CN108701710B - 制造纳米棒的方法以及通过该方法制造的纳米棒 - Google Patents
制造纳米棒的方法以及通过该方法制造的纳米棒 Download PDFInfo
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- CN108701710B CN108701710B CN201780013987.2A CN201780013987A CN108701710B CN 108701710 B CN108701710 B CN 108701710B CN 201780013987 A CN201780013987 A CN 201780013987A CN 108701710 B CN108701710 B CN 108701710B
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Abstract
提供了制造纳米棒的方法。制造纳米棒的方法包括以下步骤:提供生长衬底和支承衬底;在生长衬底的一面上使纳米材料层外延生长;在支承衬底的一面上形成牺牲层;使纳米材料层与牺牲层结合;从纳米材料层分离生长衬底;使纳米材料层平坦化;对纳米材料层进行蚀刻以形成纳米棒;以及去除牺牲层以分离出纳米棒。
Description
技术领域
本发明涉及制造纳米棒的方法以及通过该方法制造的纳米棒。
背景技术
纳米棒为具有数十乃至数百纳米的直径且具有大的长宽比的纳米大小的结构物,并且利用其的器件根据其应用而被使用在场效应晶体管(FET)、场致发射器件(FED)、发光二极管(LED)、太阳能电池(Solar cell)、气体传感器、化学传感器和生物传感器等各种领域中。
这种纳米棒的合成大致可分为2种,即,利用了使用金属催化剂的汽液固(vapor-liquid-solid,VLS)机制的气相法以及使用溶液的液相法。
气相法为利用高温的热使材料变为气体状态,并且在凝结气体状态的原子的同时合成出各种形态的纳米棒的方法。这种方法难以对纳米棒的大小或特性进行控制,以及难以使经合成的纳米棒均匀地对齐。
此外,与通过气相法合成的纳米棒相比,通过液相法制造的纳米棒的具有较多缺陷(defects)且晶体结构和光学性能差,并且与气相法同样地,存在着难以对齐和难以执行电极形成工艺的问题。
作为传统的纳米棒的制造方法,虽然存在化学聚合法、电化学聚合法、化学气相沉积法(Chemical vapor deposition,CVD)、碳热还原法(carbothermal reduction)等,但是为了获得高品质的纳米棒,如上所述的方法中需要高合成温度或者伴随着诸如反应时间、昂贵的真空设备和有害气体的使用等诸多限制。
此外,以往在从衬底分离纳米棒的工艺过程中会发生表面裂纹(crack),并且有可能会因强热能和热传递而导致受损或热损伤(thermal damage)。
发明内容
技术问题
本发明一实施方式旨在提供能够最大限度地减少纳米棒的废品率并且生产出高品质的纳米棒的制造纳米棒的方法以及通过该方法制造的纳米棒。
解决问题的手段
根据本发明一方面,提供制造纳米棒的方法,该方法包括以下步骤:提供生长衬底和支承衬底;在所述生长衬底的一面上使纳米材料层外延生长;在所述支承衬底的一面上形成牺牲层;将所述纳米材料层与所述牺牲层结合;从所述纳米材料层分离所述生长衬底;对所述纳米材料层进行平坦化;对所述纳米材料层进行蚀刻以形成纳米棒;以及去除所述牺牲层以分离出所述纳米棒。
此时,所述生长衬底可包括玻璃衬底、水晶衬底、蓝宝石衬底、塑料衬底和能够弯曲的柔性聚合物膜中的至少一种。
此时,所述生长衬底可包括氮化镓(GaN)、碳化硅(SiC)、氧化锌(ZnO)、硅(Si)、磷化镓(GaP)、尖晶石(MgAl2O4)、氧化镁(MgO)、铝酸锂(LiAlO2)、镓酸锂(LiGaO2)、砷化镓(GaAs)、氮化铝(AlN)、磷化铟(InP)和铜(Cu)中的至少一种。
此时,所述支承衬底可包括蓝宝石衬底、玻璃衬底、碳化硅衬底、硅衬底以及由金属物质构成的导电性衬底中的至少一种。
