Methods of fabricating nanostructures and nanowires and devices fabricated therefrom
Abstract
One-dimenSional nanostructures having uniformdiameters of less than approximately 200 nm. Theseinventive nanostructures, which we refer to as"nanowires", include single-cTystallinehomostructures as well as hererostructures of atleast two single-crystalline materials havingdifferent chemical compositions. Becausesingle-crystalline materials are used to form theheterostructure, the resultant heterostructure willbe single-crystalline as well. The nanowireheterostructures are generally based on aseiniconducting wire wherein the doping andcomposition are controlled in either thelongitudinal or radial directions, or in bothdirections, to yield a wire that comprisesdifferent materials. Examples of resulting nanowireheterostructures include a longitudinalheterostructure nanowire (LOHN) and a coaxialheterostructure nanowire (CoHN).

Term
No projected expiry on record.
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208 claims: 176 independent, 32 dependent
- 1一種奈米結構,包括有:一第一段,由一實質結晶材料所構成;以及一第二段,係與該第一段連接,且由不同於該第一段材質之材料所構成;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 2如申請專利範圍第1項所述之奈米結構,其中該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm。
- 3如申請專利範圍第2項所述之奈米結構,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%。
- 4如申請專利範圍第1項所述之奈米結構,其中該第二段包含有一實質結晶材料。
- 5如申請專利範圍第1項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一半導體材料。
- 6如申請專利範圍第1項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 7如申請專利範圍第1項所述之奈米結構,其中該第一段與該第二段之中至少一個表現出一塊體摻雜之半導體的電性特徵。
- 8一種奈米結構,包括有:一第一段,由一實質結晶材料所構成;以及一第二段,係與該第一段連接,且由一實質結晶材料所構成;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 9如申請專利範圍第8項所述之奈米結構,其中該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm。
- 10如申請專利範圍第9項所述之奈米結構,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%。
- 11如申請專利範圍第8項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一半導體材料。
- 12如申請專利範圍第8項所述之奈米結構,其中該第一段與該第二段包含有一半導體材料。
- 13如申請專利範圍第8項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 14如申請專利範圍第8項所述之奈米結構,其中該第一段與該第二段包含有一摻雜之半導體材料。
- 15如申請專利範圍第8項所述之奈米結構,其中該第一段與該第二段之中至少一個表現出一塊體摻雜之半導體的電性特徵。
- 16如申請專利範圍第8項所述之奈米結構,其中該第一段與該第二段表現出一塊體摻雜之半導體的電性特徵。
- 17一種奈米結構,包括有:一第一段,由一半導體材料所構成;以及一第二段,係與該第一段連接,且由一半導體材料所構成;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 18如申請專利範圍第17項所述之奈米結構,其中該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm。
- 19如申請專利範圍第18項所述之奈米結構,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%。
- 20如申請專利範圍第17項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 21如申請專利範圍第17項所述之奈米結構,其中該第一段與該第二段包含有一摻雜之半導體材料。
- 22一種奈米結構,包括有:一第一段,由一摻雜之半導體材料所構成;以及一第二段,係與該第一段連接,且由一摻雜之半導體材料所構成;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 23如申請專利範圍第22項所述之奈米結構,其中該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm。
- 24如申請專利範圍第23項所述之奈米結構,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%。
