KR101287611B1 - Method for fabricating silicon nanowire - Google Patents
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- KR101287611B1 KR101287611B1 KR1020100113212A KR20100113212A KR101287611B1 KR 101287611 B1 KR101287611 B1 KR 101287611B1 KR 1020100113212 A KR1020100113212 A KR 1020100113212A KR 20100113212 A KR20100113212 A KR 20100113212A KR 101287611 B1 KR101287611 B1 KR 101287611B1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 122
- 239000010703 silicon Substances 0.000 title claims abstract description 122
- 239000002070 nanowire Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 16
- 238000007740 vapor deposition Methods 0.000 claims abstract description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 229910003902 SiCl 4 Inorganic materials 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 6
- 230000007547 defect Effects 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000011856 silicon-based particle Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000010931 gold Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002665 PbTe Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005329 nanolithography Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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- H01L21/02518—Deposited layers
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Abstract
본 발명은 거친 표면을 갖는 실리콘 나노선 제조 방법에 관한 것이다. 상기 제조 방법은, (111) 방향 또는 (100) 방향의 실리콘 웨이퍼를 세정하는 단계; 상기 실리콘 웨이퍼의 표면에 Au, Cu, Ni, Mn 과 같은 금속 촉매 물질을 증착하는 단계; 전기화학기상증착기에 상기 실리콘 웨이퍼를 위치시키고, 아르곤(Ar)이 희석된 모노실란가스(SiH4) 또는 액화 테트라클로로실란(SiCl4)를 기체상태로 주입하여 금속 촉매 물질위에 실리콘 나노선을 성장시키는 단계;를 구비한다. The present invention relates to a method of manufacturing a silicon nanowire having a rough surface. The manufacturing method includes: cleaning a silicon wafer in a (111) direction or a (100) direction; Depositing a metal catalyst material such as Au, Cu, Ni, Mn on the surface of the silicon wafer; The silicon wafer is placed in an electrochemical vapor deposition apparatus and monosilane gas (SiH 4 ) or liquefied tetrachlorosilane (SiCl 4 ) diluted with argon (Ar) is injected in a gaseous state to grow silicon nanowires on the metal catalyst material Step.
Description
본 발명은 실리콘 나노선의 제조 방법에 관한 것으로서, 더욱 구체적으로는 내부에 생성된 적층 결함(stacking fault)에 의하여 외부에 거친 표면을 갖는 실리콘 나노선의 제조 방법에 관한 것이다. The present invention relates to a method of manufacturing silicon nano-wires, and more particularly, to a method of manufacturing silicon nano-wires having an outer rough surface by a stacking fault generated therein.
나노 기술은 기존의 실리콘 반도체 소자의 소형화의 핵심 기술인 나노 리소그라피를 통한 Top-Down 방식과 나노선, 나노 입자 등의 합성에 이용되고 있는 원자 스스로 조립되는 Bottom-Up 방식이 큰 틀을 이루고 있다. 기존의 실리콘 소자의 소형화에 이용되고 있는 Top-Down 방식은 원하는 크기와 위치의 제어면에서는 장점이 있지만 현재의 리소그라피의 기술의 최소 길이의 한계와 결정성이 좋지 않은 큰 단점을 가지고 있다. 반면에 Bottom-Up 방식은 원자 몇 개로 이루어진 입자를 합성할 수 있을 정도의 수 나노 크기까지 작은 물질을 합성할 수 있다는 점에서 장점이 있기는 하지만, 위치나 크기의 제어가 어려워 소자의 집적화 등에 문제가 있다.Nanotechnology is a top-down method through the use of nanolithography as a core technology for miniaturization of conventional silicon semiconductor devices, and a bottom-up method in which atoms are assembled by themselves, which is used for synthesis of nanowires and nanoparticles. The top-down method, which is used to miniaturize existing silicon devices, is advantageous in terms of control of the desired size and position, but has the disadvantage that the limit of the minimum length of the present lithography technology and crystallinity are poor. On the other hand, the bottom-up method is advantageous in that it can synthesize materials as small as nano-sized enough to synthesize particles composed of several atoms. However, since it is difficult to control the position and size, .
