CN109314146A - 半导体装置、pH传感器、生物传感器以及半导体装置的制造方法 - Google Patents

半导体装置、pH传感器、生物传感器以及半导体装置的制造方法 Download PDF

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CN109314146A
CN109314146A CN201780036095.4A CN201780036095A CN109314146A CN 109314146 A CN109314146 A CN 109314146A CN 201780036095 A CN201780036095 A CN 201780036095A CN 109314146 A CN109314146 A CN 109314146A
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中积诚
西康孝
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Abstract

本发明提供一种半导体装置，其特征在于，该半导体装置具有第1电极、第2电极、以及与第1电极和第2电极相接的半导体层，半导体层为包含锌(Zn)和镓(Ga)的尖晶石型的氧化物。

Description

半导体装置、pH传感器、生物传感器以及半导体装置的制造 方法
技术领域
本发明涉及半导体装置、pH传感器、生物传感器以及半导体装置的制造方法。本发明要求2016年8月3日提交的日本专利的申请号2016-152721的优先权，对于认可基于文献参考的方式进行内容插入的指定国，通过参考的方式将该申请记载的内容插入到本申请中。
背景技术
作为在薄膜晶体管(TFT)等半导体装置中使用的半导体材料，例如使用含有In、Ga和Zn的氧化物(IGZO；In-Ga-Zn-O)等无定形氧化物(参见专利文献1)。这样的现有半导体材料的化学耐久性不足，因而在制造半导体装置时，设置一种保护半导体材料免受化学损伤的结构来进行蚀刻工序等处理。
现有技术文献
专利文献
专利文献1：日本特开2013-051421号公报
发明内容
本发明的第一方式涉及一种半导体装置，其具有第1电极、第2电极、以及与第1电极和第2电极相接的半导体层，半导体层为包含锌(Zn)和镓(Ga)的尖晶石型的氧化物。
本发明的第二方式涉及一种pH传感器，其具备第一方式的半导体装置。
本发明的第三方式涉及一种生物传感器，其具备第一方式的半导体装置。
本发明的第四方式涉及一种半导体装置的制造方法，其包括下述工序：形成半导体层的工序；在半导体层上形成导电性层的工序；以及与规定的图案对应地对导电性层进行蚀刻，形成第1电极和第2电极的工序。
附图说明
图1是用于说明本实施方式的制造方法的合适示例的示意图。
图2是实施例1的ZnGa2O4烧结体的XRD测定的衍射图谱。
图3是表示实施例1的半导体特性的测定结果的曲线图。
图4是实施例1的pH传感器的示意性截面图。
图5是表示实施例1的pH传感器的测定结果的曲线图。
具体实施方式
下面对本发明的具体实施方式(以下简称为“本实施方式”)进行详细说明。以下的本实施方式是用于说明本发明的例示，并非旨在将本发明限定于以下的内容。需要说明的是，在附图中，只要不特别声明，则上下左右等的位置关系基于附图所示的位置关系。另外，附图的尺寸比例并不限于图示的比例。
本实施方式的半导体装置具有第1电极、第2电极、以及与第1电极和第2电极相接的半导体层，半导体层为包含锌(Zn)和镓(Ga)的尖晶石型的氧化物。本实施方式的半导体装置通过使用晶体结构为尖晶石型的氧化物，具有不需要额外的制造工序或额外的结构来防止因酸所致的化学损伤的优点。因此，作为本实施方式的半导体装置的结构，可以为不具有用于保护半导体层的保护层的结构。