- 25一種奈米結構,包括有:一第一段,由一實質結晶材料所構成;以及一第二段,係與該第一段連接,且由不同於該第一段材質之材料所構成;其中,該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm;以及其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 26如申請專利範圍第25項所述之奈米結構,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%。
- 27如申請專利範圍第25項所述之奈米結構,其中該第二段包含有一實質結晶材料。
- 28如申請專利範圍第25項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一半導體材料。
- 29如申請專利範圍第25項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 30如申請專利範圍第25項所述之奈米結構,其中該第一段與該第二段之中至少一個表現出一塊體摻雜之半導體的電性特徵。
- 31一種奈米結構,包括有:一第一段,由一實質結晶材料所構成;以及一第二段,係與該第一段連接,且由一實質結晶材料所構成;其中,該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm;以及其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 32如申請專利範圍第31項所述之奈米結構,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%。
- 33如申請專利範圍第31項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一半導體材料。
- 34如申請專利範圍第31項所述之奈米結構,其中該第一段與該第二段包含有一半導體材料。
- 35如申請專利範圍第31項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 36如申請專利範圍第31項所述之奈米結構,其中該第一段與該第二段包含有一摻雜之半導體材料。
- 37如申請專利範圍第31項所述之奈米結構,其中該第一段與該第二段之中至少一個表現出一塊體摻雜之半導體的電性特徵。
- 38如申請專利範圍第31項所述之奈米結構,其中該第一段與該第二段表現出一塊體摻雜之半導體的電性特徵。
- 39一種奈米結構,包括有:一第一段,由一半導體材料所構成;以及一第二段,係與該第一段連接,且由一半導體材料所構成;其中,該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm;以及其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 40如申請專利範圍第39項所述之奈米結構,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%。
- 41如申請專利範圍第40項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 42如申請專利範圍第39項所述之奈米結構,其中該第一段與該第二段包含有一摻雜之半導體材料。
- 43一種奈米結構,包括有:一第一段,由一摻雜之半導體材料所構成;以及一第二段,係與該第一段連接,且由一摻雜之半導體材料所構成;其中,該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm;以及其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 44如申請專利範圍第43項所述之奈米結構,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%。
- 45一種奈米結構,包括有:一第一段,由一實質結晶材料所構成;以及一第二段,係與該第一段連接,且由不同於該第一段材質之材料所構成;其中,該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm。其中,自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%;以及其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 46如申請專利範圍第45項所述之奈米結構,其中該第二段包含有一實質結晶材料。
- 47如申請專利範圍第45項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一半導體材料。
- 48如申請專利範圍第45項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 49如申請專利範圍第45項所述之奈米結構,其中該第一段與該第二段之中至少一個表現出一塊體摻雜之半導體的電性特徵。
- 50一種奈米結構,包括有:一第一段,由一實質結晶材料所構成;以及一第二段,係與該第一段連接,且由一實質結晶材料所構成;其中,該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm;其中,自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm;以及其中,該直徑小於200nm之線段的直徑變化不會大於該線段之長度的10%。
- 51如申請專利範圍第50項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一半導體材料。
- 52如申請專利範圍第50項所述之奈米結構,其中該第一段與該第二段包含有一半導體材料。
- 53如申請專利範圍第50項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 54如申請專利範圍第50項所述之奈米結構,其中該第一段與該第二段包含有一摻雜之半導體材料。
- 55如申請專利範圍第50項所述之奈米結構,其中該第一段與該第二段之中至少一個表現出一塊體摻雜之半導體的電性特徵。
- 56如申請專利範圍第50項所述之奈米結構,其中該第一段與該第二段表現出一塊體摻雜之半導體的電性特徵。
- 57一種奈米結構,包括有:一第一段,由一半導體材料所構成;以及一第二段,係與該第一段連接,且由一半導體材料所構成;其中,該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm;其中。自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm;以及其中,該直徑小於200nm之線段的直徑變化不會大於該線段之長度的10%。