한편, 현재 전 세계적으로 나노선에 대한 연구가 활발히 진행되고 있는데, 이는 실리콘 기술이 주종을 이루고 있는 전자산업분야의 핵심적인 반도체 칩 소형화 추세를 고려해 볼 때 전술한 Top-Down 방식은 한계에 도달하게 될 것이다. 이러한 이유로 최근 전술한 Bottom-Up 방식에 대한 연구가 활발하게 이루어지고 있다. On the other hand, researches on nanowires are being actively conducted all over the world, considering that the trend of miniaturization of semiconductor chips, which are the core of electronic industry, where silicon technology is dominant, Will be. For this reason, recent studies on the bottom-up method have been actively conducted.
전술한 Bottom-Up 방식을 이용하는 종래의 나노선 제조 방법은 VLS(Vapor-Liquid-Solid) 메커니즘을 이용한 화학 기상 증착법(Chemical Vapor Deposition)을 사용하여 나노선을 제작하게 된다. 나노선이 제작되는 구체적인 과정을 살펴보면, 먼저 Au, Ni, Cu 등과 같은 금속 촉매 물질을 원료 물질과 서로 반응시켜 고용 합금(eutectic alloy)을 형성하며, 금속 촉매 물질에 원료 물질인 수소(H2)가 희석된 모노 실란(mono-silane, SiH4)이나 테트로클로로실란(SiCl4)을 전조자(precursor)로 이용하여 과포화시 석출되는 과정을 통해 나노선이 제작된다. 이러한 방식에 의해 제조된 실리콘 나노선은 표면이 매끄러운 것이 특징이다. In the conventional nanowire manufacturing method using the bottom-up method, a nanowire is manufactured using a chemical vapor deposition method using a Vapor-Liquid-Solid (VLS) mechanism. A specific process for producing the nanowire will be described. First, a metal catalyst material such as Au, Ni, Cu or the like is reacted with the raw material to form an eutectic alloy, hydrogen (H 2 ) The nanowires are produced through the process of precipitation upon supersaturation using mono-silane (SiH 4 ) or tetrochlorosilane (SiCl 4 ) as a precursor. Silicon nanowires fabricated by this method are characterized by a smooth surface.
하지만, 표면이 매끄러운 실리콘 나노선은 표면적이 작기 때문에, 실제 응용 분야가 좁다. 따라서, 최근 거친 표면을 가진 나노선에 대한 연구들이 진행되고 있는데, 이러한 거친 표면을 가진 나노선은 열전자를 제어하여 열전도도를 100배 정도까지 낮추어 줌에 따라, ZT가 1에 근접함을 보여주는 연구도 발표된 바 있다. 하지만, 종래의 거친 표면을 갖는 나노선들은 습식 식각을 이용하여 Top-Down 방식으로 제조됨에 따라, 거친 표면을 제어하는 데 많은 한계점이 있다.
However, silicon nanowires with smooth surface have small surface area, so practical applications are narrow. Recently, research on nanowires with rough surfaces has been under way. The nanowire with such a rough surface has been studied to show that the ZT is close to 1 as the thermal conductivity is controlled to about 100 times by controlling the thermoelectron Has also been announced. However, conventional nanowires having rough surfaces are manufactured in a top-down manner using wet etching, and thus there are many limitations in controlling rough surfaces.
전술한 문제점을 해결하기 위한 본 발명의 목적은 거친 표면과 적층결함을 가짐으로써 표면적이 넓은 실리콘 나노선을 제조하는 방법을 제공하는 것이다. It is an object of the present invention to solve the above-mentioned problems and to provide a method of manufacturing a silicon nanowire having a large surface area by having a rough surface and a lamination defect.
