CN102938420A - 无定形氧化物和场效应晶体管 - Google Patents
无定形氧化物和场效应晶体管 Download PDFInfo
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- CN102938420A CN102938420A CN2012103222495A CN201210322249A CN102938420A CN 102938420 A CN102938420 A CN 102938420A CN 2012103222495 A CN2012103222495 A CN 2012103222495A CN 201210322249 A CN201210322249 A CN 201210322249A CN 102938420 A CN102938420 A CN 102938420A
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- amorphous oxide
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- oxygen
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- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Materials Engineering (AREA)
- Thin Film Transistor (AREA)
- Liquid Crystal (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
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- Physical Vapour Deposition (AREA)
Abstract
本发明涉及无定形氧化物和场效应晶体管。所述无定形氧化物包含从由Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P、Ti、Ru和F所构成的组中选择的至少一种元素,并且所述无定形氧化物的电子载流子浓度为1012/cm3或更高且低于1018/cm3。其中,所述无定形氧化物是从由以下所构成的组中选择的任一种:包含从In、Zn和Sn中选择的至少一种元素的氧化物;含有In、Zn和Sn的氧化物;含有In和Zn的氧化物;含有In和Sn的氧化物;含有In的氧化物;以及包含In、Ga和Zn的氧化物。
Description
本申请是申请日为2005年11月09日、国际申请号为PCT/JP2005/020980、国家申请号为200580038273.4、发明名称为“无定形氧化物和场效应晶体管”的专利申请的分案申请。
技术领域
本发明涉及一种无定形氧化物。本发明还涉及使用无定形氧化物的场效应晶体管。
背景技术
近年来,作为液晶技术、场致发光(EL)和相关技术发展的结果,平板显示器(FPD)得以商业化。FPD通过包括场效应薄膜晶体管(TFT)的有源矩阵电路驱动,该薄膜晶体管采用无定形硅薄膜或多晶硅薄膜作为形成在玻璃衬底上的有源层(active layer)。
为了得到FPD更小的厚度、更轻的重量和更大的冲击强度,研究了用轻质且柔性的树脂衬底来代替玻璃衬底。但是,因为在该工艺中硅薄膜晶体管的制造需要比较高的温度,所以采用硅薄膜的晶体管不能直接形成在耐热性能较差的树脂衬底上。
因此,对于TFT,研究了使用能够在较低温度下形成膜的氧化物半导体薄膜如ZnO薄膜(日本专利申请公开No.2003-298062)。
但是,使用传统氧化物半导体薄膜的TFT还不能提供与使用硅的TFT相同级别的性能。
本发明涉及一种无定形氧化物,还涉及使用该无定形氧化物的场效应晶体管。
发明内容
本发明的目的是提供一种用于诸如薄膜晶体管(TFT)的半导体器件中的有源层并用作合适的半导体的无定形氧化物,还涉及一种场效应晶体管。
按照本发明的一个方面,提供了一种包括微晶体并且电子载流子浓度低于1018/cm3的无定形氧化物。
该无定形氧化物优选包含从In、Zn和Sn中选择的至少一种元素。
可替换地,所述无定形氧化物优选是从含有In、Zn和Sn的氧化物;含有In和Zn的氧化物;含有In和Sn的氧化物;以及含有In的氧化物中任选的一种。
可替换地,所述无定形氧化物优选包含In、Ga和Zn。
按照本发明的另一方面,提供了一种无定形氧化物,其中电子迁移率随着电子载流子浓度的增加而增大。
按照本发明的另一方面,提供了一种场效应晶体管,其包括由含有微晶体的无定形氧化物形成的有源层和形成为通过栅极绝缘体面向该有源层的栅电极。
该晶体管优选是常断类型的晶体管。
按照本发明的另一方面,提供了一种成分在层厚度方向上变化并且电子载流子浓度低于1018/cm3的无定形氧化物。
该无定形氧化物优选包含从In、Zn和Sn中选择的至少一种元素。
可替换地,该无定形氧化物优选是从含有In、Zn和Sn的氧化物;含有In和Zn的氧化物;含有In和Sn的氧化物;以及含有In的氧化物中任选的一种。
可替换地,所述无定形氧化物优选包含In、Ga和Zn。
按照本发明的另一方面,提供了一种场效应晶体管,包括:
成分在层厚度方向上变化的无定形氧化物有源层,以及
形成为通过栅极绝缘体面向该有源层的栅电极,
其中所述有源层包括第一区域和第二区域,第二区域比第一区域更靠近栅极绝缘体,并且第一区域的氧浓度高于第二区域的氧浓度。
按照本发明的另一方面,提供了一种场效应晶体管,包括:
具有从In和Zn中选择的至少一种元素的无定形氧化物有源层,以及
形成为通过栅极绝缘体面向该有源层的栅电极,
其中所述有源层包括第一区域和第二区域,第二区域比第一区域更靠近栅极绝缘体,并且第二区域的In浓度高于第一区域的In浓度,或者第二区域的Zn浓度高于第一区域的Zn浓度。
按照本发明的另一方面,提供了一种成分在层厚度方向上变化的无定形氧化物,
其中电子迁移率随着电子载流子浓度的增加而增大。
按照本发明的另一方面,提供了一种场效应晶体管,包括:
具有从In和Zn中选择的至少一种元素的无定形氧化物有源层,以及
形成为通过栅极绝缘体面向该有源层的栅电极,
其中所述有源层包括第一区域和第二区域,第二区域比第一区域更靠近栅极绝缘体,并且第二区域的In浓度高于第一区域的In浓度,或者第二区域的Zn浓度高于第一区域的Zn浓度。
按照本发明的另一方面,提供了一种包含从Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P、Ti、Zr、V、Ru、Ge、Sn和F中选择的一种元素或多种元素并且电子载流子浓度低于1018/cm3的无定形氧化物。
该无定形氧化物优选包含从In、Zn和Sn中选择的至少一种元素。
可替换地,所述无定形氧化物优选是从含有In、Zn和Sn的氧化物;含有In和Zn的氧化物;含有In和Sn的氧化物;以及含有In的氧化物中任选的一种。
可替换地,所述无定形氧化物优选包含In、Ga和Zn。
按照本发明的另一方面,提供了一种包含从Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P、Ti、Zr、V、Ru、Ge、Sn和F中选择的至少一种元素的无定形氧化物,其中电子迁移率随着电子载流子浓度的增加而增大。
按照本发明的另一方面,提供了一种场效应晶体管,包括:
包含从Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P、Ti、Zr、V、Ru、Ge、Sn和F中选择的至少一种元素的无定形氧化物有源层;以及
形成为通过栅极绝缘体面向该有源层的栅电极。
此外,在本发明中,无定形氧化物优选从含有In、Zn和Sn的氧化物;含有In和Zn的氧化物;含有In和Sn的氧化物;以及含有In的氧化物中选择。
作为本发明的发明人对该氧化物半导体的调查的结果,发现上述ZnO以多晶体相的状态形成,导致载流子在多晶体晶格之间的界面上散射从而降低了电子迁移率。此外,还发现ZnO容易在其中导致氧缺位(oxygen defect),从而产生大量的载流子电子,这使得难以降低电导率。由此,即使没有向晶体管施加栅电压,也会在源极端子和漏极端子之间产生很大的电流,从而使得不可能实现TFT的常断状态和更大的晶体管开-关比(on-off ratio)。
本发明的发明人考察了在日本专利申请公开No.2000-044236中提到的无定形氧化物膜ZnxMyInzO(x+3y/2+3z/2)(M:Al和Ga中的至少一种元素)。该材料包含浓度不低于1×1018/cm3的电子载流子,并适合用作简单的透明电极。但是,在TFT沟道层中使用的包含浓度不低于1×1018/cm3的电子载流子的氧化物不能给出足够的开-关比,且不适合于常断的TFT。因此,传统的无定形氧化物膜无法提供载流子浓度低于1×1018/cm3的膜。
本发明的发明人利用载流子浓度低于1×1018/cm3的无定形氧化物作为场效应晶体管的有源层来制备TFT。发现该TFT具有期望的特性,并可用于诸如发光装置的图像显示装置。
此外,本发明的发明人考察了材料InGaO3(ZnO)m和该材料的膜形成条件,发现通过控制膜形成时的氧气气氛条件可以将该材料的载流子浓度可以控制为低于1×1018/cm3。
上述说明针对使用该无定形氧化物作为TFT的用作例如沟道层的有源层的情况。但是本发明不限于使用这种有源层的情况。
在上面的描述中,主要提及用无定形氧化物作为TFT的用作沟道的有源层。但是本发明不限于这种情况。
按照本发明,提供了一种适用于晶体管如TFT的沟道层的无定形氧化物。本发明还提供一种具有优异特性的场效应晶体管。
附图说明
图1是示出通过脉冲激光沉积方法形成的基于In-Ga-Zn-O的无定形膜的电子载流子浓度与膜形成期间的氧分压之间的关系的图;
图2是示出使用氩气通过溅射方法形成的基于In-Ga-Zn-O的无定形膜的电导率与膜形成期间的氧分压之间的关系的图;
图3是示出通过脉冲激光沉积方法形成的基于In-Ga-Zn-O的无定形膜的电子载流子数量与电子迁移率之间的关系的图;