以往，作为氧化物半导体的材料，使用ZnO、In2O3、Ga2O3、InGaZnO等，这些材料尽管显示出了高半导体特性，但对酸、碱的耐性不足。例如，在pH4以下的强酸或pH10以上的强碱的条件下，氧化物半导体被侵蚀。若为上述氧化物，则不论为无定形氧化物还是为结晶氧化物，这样的对酸、碱的耐性弱的问题均存在，人们希望上述氧化物对宽pH区域稳定。关于这一点，本实施方式的半导体装置对强酸、强碱具有高稳定性，在宽pH区域中具有高稳定性。
半导体层优选包含尖晶石型的ZnGa2O4。由此能够进一步提高对酸、碱的耐性。例如，在尖晶石型的ZnGa2O4为半导体层的情况下，可以采用氟系干蚀刻或湿蚀刻之类的加工方法。
在半导体层中，从进一步提高其半导体特性的方面考虑，优选掺杂有载体元素。作为载体元素没有特别限定，可以采用掺杂工艺中的公知的载体元素。作为具体例，可以举出1价金属、2价金属、3价金属等。这些之中，在本实施方式中，更优选在半导体层中掺杂有氢。
作为本实施方式的半导体装置，优选进一步具有与半导体层相接的绝缘层、以及隔着绝缘层与半导体层相对设置的第3电极，分别以第1电极、第2电极、第3电极作为源极、漏极、栅极来构成晶体管。
将第1电极用作源极的情况下，作为源极没有特别限定，可以采用公知的材料。作为具体例，可以举出Mo、W、Al、Cu、Cu-Al合金、Al-Si合金、Mo-W合金、Ni-P合金等的单层、这些材料的层积体等。
将第2电极用作漏极的情况下，作为漏极没有特别限定，可以采用公知的材料。作为具体例，可以举出Mo、W、Al、Cu、Cu-Al合金、Al-Si合金、Mo-W合金、Ni-P合金等的单层、这些材料的层积体等。
将第3电极用作栅极的情况下，作为栅极没有特别限定，可以采用公知的材料。作为具体例，可以举出Mo、W、Al、Cu、Cu-Al合金、Al-Si合金、Mo-W合金、Ni-P合金等的单层、这些材料的层积体等。
本实施方式的半导体装置可以适用于pH传感器、生物传感器等。如上所述，本实施方式的半导体装置对强酸、强碱具有高稳定性，由于在pH1～14这样的宽pH区域具有高稳定性，因而能够制成即使为强酸/强碱基团也能够精确地测定的pH传感器。
生物传感器(有时也称为生物传感器芯片)是利用了生物体来源的分子识别机制的化学传感器，被用作生物体内的pH变化或氧化还原反应等的化学识别元件。关于这一点，由于本实施方式的半导体装置在宽pH区域具有高稳定性，因而能够制成即使测定对象为强酸性/强碱性也能够精确地感知的生物传感器。例如，可以制成这样的生物传感器：该生物传感器测量使特定的抗体修饰于半导体表面，其上吸附特异性的DNA等检测对象时的质子量。
在现有的方案中，设置用于保护半导体层的保护层来进行测定，这种情况下，作为保护层的膜厚，要求通常为100nm左右以上，另一方面，由于抗体的常见尺寸为数nm左右，因而若设置保护层，则无法获得反映抗体尺寸的电气信息。但是，在本实施方式的半导体装置中，由于不必必须设置用于保护半导体层的保护层，也可以省略该保护层，因而能够高速且高灵敏度地进行检测。
本实施方式的半导体装置中，电子传导率等半导体特性优异，这自不消说，而且还具有以往未能达到的程度的耐酸性、耐碱性，因而能够迅速且精确地对强酸成分、光产酸剂进行检测。并且，在对半导体装置进行器件化时，由于蚀刻耐性高，因而可期待配线图案的微细化、精细化，并且还有助于作为器件的轻量化等。进而还期待扩大金属电极的材料的选择面。因此，本实施方式的半导体装置能够用于以上述传感器类以及显示屏类或各种电子设备等的广泛用途。
<制造方法>
