CN100416872C - 使用金属/半导体纳米棒的异质结构的接触织物及其制备方法 - Google Patents

使用金属/半导体纳米棒的异质结构的接触织物及其制备方法 Download PDF

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CN100416872C
CN100416872C CNB2004800161243A CN200480016124A CN100416872C CN 100416872 C CN100416872 C CN 100416872C CN B2004800161243 A CNB2004800161243 A CN B2004800161243A CN 200480016124 A CN200480016124 A CN 200480016124A CN 100416872 C CN100416872 C CN 100416872C
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CN1806344A (zh
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李奎哲
朴原一
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LG Display Co Ltd
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POHANG POLYTECHNIC SCHOOL
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Abstract

提供了使用金属/半导体纳米棒的异质结构的接触织物及其制备方法。接触电阻低的欧姆接触织物或具有整流特性的肖特基接触织物是通过将纳米尺寸的金属选择性沉积到氧化锌/半导体纳米棒的预定部分上并控制沉积金属的功函和金属/氧化锌的界面特性而形成的。接触织物可以用到各种纳米尺寸的包括肖特基二极管在内的电子元件、光学元件及其阵列中。

Description

使用金属/半导体纳米棒的异质结构的接触织物及其制备方法
技术领域
本发明涉及使用金属/半导体纳米棒的异质结构的接触织物以及其制备方法，尤其涉及使用这样的金属/半导体纳米棒的异质结构的接触织物以及其制备方法：其中，接触电阻低的欧姆接触织物或具有整流特性的肖特基接触织物是通过将纳米尺寸的金属选择性沉积到氧化锌/半导体纳米棒的预定部分上并控制沉积金属的功函和金属/氧化锌的界面特性而形成的，以将接触织物用到各种纳米尺寸的包括肖特基二极管在内的电子元件、光学元件及其阵列中。
背景技术
自从发明晶体管以来的半导体技术的惊人发展，带来了基于量子效应的很大规模集成电路和半导体激光器的进展，21世纪的信息和通信时代已经到来。当半导体元件的尺寸减小时，来自微电子工程的传统技术不能用于进一步限制设计规则。例如，由于受限于光学分辨率，光学蚀刻方法不能用于制造尺寸小于几十纳米的半导体元件。此外，这种半导体元件不能通过采用X-射线或电子束的方法制造，采用X-射线或电子束的方法不适于大规模生产并且成本高昂。因此，已开发出可以用来制造纳米尺寸半导体元件以在原子或分子水平上显示所需功能的自下至上法(bottom-upmethod)。
为了用自下至上法制造纳米元件，需要能够用来采用单一材料就可实现带有所需功能的纳米结构的技术。特别是，相应于纳米元件的电极的接触织物在供应运行所需能量方面起重要作用。此外，由于纳米元件包括接触电阻低的欧姆接触织物以及具有各种整流特性的肖特基接触织物(所述各种整流特性依赖于半导体和金属之间的功函差并依赖于半导体和金属的界面特性)，因此，必须采用控制这些特性的技术。但是，目前仍未建立在纳米元件的预定部分形成人工纳米接触织物的技术，而且迄今尚未有人研究控制纳米接触织物特性的技术。
附图说明
图1是说明本发明的采用金属/半导体纳米棒的异质结构的接触织物以及其制造方法的概图；
图2是说明本发明的采用金属/半导体纳米棒的异质结构的接触织物的阵列结构的概图；
图3是说明电流感应原子力显微镜法(current sensing atomic forcemicroscopy，简称CSAFM)的概图，进行该方法以检查本发明的其上沉积有金属的金属/半导体纳米棒的异质结构的电特性；
图4是说明根据本发明的其上未沉积金属的氧化锌/半导体纳米棒的导电率的坐标图，它是采用其上涂敷有金的探针测定的；
图5是说明根据本发明的其中金沉积在氧化锌半导体纳米棒上的金/氧化锌纳米棒的异质结构的导电率的坐标图，它是采用其上涂敷有金的探针测定的；以及