图4A、4B和4C分别示出通过脉冲激光沉积方法在氧分压为0.8Pa的氧气气氛中形成的具有InGaO3(Zn1-xMgxO)成分的膜的电导率、载流子浓度和电子迁移率相对于x值的变化;
图5是示出顶部栅极型金属绝缘体半导体场效应晶体管(MISFET)的结构的示意图;
图6是示出顶部栅极型MISFET器件的电流-电压特性的图;
图7是采用脉冲激光沉积方法的膜成型装置的示意图;
图8是采用溅射方法的膜成型装置的示意图。
具体实施方式
下面,分别按照第一至第三实施例说明第一至第三发明。然后,说明可用于本发明的无定形氧化物材料。在下面的实施例中,主要说明基于In-Ga-Zn-O的氧化物;但是,本发明不限于这些材料。
<第一实施例:具有微晶体的无定形氧化物>
按照第一实施例的本发明涉及无定形氧化物,其特征在于该无定形氧化物包含微晶体。微晶体是否包含在无定形氧化物中是通过对所形成的无定形氧化物膜的片段拍摄TEM(透射电子显微镜)照片来确定的。按照本发明的无定形氧化物膜包括In-Ga-Zn-O,该无定形氧化物膜的晶体状态的成分由InGaO3(ZnO)m(m是小于6的自然数)表示。
本说明书中的术语“无定形氧化物”代表的氧化物具有小于1018/cm3的电子载流子浓度,或展示出电子迁移率随着电子载流子浓度增加而增大的趋势,等等。尽管取决于TFT的使用类型,优选使用无定形TFT来制造常断类型的TFT。
可替换地,按照本发明的无定形氧化物膜包括In-Ga-Zn-Mg-O,该无定形氧化物膜的晶体状态的成分由InGaO3(Zn1-xMgxO)m(m是小于6的自然数,0<x≤1)表示。优选这些无定形氧化物膜具有超过1cm2/V.sec的电子迁移率。
本发明的发明人发现使用上述膜作为沟道层使得可以形成具有以下晶体管特性的柔性TFT:当TFT断开(常断)并且开/关比超过1×103时,栅电流小于0.1微安,并能被可见光穿过。
这种透明膜的特征在于电子迁移率随着导电电子数量的增加而增大。作为用于形成该透明膜的衬底,可以使用玻璃衬底、塑料衬底和塑料膜。
当用透明氧化物膜作为晶体管的沟道层时,优选采用从Al2O3、Y2O3和HfO2组成的组中选择的一种化合物或者包含从Al2O3、Y2O3和HfO2组成的组中选择的至少两种化合物的混晶化合物作为栅极绝缘体。
优选该膜(透明氧化物膜)在含有氧的气氛中在光照条件下形成,而不添加杂质离子来特意增强电阻。
<膜成分>
在具有由InGaO3(ZnO)m(m是小于6的自然数)表示的晶体状态的成分的透明无定形氧化物薄膜中,如果m值小于6,则可以稳定地保持无定形状态直到高达800℃或更高的温度。但是,随着m值增加,换句话说是ZnO与InGaO3之比增加(即膜的成分更接近于ZnO),膜变得很容易结晶。
因此,优选当用无定形膜作为无定形TFT的沟道层时,m值小于6。但是,发现当在光照条件下形成膜时,即使m值很小也可以形成微晶体。
可以用具有InGaO3(ZnO)m成分的多晶烧结体作为靶,通过气相膜形成方法来形成该膜。在气相膜形成方法中,溅射方法和脉冲激光沉积方法是合适的。此外,从大规模生产的观点来看溅射方法更为优选。
但是,这种无定形膜在一般条件下形成,主要出现氧缺位。因此,电子载流子浓度还没有减小到小于1×1018/cm3,换句话说,就电导率而言是10S/cm或更低。在使用这种传统薄膜时,不能形成常断的晶体管。但是,当通过脉冲激光沉积方法使用图7所示装置在具有超过3.2Pa的高氧分压的气氛中形成具有In-Ga-Zn-O成分和由InGaO3(ZnO)m(m是小于6的自然数)表示的晶体状态成分的透明无定形氧化物膜时,电子载流子浓度可以降低至小于1×1018/cm3。在这种情况下,衬底不被特意加热,并因此大致维持在室温下。当采用塑料膜作为衬底时,该塑料膜的温度优选维持在低于100℃。
按照本实施例,无定形氧化物包括In-Ga-Zn-O并通过脉冲激光沉积方法在光照下形成。更具体的说,本发明针对包含由InGaO3(ZnO)m(m是小于6的自然数)的晶体状态成分表示的微晶体的透明无定形氧化物膜。可以利用这种薄膜来形成常断的晶体管。
在这种薄膜中,可以获得超过1cm2/V.sec的电子迁移率和超过1×103的大开/关比。
此外,本发明针对包括In-Ga-Zn-O并通过溅射方法利用氩气在光照下形成的无定形氧化物。更具体地说,本发明针对包含由晶体状态成分InGaO3(ZnO)m(m是小于6的自然数)表示的微晶体的透明无定形氧化物薄膜。这种膜可以利用图8所示装置在具有超过1×10-2Pa的高氧分压的气氛中通过溅射方法获得。在这种情况下,衬底的温度没有特意升高,由此大致维持在室温下。当使用塑料膜作为衬底时,衬底温度优选维持在低于100℃。电子载流子的数量可以通过进一步增加氧分压来减少。
更具体地说,本发明针对在光照下通过溅射沉积方法制备的包括In-Ga-Zn-O的无定形氧化物。按照本发明,可以利用包含由InGaO3(ZnO)m(m是小于6的自然数)的晶体状态成分表示的微晶体的透明无定形氧化物薄膜形成具有超过1×103的开/关比的常断晶体管。
在通过脉冲激光沉积方法和溅射方法在光照下制备的薄膜中,电子迁移率随着导电电子数量的增加而增大。
在这种情况下,如果用多晶体InGaO3(Zn1-xMgxO)m(m是小于6的自然数,0<x≤1)作为靶,即使在低于1Pa的氧分压下也可以获得具有InGaO3(Zn1-xMgxO)m成分的高电阻无定形膜。
如上所述,通过控制氧分压可以克服氧缺位。结果是可以在不添加预定杂质离子的情况下降低电子载流子浓度。按照本发明的无定形氧化物可以通过在光照下按照图1至图5任一个所示形成薄膜来获得。当使用按照图7和图8的装置时,可以在例如下述预定范围的氧分压下形成膜。在包含微晶体的无定形状态下,微晶体的晶界界面被无定形结构覆盖(包围)。因此,能够俘获移动电子和空穴的晶界界面实际上不存在,这与如氧化锌的多晶体状态不同。结果是可以获得具有高电子迁移率的无定形薄膜。此外,导电电子的数量可以在不添加预定杂质离子的情况下减少。由于电子没有被杂质离子散射,所以可以维持高电子迁移率。按照本发明的微晶体不限于具有由InGaO3(ZnO)m(m是小于6的自然数)表示的成分的微晶体。
在采用上述透明膜的薄膜晶体管中,栅极绝缘体优选由包含从Al2O3、Y2O3和HfO2组成的组中选择的至少两种化合物的混晶化合物形成。当在栅极绝缘薄膜和沟道层薄膜之间的界面中存在缺陷(不足)时,电子迁移率减小,并且发生作为晶体管特性的滞后现象。此外,如果栅极绝缘体的类型不同,则泄漏电流变化很大。因此,需要选择合适的栅极绝缘体来作为沟道层。如果采用Al2O3膜(作为栅极绝缘体),则可以减少泄漏电流。如果使用Y2O3膜,则可以减小滞后现象。如果使用具有高介电常数的HfO2膜,则可以增加电子迁移率。此外,如果使用这些化合物的混晶(作为栅极绝缘体),则可以形成泄漏电流和滞后现象很小但电子迁移率很大的TFT。由于栅极绝缘体形成过程和沟道层形成过程可以在室温下执行,因此不仅可以形成交错结构的TFT,还可以形成反交错结构的TFT。
TFT是具有三个端子即栅极端子、源极端子和漏极端子的器件。在TFT中,用形成在诸如陶瓷、玻璃或塑料衬底的绝缘衬底上的半导体薄膜作为通过其迁移电子和空穴的沟道层。通过对栅极端子施加电压来控制流过沟道层的电流,由此切换源极端子和漏极端子之间的电流。由于TFT具有这样的切换功能,因此TFT是有源器件。注意包含在无定形氧化物中的微晶体可以通过上述光照射(具体地说通过卤素灯或UV光进行的光照射)形成,也可以通过除光照之外的其它方法来形成。
<第二实施例:无定形氧化物的成分分布>
按照该实施例,无定形氧化物的特征在于在膜厚度方向上变化的成分。
短语“在膜厚度方向上变化的成分”意思是包含在氧化物中的氧量在膜厚度方向上变化,构成氧化物的元素在中间改变(也就是成分变化),以及构成氧化物的元素的含量变化。
因此,当用无定形氧化物作为场效应晶体管的有源层(也称为沟道层)时,例如下面的构造是优选的。在具有包含在界面上相互接触的无定形氧化物和栅极绝缘体的有源层的晶体管中,无定形氧化物层构成为使得靠近界面处的氧浓度高于远离界面的区域中的氧浓度。在这种情况下,由于靠近界面的无定形氧化物层的电阻很高,因此所谓的晶体管沟道形成在远离界面的无定形氧化物层内。这种结构在界面是粗糙表面时很有利,因为可以减小电流泄漏。
也就是说,在使用上述无定形氧化物作为晶体管的有源层的情况下,优选将有源层设计为包括第一区域和比第一区域更靠近栅极绝缘体的第二区域,第二区域中的氧浓度大于在第一区域中的氧浓度。顺便提一句,这两个区域不必在其边界上可区分,但是可以逐渐地或逐步地改变其各自的成分。
尤其是,无定形氧化物的电子载流子浓度优选低于1018/cm3。
形成在衬底上的膜的方向表示不是在衬底平面中的方向上的任意方向,例如垂直于衬底平面中的方向的方向。此外,在具有由包含从In和Zn中选择的至少一种元素的无定形氧化物形成的有源层和在界面处与该有缘层接触的栅极绝缘体的晶体管中,包含在无定形氧化物层(有源层)靠近界面的区域中的In或Zn的浓度高于在远离界面的区域中的浓度。在这种情况下,可以提高电子场效应迁移率。
也就是说,在使用上述无定形氧化物作为晶体管的有源层的情况下,优选将有源层设计为包括第一区域和比第一区域更靠近栅极绝缘体的第二区域,第二区域中的In或Zn浓度大于在第一区域中的氧浓度。
根据第二发明,氧化物膜包括In-Ga-Zn-O,其成分在膜厚度方向上变化,而且其特征在于晶体状态部分的成分由InGaO3(ZnO)m(m是小于6的自然数)表示而且电子载流子浓度低于1×1018/cm3。
可替换地,按照第二发明的氧化物膜是包括In-Ga-Zn-Mg-O的透明无定形氧化物膜,而且该氧化物膜的特征在于该成分在膜厚度方向上变化,而且晶体状态部分的成分由InGaO3(Zn1-xMgxO)m(m是小于6的自然数,0<x≤1)表示,电子载流子浓度低于1×1018/cm3。注意,这些膜具有超过1cm2/V.sec的电子迁移率也是优选的。
当用上述膜作为沟道层时,可以获得具有如下晶体管特征的柔性TFT:当TFT断开(常断)时栅电流低于0.1微安,开/关比超过1×104,而且可以被可见光透过。