对本实施方式的半导体装置的制造方法的合适示例进行说明。本实施方式的制造方法可以举出包括下述工序的方法：形成半导体层的工序；在半导体层上形成导电性的层的工序；以及与规定的图案对应地对导电性的层进行蚀刻，形成第1电极和第2电极的工序。本实施方式的半导体装置中，半导体层对酸强耐受性，可耐受酸蚀刻液，因而在例如反交叠型TFT的制造等中也能够应用。图1表示用于说明本实施方式的制造方法的实例的示意图。
(S1工序)
首先在基板10的表面上形成栅极20(S1工序)。作为基板没有特别限定，可以采用公知的材料。作为具体例，可以举出例如，玻璃、硅、金属、合金、这些材料的箔片等。栅极20与上述第3电极对应。对于在基板10的表面上形成栅极20的方法没有特别限定，可以根据基板10、栅极20的材料等酌情采用合适的方法。
(S2工序)
接着在形成有栅极20侧的基板10的表面上形成绝缘层30，用绝缘层30被覆栅极20(S2工序)。作为绝缘层30没有特别限定，可以采用公知的材料。作为具体例，可以举出例如SiO2、Si3N4、SiON、Al2O3、Ta2O5、HfO2等。
(S3工序)
之后，在绝缘层30的表面上形成作为导电性层的半导体层40(S3工序)。半导体层40可以使用溅射装置形成，优选使用2个以上的阴极形成规定的半导体层40。所形成的半导体层40为包含锌(Zn)和镓(Ga)的尖晶石型的氧化物。通过使用该氧化物，半导体层40对强酸、强碱表现出强耐性。因此，作为制造工艺，可以省略对半导体层进行保护的工序等。具体地说，可以使用镓锌氧化物和锌氧化物作为靶材进行共溅射(co-sputter)，形成由尖晶石型的镓锌氧化物构成的半导体层40。
另外还可以使用下述方法：使用镓氧化物和锌氧化物作为靶材进行共溅射的方法；使用镓和锌作为靶材进行共溅射，在成膜中利用反应性气体进行氧化的方法。此外，并不限于共溅射，还可以使用下述方法：使用锌氧化物和镓氧化物的混合物作为靶材进行溅射的方法；使用锌和镓的混合物作为靶材进行溅射，在成膜中利用反应性气体进行氧化的方法。
例如，在n型半导体材料的情况下，可以利用元素掺杂、膜中的氧缺陷来制作。作为得到n型半导体的元素没有特别限定，可以举出例如Al、In、Sn、Sb、Ta等。作为产生氧缺陷的方法没有特别限定，可以采用公知的方法。具体地说，优选在厌氧气氛下或氢等还原气体气氛下实施加热处理。例如可以举出下述方法：以在溅射气体中混合有氢的状态进行成膜，利用填隙氢进行n型的载体掺杂。这些处理可以在成膜后腔室内进行，也可以作为后续工序进行烧制。
对半导体层40的成膜温度没有特别限定，从提高半导体层40的结晶性的方面出发，优选在190℃以上进行。需要说明的是，若过度加热，则会促进飞到基板10的表面的Zn粒子的蒸发，可能发生与Ga和Zn的化学计量比的偏差(组成偏差)，但通过对包含Zn或ZnO的烧结体靶材进行同时放电，能够增加膜中的Zn浓度，能够有效地防止组成偏差。
(S4工序)
进行在半导体层40上形成导电层的工序、以及与规定的图案对应地对导电层进行蚀刻来形成第1电极52和第2电极54的工序(S4)。第1电极52为源极，第2电极54为漏极。作为第1和第2电极的形成方法，可以使用通常的光刻工艺。这种情况下，在半导体层40上形成导电层，之后在导电层上形成抗蚀剂层，利用规定的图案光对抗蚀剂层进行曝光、显影。接下来对于从抗蚀剂层的开口部露出的导电层进行蚀刻，从而可以形成第1电极、第2电极。需要说明的是，作为抗蚀剂层可以使用正型的材料、也可以使用负型的材料。
在现有技术中，作为半导体材料，使用IGZO、ZnO、Ga2O3等氧化物，这些物质为两性物质，可溶解在强酸性溶液、强碱性溶液中。即，由于现有的半导体层对蚀刻中使用的溶液的耐性弱，因而在进行形成源极·漏极的蚀刻工序前，需要进行将半导体层利用作为保护层的SiO2、Al2O3等绝缘层进行保护的工序。关于这一点，根据本实施方式，由于半导体层40具有高耐酸性和耐碱性，因而即使不设置这样的保护层也能够进行蚀刻。因此能够简化半导体装置的制造工序而不进行设置用于保护半导体层的保护层的工序。