전술한 기술적 과제를 달성하기 위한 본 발명의 제1 특징은 거친 표면을 갖는 실리콘 나노선 제조 방법에 관한 것으로서, 상기 제조 방법은, 실리콘 웨이퍼를 세정하는 단계; 상기 실리콘 웨이퍼의 표면에 금속 촉매 물질을 증착하는 단계; 상기 실리콘 웨이퍼의 표면에 증착된 금속 촉매 물질의 표면에 희석 물질에 의해 희석된 모노실란가스(SiH4)를 증착시켜 실리콘 나노선을 성장시키는 단계;를 구비한다. According to a first aspect of the present invention, there is provided a method of manufacturing a silicon nanowire having a rough surface, the method comprising: cleaning a silicon wafer; Depositing a metal catalyst material on a surface of the silicon wafer; And depositing a monosilane gas (SiH 4 ) diluted by a diluent on the surface of the metal catalyst material deposited on the surface of the silicon wafer to grow silicon nanowires.
본 발명의 제2 특징에 따른 실리콘 나노선 제조 방법은, 실리콘 웨이퍼를 세정하는 단계; 상기 실리콘 웨이퍼의 표면에 금속 촉매 물질의 나노 파티클(nano-particle)을 형성하는 단계; 상기 실리콘 웨이퍼의 표면에 형성된 금속 촉매 물질의 나노 파티클의 표면에 희석 물질에 의해 희석된 모노실란가스(SiH4)를 증착시켜 실리콘 나노선을 성장시키는 단계;를 구비한다. According to a second aspect of the present invention, there is provided a method of manufacturing a silicon nanowire comprising: cleaning a silicon wafer; Forming a nano-particle of a metal catalyst material on a surface of the silicon wafer; And growing a silicon nanowire by depositing a monosilane gas (SiH 4 ) diluted by a diluent on the surface of the nanoparticle of the metal catalyst material formed on the surface of the silicon wafer.
본 발명의 제3 특징에 따른 실리콘 나노선 제조 방법은, 실리콘 웨이퍼를 세정하는 단계; 상기 실리콘 웨이퍼의 표면에 금속 촉매 물질을 증착하는 단계; 상기 실리콘 웨이퍼의 표면에 증착된 금속 촉매 물질의 표면에 액화 테트라클로로실란가스(SiCl4)에 사전에 설정된 양의 수소가스(H2)를 전달자 가스(Carrier Gas)로 사용하여 반응시켜 생성된 실리콘 입자를 증착시켜 실리콘 나노선을 성장시키는 단계;를 구비한다.According to a third aspect of the present invention, there is provided a method of manufacturing a silicon nanowire comprising: cleaning a silicon wafer; Depositing a metal catalyst material on a surface of the silicon wafer; (H 2 ) is supplied to the surface of the metal catalyst material deposited on the surface of the silicon wafer by using a predetermined amount of hydrogen gas (H 2 ) as a carrier gas in liquefied tetrachlorosilane gas (SiCl 4 ) And depositing the particles to grow silicon nanowires.
전술한 특징들에 따른 실리콘 나노선 제조 방법에 있어서, 상기 실리콘 웨이퍼는 (111) 및 (100) 중 어느 하나의 결정 방향을 갖는 것이 바람직하다. In the method for manufacturing a silicon nanowire according to the above-described characteristics, it is preferable that the silicon wafer has a crystal orientation of any one of (111) and (100).
전술한 특징들에 따른 실리콘 나노선 제조 방법에 있어서, 상기 희석 물질은 아르곤(Ar)인 것이 바람직하며, 수소 또는 질소 가스도 사용될 수 있다. In the silicon nanowire manufacturing method according to the above-described characteristics, the diluent is preferably argon (Ar), and hydrogen or nitrogen gas may also be used.
전술한 특징들에 따른 실리콘 나노선 제조 방법에 있어서, 상기 금속 촉매 물질은 Au, Cu, Ni, Mn 중 하나인 것이 바람직하다. In the silicon nanowire manufacturing method according to the above-described characteristics, the metal catalyst material is preferably one of Au, Cu, Ni, and Mn.
전술한 특징들에 따른 실리콘 나노선 제조 방법에 있어서, 상기 실리콘 나노선을 성장시키기 위하여 전기 화학 기상 증착 방법을 이용하는 것이 바람직하며, 상기 실리콘 나노선을 성장시키기 위한 온도, 시간 및 압력은 요구되는 실리콘 나노선의 두께, 길이 및 적층 결함의 주기성에 따라 결정되는 것이 더욱 바람직하다. In the method of manufacturing a silicon nanowire according to the above-described characteristics, it is preferable to use an electrochemical vapor deposition method for growing the silicon nanowire, and the temperature, time, It is more preferable to be determined according to the thickness, the length of the nanowire, and the periodicity of the lamination defect.