注意,这种透明膜的特征在于电子迁移率随着导电电子数量的增加而增大。作为用于形成透明膜的衬底,可以使用玻璃衬底、塑料衬底和塑料膜。
当用透明的氧化物膜作为晶体管的沟道层时,优选采用从Al2O3、Y2O3和HfO2组成的组中选择的一种化合物或者包含从Al2O3、Y2O3和HfO2组成的组中选择的至少两种化合物的混晶化合物作为栅极绝缘体。
优选该膜(透明氧化物膜)在含有氧的气氛中形成,而不添加杂质离子来特意增强电阻。
本发明人发现了半绝缘无定形氧化物薄膜的特殊特征。也就是说,电子迁移率随着导电电子数量的增加而增大。他们利用该膜形成TFT,并发现晶体管的特征如开/关比、夹断状态下的饱和电流以及开关速度都进一步增大。
在利用透明半绝缘无定形氧化物薄膜作为沟道层而形成的膜晶体管中,当电子迁移率大于1cm2/V.sec、优选大于5cm2/V.sec,而且电子载流子浓度低于1×1018/cm3、优选低于1×1016/cm3时,在断开时间内(没有施加栅电压)漏极和源极端子之间的电流可以减小到小于10微安,优选小于0.1微安。此外,在这种情况(利用上述薄膜)下,当电子迁移率大于1cm2/V.sec、优选大于5cm2/V.sec时,夹断之后的饱和电流可以增加到超过10微安。简而言之,开/关比可以增加到大于1×104。
在TFT中,在夹断状态下向栅极端子施加高电压,结果是在沟道中存在高浓度的电子。因此,根据本发明,饱和电流可以增加对应于电子迁移率增加的程度。结果是晶体管的几乎所有特征如开/关比、饱和电流和开关速率都增大并且得到了改善。注意,在一般的化合物中,当电子数量增加时,电子之间发生碰撞,结果是电子迁移率降低。
按照本发明的无定形氧化物可以在栅极绝缘体和栅极端子按照这种顺序依次形成在半导体沟道层上的交错(顶部栅极)结构TFT和栅极绝缘体和半导体沟道层按照这种顺序依次形成在栅极端子上的反交错(底部栅极)结构TFT中使用。
<膜成分>
在晶体部分具有由InGaO3(ZnO)m(m是小于6的自然数)表示的成分的透明无定形氧化物薄膜中,如果m值小于6,则无定形状态可以稳定地保持在高达800℃或更高的温度。但是,随着m值增加,换句话说,ZnO与InGaO3之比增加(也就是说膜的成分更接近于ZnO),膜变得更容易结晶。
为此,优选当用无定形膜作为无定形TFT的沟道层时,m值小于6。
采用上述透明膜的薄膜晶体管优选使用由包含从Al2O3、Y2O3和HfO2组成的组中选择的一种化合物的混晶化合物或包含从Al2O3、Y2O3和HfO2组成的组中选择的至少两种化合物的混晶化合物形成的栅极绝缘体。当在栅极绝缘薄膜和沟道层薄膜之间的界面中存在缺陷(不足)时,电子迁移率减小,并且发生作为晶体管特征的滞后现象。此外,如果栅极绝缘体的类型不同,则泄漏电流变化很大。为此,需要选择合适的栅极绝缘体来作为沟道层。如果采用Al2O3膜(作为栅极绝缘体),则可以减少泄漏电流。如果使用Y2O3膜,则可以减小滞后现象。如果使用具有高介电常数的HfO2膜,则可以增加电子迁移率。此外,如果使用这些化合物的混晶(作为栅极绝缘体),则可以形成泄漏电流和滞后现象很小但电子迁移率很大的TFT。由于栅极绝缘体形成过程和沟道层形成过程可以在室温下执行,因此不仅可以形成交错结构的TFT,还可以形成反交错结构的TFT。
TFT是具有三个端子即栅极端子、源极端子和漏极端子的器件。在TFT中,用形成在诸如陶瓷、玻璃或塑料衬底的绝缘衬底上的半导体薄膜作为迁移电子和空穴的沟道层。通过对栅极端子施加电压来控制流过沟道层的电流,由此切换源极端子和漏极端子之间的电流。由于该TFT具有这样的切换功能,因此该TFT是有源器件。
如上所述,第二发明针对在透明膜的膜厚度方向上的成分的改进,其中当用该透明膜形成FET时,该透明膜用作场效应晶体管(FET)的有源层。
为了更为具体地说明,在使用脉冲激光沉积方法时,通过在膜厚度方向上改变氧分压,改变脉冲激光的振荡功率或振荡频率,或者改变靶和衬底之间在膜厚度方向上的距离,来改变膜厚度方向上的成分。另一方面,在使用溅射沉积方法时,通过另外溅射靶如In2O3或ZnO来改变膜厚度方向上的成分。例如,在氧环境下形成膜时,包含在该膜中的氧的量随着靶和衬底之间的距离增加而增大。此外,在膜形成期间增加ZnO靶时,在增加Zn靶之后形成的膜中Zn的含量增加。
<第三实施例:包含添加剂的无定形氧化物>
按照本实施例的无定形氧化物的特征在于该无定形氧化物包含从Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P、Ti、Zr、V、Ru、Ge、Sn和F的组中选择的至少一种或多种元素作为添加剂。将添加剂引入无定形氧化物中是通过将该添加剂引入要用于膜形成装置的气体、引入该膜形成装置或者引入该装置中使用的靶材料中来实现的。当然,在由不含添加剂的无定形氧化物形成膜之后,可以按照后面在示例中描述的那样将该添加剂引入膜中。
无定形氧化物的电子载流子浓度优选低于1018/cm3。
按照本发明的无定形氧化物可以包括含有In-Ga-Zn-O而且其晶体状态的成分由InGaO3(ZnO)m(m是小于6的自然数)表示的透明无定形氧化物,也可以包括含有In-Ga-Zn-Mg-O而且其晶体状态的成分由InGaO3(Zn1-xMgxO)m(m是小于6的自然数,0<x≤1)表示的氧化物。对这些氧化物,还可以引入从Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P组成的组中选择的至少一种或多种元素作为添加剂。
按照这种方式,可以降低电子载流子浓度。即使电子载流子浓度明显降低,也可以防止电子载流子迁移率减小,从而使得对电子载流子浓度的控制变得容易。结果是如果用透明的无定形氧化物膜作为TFT的沟道层,则产生的TFT板具有均匀的特性,即使该板的面积很大。
当用Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P作为杂质(添加剂)时,这些杂质可以替代In、Ga、Zn、O中的任一种并用作受主,而且可以降低电子载流子密度,尽管该机制的细节未知。在一般的氧化物半导体中,由于氧浓度无法精确控制,因此会产生大量的氧缺欠。此外,在晶界中由于多晶体状态而产生缺欠的情况下,即使引入杂质大多也无法很好地控制电子载流子密度。在这个方面,按照本发明的透明无定形氧化物膜具有很少的氧缺欠,而且由于无定形状态而没有晶界。因此,考虑将杂质有效地作为受主工作。在通过增加氧分压来形成薄膜以降低电子载流子密度时,原子键的骨架变化,增加了传导带的尾态。如果电子被该尾态捕获,骨架载流子迁移率可以充分降低。但是,添加Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P使得可以控制载流子密度,同时将氧分压维持在合适的范围内。因此,可以想到电子载流子迁移率受到更少的影响。由此,当本发明与只通过控制氧分压控制电子载流子浓度和电子载流子迁移率的情况相比时,即使使用大型衬底也可以很容易地增加氧化物膜的平面内特征均匀性。
添加剂可以如下所述从Ti、Zr、V、Ru、Ge、Sn和F的组中选择。
注意,获得期望效果(在无定形膜中)所需要的杂质浓度大约是0.1至3原子百分比,这高于在由Si等形成的晶体膜中的杂质浓度。这是因为在无定形状态下杂质原子进入用于控制价电子的有效位置的概率低于在晶体状态下的概率。更为一般地,通过杂质引入方法将期望的杂质引入靶。在杂质是例如C、N、P的情况下,可以通过将诸如CH4、NO和PH3的气体和氧一起引入气氛中来引入该杂质。当引入金属元素作为杂质时,在形成透明无定形氧化物膜之后,将该膜与包含该金属元素离子的溶液或糊剂接触。此外,当采用具有高耐热性的衬底如玻璃时,这些金属元素事先包含在该衬底中,然后在膜形成期间或之后加热该衬底,由此将该金属元素扩散到透明无定形氧化物膜中。作为Na源,例如可以使用苏打玻璃,因为其含有10到20原子百分比的钠。
图5示出TFT器件的典型结构。在TFT器件中,可以有效降低电子载流子密度的部分是夹在漏电极5和源电极6之间的沟道层2的部分。相反,有利的是沟道层2与漏电极5和源电极6接触的部分具有高电子载流子密度。这是因为该部分可以保持与电子的良好接触。换句话说,该部分的杂质浓度优选很低。这种构造可以通过在形成漏电极5和源电极6之后并在形成栅极绝缘膜3之前使沟道层2与包含杂质的溶液接触来实现。通过这种方式,可以用漏电极5和源电极6作为掩膜来扩散该杂质。
在图5中,沟道层2的尤其是与衬底接触的部分不容易在栅电极4针对电子载流子密度的控制之下。因此,如果将该部分的电子载流子密度事先抑制得很低以增加开/关比是很有用的。然后,尤其是增加面向衬底的界面上的杂质的浓度是很有效的。这种结构可以通过按照开始以过量的浓度供应该气体然后逐渐减小浓度的方式控制将要引入气氛中的诸如CH4、NO和PH3的气体的浓度来获得。可替换地,在衬底中事先包含诸如Na的杂质的情况下,这种结构可以通过在合适的温度下加热该衬底以扩散Na来获得。
作为添加剂,可以将从Ti、Zr、V、Ru、Ge、Sn和F的组中选择的至少一种或多种元素引入无定形氧化物中。在这种情况下,预计电子迁移率可以增加到1cm2/V.sec或更大,进一步达到5cm2/V.sec或更大,同时保持电子载流子浓度低于1×1018/cm3。即使电子场效应迁移率增加,电子载流子浓度却几乎不相应增加。因此,当用该透明无定形氧化物膜作为沟道层时,可以获得具有高开/关比和夹断期间的大饱和电流以及高开关速度的TFT。此外,与只通过调整氧分压来控制电子载流子浓度和电子载流子迁移率的情况相比,即使使用大型衬底也很容易提高氧化物膜特征的平面内均匀性。
尽管该机制的细节未知,但是在通过增加氧分压来形成氧化物时,在导带下的部分的尾态密度也会增加,从而迁移率可以降低。但是,可以想到诸如Ti、Zr、V、Ru、Ge、Sn和F的杂质作用于原子键的骨架,由此减少了尾态,从而导致电子载流子迁移率提高同时电子载流子密度保持不变。