图6是说明本发明金/钛/氧化锌纳米棒的异质结构的导电率的坐标图，该导电率是采用其上涂敷有金的探针测定的，其中异质结构是通过将钛和金连续沉积在氧化锌纳米棒上并进行热退火而制造的。
发明内容
本发明提供了采用金属/半导体纳米棒的异质结构的接触织物，其中接触电阻低的欧姆接触织物或具有整流特性的肖特基接触织物通过将纳米尺寸的金属选择性沉积到氧化锌/半导体纳米棒的预定部分上并控制沉积金属的功函和金属/氧化锌的界面特性而形成，以将接触织物用到各种纳米尺寸的包括肖特基二极管在内的电子元件、光学元件及其阵列中。
本发明还提供了采用金属/半导体纳米棒的异质结构制造接触织物的方法，其中接触电阻低的欧姆接触织物或具有整流特性的肖特基接触织物通过将纳米尺寸的金属选择性沉积到氧化锌/半导体纳米棒的预定部分上并控制沉积金属的功函和金属/氧化锌的界面特性而形成，以将接触织物用到各种纳米尺寸的包括肖特基二极管在内的电子元件、光学元件及其阵列中。
发明效果
根据本发明，接触电阻低的欧姆接触织物或具有整流特性的肖特基接触织物可通过在氧化锌纳米棒的预定部分上以纳米尺寸形成金属接触织物并控制沉积金属接触织物的电特性而形成的。尤其是，本发明描述的技术可以用于开发满足所需功能的功能纳米结构。此外，本发明可用于开发采用垂直安置的纳米材料的电子元件以及采用光学元件阵列的高度集成电路。
另一方面，本发明可以通过将纳米尺寸的金属选择性沉积到氧化锌/半导体纳米棒的预定部分上并控制沉积金属的功函和金属/氧化锌之间的界面特性而形成接触电阻低的欧姆接触织物或具有整流特性的肖特基接触织物。另外，接触织物可以用于包括纳米尺寸二极管在内的电子元件、光学元件、及其阵列。
具体实施方式
根据本发明的一个方面，提供了使用金属/半导体纳米棒的异质结构的接触织物，所述接触织物包含：在预定的基材上生长的半导体纳米棒；以及沉积在半导体纳米棒的预定部分上的金属，其中在纳米棒和金属之间存在低接触电阻欧姆特性或整流肖特基特性，所述特性依赖于纳米棒和金属之间的界面特性并且依赖于功函之间的差值。
根据本发明的一些特定实施方案，接触织物可以在肖特基二极管、晶体管、光学检测元件、发光元件、传感元件、纳米系统、集成电路、和阵列电路中用作肖特基接触织物或欧姆接触织物。
纳米棒和接触织物的直径可能小于500nm。半导体纳米棒可能包括选自氧化锌、氧化钛、GaN、Si、InP、InAs、GaAs及它们的合金中的至少一种材料。
当半导体纳米棒为n型半导体并与金属形成肖特基接触织物时，沉积在半导体纳米棒上的金属可能包括选自Ni，Pt，Pd，Au，W，和硅化物金属(包括PtSi和NiSi)的至少一种材料，每一种所列材料的功函都大于半导体纳米棒与电子的亲和力。
半导体纳米棒为n型半导体并与金属形成欧姆接触织物时，直接沉积在半导体纳米棒上的金属可能包括选自Ti，Al，In的至少一种材料，每一种所列材料的功函都低于半导体纳米棒的功函。
Au或Pt可沉积在金属上。金属沉积后可能在低于1000℃的温度下进行热退火以改善接触织物的电特性。
本发明的另外一个方面提供了使用金属/半导体纳米棒的异质结构制造接触织物的方法，该方法包括：垂直地或以某一方向在预定基材上生长半导体纳米棒；以及用溅射法或热蒸发法或电子束蒸发法将金属沉积到半导体纳米棒的预定部分上，其中在纳米棒和金属之间存在低接触电阻欧姆特性或存在整流肖特基特性，所述特性依赖于纳米棒和金属之间的界面特性并且依赖于功函之间的差值。
实施方案
下面参照附图详细描述本发明的使用金属/半导体纳米棒的异质结构的接触织物及其制备方法。已知技术或结构的详细描述会使得本发明主题模糊、不突出，此处不再赘述。说明书和权利要求书中通篇使用的基于相应元件的功能而定义的技术术语可能随用户或操作者的意图或具体环境而变化。因此，这些技术术语的定义应当基于说明书和权利要求书的上下文确定。
参照图1，给出了说明本发明使用金属/半导体纳米棒的异质结构的接触织物及其制备方法的概图。这时，用金属有机气相外延生长(MOVPE)法在某一方向上或垂直地在基材10上生长氧化锌/半导体纳米棒12。然后，用溅射法或热蒸发法或电子束蒸发法在纳米棒12上沉积金属14’。此处，将金属14’选择性沉积在纳米棒12的尖端处，结果形成具有清晰界面的金属/半导体异质结构。此外，可以在纳米棒12的尖端处沉积各种金属。优选纳米棒12和沉积于纳米棒12上的金属的直径均小于500nm。此外，可通过热退火期间发生的界面反应控制界面的电特性。优选在低于1000℃的温度下进行热退火。可根据沉积金属的种类或随后将描述的热退火控制欧姆特性和肖特基特性。
图2是说明金属/半导体纳米棒的异质结构阵列(其在大面积上垂直生长)的高度集成电路的概图。此处，为了控制光学元件或纳米电子元件的每一种而将接触织物连接到金属/半导体纳米棒的上部和下部。