- 58如申請專利範圍第57項所述之奈米結構,其中該第一段與該第二段之中至少一個包含有一摻雜之半導體材料。
- 59如申請專利範圍第57項所述之奈米結構,其中該第一段與該第二段包含有一摻雜之半導體材料。
- 60一種奈米結構,包括有:一第一段,由一摻雜之半導體材料所構成;以及一第二段,係與該第一段連接,且由一摻雜之半導體材料所構成;其中,該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm;其中,自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該第一段中心處成份的99%;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm;以及其中,該直徑小於200nm之線段的直徑變化不會大於該線段之長度的10%。
- 61如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中至少一線段之直徑小於200nm,且該直徑範圍為5~50nm。
- 62如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中至少一線段之直徑小於200nm,且該直徑小於200nm之線段的直徑變化不會大於該線段之長度的10%。
- 63如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第二段係縱向相鄰於該第一段。
- 64如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第二段係軸向相鄰於該第一段。
- 65如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第一段包含有一實質單晶材料。
- 66如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第二段包含有一實質單晶材料。
- 67如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第一段與該第二段形成一p-n接合面。
- 68如申請專利範圍第67項所述之奈米結構,其中該奈米結構包含有一半導體元件。
- 69如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第一段與該第二段形成一p-i接合面。
- 70如申請專利範圍第69項所述之奈米結構,其中該奈米結構包含有一半導體元件。
- 71如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第一段與該第二段形成一i-n接合面。
- 72如申請專利範圍第71項所述之奈米結構,其中該奈米結構包含有一半導體元件。
- 73如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,更包含有一電極,係與該第一段與該第二段之中至少一個形成電連接。
- 74如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第一段與該第二段之中至少一個的材料是選自於Ⅱ族、Ⅲ族、Ⅳ族、Ⅴ族或Ⅵ族元素。
- 75如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第一段與該第二段之中至少一個係埋入一聚合物母體中。
- 76如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該第一段與該第二段之中至少一個的至少一部分係被一護套所覆蓋。
- 77如申請專利範圍第76項所述之奈米結構,其中該護套包含有一非晶質材料。
- 78如申請專利範圍第76項所述之奈米結構,其中該護套包含有一實質結晶材料。
- 79如申請專利範圍第78項所述之奈米結構,其中該實質結晶材料為實質單結晶。
- 80如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該奈米線是下列元件的一個功能部件,包含有:聲子帶隙元件、量子點元件、熱電元件、光子元件、奈米電機致動器、奈米電機感應器、場效電晶體、紅外線偵測器、共振穿遂二極體、單電子電晶體、磁感應器、發光元件、光學調整器、光學偵測器、光學導波管、光學耦合器、光學開關以及雷射。
- 81如申請專利範圍第1、8、17、22、25、31、39、43、45、50、57或60項所述之奈米結構,其中該奈米結構是一奈米結構陣列的一個單元。
- 82一種奈米結構,包括有:一第一段,由一材料所構成;一第二段,係與該第一段連接,且由一材料所構成;以及一第三段,係與該第一段與該第二段之中至少一個連接,且由一材料所構成;其中,至少一個線段包含有一實質均勻的直徑,且該直徑小於200nm;其中,至少兩個線段是由不同材料所構成;以及其中,至少兩個線段是相鄰的。
- 83如申請專利範圍第82項所述之奈米結構,其中該直徑小於200nm之線段的直徑變化不會大於該線段之長度的10%。
- 84如申請專利範圍第82項所述之奈米結構,其中該奈米結構變遷自至少一線段至相鄰之線段之距離範圍為一原子層~20nm。
- 85如申請專利範圍第82項所述之奈米結構,其中自至少一線段至一相鄰線段之變遷係起始於一朝向該相鄰線段之端點,該線段之該端點成份降低成為該線段中心處成份的99%。
- 86如申請專利範圍第82項所述之奈米結構,其中至少兩個線段是縱向相鄰的。
- 87如申請專利範圍第82項所述之奈米結構,其中該第二段係軸向縱向相鄰於該第一段,且該第三段係縱向相鄰於該第二段。
- 88如申請專利範圍第82項所述之奈米結構,其中至少兩個線段是軸向相鄰的。
- 89如申請專利範圍第82項所述之奈米結構,其中至少一線段的材料包含有一實質結晶材料。
- 90如申請專利範圍第89所述之奈米結構,其中該實質結晶材料為實質單結晶。
- 91如申請專利範圍第82項所述之奈米結構,其中至少一線段的材料包含有一半導體材料。
- 92如申請專利範圍第82項所述之奈米結構,其中至少一線段的材料包含有一摻雜之半導體材料。
- 93如申請專利範圍第82項所述之奈米結構,其中至少一線段顯現出一塊體之摻雜半導體的電性特徵。
- 94如申請專利範圍第82項所述之奈米結構,其中至少一線段之直徑小於200nm,且該直徑範圍為5~50nm。
- 95如申請專利範圍第82項所述之奈米結構,其中至少兩線段形成一p-n接合面。