优选以大约0.1至3原子百分比或0.01至1原子百分比范围内的浓度使用上述这些杂质。术语“原子百分比”是指在氧化物中含有的组成元素的原子数量的比例。注意,如果难以测量氧的含量,则上述范围可以通过除氧之外的其它组成元素的原子数量的比例来定义。更为一般地,通过用于引入杂质的方法将期望的杂质引入靶中。在杂质是F的情况下,可以通过将诸如SF6、SiF4或CLF3的气体和氧一起引入气氛中来将杂质F引入膜中。当引入金属元素作为杂质时,在形成透明无定形氧化物膜之后,将该膜与含有该金属元素离子的溶液或糊剂接触。
图5示出TFT器件的典型结构。在TFT器件中,需要特别高的电子迁移率的部分是沟道层2的与栅极绝缘体3接触的部分。然后,尤其是在与栅极绝缘体膜3接触的界面中增加本发明的杂质浓度是有效的。这种结构可以通过在沟道层形成期间将诸如SF6、SiF4或CLF3的气体引入气氛中同时增加该气体的浓度(从较低的水平开始)来获得。
在本发明中,很重要的是原子键结构可以通过控制氧的量(氧缺位量)来合适地形成。
在上面的描述中,通过在包含预定量的氧的气氛中形成膜来控制透明氧化物膜中的氧的量。还优选在形成氧化物膜之后,在含有氧的气氛中对该氧化物膜进行处理,由此控制(降低或增加)氧缺位量。
为了有效控制氧缺位量,在含有氧的气氛中在从0到300℃(两个端点都包括)、优选从25到250℃(两个端点都包括)、更为优选的是从100到200℃(两个端点都包括)的温度下处理膜。
当然,不仅膜形成而且膜形成之后的膜处理都可以在含有氧的气氛中进行。此外,只要获得预定的电子载流子浓度(低于1×1018/cm3),就可以在不控制氧分压的情况下形成膜,此后可以在含有氧的气氛中处理该膜。
在本发明中,最低电子载流子浓度根据所获得的氧化物膜的用途而改变,更具体地说,根据器件、电路和装置的类型而改变;但是,例如1×1014/cm3或更大是优选的。
下面,详细描述可应用于实施例1至3的无定形氧化物。向无定形氧化物或其制造方法增加以下条件。在按照第一实施例的发明中,向制造条件增加光照。在按照第二实施例的发明中,采用在示例中描述的用于改变膜成分的手段。在按照第三实施例的发明中,除了膜形成条件之外,还采用用于添加杂质的气体和靶,或者在膜形成之后可以采用用于向下面所给出的无定形氧化物添加杂质的预定方法。
(无定形氧化物)
下面说明本发明上述实施例1至实施例3中采用的有源层。
本发明的无定形氧化物中的电子载流子浓度是在室温下测量的值。室温是在0℃到大约40℃范围内的温度,如25℃。本发明无定形氧化物中的电子载流子浓度不需要在从0℃到40℃的整个范围内都低于1×1018/cm3。例如,在25℃的温度下低于1×1018/cm3的电子载流子浓度是可以接受的。在更低的,不高于1×1017/cm3或不高于1×1016/cm3的电子载流子浓度下,可以高产量地制作常断的TFT。
在本说明书中,描述“低于1018/cm3”意思是“优选低于1×1018/cm3而且更为优选的是低于1.0×1018/cm3”。
可以通过测量霍耳效应来测量电子载流子浓度。
本发明的无定形氧化物是一种展现出光环(halo)图案而且在X射线衍射频谱中没有特征衍射线的氧化物。
在本发明的无定形氧化物中,电子载流子浓度的下限例如是1×1012/cm3,但不限于此,只要能用作TFT的沟道层就可以。
因此,在本发明中,通过象在下面描述的示例中那样控制无定形氧化物的材料、成分比、制作条件等等,将电子载流子浓度调节到例如从1×1012/cm3到1×1018/cm3的范围内,优选从1×1013/cm3到1×1017/cm3的范围内,更为优选的是从1×1015/cm3到1×1016/cm3的范围内。
除InZnGa氧化物之外,可以从In氧化物、InxZn1-x氧化物(0.2≤x≤1)、InxSn1-x氧化物(0.8≤x≤1)和Inx(Zn,Sn)1-x氧化物(0.15≤x≤1)中合适地选择无定形氧化物。Inx(Zn,Sn)1-x氧化物还可以由Inx(ZnySn1-y)1-x(0≤y≤1)来表示。
当In氧化物既不包含Zn又不包含Sn时,In可以部分地被Ga代替:InxGa1-x氧化物(0≤x≤1)。
下面详细描述由本发明的发明人制备的电子载流子浓度为1×1018/cm3的无定形氧化物。
一组上述氧化物特征性地由晶体状态的由InGaO3(ZnO)m(m是小于6的自然数)表示的In-Ga-Zn-O构成,并包含浓度低于1×1018/cm3的电子载流子。
另一组上述氧化物特征性地由晶体状态的由InGaO3(Zn1-xMgxO)m(m是小于6的自然数,0<x≤1)表示的In-Ga-Zn-Mg-O构成,并且包含浓度低于1×1018/cm3的电子载流子。
由这种氧化物构成的膜优选设计为展现出高于1cm2/V.sec的电子迁移率。
通过用上述膜作为沟道层,TFT可以制备成常断而且在晶体管断开状态下栅电流小于0.1微安,开-关比高于1×103,对可见光透明并且是柔性的。
在上述膜中,电子迁移率随着导电电子的增加而增大。形成透明膜的衬底包括玻璃板、塑料板和塑料膜。
在使用上述无定形氧化物膜作为沟道层时,至少一个由Al2O3、Y2O3或HfO2或其混晶化合物构成的层可用作栅极绝缘体。
在优选实施例中,该膜在含有氧气的气氛中形成,但没有特意向该无定形氧化物中添加杂质来增大电阻。
本发明的发明人发现半绝缘氧化物的无定形薄膜具有其中的电子迁移率随着导电电子数量的增加而增大的特性,还发现利用该膜制备的TFT在诸如开-关比、夹断状态中的饱和电流以及切换率的晶体管特性方面得到了改善。由此,可以利用该无定形氧化物来制作常断类型的TFT。
通过用该无定形氧化物薄膜作为膜晶体管的沟道层,电子迁移率可以高于1cm2/V.sec,优选高于5cm2/V.sec。在载流子浓度低于1×1018/cm3,优选低于1×1018/cm3时,断开状态下(没有施加栅电压)漏极端子和源极端子之间的电流可以控制为低于10微安,优选低于0.1微安。此外,利用该薄膜,对于高于1cm2/V.sec、优选高于5cm2/V.sec的电子迁移率来说,夹断之后的饱和电流可以提高到10微安或更高,而且开-关比可以提高到高于1×103。
在TFT的夹断状态中,向栅极端子施加高电压,电子以高密度存在于沟道中。因此,按照本发明,饱和电流可以对应于电子迁移率的增加而增大。由此,可以改善晶体管特性,如提高开-关比,增大饱和电流和增加切换率。相反,在常见的化合物中,因为电子之间的碰撞,电子的增加降低了电子迁移率。
上述TFT的结构可以是交错(顶部栅极)结构,其中栅极绝缘体和栅极端子依次形成在半导体沟道层上;也可以是反交错(底部栅极)结构,其中栅极绝缘体和半导体沟道层依次形成在栅极端子上。
(膜形成的第一过程:PLD过程)
具有晶体状态的成分InGaO3(ZnO)m(m是小于6的自然数)的无定形氧化物薄膜在m小于6时一直到800℃或更高的温度下都是稳定的,而随着m的增加,也就是随着ZnO与InGaO3之比增加到接近ZnO的成分,该氧化物趋向于结晶。因此,为了用作无定形TFT的沟道层,该氧化物的值m优选小于6。
优选通过气相膜形成过程利用具有InGaO3(ZnO)m成分的多晶烧结体作为靶来执行膜形成。在气相膜形成过程中,溅射和脉冲激光汽相沉积是合适的。溅射尤其适用于大批量制作。
但是,在常见条件下形成无定形膜时,可能发生氧缺位,从而无法达到低于1×1018/cm3的电子载流子浓度和低于10S/cm的电导率。利用这种膜,无法构成常断的晶体管。
本发明的发明人利用图7所示的装置通过脉冲激光汽相沉积制作了In-Ga-Zn-O膜。
该膜形成是利用如图7所示的PLD膜形成装置来实施的。
在图7中,附图标记表示如下:701是RP(旋转泵);702是TMP(涡轮分子泵);703是预备腔;704是用于RHEED的电子枪;705是用于旋转和垂直移动衬底的衬底保持装置;706是激光引入窗口;707是衬底;708是靶;709是原子团源;710是气体入口;711是用于旋转和垂直移动靶的靶保持装置;712是旁路线;713是主线;714是TMP(涡轮分子泵);715是RP(旋转泵);716是钛吸气泵;717是遮挡板;718是IG(离子压力计);719是PG(皮拉尼压力计);720是BG(baratron gage,巴拉脱压力计);721是生长腔。
采用KrF受激准分子激光通过脉冲激光汽相沉积在SiO2的玻璃衬底(Corning公司:1737)上沉积In-Ga-Zn-O类型的无定形氧化物半导体薄膜。作为在沉积之前的预处理,用丙酮、乙醇和超纯水以超声方式清洗衬底各5分钟以进行脱脂,并在空气中在100℃下干燥。
多晶体靶是InGaO3(ZnO)4烧结体(尺寸:直径20mm,厚5mm),其通过将作为源材料的In2O3、Ga2O3和ZnO(每个是4N试剂)湿法混合(溶剂:乙醇),锻烧该混合物(1000℃,2小时),干法压碎该混合物,并烧结该混合物(1550℃,2小时)来制备。该靶具有90S/cm的电导率。
该膜形成通过将生长腔的最终真空度控制为2×10-6Pa,将生长期间的氧分压控制在6.5Pa来进行。生长腔721中的氧分压是6.5Pa,衬底温度是25℃。靶708和膜保持衬底707之间的距离是30mm,通过引入窗口716引入的功率在1.5-3mJ/cm2/脉冲的范围内。脉冲宽度是20nsec,重复频率是10Hz,照射点的尺寸是1×1毫米见方。在上述条件下,该膜以7nm/min的速度形成。
通过小角度X射线散射方法(SAXS)(薄膜方法,入射角:0.5°)来检查所产生的薄膜:没有观察到清楚的衍射峰值。由此判断所获得的In-Ga-Zn-O类型薄膜是无定形的。从X射线的反射率及其图案分析中,发现均方粗糙度(Rrms)大约是0.5nm,膜厚度大约是120nm。根据荧光X射线光谱仪分析(XRF),发现该膜的金属成分是In:Ga:Zn=0.98:1.02:4。电导率小于大约1×10-2S/cm。电子载流子浓度估计不超过1×10-16/cm3。电子迁移率估计大约是5cm2/V.sec。根据光吸收频谱分析,估计所产生的无定形薄膜的光带隙能量宽度大约是3eV。
上述结果表明所获得的In-Ga-Zn-O类型薄膜是一种透明的平薄膜,具有接近晶体InGaO3(ZnO)4的成分的无定形相,具有更少的氧缺位,并具有更低的电导率。
下面参照图1具体说明上述膜形成。图1示出在与上述例子相同的膜形成条件下,所形成的透明无定形氧化物薄膜中的电子载流子浓度相对于用于假设晶体状态的InGaO3(ZnO)m(m是小于6的自然数)成分的膜的氧分压的依赖关系。