图3是说明电流感应原子力显微镜(CSAFM)法的概图，进行该方法是为了检测图1所示金属/半导体纳米棒的异质结构的电特性。此处，将其上涂敷有金属的探针15放置于金属/半导体纳米棒的异质结构12或14的尖端上，并使用导电率优异的下层10检查金属/半导体纳米棒的每个异质结构的电特性。附图标记18表示AFM尖端。
图4是说明其上没有沉积金属的氧化锌/半导体纳米棒12的导电率的坐标图，其中使用其上涂敷有金的探针15检查导电率。参照图4，示出了由于肖特基势垒产生的不对称电流-电压(I-V)特性，肖特基势垒是通过金尖端15’和氧化锌纳米棒12之间的结合结构自然形成的。但是，由于金尖端15’非常锋利，在低反向偏压下发生击穿。
图5是说明金/氧化锌纳米棒的异质结构的导电率的坐标图，其中金14沉积于氧化锌/半导体纳米棒12上并且使用参照图4描述的探针15检查导电率。参照图5的坐标图，通过在沉积金14和氧化锌12之间的结合结构形成肖特基势垒，导致电流-电压(I-V)整流特性。具体地说，示出了其中直到约-8V仍未发生击穿的优异肖特基特性。肖特基特性优异归功于金的功函大，因此其他金属如果功函大也能够产生优异的肖特基特性。
图6说明了金/钛/氧化锌纳米棒的异质结构的导电率，该异质结构是通过将钛14和金14’连续沉积到氧化锌纳米棒12上并进行热退火形成的，其中使用参照图4-5描述的探针15检查导电率。参照图6的坐标图，从具有在钛14和氧化锌12之间的界面处形成的低接触电阻的欧姆接触织物得到线性电流-电压(I-V)特性。正是由于钛的功函小，因而得到了线性电流-电压(I-V)特性，并且正是因为热退火才增强了使电流易于流动的隧道效应。因此，除钛以外，具有小功函的金属也能够产生线性电流-电压(I-V)特性。
本发明中，金属14’被沉积在半导体(氧化锌)纳米棒12上，纳米棒12在基材10上垂直地或以某一方向生长，并且在沉积金属14’上进行热退火以形成纳米尺寸的接触织物14。在具有n型半导体的氧化锌纳米棒12的情况下，可以使用与肖特基接触织物金属功函同样大的Ni，Pt，Pd，Au，W，和硅化物如PtSi和NiSi形成大能垒肖特基接触织物。
此外，可使用功函小的Ti或Al并通过界面反应降低接触电阻形成n型氧化锌纳米棒12的欧姆接触织物。作为替代方案，本发明接触织物可以使用各种金属(包括Cu，Ag，Mn，Fe和Co)制备。
下文中，将参照如下实施例更详细地描述本发明。举出下面这些实施例仅仅为了说明而不是要限制本发明的范围。
实施例1
金属/氧化锌纳米棒的生长(参照图1)
使用热蒸发法或电子束蒸发法在通常使用的以某一方向排列的氧化锌/半导体纳米棒上沉积金和钛/金。此处，金沉积到约20nm的厚度，并且，钛/金分别沉积至10nm和20nm的厚度。用于蒸发金属的电子束的加速电压和发射电流分别为4-20kV和40-400mA。沉积金属时反应器的压力为10-5mmHg，基材的温度为室温。沉积金属前后使用电子显微镜检查氧化锌纳米棒阵列。结果发现，金属已经被选择性沉积到纳米棒的尖端上，并且纳米棒的直径和现状没有显著变化。
金属/氧化锌纳米棒的电特性的测定(参照图4-6)
使用电流感应原子力显微镜(CSAFM)测定金属/氧化锌纳米棒的异质结构的电特性。尤其是，使用其上涂敷有金的探针扫描金属/氧化锌纳米棒的异质结构阵列，以测定各纳米棒的位置。为了得到AFM图像，在扫描异质结构阵列时施加0.12N/m的弹性系数。当测定电流-电压(I-V)特性时，横跨尖端和下面的氧化锌导电层施加电压。在室温下进行该试验，重复20次，获得I-V曲线。
为检测金属沉积在氧化锌纳米棒上之后的电特性变化，使用氧化锌纳米棒、金/氧化锌纳米棒的异质结构、和金/钛/氧化锌纳米棒的异质结构在相同条件下测定I-V特性。此外，测定I-V特性时向尖端施加20-40nN。
参见说明其上未沉积金属的氧化锌纳米棒的I-V曲线的图4的坐标图，由于通过金尖端和氧化锌之间的结合结构形成的肖特基势垒，正向电流平稳，但是反向电流不平稳而导致I-V特性不对称。但是，由于金尖端很锋利，在低反向偏压下发生击穿。
另一方面，如果是其上沉积有金的金/氧化锌纳米棒的异质结构，则由于金和氧化锌之间的结合结构而形成肖特基势垒；但是，在金尖端上产生的高电场可以抑制低反向偏压下的击穿，这是因为在氧化锌和沉积于氧化锌纳米棒上的金层之间形成了金属/半导体结合。参照图5的坐标图，肖特基特性得以改善，使得即使在约8V下也能够抑制击穿。采用具有大功函的Ni，Pt，Pd，W，和硅化物如PtSi和NiSi可以形成类似的肖特基接触织物。
接触电阻低的欧姆接触织物在供应元件运行所需能量方面起着最要作用。为了制造这种欧姆接触织物，在一个实施例中，在氧化锌纳米棒上依次沉积钛和金，并且在300-500℃温度下快速热退火。参见图6的坐标图，得到了典型的欧姆接触电阻的线性I-V曲线，并且由于接触电阻低，电流大增。使用能够通过界面反应降低接触电阻的In，Ti/Al，和Al/Au可以形成欧姆接触织物。