- 96如申請專利範圍第82項所述之奈米結構,其中至少兩線段形成一p-i接合面。
- 97如申請專利範圍第82項所述之奈米結構,其中至少兩線段形成一i-n接合面。
- 98如申請專利範圍第82項所述之奈米結構,其中該線段形成一p-n-p接合面。
- 99如申請專利範圍第82項所述之奈米結構,其中該線段形成一n-p-n接合面。
- 100如申請專利範圍第82項所述之奈米結構,其中該線段形成一p-i-n接合面。
- 101如申請專利範圍第82項所述之奈米結構,其中該線段形成一p-i-p接合面。
- 102如申請專利範圍第95、96、97、98、99、100或101項所述之奈米結構,其中該奈米結構包含有一半導體元件。
- 103如申請專利範圍第82項所述之奈米結構,更包含有一電極,係與至少一個線段形成電連接。
- 104如申請專利範圍第82項所述之奈米結構,其中至少一個線段的材料是選自於Ⅱ族、Ⅲ族、Ⅳ族、Ⅴ族或Ⅵ族元素。
- 105如申請專利範圍第82項所述之奈米結構,其中至少一個線段係埋入一聚合物母體中。
- 106如申請專利範圍第82項所述之奈米結構,其中至少一個線段的至少一部分係被一護套所覆蓋。
- 107如申請專利範圍第106項所述之奈米結構,其中該護套包含有一非晶質材料。
- 108如申請專利範圍第106項所述之奈米結構,其中該護套包含有一實質結晶材料。
- 109如申請專利範圍第108項所述之奈米結構,其中該實質結晶材料為實質單結晶。
- 110如申請專利範圍第82項所述之奈米結構,其中該奈米線是下列元件的一個功能部件,包含有:聲子帶隙元件、量子點元件、熱電元件、光子元件、奈米電機致動器、奈米電機感應器、場效電晶體、紅外線偵測器、共振穿遂二極體、單電子電晶體、磁感應器、發光元件、光學調整器、光學偵測器、光學導波管、光學耦合器、光學開關以及雷射。
- 111如申請專利範圍第82項所述之奈米結構,其中該奈米結構是一奈米結構陣列的一個單元。
- 112一種奈米結構的製作方法,包含有下列步驟:分解一媒介液體中的一第一氣體反應物,然後成長一第一段;以及分解該媒介液體中的一第二氣體反應物,然後成長一第二段,該第二段係與該第一段連接且由不同於該第一段材質之材料所構成;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 113如申請專利範圍第112項所述之奈米結構的製作方法,其中每一個氣體反應物以及該媒介液體係形成一相同組成之液體合金,且每一線段係形成自該液體合金之飽和處。
- 114如申請專利範圍第112項所述之奈米結構的製作方法,其中該第二氣體反應物包含有一氣體,是由運用於物種成長之雷射移蝕所提供的,且該第二段包含有該第一氣體反應物以及該第二氣體反應物之種類的組合。
- 115一種奈米結構的製作方法,包含有下列步驟:分解一媒介液體中的一氣體反應物,然後成長一第一段;以及於該第一段上塗佈一不同成份材料,以形成一第二段;其中,該第一段以及該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 116如申請專利範圍第115項所述之奈米結構的製作方法,其中該氣體反應物以及該媒介液體係形成一液體合金,且該第一段係形成自該液體合金之飽和處。
- 117一種奈米結構的製作方法,包含有下列步驟:(a)分解一媒介液體中的一第一氣體反應物,然後成長一第一材料,以形成一第一段;(b)分解該媒介液體中的一第二氣體反應物,然後成長一第二材料,以形成一與該一段相連接之第二段;(c)該氣體反應物以及該媒介液體係形成一液體合金,且該第一段與該第二段均形成自一液態合金的飽和處(d)於至少一線段之至少一部份塗佈一第三材料,以形成一第三段;(e)該第一材料、該第二材料與該第三材料之中至少兩個為不同成份;以及(f)該第一段、該第二段以及該第三段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 118一種奈米結構的製作方法,包含有下列步驟:分解一媒介液體中的一第一氣體反應物,然後成長一第一材料,以形成一第一段;分解該媒介液體中的一第二氣體反應物,然後成長一第二材料,以形成一與該第一段相連接之第二段;以及分解該媒介液體中的一第三氣體反應物,然後成長一第三材料,以形成一與該第二段相連接之第三段;其中,該第一段、該第二段以及該第三段係為縱向相鄰;其中,該第二段位於該第一段以及該第三段之間;以及其中,該第一段、該第二段以及該第三段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 119如申請專利範圍第118項所述之奈米結構的製作方法,其中該第一、第二與第三氣體反應物之中至少有兩者為相同的,且該第一段、該第二段以及該第三段之中至少兩者由相同材質所構成。
- 120如申請專利範圍第118項所述之奈米結構的製作方法,其中該氣體反應物以及該媒介液體係形成一液體合金,且該奈米結構線段係形成自該液體合金之飽和處。
- 121如申請專利範圍第118項所述之奈米結構的製作方法,其中該至少一種氣體反應物包含有一氣體,是由運用於物種成長之雷射移蝕所提供的,且至少一奈米結構線段包含有該第一氣體反應物以及該第二氣體反應物之種類的組合。
- 122一種奈米線異質結構的製作方法,包含有下列步驟:分解一媒介液體中的一第一氣體反應物,然後成長一第一材料,以形成一第一段;以及分解該媒介液體中的一第二氣體反應物,然後成長一與該第一材料不同的第二材料,以形成一與該第一段呈現縱向連接之第二段;其中,該第一、第二氣體反應物以及該媒介液體係形成兩種不同成份的液體合金;其中,該第一段與該第二段係分別形成自相關氣體反應物成份之該液體合金之飽和處;以及其中,該第一段與該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 123一種奈米結構的製作方法,包含有下列步驟:分解一媒介液體中的一第一氣體反應物,然後成長一第一材料,以形成一第一段;以及依序雷射移蝕該第一氣體反應物中的成長物種,以形成一第二氣體反應物;以及分解該媒介液體中的一第二氣體反應物,然後成長一與該第一材料不同的第二材料,以形成一與該第一段呈現縱向相連接之第二段;其中,該第二段包含有該第一氣體反應物以及該第二氣體反應物之種類的組合;以及其中,該第一段與該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 124如申請專利範圍第123項所述之奈米結構的製作方法,其中該第一、第二氣體反應物以及該媒介液體係形成兩種不同成份的液體合金,且該第一段與該第二段係分別形成自相關氣體反應物成份之該液體合金之飽和處。