通过在与上述例子相同的条件下,在氧分压大于4.5Pa的气氛中形成膜,电子载流子浓度可以降低到1×1018/cm3,如图1所示。在该膜形成过程中,衬底保持在接近室温的温度下而没有特意加热。为了用柔性塑料膜作为衬底,衬底温度优选保持在低于100℃的温度下。
更高的氧分压使得能够降低电子载流子浓度。例如,如图1所示,在衬底温度为25℃、氧分压为5Pa时形成的薄InGaO3(ZnO)4膜具有1×1016/cm3的更低的电子载流子浓度。
在获得的薄膜中,电子迁移率高于1cm2/V.sec,如图2所示。但是,在该例子中,通过脉冲激光汽相沉积在高于6.5Pa的氧分压下沉积的膜具有粗糙的表面,不适于作TFT的沟道层。
因此,可以利用在上述例子中通过脉冲激光汽相沉积方法在高于4.5Pa、优选高于5Pa但低于6.5Pa的氧分压下形成的晶体状态的由InGaO3(ZnO)m(m是小于6的自然数)表示的透明薄无定形氧化物来构成常断类型的晶体管。
上述获得的薄膜展示出高于1cm2/V的电子迁移率,而且开-关比可以高于1×103。
如上所述,在通过PLD方法在该例子中示出的条件下形成InGaZn氧化物膜时,将氧分压控制在优选从4.5Pa到6.5Pa的范围内。
为了达到1×1018/cm3的电子载流子浓度,应当控制氧分压条件、膜形成装置的结构、膜形成材料的类型和成分。
接着,通过用上述装置在6.5Pa的氧分压下形成无定形氧化物来制作如图5所示的顶部栅极类型MISFET元件。具体地说,在玻璃衬底1上,通过上述形成无定形薄Ga-Ga-Zn-O膜的方法形成120nm厚的半绝缘无定形InGaO3(ZnO)4膜以用作沟道层2。此外,在其上通过脉冲激光沉积在该腔中低于1Pa的氧分压下分别以30nm的厚度层叠具有更高电导率的InGaO3(ZnO)4膜和金膜。然后,通过光刻和剥离方法形成漏极端子5和源极端子6。最后,通过电子束汽相沉积方法形成用作栅极绝缘体3的Y2O3膜(厚度:90nm,相对介电常数:大约15,漏电流密度:施加0.5MV/cm时是1×10-3A/cm3)。在该膜上形成金膜,并通过光刻和剥离形成栅极端子4。
MISFET元件特性的评估
图6示出在室温下测量的MISFET元件的电流-电压特性。从漏电流IDS随着漏电压VDS的增加而增大的情况来看,该沟道应理解为n型半导体。这与无定形In-Ga-Zn-O型半导体是n型的事实相符。IDS在VDS=6V时饱和(夹断),这是半导体晶体管的典型性能。根据对增益特性的检查,发现在施加VDS=4V的情况下栅电压VGS的阈值大约是-0.5V。在VG=10V时导致IDS=1.0×10-5A的电流。这对应于通过栅极偏压在In-Ga-Zn-O型无定形半导体薄膜中的载流子感生。
该晶体管的开-关比高于1×103。根据输出特性,计算出场效应迁移率大约是7cm2(Vs)-1。根据相同的测量,可见光的照射不会改变所制作的元件的晶体管特性。
按照本发明,可以制作这样的薄膜晶体管,其具有包含更低浓度电子载流子以实现更高电阻并展示出更高电子迁移率的沟道层。
上述无定形氧化物具有电子迁移率随着电子载流子浓度的增加而增大的优异特性,并展示出简并导电性。在该示例中,薄膜形成在玻璃衬底上。但是塑料板或塑料膜可以用作衬底,因为膜形成可以在室温下进行。此外,在该示例中获得的无定形氧化物仅吸收很少的可见光,从而给出透明的柔性TFT。
(膜形成的第二过程:溅射过程(SP过程))
下面说明利用氩气作为环境气体通过高频SP过程的膜形成。
利用图8所示的装置来实施SP过程。在图8中,附图标记表示如下:807是用于形成膜的衬底;808是靶;805是具有冷却机构的衬底保持装置;814是涡轮分子泵;815是旋转泵;817是遮挡板;818是离子压力计;819是皮拉尼压力计;821是生长腔;830是闸门阀。
用于膜形成的衬底807是SiO2玻璃衬底(Corning公司:1737),该玻璃衬底已经用丙酮、乙醇和超纯水以超声方式分别清洗5分钟以进行脱脂,并在空气中在100℃下干燥。
所述靶是具有InGaO3(ZnO)4成分的多晶烧结体(尺寸:直径20mm,厚5mm),其通过将源材料In2O3、Ga2O3和ZnO(每个是4N试剂)湿法混合(溶剂:乙醇),锻烧该混合物(1000℃,2小时),干法压碎该混合物,并烧结该混合物(1550℃,2小时)来制备。靶808具有90S/cm的电导率,是半绝缘的。
生长腔821的最终真空度控制为1×10-4Pa。在生长期间,氧和氩气的总压力恒定地保持在4到0.1×10-1Pa的范围内。氩与氧的分压比在从1×10-3到2×10-1Pa的氧分压范围内变化。
衬底温度是室温。靶808和用于膜形成的衬底807之间的距离是30mm。
输入的电功率是RF 180W,膜形成速率是10nm/min。
通过小角度X射线散射方法(SAXS)(薄膜方法,入射角:0.5°)来检查所产生的薄膜:没有观察到清楚的衍射峰值。由此判断所获得的In-Ga-Zn-O类型薄膜是无定形的。从X射线的反射率及其图案分析中,发现均方粗糙度(Rrms)大约是0.5nm,膜厚度大约是120nm。根据荧光X射线光谱仪分析(XRF),发现该膜的金属成分是In:Ga:Zn=0.98:1.02:4。
该膜在环境气体的不同氧分压下形成,并测量所产生的无定形氧化物膜的电导率。图3示出其结果。
如图3所示,可以通过在氧分压高于3×10-2Pa的气氛中进行膜形成来将电导率降至低于10S/cm。电子载流子数目可以通过增加氧分压来减少。
如图3所示,例如,在衬底温度为25℃、氧分压为1×10-1Pa时形成的薄InGaO3(ZnO)4膜具有1×10-10S/cm的更低的电导率。此外,在氧分压为1×10-1Pa时形成的薄InGaO3(ZnO)4膜具有过高的电阻,从而具有不可测量的电导率。对于该膜,尽管不能测量电子迁移率,也可以通过从高电子载流子浓度的膜的值外推来估计出电子迁移率大约是1cm2/V.sec。
因此,可以通过利用通过溅射汽相沉积在含有分压高于3×10-2Pa、优选高于5×10-1Pa的氧的氩气气氛中制作的、由晶体状态的由InGaO3(ZnO)m(m是小于6的自然数)表示的In-Ga-Zn-O构成的透明无定形氧化物薄膜,来获得开-关比高于1×103的常断晶体管。
在使用该示例中采用的装置和材料时,通过溅射进行的膜形成在从3×10-2Pa到5×10-1Pa的氧分压范围内进行。顺便提一句,在通过脉冲激光汽相沉积或溅射制作的薄膜中,电子迁移率随着导电电子数量的增加而增大。
如上所述,通过控制氧分压可以减少氧缺位,由此可以减小电子载流子浓度。在无定形薄膜中,因为在不同于多晶体状态的无定形状态中基本上不存在晶界,所以电子迁移率可以很高。
顺便提一句,用200μm厚的聚对苯二甲酸乙二醇酯(PET)膜替换玻璃衬底不会改变其上面形成的InGaO3(ZnO)4无定形氧化物膜的特性。
利用多晶体InGaO3(Zn1-xMgxO)m作为靶,甚至在低于1Pa的氧分压下,也可以获得高电阻无定形膜InGaO3(Zn1-xMgxO)m(m是小于6的自然数,0<x≤1)。例如,利用80原子百分比的Zn被Mg代替的靶,可以通过脉冲激光沉积在含有分压为0.8Pa的氧的气氛中实现低于1×1016/cm(电阻:大约是1×10-2S/cm)的电子载流子浓度。在这种膜中,电子迁移率低于无Mg膜的电子迁移率,但是减小的程度很小:电子迁移率在室温下是5cm2/V.sec,比无定形硅的电子迁移率高大约一位。当在相同的条件下形成膜时,增加Mg的含量将同时降低电导率和电子迁移率。因此Mg的含量优选在20%到85%内变化(0.2<x<0.85)。
在采用上述无定形氧化物膜的薄膜晶体管中,栅极绝缘体优选包括含有Al2O3、Y2O3、HfO2及其化合物中的两种或更多的混晶化合物。
在栅极绝缘薄膜和沟道层薄膜之间的界面上存在缺陷降低了电子迁移率,并导致晶体管特性的滞后现象。此外,电流泄漏很大程度上取决于栅极绝缘体的类型。因此,应当选择适合用于沟道层的栅极绝缘体。可以利用Al2O3膜来降低电流泄漏,可以利用Y2O3膜来减小滞后现象,可以利用具有高介电常数的HfO2膜来增大电子迁移率。利用上述化合物的混晶,可以形成产生更小电流泄漏、更低滞后现象并展现更高电子迁移率的TFT。由于栅极绝缘体形成过程和沟道层形成过程可以在室温下进行,因此可以按照交错结构或反交错结构来形成TFT。
由此形成的TFT是具有栅极端子、源极端子和漏极端子的三端子元件。该TFT通过在陶瓷、玻璃或塑料的绝缘衬底上形成半导体薄膜作为用于电子或空穴迁移的沟道层来形成,并用作有源元件,具有通过对栅极端子施加电压来控制流过沟道层的电流并切换源极端子和漏极端子之间的电流的功能。
在本发明中,重要的是通过控制氧缺位量来达到期望的电子载流子浓度。
在上述描述中,通过控制膜形成气氛中的氧浓度来控制无定形氧化物膜中的氧含量。另外,作为优选实施例,通过在含有氧的气氛中对该氧化物膜进行后处理来控制(减少或增加)氧缺位量。
为了有效控制氧缺位量,含有氧的气氛的温度控制在从0到300℃、优选从25到250℃、更为优选的是从100到200℃的范围内。
当然,膜可以在含有氧的气氛中形成,并在含有氧的气氛中进行后处理。另外,只要可以获得期望的电子载流子浓度(低于1×1018/cm3),可以在不控制氧分压的情况下形成膜,并在含有氧的气氛中进行后处理。
在本发明中,电子载流子浓度的下限根据采用所制作的氧化物膜的元件、电路和器件的类型例如是1×1014/cm3。
(更宽的材料范围)
在调查其它用于该系统的材料之后,发现由Zn、In和Sn元素的至少一种氧化物构成的无定形氧化物可用作低载流子浓度和高电子迁移率的无定形氧化物膜。发现该无定形氧化物膜具有导电电子数量的增加导致电子迁移率增大的特殊特性。利用该膜可以制作晶体管特性如开-关比、夹断状态的饱和电流和切换率非常优异的常断类型TFT。
在本发明中,具有以下(a)至(h)任一种特性的氧化物都是有用的:
(a)电子载流子浓度低于1×1018/cm3的无定形氧化物;
(b)电子迁移率随着电子载流子浓度的增加而增大的无定形氧化物;