在利用酸性溶液进行蚀刻的情况下，上述本实施方式的优点更为显著。由于通常的光刻工艺中使用的抗蚀剂材料为碱溶性的，因而通过使用酸性溶液，抗蚀剂层不会溶解，而能够合适地进行导电层的蚀刻。
(S5工序)
之后可以在由S4工序形成的第1电极52、第2电极54上形成钝化层60，得到半导体装置A。可以通过在基板10的最外表面形成钝化层60而使其钝化(不導態化)。由此，能够保护半导体装置A的内部免受外界的水分或金属离子等的影响。作为钝化层60的材料没有特别限定，可以采用公知的材料。另外，钝化层60的形成方法没有特别限定，可以采用公知的方法。需要说明的是，在本实施方式中，对具有钝化层60的半导体装置的制造方法进行了说明，但钝化层60并非必须的构成，根据半导体装置的用途，也可以为不具有钝化层60的构成。
实施例
通过以下的实施例和比较例更详细地说明本发明，但本发明并不受以下实施例的任何限定。
<实施例1>
准备ZnGa2O4的烧结体靶材和ZnO的烧结体靶材。进行同时放电，使薄膜中的Ga与Zn的摩尔比为Ga:Zn＝2:1，得到ZnGa2O4薄膜。需要说明的是，作为溅射气体使用含3％氢的Ar，在背压为1×10-4Pa以下、成膜压力为0.22Pa、基板温度为190℃的条件下进行成膜。
对于所得到的ZnGa2O4薄膜，利用XRD(X射线衍射法)进行θ-2θ测定。图2中示出了ZnGa2O4薄膜的XRD测定的衍射图谱。其结果能够确认到(222)面取向的尖晶石型的ZnGa2O4的图案，表示所得到的ZnGa2O4薄膜为尖晶石型的ZnGa2O4薄膜。
接下来，制作使用上述尖晶石型的ZnGa2O4薄膜作为半导体层的薄膜晶体管。作为基板使用在n型掺杂(磷掺杂)的硅晶片上形成有150nm的热氧化膜的基板，在上述的成膜条件下在该热氧化膜上进行ZnGa2O4的成膜。
之后，利用溅射法进行作为源极·漏极的Cu电极的成膜，将基板的硅晶片作为栅极、将热氧化膜作为栅极绝缘膜，从而得到半导体装置。对于所得到的半导体装置的半导体特性，使用半导体参数分析仪(4200-SCS、KEITHLEY公司制造)进行晶体管特性的测定。将其结果示于图3。图3中，横轴表示施加至栅极的电压，纵轴表示在漏极检测出的电流值。如图3所示，确认到本实施例的半导体装置显示出了n型的半导体特性。另外，本实施例的半导体装置显示出了迁移率：1.1cm2/V·s、载体密度：1×1017cm-3、开关比(On/Off比)：1×105的特性。
(pH传感器)
(实验a)
使用上述得到的半导体装置制作pH传感器(Ion Sensitive-FET；离子敏感场效应晶体管)。图4中示出了pH传感器的示意性构成图。pH传感器B具有：在基础层12上形成了热氧化膜14的硅制基板10、设置在基板10上的具有半导体层(ZnGa2O4:H2)40和Ag电极70、71的半导体装置、设置在半导体装置上的硅橡胶制样品池(プール)80、以及设置在样品池80内的参比电极90。需要说明的是，作为参比电极90使用了Ag/AgCl电极(银-氯化银电极)。并且，将作为测定对象的溶液S(酸性溶液的情况下为盐酸、碱性溶液的情况下为氢氧化钠溶液)加入到样品池80中，测定参比电极90与Ag电极71的电位差。需要说明的是，作为溶液S，准备制备成pH1、pH7、pH14的溶液，在将各溶液加入到样品池80中1秒后开始测定。参比电极90和Ag电极71的电位差依赖于溶液中的质子浓度。通过测定该电位差而求出溶液中的质子浓度，以pH值形式进行计算是pH传感器的测定原理。