Claims (15)

1. 一种接触织物，其采用了金属或硅化物金属/半导体纳米棒的异质结构，所述接触织物包含：
在预定基材上生长的半导体纳米棒；和
在半导体纳米棒的预定部分上沉积的金属或硅化物金属，
其中在纳米棒和金属或硅化物金属之间有低接触电阻欧姆特性或有整流肖特基特性，所述特性依赖于纳米棒和金属或硅化物金属之间的界面的特性并且依赖于功函之间的差值。
2. 权利要求1所述的接触织物，其在肖特基二极管、晶体管、发光元件、传感元件和集成电路中用作肖特基接触织物或欧姆接触织物。
3. 权利要求1所述的接触织物，其中纳米棒和接触织物的直径均小于500nm。
4. 权利要求1所述的接触织物，其中半导体纳米棒包括选自氧化锌、氧化钛、GaN、Si、InP、InAs、GaAs、及它们的合金的至少一种材料。
5. 权利要求2所述的接触织物，其中当半导体纳米棒为n型半导体并且与金属或硅化物金属形成肖特基接触织物时，沉积在半导体纳米棒上的金属或硅化物金属包括选自Ni、Pt、Pd、Au、W、PtSi和NiSi中的至少一种材料，每一种所列材料的功函都大于半导体纳米棒与电子的亲和力。
6. 权利要求2所述的接触织物，其中当半导体纳米棒为n型半导体并与金属形成欧姆接触织物时，直接沉积在半导体纳米棒上的金属包括选自Ti，Al，In的至少一种材料，每一种所列材料的功函都低于半导体纳米棒的功函。
7. 权利要求6所述的接触织物，其中Au或Pt沉积在金属上。
8. 权利要求5-7中任一项所述的接触织物，其中金属沉积后在低于1000℃的温度下进行热退火以改善接触织物的电特性。
9. 制备采用了金属或硅化物金属/半导体纳米棒的异质结构的接触织物的方法，该方法包括：
垂直地或以某一方向在预定基材上生长半导体纳米棒；以及
用溅射法或热蒸发法或电子束蒸发法将金属或硅化物金属沉积到半导体纳米棒的预定部分上，
其中在纳米棒和金属或硅化物金属之间存在有低接触电阻欧姆特性或有整流肖特基特性，所述特性依赖于纳米棒和金属或硅化物金属之间的界面的特性并且依赖于功函之间的差值。
10. 权利要求9所述的方法，其中生长的纳米棒和沉积的接触织物的直径均小于500nm。
11. 权利要求9所述的方法，其中半导体纳米棒包括选自氧化锌、氧化钛、GaN、Si、InP、InAs、GaAs、及其合金的至少一种材料。
12. 权利要求9所述的方法，其中当半导体纳米棒为n型半导体并且与金属或硅化物金属形成肖特基接触织物时，沉积在半导体纳米棒上的金属或硅化物金属包括选自Ni、Pt、Pd、Au、W、PtSi和NiSi中的至少一种材料，每一种所列材料的功函都大于半导体纳米棒与电子的亲和力。
13. 权利要求9所述的方法，其中当半导体纳米棒为n型半导体并与金属形成欧姆接触织物时，直接沉积在半导体纳米棒上的金属包括选自Ti，Al，In的至少一种材料，每一种所列材料的功函都低于半导体纳米棒的功函。
14. 权利要求13所述的方法，还包括将Au或Pt沉积到金属上。
15. 权利要求12-14中任一项所述的方法，还包括在金属沉积后在低于1000℃的温度下进行热退火以改善接触织物的电特性。
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