(室温表示从大约0℃到大约40℃的温度。术语“无定形化合物”表示一种在X射线衍射频谱中只展示出光环图案而没有展示出特征衍射图案的化合物。电子迁移率表示通过霍耳效应测量的电子迁移率。)
(c)在(a)或(b)中提到的、电子迁移率在室温下高于0.1cm2/V.sec的无定形氧化物;
(d)在(b)至(c)中任何一项中提到的、展示出简并导电性的无定形氧化物;
(术语“简并导电性”表示这样一种状态,其中电阻的温度依赖关系中的热激活能量不高于30meV。)
(e)在(a)至(d)中任何一项所述的、包含Zn、In和Sn中至少一种元素作为构成元素的无定形氧化物;
(f)由(e)提到的无定形氧化物和以下元素中的另外至少一种构成的无定形氧化物膜:
原子序号低于Zn的第2族元素M2(Mg和Ca),
原子序号低于In的第3族元素M3(B、Al、Ga和Y),
原子序号低于Sn的第4族元素M4(Si、Ge和Zr),
第5族元素M5(V、Nb和Ta)以及Lu和W以降低电子载流子浓度;
(g)在(a)至(f)中任何一项所提到的无定形氧化物膜,由具有晶体状态的In1-xM3xO3(Zn1-yM2yO)m(0≤x≤1;0≤y≤1;m是0或小于6的自然数)成分的单一化合物构成,或m不同的上述化合物的混合物构成,例如,M3是Ga,M2是Mg;
(h)在(a)至(g)中任何一项所提到的、形成在塑料衬底或塑料膜上的无定形氧化物膜。
本发明还提供采用上述无定形氧化物或无定形氧化物膜作为沟道层的场效应晶体管。
制备这样的场效应晶体管,其采用电子载流子浓度低于1×1018/cm3但高于1×1015/cm3的无定形氧化物膜作为沟道层,并具有源极端子、漏极端子、插入了栅极绝缘体的栅极端子。当在源极端子和漏极端子之间施加大约5V的电压而没有施加栅电压时,源极和漏极端子之间的电流大约是1×10-7安培。
氧化物晶体中的电子迁移率随着金属离子的s轨道的重叠增加而增大。在具有较高原子序号的Zn、In或Sn的氧化物晶体中,电子迁移率在0.1到200cm2/V.sec的范围内。
在氧化物中,氧和金属离子通过离子键结合而没有化学键的取向,具有随机的结构。因此在无定形状态下的氧化物中,电子迁移率与晶体状态下的电子迁移率相当。
另一方面,用较低原子序号的元素来代替Zn、In或Sn会降低电子迁移率。由此,本发明的无定形氧化物中的电子迁移率在大约0.01到20cm2/V.sec的范围内。
在具有由上述氧化物构成的沟道层的晶体管中,优选由Al2O3、Y2O3和HfO2或包含其中两种或更多的混晶化合物来形成栅极绝缘体。
在栅极绝缘薄膜和沟道层薄膜之间的界面上存在缺陷降低了电子迁移率,并导致晶体管特性的滞后现象。此外,电流泄漏很大程度上取决于栅极绝缘体的类型。因此,应当选择适合用于沟道层的栅极绝缘体。可以利用Al2O3膜来降低电流泄漏,可以利用Y2O3膜来减小滞后现象,可以利用具有高介电常数的HfO2膜来增大电子迁移率。利用上述化合物的混晶,可以形成产生更小电流泄漏、更低滞后现象并展现更高电子迁移率的TFT。由于栅极绝缘体形成过程和沟道层形成过程可以在室温下进行,因此可以按照交错结构或反交错结构来形成TFT。
In2O3氧化物膜可以通过气相过程来形成,在大约0.1Pa的氧分压下向膜形成气氛增加湿度会使形成的膜无定形。
ZnO和SnO2分别无法容易地形成为无定形膜状态。为了形成无定形状态的ZnO膜,添加20原子百分比的In2O3。为了形成无定形状态的SnO2膜,添加90原子百分比的In2O3。在形成Sn-In-O类型的无定形膜时,在膜形成气氛中引入大约0.1Pa的分压的气态氮。
可以向上述无定形膜添加能够形成络合氧化物的元素,该元素从原子序号低于Zn的第2族元素M2(Mg和Ca)、原子序号低于In的第3族元素M3(B、Al、Ga和Y)、原子序号低于Sn的第4族元素M4(Si、Ge和Zr)、第5族元素M5(V、Nb、Ta)以及Lu和W中选择。上述元素的添加在室温下稳定了无定形膜,并加宽了用于形成无定形膜的成分范围。
具体地说,添加倾向于形成共价键的B、Si或Ge有利于无定形相稳定。添加由离子半径极为不同的离子构成的络合氧化物有利于无定形相稳定。例如,在In-Zn-O系统中,为了形成在室温下稳定的膜,应当包含超过大约20原子百分比的In。但是,添加含量等同于In的Mg使得能够在不低于约15原子百分比的In的成分范围内形成稳定的无定形膜。
在气相膜形成中,通过控制膜形成气氛可以获得电子载流子浓度在1×1015/cm3到1×1018/cm3范围内的无定形氧化物膜。
无定形氧化物膜可以通过汽相过程,如脉冲激光汽相沉积过程(PLD过程)、溅射过程(SP过程)和电子束汽相沉积,来适当地形成。在汽相过程中,PLD过程适于使材料合成控制变得容易,而SP过程适于大批量制作。但是,膜形成过程不限于此。
(通过PLD过程形成In-Zn-Ga-O类型的无定形氧化物膜)
In-Zn-Ga-O类型的无定形氧化物通过采用KrF受激准分子激光的PLD过程沉积在玻璃衬底(Corning公司:1737)上,其中用多晶烧结体作为具有InGaO3(ZnO)或InGaO3(ZnO)4成分的靶。
采用上面已描述过的图7所示的装置,膜形成条件和前面针对该装置所描述的条件相同。
衬底温度是25℃。
通过小角度X射线散射方法(SAXS)(薄膜方法,入射角:0.5°)来检查所产生的两个薄膜:没有观察到清楚的衍射峰值,这表示用两种不同靶制作的In-Ga-Zn-O类型薄膜都是无定形的。
从玻璃衬底的In-Zn-Ga-O类型无定形氧化物膜的X射线反射率及其图案分析中,发现该薄膜的均方粗糙度(Rrms)大约是0.5nm,膜厚度大约是120nm。根据荧光X射线光谱仪分析(XRF),发现用InGaO3(ZnO)的多晶烧结体作为靶获得的膜包含成分比为In:Ga:Zn=1.1:1.1:0.9的金属,而用InGaO3(ZnO)4的多晶烧结体作为靶获得的膜包含成分比为In:Ga:Zn=0.98:1.02:4的金属。
无定形氧化物膜在膜形成气氛的各种氧分压下用具有InGaO3(ZnO)4成分的靶来形成。测量所形成的无定形氧化物膜的电子载流子浓度。图1示出其结果。通过在氧分压高于4.2Pa的气氛中形成膜,可以将电子载流子浓度降低到低于1×1018/cm3,如图1所示。在该膜形成中,衬底保持在接近室温的温度而无需特意加热。在氧分压低于6.5Pa时,所获得的无定形氧化物膜的表面是平的。
在氧分压为5Pa时,在用InGaO3(ZnO)4靶形成的无定形膜中,电子载流子浓度为1×1016/cm3,电导率是1×10-2S/cm,电子迁移率估计大约是5cm2/V.sec。根据光吸收频谱分析,估计所产生的无定形薄膜的光带隙能量宽度大约是3eV。
更高的氧分压进一步降低了电子载流子浓度。如图1所示,在衬底温度为25℃、氧分压为6Pa时形成的In-Zn-Ga-O类型的无定形氧化物膜中,电子载流子浓度降低到8×1015/cm3(电导率:大约是8×10- 3S/cm)。膜中的电子迁移率估计是1cm2/V.sec或更大。但是,通过PLD过程,在氧分压为6.5Pa或更高时,沉积的膜具有粗糙的表面,不适于用作TFT的沟道层。
In-Zn-Ga-O类型的无定形氧化物膜在膜形成气氛的各种氧分压下用具有InGaO3(ZnO)4成分的多晶烧结体构成的靶来形成。针对电子载流子浓度和电子迁移率之间的关系来检查所产生的膜。图2示出了该结果。对应于电子载流子浓度从1×1016/cm3增加到1×1020/cm3,电子迁移率也从3cm2/V.sec增加到大约11cm2/V.sec。在用多晶体烧结InGaO3(ZnO)靶获得的无定形氧化物膜中也观察到相同的趋势。
形成在代替玻璃衬底的200μm厚的聚对苯二甲酸乙二醇酯(PET)膜上的In-Zn-Ga-O类型无定形氧化物膜具有类似的特性。
(通过PLD过程来形成In-Zn-Ga-Mg-O类型的无定形氧化物膜)
通过PLD过程用InGaO3(Zn1-xMgxO)4(0<x≤1)靶在玻璃衬底上形成InGaO3(Zn1-xMgxO)4(0<x≤1)膜。所采用的装置是如图7所示的装置。
SiO2玻璃衬底(Corning公司:1737)用作衬底。作为预处理,用丙酮、乙醇和超纯水以超声方式分别清洗衬底5分钟以进行脱脂,并在空气中在100℃下干燥。该靶是InGaO3(Zn1-xMgxO)4(x=1-0)的烧结体(尺寸:直径20mm,厚5mm)。
该靶通过将源材料In2O3、Ga2O3和ZnO(每个是4N试剂)湿法混合(溶剂:乙醇),锻烧该混合物(1000℃,2小时),干法压碎该混合物,并烧结该混合物(1550℃,2小时)来制备。生长腔中的最终压力是2×10-6Pa。生长期间的氧分压控制在0.8Pa。衬底温度是室温(25℃)。靶和用于形成膜的衬底之间的距离是30mm。KrF受激准分子激光以1.5mJ/cm2/脉冲的功率照射,其脉冲宽度为20nsec,重复频率是10Hz,照射点的尺寸是1×1毫米见方。膜形成速度是7nm/min。在该膜形成气氛中的氧分压是0.8Pa。衬底温度是25℃。
通过小角度X射线散射方法(SAXS)(薄膜方法,入射角:0.5°)来检查所产生的薄膜:没有观察到清楚的衍射峰值。因此,所获得的In-Ga-Zn-Mg-O类型薄膜是无定形的。所产生的膜具有平坦的表面。
利用不同x值(Mg的含量不同)的靶,在氧分压为0.8Pa的膜形成气氛中形成In-Zn-Ga-Mg-O类型的无定形氧化物膜,以调查导电性、电子载流子浓度和电子迁移率对x值的依赖性。
图4A、4B和4C示出其结果。在x值高于0.4时,在氧分压为0.8Pa的膜形成气氛下通过PLD过程形成的无定形氧化物膜中,电子载流子浓度降低到小于1×1018/cm3。在x值高于0.4的无定形膜中,电子迁移率高于1cm2/V。
如图4A、4B和4C中所示,可以在通过脉冲激光沉积过程用80原子百分比的Zn被Mg代替的靶而且在0.8的氧分压下制备的膜(电阻:大约是1×10-2S.cm)中实现低于1×1016/cm3的电子载流子浓度。在这种膜中,与无Mg膜相比,减小了电子迁移率,但是减小的程度很小。该膜中的电子迁移率大约是5cm2/V.sec,比无定形硅的电子迁移率高大约一位。在相同的膜形成条件下,膜中的电导率和电子迁移率都随着Mg含量的增加而降低。因此,膜中的Mg含量优选大于20原子百分比且低于85原子百分比(0.2<x<0.85),更为优选的是0.5<x<0.85。