图5中示出了表示实施例1的pH传感器的测定结果的曲线图。横轴表示时间、纵轴表示参比电极90与Ag电极71之间的电位差。如图5所示可确认到，即使为pH1、pH14的溶液，测定值(pH值)也不会随着时间发生显著变化，能够长时间稳定地测定。另外，尽管在将溶液S加入到样品池80中1秒后开始测定，但在1秒后就检测出电位差，也确认得到了高速的响应。
(实验b)
在实验a的pH1的溶液S的测定后，将半导体层40和Ag电极70、71用水清洗，使用pH1的溶液S再次进行同样的测定实验。其结果得到了同样的值，确认到具有再现性。另外，在pH14的溶液S的测定后，将半导体层40和Ag电极70、71用水清洗，使用pH14的溶液S再次进行同样的测定实验。其结果得到了同样的值，确认到具有再现性。由实验b的结果确认到，本实施例的pH传感器的测定值具有再现性，同时确认到，即使在pH1、pH14的强酸性、强碱性的条件下，pH传感器的半导体层40也不会被侵蚀，而能够稳定地反复使用。
由以上确认到，本pH传感器尽管不具有用于保护半导体层的绝缘膜，但能够以高灵敏度高速且稳定地进行pH测定。
<比较例1～5>
分别准备包含锌(Zn)和镓(Ga)的尖晶石型的氧化物(实施例1)和作为除此以外的氧化物的表1所示的氧化物(比较例1～5)，进行pH1～6的溶液中的稳定性的评价。具体地说，按以下要点进行了实验。
分别准备pH1、2、3、4、5、6的盐酸，将它们在各氧化物半导体的表面滴加1mL，在室温、1气压的条件下静置10分钟。之后基于下述基准目视评价表面的稳定性。
○：表面完全无变化。
△：表面被溶液部分侵蚀。
×：表面被溶液侵蚀。
[表1]
由表1可知，实施例1在pH1～6的全部区域未发生表面侵蚀，确认到对强酸具有高耐性。
符号的说明
10…基板、12…基础层、14…热氧化膜、20…栅极、30…绝缘层、40…半导体层、52…第1电极、54…第2电极、60…钝化层、70、71…Ag电极、80…样品池、90…参比电极、A…半导体装置、B…pH传感器、S…溶液。

Claims (10)

1.一种半导体装置，其特征在于，
该半导体装置具有：
第1电极，
第2电极，以及
与所述第1电极和所述第2电极相接的半导体层，
所述半导体层为包含锌(Zn)和镓(Ga)的尖晶石型的氧化物。
2.如权利要求1所述的半导体装置，其特征在于，所述半导体层为尖晶石型的ZnGa2O4。
3.如权利要求1或2所述的半导体装置，其特征在于，所述半导体层掺杂有载体元素。
4.如权利要求1或2所述的半导体装置，其特征在于，所述半导体层掺杂有氢。
5.如权利要求1～4中任一项所述的半导体装置，其特征在于，
该半导体装置进一步具有：
与所述半导体层相接的绝缘层，以及
隔着所述绝缘层与所述半导体层相对设置的第3电极，
分别以所述第1电极、所述第2电极、所述第3电极作为源极、漏极、栅极来构成晶体管。
6.一种pH传感器，其特征在于，其具备权利要求1～5中任一项所述的半导体装置。
7.一种生物传感器，其特征在于，其具备权利要求1～5中任一项所述的半导体装置。
8.一种半导体装置的制造方法，其是权利要求1～5中任一项所述的半导体装置的制造方法，其特征在于，该制造方法包括下述工序：
形成所述半导体层的工序，
在所述半导体层上形成导电层的工序，以及
与规定的图案对应地对所述导电层进行蚀刻，形成所述第1电极和所述第2电极的工序。
9.如权利要求8所述的半导体装置的制造方法，其特征在于，用酸性溶液进行所述蚀刻。
10.如权利要求8或9所述的半导体装置的制造方法，其特征在于，在190℃以上进行所述半导体层的形成工序。
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