- 125一種摻雜半導體超晶格之奈米結構的製作方法,包含有下列步驟:將一氣體反應物通入一反應爐的反應艙體中,其中該反應艙體包含有一塗佈有反應金屬的基板;將該反應艙體加熱至一溫度,其可使該反應金屬液化成為至少一個液滴;將該反應氣體分解至該液滴中直至飽和,其可使一第一段成核與成長;以及將一摻質與該氣體反應物分解至該液滴中直至飽和,其可使一摻雜之第二段在該第一段上進形成核與成長;其中,該第一段與該第二段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。
- 126如申請專利範圍第125項所述之摻雜半導體超晶格之奈米結構的製作方法,其中該基板中主要包含有Ⅲ族以及Ⅳ族元素。
- 127如申請專利範圍第125項所述之摻雜半導體超晶格之奈米結構的製作方法,其中該金屬包含有金。
- 128如申請專利範圍第127項所述之摻雜半導體超晶格之奈米結構的製作方法,其中該金包含有膠態金(colloidal gold)。
- 129如申請專利範圍第125項所述之摻雜半導體超晶格之奈米結構的製作方法,其中該基板包含有矽,且該金屬包含有金。
- 130如申請專利範圍第125項所述之摻雜半導體超晶格之奈米結構的製作方法,其中該反應爐包含有一石英反應爐管。
- 131如申請專利範圍第125項所述之摻雜半導體超晶格之奈米結構的製作方法,其中該氣體反應物包含有H 2 與SiC1 4 的混合物。
- 132一種Si/SiGe超晶格之奈米線異質結構的製作方法,包含有下列步驟:於一基板上沉積一Au層;將該基板放置於一石英反應爐管中;將一包含有H 2 與SiCl 4 的混合氣體反應物通入該反應爐管中;將該反應爐管加熱至一溫度,其可使該Au層液化成為至少一個奈米規格的Au-Si合金液滴;將該反應氣體分解至該液滴中直至飽和,其可成核與成長出一Si線段;在成長該Si線段的過程中,雷射移蝕一Ge靶材以產生一Ge氣相;以及沉積Ge與Si物種於該Au-Si合金液滴中直至飽和,其可於該Si線段上成核與成長出一SiGe線段;其中,該Si線段與該SiGe線段之中至少一個包含有一實質均勻的直徑,且該直徑小於200nm。格之奈米結構的製作方法,其中該氣體反應物包含有H 2 與SiCl 4 的混合物。
- 133如申請專利範圍第132項所述之一種Si/SiGe超晶格之奈米線異質結構的製作方法,另包含有一步驟:開啟關閉該雷射之脈衝,可使該Si/SiGe超晶格形成塊體狀連接。
- 134如申請專利範圍第132項所述之一種Si/SiGe超晶格之奈米線異質結構的製作方法,其中該基板中主要包含有Ⅲ族以及Ⅳ族元素。
- 135如申請專利範圍第132項所述之一種Si/SiGe超晶格之奈米線異質結構的製作方法,其中該Au層包含有膠態金(colloidal gold)。
- 136如申請專利範圍第132項所述之一種Si/SiGe超晶格之奈米線異質結構的製作方法,其中該基板金包含有矽。
- 137如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中直徑小於200nm之線段的直徑變化不會大於該線段之長度的10%。
- 138如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中該奈米結構變遷自該第一段至該第二段之距離範圍為一原子層~20nm。
- 139如申請專利範圍第138項所述之製作方法,其中自該第一段至該第二段之變遷係起始於一朝向該第二段之端點,該第一段之該端點成份降低成為該線段中心處成份的99%。
- 140如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中至少一線段包含有一實質結晶材質。
- 141如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中至少一線段包含有一實質單結晶材質。
- 142如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中至少一線段包含有一半導體材質。
- 143如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,另包含有一步驟:對至少一線段進行摻雜。
- 144如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中至少一線段之直徑小於200nm,且該直徑範圍為5~50nm。
- 145如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中該第二段係縱向相鄰於該第一段。
- 146如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中該第二段係軸向相鄰於該第一段。
- 147如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,另包含有一步驟:對該第一段以及該第二段進行摻雜,以形成一p-n接合面。
- 148如申請專利範圍第147項所述之製作方法,其中該奈米結構包含有一半導體材料。
- 149如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,另包含有一步驟:對該第一段以及該第二段進行摻雜,以形成一p-i接合面。
- 150如申請專利範圍第149項所述之製作方法,其中該奈米結構包含有一半導體材料。
- 151如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,另包含有一步驟:對該第一段以及該第二段進行摻雜,以形成一i-n接合面。
- 152如申請專利範圍第151項所述之製作方法,其中該奈米結構包含有一半導體材料。
- 153如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,更包含有一步驟:形成一電極,以與該第一段與該第二段之中至少一個形成電連接。
- 154如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中該第一段與該第二段之中至少一個的材料是選自於Ⅱ族、Ⅲ族、Ⅳ族、Ⅴ族或Ⅵ族元素。
- 155如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中該第一段與該第二段之中至少一個係埋入一聚合物母體中。
- 156如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中該第一段與該第二段之中至少一個的至少一部分係被一護套所覆蓋。
- 157如申請專利範圍第156項所述之製作方法,其中該護套包含有一非晶質材料。
- 158如申請專利範圍第156項所述之製作方法,其中該護套包含有一實質結晶材料。