전술한 특징들에 따른 실리콘 나노선 제조 방법에 있어서, 상기 실리콘 나노선을 성장시키는 단계는, 실리콘 웨이퍼를 전기화학기상증착기내에 외치시킨 후, 상기 전기화학기상증착기를 사전에 설정된 온도를 유지한 상태에서 액화 테트라클로로실란(SiCl4)에 사전에 설정된 양의 수소(H2) 가스를 전달자 가스(Carrier Gas)로 사용하여 반응시켜 생성된 실리콘 입자를 주입하여 사전에 설정된 시간 동안 실리콘 나노선을 성장시키는 것이 바람직하다.In the method for manufacturing a silicon nanowire according to the above-described characteristics, the step of growing the silicon nanowire may include: after shining a silicon wafer in an electrochemical vapor deposition apparatus, the electrochemical vapor deposition apparatus is maintained at a predetermined temperature (H 2 ) gas as a carrier gas to a liquefied tetrachlorosilane (SiCl 4 ) and injecting the generated silicon particles to grow silicon nanowires for a predetermined time .
전술한 특징들에 따른 실리콘 나노선 제조 방법에 있어서, 상기 전기화학기상증착기의 온도, 시간 및 수소가스(H2)의 양은 요구되는 실리콘 나노선의 두께, 길이 및 적층 결함의 주기성에 따라 결정되는 것이 바람직하다.In the silicon nanowire manufacturing method according to the above-described characteristics, the temperature, the time and the amount of the hydrogen gas (H 2 ) of the electrochemical vapor deposition apparatus are determined depending on the thickness, length and periodicity of the lamination defect required for the silicon nanowire desirable.
전술한 특징들에 따른 실리콘 나노선 제조 방법에 있어서, 상기 성장된 실리콘 나노선은 외부에 적층 결함(Stacking Fault)이 생성된 것이 바람직하다. In the method of manufacturing a silicon nanowire according to the above-described characteristics, it is preferable that a stacking fault is generated outside the grown silicon nanowire.
본 발명에 의한 실리콘 나노선 제조 방법은 외부에 생성된 적층 결함(Stacking Fault)에 의하여 거친 표면을 가지게 되고, 그 결과 종래의 매끄러운 표면을 갖는 실리콘 나노선에 비해 넓은 표면적을 갖게 된다. 이러한 넓은 표면적을 갖는 실리콘 나노선은 셀 분리 기술에 응용되거나 센서 및 태양 전지 등에 응용될 수 있다. 그뿐만 아니라, 전자 및 열전자를 제어하여 열전 소자에 응용가능성이 높기 때문에, 환경성과 경제성이 좋지 못한 BiTe, PbTe 물질을 기반으로 한 열전 소자들을 대체할 수 있게 된다. The method of producing a silicon nanowire according to the present invention has a roughened surface due to an externally generated stacking fault, and as a result, it has a larger surface area than that of a conventional silicon nano wire having a smooth surface. Silicon nanowires having such a large surface area can be applied to cell separation technology, sensors, and solar cells. In addition, it is possible to substitute thermoelectric elements based on BiTe and PbTe materials which have poor environmental and economical efficiency because they have high possibility of application to thermoelectric elements by controlling electrons and thermoelectrons.
도 1은 본 발명의 바람직한 실시예에 따른 거친 표면을 갖는 실리콘 나노선 제조 방법을 순차적으로 설명하는 흐름도이다.
도 2는 본 발명의 바람직한 실시예에 따라 제조된 실리콘 나노선들의 SEM 사진이다.
도 3은 본 발명의 바람직한 실시예에 따라 제조된 실리콘 나노선들의 TEM 사진이다. 1 is a flowchart sequentially illustrating a method of manufacturing a silicon nanowire having a rough surface according to a preferred embodiment of the present invention.
2 is a SEM photograph of silicon nanowires manufactured according to a preferred embodiment of the present invention.