形成在代替玻璃衬底的200μm厚的聚对苯二甲酸乙二醇酯(PET)膜上的InGaO3(Zn1-xMgxO)4(0<x≤1)无定形膜具有类似的特性。
(通过PLD过程来形成In2O3无定形氧化物膜)
通过采用KrF受激准分子激光的PLD过程用In2O3多晶烧结体构成的靶在200μm厚的PET膜上形成In2O3膜。
采用图7所示的装置。用于形成膜的衬底是SiO2玻璃衬底(Corning公司:1737)。
作为在沉积之前的预处理,用丙酮、乙醇和超纯水以超声方式清洗衬底各5分钟以进行脱脂,并在空气中在100℃下干燥。
该靶是In2O3烧结体(尺寸:直径20mm,厚5mm),其通过锻烧源材料In2O3(4N试剂)(1000℃,2小时),干法压碎,和烧结(1550℃,2小时)来制备。
生长腔的最终真空度是2×10-6Pa,生长期间的氧分压是5Pa,衬底温度是25℃。
水蒸气分压是0.1Pa,通过施加200W由氧原子团产生组件来产生氧原子团。
靶和膜保持衬底之间的距离是40mm,KrF受激准分子激光的功率在0.5mJ/cm2/脉冲,脉冲宽度是20nsec,重复频率是10Hz,照射点的尺寸是1×1毫米见方。
膜形成速率是3nm/min。
通过小角度X射线散射方法(SAXS)(薄膜方法,入射角:0.5°)来检查所产生的薄膜:没有观察到清楚的衍射峰值,这表示所获得的In-O类型氧化物膜是无定形的。膜厚度是80nm。
在所获得的In-O类型无定形氧化物膜中,电子载流子浓度是5×1017/cm3,电子迁移率大约是7cm2/V.sec。
(通过PLD过程形成In-Sn-O类型无定形氧化物膜)
通过采用KrF受激准分子激光的PLD过程用(In0.9Sn0.1)O3.1多晶烧结体构成的靶在200μm厚的PET膜上形成In-Sn-O型氧化物膜。所采用的装置如图7所示。
用于形成膜的衬底是SiO2玻璃衬底(Corning公司:1737)。
作为在沉积之前的预处理,用丙酮、乙醇和超纯水以超声方式清洗衬底各5分钟以进行脱脂,并在空气中在100℃下干燥。
该靶是In2O3-SnO2烧结体(尺寸:直径20mm,厚5mm),其通过湿法混合源材料In2O3-SnO2(4N试剂)(溶剂:乙醇),锻烧该混合物(1000℃,2小时),干法压碎,和烧结(1550℃,2小时)该混合物来制备。
衬底保持在室温下。氧分压是5Pa。氮分压是0.1Pa。通过施加200W由氧原子团产生组件来产生氧原子团。
靶和膜保持衬底之间的距离是30mm,KrF受激准分子激光的功率在1.5mJ/cm2/脉冲,脉冲宽度是20nsec,重复频率是10Hz,照射点的尺寸是1×1毫米见方。
膜形成速率是6nm/min。
通过小角度X射线散射方法(SAXS)(薄膜方法,入射角:0.5°)来检查所产生的薄膜:没有观察到清楚的衍射峰值,这表示所获得的In-Sn-O类型氧化物膜是无定形的。
在所获得的In-Sn-O类型无定形氧化物膜中,电子载流子浓度是8×1017/cm3,电子迁移率大约是5cm2/V.sec。膜厚度是100nm。
(通过PLD过程形成In-Ga-O型无定形氧化物膜)
用于形成膜的衬底是SiO2玻璃衬底(Corning公司:1737)。
作为在沉积之前的预处理,用丙酮、乙醇和超纯水以超声方式清洗衬底各5分钟以进行脱脂,并在空气中在100℃下干燥。
该靶是(In2O3)1-x-(Ga2O3)x(x=0-1)的烧结体(尺寸:直径20mm,厚5mm)。例如,在x=0.1时,该靶是(In0.9Ga0.1)2O3的多晶烧结体。
该靶通过湿法混合源材料In2O3-Ga2O2(4N试剂)(溶剂:乙醇),锻烧该混合物(1000℃,2小时),干法压碎,和烧结(1550℃,2小时)该混合物来制备。
生长腔的最终压力是2×10-6Pa。生长期间的氧分压是1Pa。
衬底保持在室温下。靶和膜保持衬底之间的距离是30mm。KrF受激准分子激光的功率在1.5mJ/cm2/脉冲。脉冲宽度是20nsec。重复频率是10Hz。照射点的尺寸是1×1毫米见方。膜形成速率是6nm/min。
衬底温度是25℃。氧压力是1Pa。通过小角度X射线散射方法(SAXS)(薄膜方法,入射角:0.5°)来检查所产生的薄膜:没有观察到清楚的衍射峰值,这表示所获得的In-Ga-O类型氧化物膜是无定形的。膜厚度是120nm。
在所获得的In-Ga-O类型无定形氧化物膜中,电子载流子浓度是8×1016/cm3,电子迁移率大约是1cm2/V.sec。
(制备具有In-Zn-Ga-O型无定形氧化物膜(玻璃衬底)的TFT元件)
制备如图5所示的顶部栅极类型的TFT元件。
首先,在玻璃衬底1上,通过上述PLS装置用具有InGaO3(ZnO)4成分的多晶烧结体构成的靶在5Pa的氧分压下制备In-Ga-Zn-O型无定形氧化物膜。所形成的In-Ga-Zn-O膜为120nm厚,并用作沟道层2。
此外,在其上通过PLD方法在该腔中低于1Pa的氧分压下分别以30nm的厚度层叠具有更高电导率的另一个In-Ga-Zn-O型无定形膜和金层。通过光刻和剥离方法从其中形成漏极端子5和源极端子6。
最后,通过电子束汽相沉积形成Y2O3膜作为栅极绝缘体3(厚度:90nm,相对介电常数:大约15,漏电流密度:施加0.5MV/cm时是1×10-3A/cm3)。此外,在该膜上形成金膜,并通过光刻和剥离从其中形成栅极端子4。沟道长度是50μm,沟道宽度是200μm。
TFT元件特性的评估
图6示出TFT元件在室温下的电流-电压特性。漏电流IDS随着漏电压VDS的增加而增大,这表明该沟道是n型导电型。
这与无定形In-Ga-Zn-O型半导体是n型的事实相符。IDS在VDS=6V时饱和(夹断),这是半导体晶体管的典型性能。根据对增益特性的检查,发现在施加VDS=4V的情况下栅电压VGS的阈值大约是-0.5V。在VG=10V时导致IDS=1.0×10-5A的电流。这对应于通过栅极偏压在作为绝缘体的In-Ga-Zn-O型无定形半导体薄膜中的载流子感生。
该晶体管的开-关比高于1×103。根据输出特性,计算出在饱和区域中场效应迁移率大约是7cm2(Vs)-1。根据相同的测量,可见光的照射不会改变所制作的元件的晶体管特性。
电子载流子浓度低于1×1018/cm3的无定形氧化物可以用作TFT的沟道层。优选的是,电子载流子浓度小于1×1017/cm3。更为优选的是小于1×1016/cm3。
(制备具有In-Zn-Ga-O型无定形氧化物膜(无定形衬底)的TFT元件)
制备如图5所示的顶部栅极类型的TFT元件。
首先,在聚对苯二甲酸乙二醇酯(PET)膜1上,通过上述PLS装置用具有InGaO3(ZnO)成分的多晶烧结体构成的靶在氧分压为5Pa的气氛中制备In-Ga-Zn-O型无定形氧化物膜。所形成的膜为120nm厚,并用作沟道层2。
此外,在其上通过PLD方法在该腔中低于1Pa的氧分压下分别以30nm的厚度层叠具有更高电导率的另一个In-Ga-Zn-O型无定形膜和金层。通过光刻和剥离方法从其中形成漏极端子5和源极端子6。
最后,通过电子束汽相沉积方法形成栅极绝缘体3。此外在该膜上形成金膜,并通过光刻和剥离从其中形成栅极端子4。沟道长度是50μm,沟道宽度是200μm。分别利用以下三种栅极绝缘体的一种来制备上述结构的三种TFT:Y2O3(140nm厚),Al2O3(130μm厚),HfO2(140μm厚)。
TFT元件特性的评估
形成在PET膜上的TFT元件在室温下具有类似于图6所示的电流-电压特性。漏电流IDS随着漏电压VDS的增加而增大,这表明该沟道是n型导电型。这与无定形In-Ga-Zn-O型半导体是n型的事实相符。IDS在VDS=6V时饱和(夹断),这是半导体晶体管的典型性能。在VG=0V时导致IDS=1.0×10-8A的电流,在VG=10V时导致IDS=2.0×10- 5A的电流。这对应于通过栅极偏压在作为绝缘体的In-Ga-Zn-O型无定形半导体氧化物膜中的载流子感生。
该晶体管的开-关比高于1×103。根据输出特性,计算出在饱和区域中场效应迁移率大约是7cm2(Vs)-1。
形成在PET膜上的元件以30nm的曲率半径弯曲,并在该状态下测量晶体管特性。但是没有观察到晶体管特性的变化。可见光的照射不会改变该晶体管特性。
采用Al2O3膜作为栅极绝缘体的TFT也具有类似于图6所示的晶体管特性。在VG=0V时导致IDS=1.0×10-8A的电流,在VG=10V时导致IDS=5.0×10-6A的电流。该晶体管的开-关比高于1×102。根据输出特性,计算出在饱和区域内的场效应迁移率大约是2cm2(Vs)-1。
采用HfO2膜作为栅极绝缘体的TFT也具有类似于图6所示的晶体管特性。在VG=0V时导致IDS=1×10-8A的电流,在VG=10V时导致IDS=1.0×10-6A的电流。该晶体管的开-关比高于1×102。根据输出特性,计算出在饱和区域内的场效应迁移率大约是10cm2(Vs)-1。
(通过PLD过程制备采用In2O3无定形氧化物膜的TFT元件)
制备如图5所示的顶部栅极类型的TFT元件。
首先,在聚对苯二甲酸乙二醇酯(PET)膜1上,通过PLD方法形成厚度为80nm的In2O3型无定形氧化物膜作为沟道层2。
此外,在其上通过PLD方法在该腔中的氧分压低于1Pa、向氧原子团产生组件施加零伏的电压时分别以30nm的厚度层叠具有更高电导率的另一个In2O3无定形膜和金层。通过光刻和剥离方法从其中形成漏极端子5和源极端子6。
最后,通过电子束汽相沉积方法形成Y2O3膜作为栅极绝缘体3。此外在该膜上形成金膜,并通过光刻和剥离从其中形成栅极端子4。
TFT元件特性的评估
在室温下检查形成在PET膜上的TFT元件的电流-电压特性。漏电流IDS随着漏电压VDS的增加而增大,这表明该沟道是n型导体。这与无定形In-O型无定形氧化物膜是n型导体的事实相符。IDS在大约VDS=6V时饱和(夹断),这是晶体管的典型性能。在VG=0V时导致IDS=2×10-8A的电流,在VG=10V时导致IDS=2.0×10-6A的电流。这对应于通过栅极偏压在作为绝缘体的In-O型无定形氧化物膜中的电子载流子感生。
