置在所述栅极结构与所述中间层之间。
2.根据权利要求1所述的器件，其中形成在所述石墨烯层上的所述第一栅极结构对应于所述中间层的所述第一区域。
3.根据权利要求1所述的器件，其中形成在所述石墨烯层上的所述第二栅极结构对应于所述中间层的所述第一区域与所述第二区域之间的间隔。
4.根据权利要求1所述的器件，其中所述中间层形成在支撑结构上。
5.根据权利要求1所述的器件，其中所述第一栅极结构包括栅极绝缘层和第一栅极。
6.根据权利要求1所述的器件，其中所述第二栅极结构包括栅极绝缘层和第二栅极。
7.根据权利要求1所述的器件，其中所述第一栅极结构包括铁电层和第一栅极。
8.根据权利要求1所述的器件，其中所述第二栅极结构包括铁电层和第二栅极。
9.根据权利要求1所述的器件，其中所述第一栅极结构包括第一隧穿氧化物层、第一浮置栅极、第一阻挡氧化物层以及第一栅极。
10.根据权利要求1所述的器件，其中所述第二栅极结构包括第二隧穿氧化物层、第二浮置栅极、第二阻挡氧化物层以及第二栅极。
11.一种形成石墨烯电子器件的方法，所述方法包括：
在衬底上形成半导体层、第一导电层以及第二导电层，其中所述第一导电层位于所述半导体层上，且所述第二导电层与所述半导体层和所述第一导电层间隔开；
通过将绝缘材料施加在所述衬底、所述半导体层、所述第一导电层以及所述第二导电层上而形成中间层；
去除所述衬底，并在所述中间层、所述半导体层以及所述第二导电层上形成石墨烯层；以及
在所述石墨烯层上形成第一栅极结构和第二栅极结构。
12.根据权利要求11所述的方法，还包括：在形成所述中间层之后，在所述中间层上形成支撑结构。
13.根据权利要求11所述的方法，其中所述衬底包括硅和硅氧化物层，所述衬底通过蚀刻所述硅氧化物层而去除。
14.根据权利要求11所述的方法，其中所述衬底包括透明衬底，所述衬底通过激光剥离工艺而去除。
15.根据权利要求11所述的方法，其中在所述中间层上形成催化剂层之后，所述石墨烯层通过热解方法或者化学气相沉积方法而形成在所述催化剂层上。
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