此时,所述纳米材料层可包括氧化锌(ZnO)、氮化镓(GaN)、砷化镓(GaAs)、碳化硅(SiC)、氧化锡(SnO2)、磷化镓(GaP)、磷化铟(InP)、硒化锌(ZnSe)、二硫化钼(MoS2)和硅(Si)中的至少一种。
此时,可通过金属有机化学气相沉积法(metal organic chemical vapordeposition,MOCVD)使所述纳米材料层外延生长。
此时,在所述生长衬底的一面上使纳米材料层外延生长的步骤可包括:对所述纳米材料层的沉积厚度进行调节以调节纳米棒的长度的步骤。
此时,所述牺牲层可以是用于与所述纳米材料层接合的绝缘层以及沉积到所述绝缘层的上表面上以供所述绝缘层进行接合的金属层。
此时,所述牺牲层可以是金(Au)、钛(Ti)、铁(Fe)、氧化硅(SiO2)或氮化硅(SiN)。
此时,在从所述纳米材料层分离所述生长衬底的步骤中,可通过激光剥离(laserlift-off,LLO)法、化学剥离(chemical lift-off,CLO)法和电化学剥离(electrochemicallift-off,ELO)法从所述纳米材料层分离所述生长衬底。
此时,可包括通过机械化学抛光(Chemical Mechanical Polishing,CMP)法对经分离的纳米材料层进行平坦化的过程。
此时,在去除所述牺牲层以分离出纳米棒的步骤中,当所述牺牲层为氧化硅时,可使用缓冲氧化蚀刻液(buffered oxide etchant,BOE)去除所述牺牲层。
此时,在去除所述牺牲层以分离出纳米棒的步骤中,当所述牺牲层为金属层时,可使用金属蚀刻液(Metal Etchant)去除所述牺牲层。
根据本发明另一方面,提供通过前述的制造纳米棒的方法制造出的纳米棒。
发明效果
根据本发明一实施方式的制造纳米棒的方法以及通过该方法制造的纳米棒因包括牺牲层而在支承衬底上进行纳米棒分离工艺时容易地分离纳米棒,从而能够最大限度地减少纳米棒的废品率并且生产出高品质的纳米棒。
附图说明
图1为示出根据本发明一实施方式的制造纳米棒的方法的顺序图。
图2(a)至图2(g)为顺序地示出通过根据本发明一实施方式的制造纳米棒的方法制造的纳米棒的制造过程的剖视图。
具体实施方式
在下文中,参照附图对本发明实施方式进行详细说明,以便本发明所属技术领域的普通技术人员能够容易地实施。本发明能够被实现为各种不同的形态,并且本文中所说明的实施方式不限于此。为了明确地说明本发明,在附图中省略了与说明无关的部分,并且在整个说明书中,对相同或相似的构成要素赋予相同的附图标记。
在说明书中,“包括”或“具有”等措辞应理解为指示说明书中记载的特征、数字、步骤、动作、构成要素、部件或它们的组合的存在,而不是提前排除一个或多个其他特征、数字、步骤、动作、构成要素、部件或它们的组合的存在或附加可能性。此外,当层、膜、区域、板等部分被称为在其他部分“上”时,其不仅包括“直接”在其他部分“上”的情况,而且还包括它们中间存在另外一部分的情况。相反,当层、膜、区域、板等部分被称为在其他部分“下”时,其不仅包括“直接”在其他部分“下”的情况,而且还包括它们中间存在有另外一部分的情况。
在下文中,将参照附图对根据本发明一实施方式的纳米棒的制造方法以及利用该方法获得的纳米棒进行更加详细的说明。
图1为示出根据本发明一实施方式的纳米棒的制造方法的顺序图。图2(a)至图2(g)为顺序地示出通过根据本发明一实施方式的制造纳米棒的方法制造的纳米棒的制造过程的剖视图。
参照图1,制造纳米棒的方法可包括:提供生长衬底和支承衬底的步骤(S10);在生长衬底的一面上使纳米材料层外延生长的步骤(S20);在支承衬底的一面上形成牺牲层的步骤(S30);将纳米材料层与牺牲层结合的步骤(S40);从纳米材料层分离生长衬底的步骤(S50);对纳米材料层进行平坦化的步骤(S60);对纳米材料层进行蚀刻以形成纳米棒的步骤(S70);以及去除牺牲层并分离出纳米棒的步骤(S80)。