该晶体管的开-关比高于1×102。根据输出特性,计算出饱和区域中的场效应迁移率大约是1×10cm2(Vs)-1。形成在玻璃衬底上的TFT元件具有相似的特性。
形成在PET膜上的元件以30nm的曲率半径弯曲,并在该状态下测量晶体管特性。但是没有观察到晶体管特性的变化。
(通过PLD过程制备采用In-Sn-O型无定形氧化物膜的TFT元件)
制备如图5所示的顶部栅极类型的TFT元件。
首先,在聚对苯二甲酸乙二醇酯(PET)膜1上,通过PLD方法形成厚度为100nm的In-Sn-O型无定形氧化物膜作为沟道层2。
此外,在其上通过PLD方法在该腔中的氧分压低于1Pa、向氧原子团产生组件施加零伏的电压时分别以30nm的厚度层叠具有更高电导率的另一个In-Sn-O无定形膜和金层。通过光刻和剥离方法从其中形成漏极端子5和源极端子6。
最后,通过电子束汽相沉积方法形成Y2O3膜作为栅极绝缘体3。此外在该膜上形成金膜,并通过光刻和剥离从其中形成栅极端子4。
TFT元件特性的评估
在室温下检查形成在PET膜上的TFT元件的电流-电压特性。漏电流IDS随着漏电压VDS的增加而增大,这表示该沟道是n型导体。这与无定形In-Sn-O型无定形氧化物膜是n型导体的事实相符。IDS在大约VDS=6V时饱和(夹断),这是晶体管的典型性能。在VG=0V时导致IDS=5×10-8A的电流,在VG=10V时导致IDS=5.0×10-5A的电流。这对应于通过栅极偏压在作为绝缘体的In-Sn-O型无定形氧化物膜中的电子载流子感生。
该晶体管的开-关比高于1×103。根据输出特性,计算出饱和范围中的场效应迁移率大约是5cm2(Vs)-1。形成在玻璃衬底上的TFT元件具有相似的特性。
形成在PET膜上的元件以30nm的曲率半径弯曲,并在该状态下测量晶体管特性。没有因此导致晶体管特性的变化。
(通过PLD过程制备采用In-Ga-O型无定形氧化物膜的TFT元件)
制备如图5所示的顶部栅极类型的TFT元件。
首先,在聚对苯二甲酸乙二醇酯(PET)膜1上,通过示例6所示的PLD方法形成厚度为120nm的In-Ga-O型无定形氧化物膜作为沟道层2。
此外,在其上通过PLD方法在该腔中的氧分压低于1Pa、向氧原子团产生组件施加零伏的电压时分别以30nm的厚度层叠具有更高电导率的另一个In-Ga-O无定形膜和金层。通过光刻和剥离方法从其中形成漏极端子5和源极端子6。
最后,通过电子束汽相沉积方法形成Y2O3膜作为栅极绝缘体3。此外在该膜上形成金膜,并通过光刻和剥离从其中形成栅极端子4。
TFT元件特性的评估
在室温下检查形成在PET膜上的TFT元件的电流-电压特性。漏电流IDS随着漏电压VDS的增加而增大,这表明该沟道是n型导体。这与无定形In-Ga-O型无定形氧化物膜是n型导体的事实相符。IDS在大约VDS=6V时饱和(夹断),这是晶体管的典型性能。在VG=0V时导致IDS=1×10-8A的电流,在VG=10V时导致IDS=1.0×10-6A的电流。这对应于通过栅极偏压在作为绝缘体的In-Ga-O型无定形氧化物膜中的电子载流子感生。
该晶体管的开-关比大约是1×102。根据输出特性,计算出饱和范围中的场效应迁移率大约是0.8cm2(Vs)-1。形成在玻璃衬底上的TFT元件具有相似的特性。
形成在PET膜上的元件以30nm的曲率半径弯曲,并在该状态下测量晶体管特性。没有因此导致晶体管特性的变化。
电子载流子浓度低于1×1018/cm3的无定形氧化物可以用作TFT的沟道层。优选的是,电子载流子浓度不高于1×1017/cm3。,更为优选的是不高于1×1016/cm3。
下面说明本发明的示例。
<示例1:制备包含微晶体的无定形In-Ga-Zn-O薄膜>
利用图7所示的装置制备膜。用具有InGaO3(ZnO)4成分的多晶烧结体作为靶来执行使用KrF受激准分子激光的脉冲激光沉积方法。在玻璃衬底(Corning公司制造的1737)上,沉积包含微晶体的基于In-Ga-Zn-O的无定形氧化物半导体薄膜。在膜形成步骤中,用卤素灯(20mW/cm2)照射衬底表面。通过对膜片段进行TEM(透射电子显微镜)观察来确认是否存在微晶体。
<制备MISFET(金属绝缘体半导体场效应晶体管)器件>
制造如图5所示的顶部栅极类型的MISEFT。首先,根据上述用于制备包含微晶体的无定形In-Ga-Zn-O薄膜的方法在玻璃衬底(1)上形成包含微晶体、厚度为30nm并用作沟道层(2)的半绝缘无定形InGaO3(ZnO)4膜。此外,在所产生的结构上,在将腔中的氧分压设置为低于1Pa的同时通过脉冲激光沉积方法分别以30nm的厚度层叠具有高电导率的InGaO3(ZnO)x膜和金膜。然后,通过光刻和剥离方法形成漏极端子(5)和源极端子(6)。最后,通过电子束沉积方法形成Y2O3膜作为栅极绝缘体3(所获得的膜具有90至110nm的厚度,相对介电常数大约15,漏电流密度在施加0.5MV/cm的电流时是1×10-3A/cm3)。此后,在所形成的结构上形成金膜,然后,通过光刻和剥离方法形成栅极端子(4)。通过这种方式形成场效应晶体管。
该晶体管的开/关比超过1×104。在基于功率特性计算场效应迁移率时,得出饱和区域中的电子场效应迁移率大约是7.5cm2(Vs)-1。用可见光照射由此制造的器件并进行相同的测量。结果是没有观察到晶体管特性的变化。
此外,在上述用于制造包含微晶体的In-Ga-Zn-O薄膜的示例中,当用功率密度为0.3mW/cm2至100mW/cm2的光照射衬底时获得有益的结果。因此,该晶体管的开/关比可以增大,并可以获得大的电子场效应迁移率。为此,光照射是优选的。尽管根据无定形氧化物膜中微晶体的量而不同,通常如果通过X射线衍射检测到峰值则确定存在微晶体。
<示例2:制备具有在膜厚度方向上的成分分布的无定形In-Ga-Zn-O薄膜>
利用具有InGaO3(ZnO)4成分的多晶烧结体作为靶,通过使用KrF受激准分子激光的脉冲激光沉积方法,在玻璃衬底(Corning公司制造的1737)上沉积具有在膜厚度方向上的成分分布的基于In-Ga-Zn-O的无定形氧化物半导体薄膜。该膜在内部氧分压在预定范围内的腔中沉积,同时将靶和衬底之间的距离增加到5mm。随着距离的增加,并入到所形成的膜中的氧的量也增加。注意,衬底的温度设置在25℃。
在示例2(用于形成具有在膜厚度方向上的成分分布的薄膜)中,可以通过改变膜厚度方向上的氧分压来改变成分,可替换地,可以通过改变脉冲激光的振荡功率或振荡频率来改变成分。通过这种方式,可以减小泄漏电流或者增加晶体管的开/关比,并且增大电子场效应迁移率。
<示例3:制备具有在膜厚度方向上的成分分布的无定形In-Ga-Zn-O薄膜>
该膜是通过使用氩气的溅射方法来形成的。作为靶,制备(1)具有InGaO3(ZnO)4成分的多晶烧结体以及(2)氧化锌烧结体。然后,在玻璃衬底(Corning公司制造的1737)上沉积具有在膜厚度方向上的成分分布的无定形In-Ga-Zn-O薄膜。通过溅射方法,在具有预定氧分压的气氛中,首先通过利用靶(1),然后同时利用靶(1)和靶(2),来形成该膜。通过这种方式,可以制备具有在膜厚度方向上的成分分布的无定形In-Ga-Zn-O薄膜。注意,衬底的温度设置在25℃。
具有在膜厚度方向上的成分分布的无定形In-Ga-Zn-O薄膜可以通过以下方式来制备。该成分通过同时或分开溅射In2O3靶或改变膜厚度方向上的氧分压、或可替换地通过在溅射步骤中对每种靶改变膜厚度方向上的电力供应来分布在膜厚度方向上。具体地说,在靠近栅极绝缘体的无定形薄膜中,电子场效应迁移率预计随着In2O3或ZnO量的增加而增大。
<示例4:制备无定形In-Ga-Zn-O(N)薄膜>
下面说明制备包含氮(N)作为添加剂的无定形氧化物的方法。
利用InGaO3(ZnO)4多晶烧结体作为靶,通过使用KrF受激准分子激光的脉冲激光沉积方法,在与上面相同类型的玻璃衬底上沉积包含氮(N)作为杂质的基于In-Ga-Zn-O的无定形氧化物半导体薄膜(简称为“In-Ga-Zn-O(N)”)。注意,腔中的氧分压设置为例如4Pa,氮分压设置为1Pa,衬底温度设置为25℃。薄膜中氧和氮的成分比例优选大约是50:1,这是通过次级离子质谱法(SIMS)分析的。
<示例5:制备无定形In-Ga-Zn-O(Ti)薄膜>
利用具有InGaO3(ZnO)4成分的多晶烧结体作为靶,通过使用KrF受激准分子激光的脉冲激光沉积方法,在玻璃衬底(Corning公司制造的1737)上沉积基于In-Ga-Zn-O的无定形氧化物半导体薄膜。将所产生的基于In-Ga-Zn-O的薄膜浸在保持为80℃的三氯化钛水溶液中。此后将该膜取出并在空气中在300℃下退火。通过这种方式,可以将Ti作为杂质引入到该无定形氧化物中。通过用SIMS分析从该薄膜表面到底部的Ti浓度,发现最外表面的Ti浓度大约是0.5%,并朝着底部逐渐减小。
按照本发明的无定形氧化物可用于晶体管的沟道层。这种晶体管可以用作LCD和有机EL显示器的开关装置。可替换地,该无定形氧化物可以涂敷在诸如塑料膜的柔性材料上,以形成半导体薄膜。这种半导体薄膜可以广泛地用作柔性显示器、IC卡和ID标签的板(panel)。
本申请要求2004年11月10日提交的日本专利申请No.2004-326687的优先权,通过引用将其合并于此。
Claims (3)
1.一种无定形氧化物,所述无定形氧化物包含从由Li、Na、Mn、Ni、Pd、Cu、Cd、C、N、P、Ti、Ru和F所构成的组中选择的至少一种元素,并且所述无定形氧化物的电子载流子浓度为1012/cm3或更高且低于1018/cm3,
其中,所述无定形氧化物是从由以下所构成的组中选择的任一种:包含从In、Zn和Sn中选择的至少一种元素的氧化物;含有In、Zn和Sn的氧化物;含有In和Zn的氧化物;含有In和Sn的氧化物;含有In的氧化物;以及包含In、Ga和Zn的氧化物。
2.根据权利要求1所述的无定形氧化物,其中,所述无定形氧化物的电子迁移率随着电子载流子浓度的增加而增大。
3.一种场效应晶体管,包括:
由根据权利要求1或2所述的无定形氧化物形成的有源层;以及
形成为经由栅极绝缘体面向所述有源层的栅电极。
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