3 is a TEM photograph of silicon nanowires manufactured according to a preferred embodiment of the present invention.
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시예에 따른 거친 표면을 갖는 실리콘 나노선 제조 방법을 구체적으로 설명한다. Hereinafter, a method of manufacturing a silicon nanowire having a rough surface according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.
도 1을 참조하면, 먼저 (111) 결정 방향을 갖는 실리콘 웨이퍼를 아세톤 및 이소프로필렌알코올(Isopropyl alcohol; IPA)로 세정한다(단계 100). 이때 실리콘 웨이퍼는 (111) 방향외에도 결정 성장이 용이한 다른 결정 방향의 것도 사용될 수 있다. Referring to FIG. 1, a silicon wafer having a (111) crystal orientation is first cleaned with acetone and isopropyl alcohol (IPA) (step 100). In this case, the silicon wafer may have other crystal orientations other than the (111) direction, which facilitates crystal growth.
다음, 전자빔 증착 방법(E-beam evaporation)을 이용하여 실리콘 웨이퍼의 표면에 금속 촉매 물질을 1-5nm 증착한다. 이때, 금속 촉매 물질은 Au, Ni, Cu, Mn 등이 사용될 수 있다(단계 110). Next, a metal catalyst material is deposited to a thickness of 1-5 nm on the surface of a silicon wafer using an E-beam evaporation method. At this time, Au, Ni, Cu, Mn, or the like may be used as the metal catalyst material (Step 110).
다음, 실리콘 웨이퍼를 적당 크기로 절단한다(단계 120).Next, the silicon wafer is cut to a proper size (step 120).
다음, 전기 화학 기상 증착 방법을 이용하여 상기 실리콘 웨이퍼의 표면에 실리콘 나노선을 성장시키기 위하여, 전기 화학 기상 증착기에 실리콘 웨이퍼를 위치시키고, 450~700℃ 를 유지하는 상태에서 아르곤(Ar)이 희석된 모노실란(SiH4) 가스를 5-10sccm 주입하여, 2-4시간동안 실리콘 나노선을 성장시킨다(단계 130). 본 발명의 다른 실시형태는, 아르곤(Ar)을 대신하여 수소나 질소가 희석된 모노실란 가스를 주입하여 실리콘 나노선을 성장시킬 수도 있다. Next, in order to grow silicon nanowires on the surface of the silicon wafer using an electrochemical vapor deposition method, a silicon wafer is placed in an electrochemical vapor deposition apparatus, and argon (Ar) is diluted in a state of being maintained at 450 to 700 ° C (SiH 4 ) gas is injected at 5-10 sccm to grow silicon nanowires for 2-4 hours (step 130). In another embodiment of the present invention, a silicon nanowire may be grown by injecting monosilane gas diluted with hydrogen or nitrogen instead of argon (Ar).
또한, 본 발명의 또 다른 실시형태는, 상기 모노실란(SiH4) 가스를 대신하여 액화 테트라클로로실란(SiCl4)에 수소(H2) 가스를 전달자 가스로 이용하여 주입할 수도 있다. 상기 액화 테트라클로로실란(SiCl4)를 주입할 경우, 수소(H2)를 함께 주입시킴으로써 실리콘(Si)과 염화수소(HCl)로 분리시킬 수 있다. 상기 실리콘(Si)는 실리콘 나노선을 성장시키는데 사용되고, 상기 염화수소(HCl)은 실리콘 나노선 표면에 붙어서 상기 실리콘 나노선의 표면을 패시베이션(passivation) 시키는데 사용된다. 즉, 염화수소(HCl)의 농도가 높으면 패시베이션(passivation)이 많이 이루어져 매끄러운 표면이 되고, 염화수소(HCl)의 농도가 낮으면 패시베이션(passivation)이 적게 이루어져 거친 표면이 되는 것이다. 여기서, 상기 테트라클로로실란(SiCl4)으로부터 해리된 염소(Cl)와 수소(H2)가 결합하여 염화수소(HCl)를 형성하는 것이므로, 염화수소(HCl)의 농도는 수소(H2)의 주입량에 비례한다.In still another embodiment of the present invention, hydrogen (H 2 ) gas may be injected into liquefied tetrachlorosilane (SiCl 4 ) instead of the monosilane (SiH 4 ) gas as a carrier gas. When the liquefied tetrachlorosilane (SiCl 4 ) is injected, it can be separated into silicon (Si) and hydrogen chloride (HCl) by injecting hydrogen (H 2 ) together. The silicon (Si) is used to grow silicon nanowires, and the hydrogen chloride (HCl) is used to passivate the surface of the silicon nanowires attached to the surface of the silicon nanowires. That is, when the concentration of hydrogen chloride (HCl) is high, a lot of passivation is performed to form a smooth surface, and when the concentration of hydrogen chloride (HCl) is low, passivation is less and the surface becomes rough. Here, the injection amount of the tetrachlorosilane the chlorine (Cl) and hydrogen (H 2) is because of forming a hydrogen chloride (HCl) in combination, hydrogen chloride (HCl) concentration of hydrogen (H 2) of dissociation from (SiCl 4) It is proportional.