由此,根据本发明一实施方式的制造纳米棒的方法能够最大限度地减少因从支承衬底13分离纳米棒1的工艺而导致的纳米棒的废品率并且生产出高品质的纳米棒。
参照图1和图2(a),在提供生长衬底和支承衬底的步骤(S10)中,提供用于供纳米材料层15生长的生长衬底11和进行支承以形成牺牲层17、19的支承衬底13。
另外,参照图2(a),生长衬底11可以是玻璃衬底、水晶衬底、蓝宝石衬底、塑料衬底和能够弯曲的柔性聚合物膜中的至少一种。此外,生长衬底11可包括透光性衬底。
此时,生长衬底11可包括氮化镓(GaN)、碳化硅(SiC)、氧化锌(ZnO)、硅(Si)、磷化镓(GaP)、尖晶石(MgAl2O4)、氧化镁(MgO)、铝酸锂(LiAlO2)、镓酸锂(LiGaO2)、砷化镓(GaAs)、氮化铝(AlN)、磷化铟(InP)和铜(Cu)中的至少一种。然而,只要能够使纳米材料层15外延(epi)生长,则生长衬底11不受限制。
另外,参照图2(a),支承衬底13可以是蓝宝石衬底、玻璃衬底、碳化硅衬底、硅衬底和由金属物质构成的导电性衬底中的任一种。此外。支承衬底13也可以是如PCB等的电路衬底和包括陶瓷的陶瓷衬底。
参照图1和图2(b),在生长衬底的一面上使纳米材料层外延生长的步骤(S20)中,可在生长衬底11的一面上使作为纳米棒1的材料的纳米材料层15外延生长。
此时,在生长衬底的一面上使纳米材料层外延生长的步骤(S20)可包括:对纳米材料层15的沉积厚度进行调节以调节纳米棒1的长度的步骤。
此外,在生长衬底的一面上使纳米材料层外延生长的步骤(S20)中,可在生长衬底11的一面(如图2(b)中所示的上表面)上使纳米材料层15外延生长。
此时,外延生长(Epitaxial growth)是指在某种结晶衬底上使相同材料或不同材料的结晶在特定方向上生长的方式,其亦可称为磊晶(Epitaxy)。
此外,在衬底上使相同材料的结晶生长的方式被称为同质外延(homoepitaxy)或者被简称为EPI,而使不同材料的结晶生长的方式被称为异质外延(heteroepitaxy)。
另外,纳米材料层15作为构成纳米棒1的纳米材料物质,其可以包括氧化锌(ZnO)、氮化镓(GaN)、砷化镓(GaAs)、碳化硅(SiC)、氧化锡(SnO2)、磷化镓(GaP)、硒化锌(ZnSe)、二硫化钼(MoS2)和硅(Si)中的任一种,但不限于此。
在本发明一实施方式中,纳米材料层15可竖直生长,并且可以是能够形成具有较大长宽比的纳米棒的所有类型的纳米材料。
另外,参照图1,在使纳米材料层外延生长的步骤(S20)中所使用的沉积方法可包括原子层沉积法(ALD)、反应性溅射(reactive sputtering)、离子注入法(ionimplantation)、磁控溅射(magnetron sputtering)、激光沉积法(laser ablation)、离子束沉积法(ion beam deposition)、化学气相沉积法(chemical vapor deposition)和等离子化学沉积法(plasma enhanced CVD)中的至少一种。
然而,优选地,根据本发明一实施方式的外延生长可使用金属有机化学气相沉积法(metal organic chemical vapor deposition,MOCVD)。即,可使用金属有机化学气相沉积装置使纳米材料层15外延生长。
此时,金属有机化学气相沉积装置中所使用的有机金属化合物可使用诸如三甲基镓(Ga(CH3)3)、三甲基铝(Al(CH3)3)、磷酸三乙酯((C2H5O)3PO)的、具有甲基或乙基等烷基的化合物作为原料。
另外,纳米材料层15是用于通过随后的工艺形成纳米棒1的层。在本发明一实施方式中,在对纳米材料层的沉积厚度进行调节以调节纳米棒的长度的步骤(S21)中,由于纳米材料层15的厚度对应于通过随后的工艺形成的纳米棒1的长度,因此通过对纳米材料层15的沉积厚度进行调节来调节纳米棒1的长度。
在本发明一实施方式中,虽然未示出,但是生长衬底11与纳米材料层15之间根据需要还可以形成有外延生长所需的缓冲层(未示出)。此时,缓冲层可以是为了最大限度地减少生长衬底11与纳米材料层15的晶格失配而形成。