- 159如申請專利範圍第158項所述之製作方法,其中該實質結晶材料為實質單結晶。
- 160如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中該奈米線是下列元件的一個功能部件,包含有:聲子帶隙元件、量子點元件、熱電元件、光子元件、奈米電機致動器、奈米電機感應器、場效電晶體、紅外線偵測器、共振穿遂二極體、單電子電晶體、磁感應器、發光元件、光學調整器、光學偵測器、光學導波管、光學耦合器、光學開關以及雷射。
- 161如申請專利範圍第112、115、117、118、122、123、125或132項所述之製作方法,其中該奈米結構是一奈米結構陣列的一個單元。
- 162162一種奈米雷射,包含有:一奈米結構,其包含有一實質均勻的直徑,且該直徑小於200nm;以及一幫浦源。
- 163如申請專利範圍第162項所述之奈米雷射,其中該奈米結構係由不同成份組成之複數個線段所構成。
- 164如申請專利範圍第162項所述之奈米雷射,其中該幫浦源之配置是用來激發該奈米結構中的居量反轉。
- 165一種奈米雷射,包含有:一奈米結構,其乃由不同成份組成之複數個縱向相鄰的線段所構成,其中至少一個線段包含有一實質均勻的直徑,且該直徑小於200nm;以及一幫浦源。
- 166如申請專利範圍第165項所述之奈米雷射,其中該幫浦源之配置是用來激發該奈米結構中的居量反轉。
- 167一種奈米雷射,包含有:一奈米結構,其乃由不同成份組成之複數個縱向相鄰的線段所構成,其中至少一個線段包含有一實質均勻的直徑,且該直徑小於200nm;以及一幫浦源,其配置是用來激發該奈米結構中的居量反轉。
- 168一種奈米雷射,包含有:一奈米結構,其包含有一實質均勻的直徑,且該直徑小於200nm;複數個量子點,係置於該奈米結構中;以及一幫浦源。
- 169如申請專利範圍第168項所述之奈米雷射,其中該奈米結構係由不同成份組成之複數個線段所構成。
- 170如申請專利範圍第169項所述之奈米雷射,其中該幫浦源之配置是用來激發該量子點中的居量反轉。
- 171一種奈米雷射,包含有:一奈米結構,其乃由不同成份組成之複數個縱向相鄰的線段所構成,其中至少一個線段包含有一實質均勻的直徑,且該直徑小於200nm;複數個量子點,係置於該奈米結構中;以及一幫浦源。
- 172如申請專利範圍第171項所述之奈米雷射,其中該幫浦源之配置是用來激發該量子點中的居量反轉。
- 173一種奈米雷射,包含有:一奈米結構,其乃由不同成份組成之複數個縱向相鄰的線段所構成,其中至少一個線段包含有一實質均勻的直徑,且該直徑小於200nm;複數個量子點,係置於該奈米結構中;以及一幫浦源,其配置是用來激發該量子點中的居量反轉。
- 174如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該奈米結構包含有一實質結晶材質。
- 175如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該實質結晶材質為一實質單結晶材質。
- 176如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該奈米結構之直徑範圍為5~50nm。
- 177如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該奈米結構的直徑變化不會大於該線段之長度的10%。
- 178如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該奈米結構的材料是選自於II族、Ⅲ族、Ⅳ族、Ⅴ族或Ⅵ族元素。
- 179如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該奈米結構係埋入一聚合物母體中。
- 180如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該奈米結構是一奈米結構陣列的一個單元。
- 181如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該幫浦源包含有一光學脈衝源。
- 182如申請專利範圍第181項所述之奈米雷射,其中該光學脈衝源包含有一脈衝雷射。
- 183如申請專利範圍第162、165、167、171或173項所述之奈米雷射,其中該幫浦源包含有一導電脈衝源。
- 184如申請專利範圍第183項所述之奈米雷射,其中該導電脈衝源包含有一陰極與一陽極。
- 185如申請專利範圍第184項所述之奈米雷射,其中該陽極與該奈米結構形成一電連接。
- 186如申請專利範圍第185項所述之奈米雷射,其中該電連接係為一歐姆接觸。
- 187如申請專利範圍第185項所述之奈米雷射,其中該電連接係為一直接接觸。
- 188如申請專利範圍第184項所述之奈米雷射,其中該陰極與該奈米結構形成一電連接。
- 189如申請專利範圍第188項所述之奈米雷射,其中該電連接係為一歐姆接觸。
- 190如申請專利範圍第188項所述之奈米雷射,其中該電連接係為一直接接觸。
- 191如申請專利範圍第184項所述之奈米雷射,其中該陽極與該陰極皆與該奈米結構形成一電連接。
- 192如申請專利範圍第191項所述之奈米雷射,其中該電連接係為一歐姆接觸。
- 193如申請專利範圍第191項所述之奈米雷射,其中該電連接係為一直接接觸。
- 194如申請專利範圍第162、165、167、168、171或173項所述之奈米雷射,其中該奈米結構包含有一第一端以及一第二端,且該第一端以及該第二端均包含有反射表面。
- 195如申請專利範圍第194項所述之奈米雷射,其中該奈米結構包含有一開口。
- 196一種奈米雷射,包含有:一具有多個切面、單結晶之ZnO奈米結構,其包含有一實質均勻的直徑,且該直徑小於200nm;該奈米結構包含有一第一端以及一第二端;該第一端包含有一磊晶介面,係自該奈米結構延伸而形成於該奈米結構與一藍寶石基材之間;以及該第一端與該第二端包含有相對應之反射表面;其中,該奈米結構之功能是用作為該端點面之間的一個共振開口。
- 197如申請專利範圍第196項所述之奈米雷射,其中該奈米結構係埋入一聚合物母體中。
- 198如申請專利範圍第196項所述之奈米雷射,其中該奈米結構是一奈米結構陣列的一個單元。
- 199如申請專利範圍第196項所述之奈米雷射,另包含有一幫浦源。
- 200如申請專利範圍第199項所述之奈米雷射,其中該幫浦源包含有一光學脈衝源。
- 201如申請專利範圍第200項所述之奈米雷射,其中該光學脈衝源包含有一脈衝雷射。
- 202如申請專利範圍第199項所述之奈米雷射,其中該幫浦源包含有一導電脈衝源。