또한, 본 발명에 따라 실리콘 나노선을 성장시키기 위한 온도, 압력, 성장시간은 원하는 실리콘 나노선의 두께, 길이 및 거친 표면의 주기성에 따라 결정될 수 있다.
In addition, the temperature, pressure, and growth time for growing silicon nanowires according to the present invention can be determined according to the thickness, length, and periodicity of the rough surface of the desired silicon nanowires.
도 2는 본 발명에 의하여 성장된 실리콘 나노선에 대한 주사전자현미경(Field Emission Scanning Electron Microscope) 사진이며, 도 3은 TEM(Transmission Electron Microscope) 사진이다. 도 2 및 도 3을 통해 알 수 있는 바와 같이, 본 발명에 따른 실리콘 나노선 제조 방법에 의하여 제작된 실리콘 나노선은 외부에 생성된 적층 결함(Stacking Fault)에 의하여 거친 표면이 형성되며, 그 결과 넓은 표면적을 갖게 된다. 여기서, 적층 결함(Stacking Fault)이 발생하는 이유는, 실리콘 나노선 끝 쪽에 있는 금입자(Au)들이 상기 실리콘 나노선의 벽면으로 흘러내려 작은 파티클 형태로 존재하는데, 상기 금입자(Au)가 존재하는 곳은 표면에너지가 낮아 실리콘분자(Si)들이 다른 표면보다 쉽게 달라붙을 수 있기 때문이다. 즉, 실리콘분자(Si)들이 상기 금입자(Au)를 중심으로 달라붙게 되므로, 상기 실리콘 분자(Si)들은 다수 개의 금입자들마다 서로 다른 방향으로 성장하게 되어 각각 실리콘 나노선 표면 위에 다시 성장된 경계면에서 적층 결함(Stacking Fault)이 발생하게 되는 것이다.FIG. 2 is a scanning electron microscope (SEM) image of a silicon nanowire grown by the present invention, and FIG. 3 is a TEM (Transmission Electron Microscope) photograph. As can be seen from FIGS. 2 and 3, the silicon nanowires fabricated by the method of manufacturing a silicon nanowire according to the present invention have a roughened surface formed by an external stacking fault, Resulting in a large surface area. The reason why stacking faults occur is that gold particles (Au) at the end of the silicon nanowire flow down to the wall surface of the silicon nanowire and exist in the form of small particles, and the gold particles (Au) This is because the surface energy is so low that silicon molecules (Si) can stick easily to other surfaces. That is, since silicon molecules (Si) stick to the gold particles (Au) as a center, the silicon molecules (Si) grow in different directions for each of a plurality of gold particles, A stacking fault occurs at the interface.