参照图1和图2(b),在支承衬底的一面上形成牺牲层的步骤(S30)中,可在支承衬底13的一面(例如,如图2(b)中所示的上表面)上形成牺牲层。
此时,在本发明一实施方式中,牺牲层作为金属层19和绝缘层17,其可以使用金属、氧化物和氮化物,并且可以是金(Au)、钛(Ti)或铁(Fe),以及氧化硅(SiO2)或氮化硅(SiN),但不限于此。
此外,对于牺牲层,可在绝缘层17上沉积较薄的金属层19,以将纳米材料层15与绝缘层17接合。
另外,在支承衬底13的上表面上形成牺牲层时,尽管可以在支承衬底13的上表面上设置结合层(未示出)以将支承衬底13与牺牲层进行结合,但是在由能够在没有结合层的情况下进行结合的结构或材料形成的情况下,结合层可被省略。
参照图1和图2(c),在使纳米材料层与牺牲层结合的步骤(S40)中,通过将纳米材料层15的上表面与金属层19的上表面结合来使纳米材料层15与绝缘层17接合。
在后续对纳米材料层15进行蚀刻以形成纳米棒1时,作为牺牲层的金属层19和绝缘层17可以是蚀刻停止层。因此,使得纳米材料层15的蚀刻液不会渗透到支承衬底13中。
另外,参照图1和图2(d),在从纳米材料层分离生长衬底的步骤(S50)中,从纳米材料层15分离生长衬底11。
此时,从纳米材料层15分离生长衬底11的方法可以是激光剥离(laser lift-off,LLO)法、化学剥离(chemical lift-off,CLO)法和电化学剥离(electrochemical lift-off,ELO)法。
此时,激光剥离(LLO)法是在生长衬底11上使纳米材料层15生长并在纳米材料层15上结合牺牲层17之后,照射激光束以从生长衬底11分离纳米材料层15的技术。
此时,化学剥离(CLO)法是在生长衬底11上使牺牲层生长之后,使纳米材料层15生长,并在纳米材料层15上结合牺牲层之后,使用蚀刻液从生长衬底11分离纳米材料层15的技术。此时,蚀刻液使牺牲层选择性地被蚀刻。
此时,电化学剥离(ELO)法在生长衬底11上使纳米材料层15生长,并且使用金属(Metal)阳极通过电化学蚀刻形成多孔性纳米材料层15。然后,使纳米材料层15再次生长,并且在纳米材料层15上结合牺牲层之后,从生长衬底11分离纳米材料层15。
此时,在对分离出的纳米材料层进行平坦化的步骤(S60)中,可通过机械化学抛光(Chemical Mechanical Polishing,CMP)法执行平坦化过程。
另外,参照图1和图2(e),在对纳米材料层进行蚀刻以形成纳米棒的步骤(S70)中,在蚀刻纳米材料层15时通过在注入或者不注入蚀刻液的状态下选择性地进行蚀刻而形成纳米棒1。
此时,形成与纳米材料层15选择性地进行蚀刻的掩模材料层,并且掩模材料层作为绝缘层,其可以是氧化硅(SiO2)或氮化硅(SiN),但不限于此。
此时,蚀刻溶液可包括硫酸、磷酸或氢氧化钾、氢氧化钠。另外,纳米材料层15通过自上而下(top-down)的方式进行干式蚀刻以形成竖直生长的纳米棒1。
这种自上而下(top-down)的方式是在大面积玻璃衬底的子像素位置处以一一对应的方式逐个排列通过自上而下(top-down)的方式制造的微型LED器件来实现显示器的方法。然而,此时,纳米棒1的一端部与牺牲层接合。
在本文中,干式蚀刻中所使用的蚀刻气体可以是基于氯(Cl2)或烃(CH4)的气体,但不限于此。此时,在本发明一实施方式中,牺牲层起到蚀刻停止层的作用,即,在使用蚀刻溶液蚀刻纳米材料层15时不会被蚀刻溶液蚀刻。
此外,在蚀刻工艺中可使用干式蚀刻法和湿式蚀刻法。此时,与湿式蚀刻法不同地,干式蚀刻法能够进行单向蚀刻,而湿式蚀刻法可实现各向同性(isotropic)蚀刻,从而能够在所有方向上进行蚀刻。
参照图1和图2(f),在去除牺牲层以分离出纳米棒的步骤(S80)中,通过去除与纳米棒1的一端部接合的牺牲层,从而容易地从支承衬底13分离纳米棒1。