- 203如申請專利範圍第202項所述之奈米雷射,其中其中該導電脈衝源包含有一陰極與一陽極。
- 204如申請專利範圍第203項所述之奈米雷射,其中該陽極與該奈米結構形成一電連接。
- 205如申請專利範圍第203項所述之奈米雷射,其中該陰極與該奈米結構形成一電連接。
- 206如申請專利範圍第203項所述之奈米雷射,其中該陽極與陰極均與該奈米結構形成一電連接。
- 207如申請專利範圍第204、205或206項所述之奈米雷射,其中該電連接係為一歐姆接觸。
- 208如申請專利範圍第204、205或206項所述之奈米雷射,其中該電連接係為一直接接觸。
Independent claims208
372 paragraphs in 1 section, as filed
Nano structure and nano wire manufacturing method and manufacturing device
METHODS OF FABRICATING NANOSTRUCTURES AND NANOWIRESAND DEvICES FABRICATED THEREFROM
<p>Heterostructure nanowires. . . 10</p><p>Longitudinal heterostructure nanowires. . . 12</p><p>Axis. . . 14</p><p>jacket. . . 16</p><p>Joint surface. . . 18</p><p>Line segment. . . 20</p><p>Line segment. . . twenty two</p><p>Joint surface. . . twenty four</p><p>Superlattice line segment. . . 26, 28, 30</p><p>Axial heterostructure nanowires. . . 32</p><p>Axis. . . 34</p><p>The first section of the sheath. . . 36</p><p>The second section of the sheath. . . 38</p><p>Axial heterostructure nanowires. . . 40</p><p>The first section of the axis. . . 42</p><p>The second section of the axis. . . 44</p><p>jacket. . . 46</p><p>Axial heterostructure nanowires. . . 48</p><p>The first section of the axis. . . 50</p><p>The second section of the axis. . . 52</p><p>The first section of the sheath. . . 54</p><p>The second section of the sheath. . . 56</p><p>Axial heterostructure nanowires. . . 58</p><p>Superlattice line segment. . . 60, 62, 64, 66, 68, 70</p><p>jacket. . . 72</p><p>Axial heterostructure nanowires. . . 74</p><p>Single section axis. . 76</p><p>jacket. . . 78</p><p>Axial heterostructure nanowires. . . 80</p><p>The first segment of the LOHN axis. . . 82</p><p>The second section of LOHN axis. . . 84</p><p>jacket. . . 86</p><p>p-n junction element. . . 88</p><p>Heterogeneous structure of nanowires. . . 90</p><p>Silicon substrate. . . 100</p><p>Au nanoclusters. . . 104</p><p>Au-Si alloy droplets. . . 106</p><p>Si nanowire. . . 108</p><p>One-dimensional superlattice. . . 130</p><p>Doping. . . 140</p><p>Free carriers. . . 142</p><p>Quantum dot state. . . 144</p><p>structure. . . 150</p><p>Piezoelectric or thermoelectric nanowires. . . 160</p><p>Conductive substrate. . . 162</p><p>AFM cantilever probe. . . 164</p><p>Voltage sensor. . . 166</p><p>Metal catalyst cover. . . 168</p><p>Nanowire growth equipment. . . 170</p><p>Reaction furnace. . . 172</p><p>Quartz reaction tube. . . 174</p><p>Silicon wafer. . . 176</p><p>Entrance. . . 178</p><p>Computer program laser pulse. . . 180</p><p>Pure Ge target. . . 182</p><p>exit. . . 184</p><p>Au film. . . 186</p><p>Au-Si alloy. . . 188</p><p>Si nanowire. . . 190</p><p>SiGe alloy. . . 192</p><p>SiSiGe superlattice. . . 194</p><p>Nanowire array. . . 200</p><p>Si substrate. . . 202</p><p>Nanowires. . . 206</p><p>top. . . 204</p><p>Thermoelectric elements. . . 210</p><p>Upper and lower insulating substrates. . . 