기존의 나노선과는 달리 더 넓은 표면적을 갖는 거친 표면의 실리콘 나노선은 세포분리기술, 센서, 태양전지 등에 응용가능하다. 또한, 거친 표면의 실리콘 나노선은 열전 소자로서, 기존의 벌크(bulk) 실리콘보다 100배 낮은 열전도도를 갖는 동시에 figure of merit(ZT)가 단일 실리콘 나노선으로는 0.6이며, 정렬된 실리콘 나노선으로 이루어진 소자는 1이다. 본 발명에 따라 제조된 실리콘 나노선의 적층 결함(Stacking Fault)은 실리콘 나노선을 통하여 지나가는 전자 및 열전자를 조절하여 기존의 나노선들보다 더 낮은 열전도도를 갖게 함과 동시에 높은 figure of merit을 지닐 수 있도록 하여, 기존의 벌크 기반의 열전소자 물질인 BiTe, PbTe를 대체할 수 있다. Unlike conventional nano-wires, rough surface silicon nano-wires with larger surface area can be applied to cell separation technology, sensors, and solar cells. Silicon nanowires on a rough surface are thermoelectric devices that have a thermal conductivity 100 times lower than conventional bulk silicon and have a figure of merit (ZT) of 0.6 for a single silicon nanowire, Is 1. Stacking faults of silicon nanowires fabricated according to the present invention can control electrons and thermal electrons passing through silicon nanowires to have a lower thermal conductivity than conventional nanowires and to have a high figure of merit To replace the conventional bulk-based thermoelectric elements BiTe and PbTe.
한편, 본 발명의 다른 실시예에 따른 실리콘 나노선 제조 방법은, 세정된 실리콘 웨이퍼위에 금속 촉매 물질로 된 나노 파티클(nano-particle)을 형성하고, 그 위에 실리콘 나노선을 성장시키는 것을 특징으로 한다.
According to another embodiment of the present invention, there is provided a method of fabricating a silicon nanowire comprising: forming a nanoparticle of a metal catalyst material on a cleaned silicon wafer; and growing a silicon nanowire thereon .
이상에서 본 발명에 대하여 그 바람직한 실시예를 중심으로 설명하였으나, 이는 단지 예시일 뿐 본 발명을 한정하는 것이 아니며, 본 발명이 속하는 분야의 통상의 지식을 가진 자라면 본 발명의 본질적인 특성을 벗어나지 않는 범위에서 이상에 예시되지 않은 여러 가지의 변형과 응용이 가능함을 알 수 있을 것이다. 그리고, 이러한 변형과 응용에 관계된 차이점들은 첨부된 청구 범위에서 규정하는 본 발명의 범위에 포함되는 것으로 해석되어야 할 것이다. While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be understood that various changes and modifications may be made without departing from the spirit and scope of the invention. It is to be understood that the present invention may be embodied in many other specific forms without departing from the spirit or essential characteristics thereof.
본 발명에 따른 거친 표면을 갖는 실리콘 나노선 제조 방법은 실리콘 나노선에 높은 표면적을 제공함으로써, 가스 센서나 바이오센서 등과 같은 센서에 이용이 가능할 뿐만 아니라, 단일 면적당 많은 태양 빛을 집적하여야 하는 태양 전지에도 이용 가능하다. 또한, 나노선을 기반으로 한 세포 분리 기술에도 적용되어 높은 수율을 기대할 수 있다. The method of manufacturing a silicon nanowire having a rough surface according to the present invention can provide a high surface area to a silicon nanowire and thus can be used for a sensor such as a gas sensor or a biosensor, Lt; / RTI > In addition, it can be applied to cell separation technology based on nanowire, and high yield can be expected.
또한, 본 발명에 따른 실리콘 나노선 제조 방법은, 외부의 거친 표면과 외부의 적층 결함으로 인하여 기존의 벌크형 실리콘이 갖는 ZT보다 높은 값을 지닐 수 있어 열전 소자에도 응용이 가능하다. In addition, the method of manufacturing a silicon nanowire according to the present invention can be applied to a thermoelectric device because it can have a higher value than the ZT of a conventional bulk silicon due to an external rough surface and external lamination defects.
또한, 본 발명에 따른 실리콘 나노선 제조 방법은 나노 기술을 기반으로 이루어진 전자통신분야에 이용될 수 있을 뿐만 아니라 태양광이나 열전소자와 같은 에너지 산업 및 바이오 산업에도 널리 사용될 수 있다.