由此,根据本发明一实施方式的制造纳米棒的方法能够最大限度地减少纳米棒的废品率并且生产出高品质的纳米棒。
此时,在牺牲层由作为绝缘层17的氧化硅形成的情况下,可使用缓冲氧化蚀刻液(buffered oxide etchant,BOE)来去除牺牲层。
此时,氧化蚀刻液中的氢氟酸(HF)与作为绝缘层17的氧化硅(SiO2)或氮化硅(SiN)选择性地进行反应并形成四氟化硅(SiF4),从而去除牺牲层。
此时,在牺牲层为金属层19的情况下,可使用金属蚀刻液(Metal Etchant)去除上述牺牲层。此时,通过蚀刻来去除牺牲层的方法可通过将衬底浸没在BOE中来去除。
根据本发明一实施方式的制造纳米棒的方法以及通过该方法制造的纳米棒通过包括牺牲层在支承衬底上所进行的纳米棒分离工艺中容易地分离纳米棒,从而能够最大限度地减少纳米棒的废品率并且生产出高品质的纳米棒。
虽然在上文中对本发明一实施方式进行了说明,但是本发明的思想并不受限于本说明书中提出的实施方式,且理解本发明的思想的技术人员能够在相同的思想范围内通过构成要素的附加、变更、删除、添加等容易地提出其他实施方式,而这种实施方式也应落入本发明的思想范围内。
工业可用性
本发明一实施方式旨在提供能够最大限度地减少纳米棒的废品率并且生产出高品质的纳米棒的制造纳米棒的方法以及通过该方法制造的纳米棒。
Claims (14)
1.制造纳米棒的方法,包括以下步骤:
提供生长衬底和支承衬底;
在所述生长衬底的一面上使纳米材料层外延生长;
在所述支承衬底的一面上形成牺牲层;
将所述纳米材料层与所述牺牲层结合;
从所述纳米材料层分离所述生长衬底;
对所述纳米材料层进行平坦化;
对所述纳米材料层进行蚀刻以形成纳米棒;以及
去除所述牺牲层以分离出所述纳米棒。
2.如权利要求1所述的制造纳米棒的方法,其中,所述生长衬底包括玻璃衬底、水晶衬底、蓝宝石衬底、塑料衬底和能够弯曲的柔性聚合物膜中的至少一种。
3.如权利要求1所述的制造纳米棒的方法,其中,所述生长衬底包括氮化镓、碳化硅、氧化锌、硅、磷化镓、尖晶石、氧化镁、铝酸锂、镓酸锂、砷化镓、氮化铝、磷化铟和铜中的至少一种。
4.如权利要求1所述的制造纳米棒的方法,其中,所述支承衬底包括蓝宝石衬底、玻璃衬底、碳化硅衬底、硅衬底以及由金属物质构成的导电性衬底中的至少一种。
5.如权利要求1所述的制造纳米棒的方法,其中,所述纳米材料层包括氧化锌、氮化镓、砷化镓、碳化硅、氧化锡、磷化镓、磷化铟、硒化锌、二硫化钼和硅中的至少一种。
6.如权利要求1所述的制造纳米棒的方法,其中,通过金属有机化学气相沉积法使所述纳米材料层外延生长。
7.如权利要求6所述的制造纳米棒的方法,其中,在所述生长衬底的一面上使纳米材料层外延生长的步骤包括以下步骤:
对所述纳米材料层的沉积厚度进行调节以调节纳米棒的长度。
8.如权利要求1所述的制造纳米棒的方法,其中,所述牺牲层包括用于与所述纳米材料层接合的绝缘层和沉积到所述绝缘层的上表面以供所述绝缘层进行接合的金属层。
9.如权利要求8所述的制造纳米棒的方法,其中,所述牺牲层包括金、钛、铁、氧化硅和氮化硅中的至少一种。
10.如权利要求1所述的制造纳米棒的方法,其中,在从所述纳米材料层分离所述生长衬底的步骤中,通过激光剥离法、化学剥离法和电化学剥离法中的一种从所述纳米材料层分离所述生长衬底。
11.如权利要求10所述的制造纳米棒的方法,其中,在对所述纳米材料层进行平坦化的步骤中,通过机械化学抛光法对与所述生长衬底分离的纳米材料层进行平坦化。
12.如权利要求9所述的制造纳米棒的方法,其中,在去除所述牺牲层以分离出纳米棒的步骤中,当所述牺牲层为氧化硅时,使用缓冲氧化蚀刻液去除所述牺牲层。
13.如权利要求9所述的制造纳米棒的方法,其中,在去除所述牺牲层以分离出纳米棒的步骤中,当所述牺牲层为金属层时,使用金属蚀刻液去除所述牺牲层。
14.纳米棒,所述纳米棒通过如权利要求1至13中任一项所述的制造纳米棒的方法制造。
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