In addition, the method of manufacturing a silicon nanowire according to the present invention can be widely used not only in the field of electronic communication based on nanotechnology but also in the energy industry such as sunlight and thermoelectric devices and the bio industry.
Claims (12)
상기 실리콘 웨이퍼의 표면에 금속 촉매 물질을 증착하는 단계;
상기 실리콘 웨이퍼의 표면에 증착된 금속 촉매 물질의 표면에 희석 물질에 의해 희석된 모노실란가스(SiH4)를 증착시켜 실리콘 나노선을 성장시키는 단계;
를 구비하고,
상기 실리콘 나노선을 성장시키는 단계는, 실리콘 웨이퍼를 전기화학기상증착기내에 위치시킨 후, 상기 전기화학기상증착기내로 희석물질에 의해 희석된 모노실란가스를 주입시켜 실리콘 나노선을 성장시키는 것을 특징으로 하는 실리콘 나노선 제조 방법. Cleaning the silicon wafer;
Depositing a metal catalyst material on a surface of the silicon wafer;
Depositing monosilane gas (SiH 4 ) diluted by a diluent on the surface of the metal catalyst material deposited on the surface of the silicon wafer to grow silicon nanowires;
And,
Wherein the step of growing the silicon nanowires comprises the steps of positioning a silicon wafer in an electrochemical vapor deposition apparatus and then injecting a monosilane gas diluted by a diluting material into the electrochemical vapor deposition apparatus to grow silicon nanowires Silicon nanowire manufacturing method.
상기 실리콘 웨이퍼의 표면에 금속 촉매 물질의 나노 파티클(nano-particle)을 형성하는 단계;
상기 실리콘 웨이퍼의 표면에 형성된 금속 촉매 물질의 나노 파티클의 표면에 희석 물질에 의해 희석된 모노실란가스(SiH4)를 증착시켜 실리콘 나노선을 성장시키는 단계;
상기 실리콘 나노선을 성장시키는 단계는, 실리콘 웨이퍼를 전기화학기상증착기내에 위치시킨 후, 상기 전기화학기상증착기내로 희석물질에 의해 희석된 모노실란가스를 주입시켜 실리콘 나노선을 성장시키는 것을 특징으로 하는 실리콘 나노선 제조 방법. Cleaning the silicon wafer;
Forming a nano-particle of a metal catalyst material on a surface of the silicon wafer;
Depositing monosilane gas (SiH 4 ) diluted with a diluent on the surface of the nanoparticle of the metal catalyst material formed on the surface of the silicon wafer to grow silicon nanowires;
Wherein the step of growing the silicon nanowires comprises the steps of positioning a silicon wafer in an electrochemical vapor deposition apparatus and then injecting a monosilane gas diluted by a diluting material into the electrochemical vapor deposition apparatus to grow silicon nanowires Silicon nanowire manufacturing method.
상기 실리콘 웨이퍼의 표면에 금속 촉매 물질을 증착하는 단계;
상기 실리콘 웨이퍼의 표면에 증착된 금속 촉매 물질의 표면에 액화 테트라클로로실란가스(SiCl4)에 수소가스(H2)를 전달자 가스(Carrier Gas)로 사용하여 반응시켜 생성된 실리콘 입자를 증착시켜 실리콘 나노선을 성장시키는 단계;
를 구비하는 실리콘 나노선 제조 방법.Cleaning the silicon wafer;
Depositing a metal catalyst material on a surface of the silicon wafer;
The surface of the metal catalyst material deposited on the surface of the silicon wafer is reacted with liquefied tetrachlorosilane gas (SiCl 4 ) using hydrogen gas (H 2 ) as a carrier gas, Growing a nanowire;
Wherein the silicon nanowires are formed on the silicon nanowires.
4. The method according to any one of claims 1 to 3, wherein the grown silicon nanowire has a stacking fault outside thereof.
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| KR20180068574A (en) | 2016-12-14 | 2018-06-22 | 광운대학교 산학협력단 | Method for controlling of growth of self-assembled Au nanoparticles on GaN |
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| KR102517722B1 (en) | 2021-05-31 | 2023-04-04 | 주식회사 비이아이랩 | Method for Silicon Synthesis using Gas-phase Electroreduction |
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