212, 214</p><p>n-doped nanowire array. . . 216</p><p>Base. . . 218</p><p>p-doped nanowire arrays. . . 224</p><p>Polymer matrix. . . 222</p><p>Nanowire array. . . 224</p><p>Base. . . 226</p><p>Nanowires. . . 228</p><p>Polymer matrix. . . 230</p><p>Metal contact pads. . . 232, 234, 236, 238, 240</p><p>Nanowire polymer synthesis array. . . 250</p><p>Nanowires. . . 252</p><p>Polymer matrix. . . 254</p><p>Light emitting diode/laser diode emitted by electrons. . . 260</p><p>Nanowires. . . 262</p><p>p-n junction surface. . . 264</p><p>n-type semiconductor. . . 266</p><p>p-type semiconductor. . . 268</p><p>Positive electrode. . . 270</p><p>Negative electrode. . . 272</p><p>LOHN. . . 280</p><p>point. . . 282</p><p>Three terminal pn-pLOHN. . . 290</p><p>P-type material. . . 292</p><p>N-type material. . . 294</p><p>P-type material. . . 296</p><p>Three-terminal LOHN. . . 300</p><p>Axial configuration. . . 310</p><p>Contact electrode. . . 312, 314</p><p>Horizontal configuration. . . 320</p><p>electrode. . . 322, 324</p><p>Nano laser. . . 330</p><p>ZnO nanowires. . . 332</p><p>Sapphire substrate. . . 334</p><p>section. . . 336, 338</p>
Figure 1 shows the technology for efficiently converting different types of energy.
Figure 2 shows that the COHN heterostructure of the present invention has a sheath on the shaft.
Figure 3 shows that the LOHN of the present invention has five line segments.
Figure 4 shows that the COHN of the present invention has a shaft and two sections of sheath.
Figure 5 shows that the COHN of the present invention has a two-axis center and a section of sheath.
Figure 6 shows that the COHN of the present invention has a two-axis center and two-stage sheath.
Figure 7 shows that the COHN of the present invention has multiple superlattice line segments and a sheath.
Figure 8 shows that the COHN of the present invention has a single-segment axis and a sheath only surrounds a part of the single-segment axis.
Figure 9 shows that the COHN of the present invention has two sections of LOHN axis and a sheath only surrounds a part of the axis.
Figure 10 shows that the nanowire heterostructure of the present invention is a pn junction device.
Figure 11 shows that the nanowire heterostructure of the present invention is a pnp, npn, pin or pip junction device.
Figure 12 shows that the actual observation time of nanowire growth can reflect the VLS mechanism.
Figure 13 shows the pn junction of LOHN of the present invention containing Si.
Figure 14 shows a one-dimensional superlattice composed of SiGe.
Figure 15 shows the conductive band gap of the COHN of the present invention.
Figure 16 shows the conductive band gap of the LOHN of the present invention.
Figures 17 and 18 show the BEEM spectral characteristics of individual quantum dots automatically polymerized by GaSb/GaAs.
Figure 19 shows that the confinement effect will enable the structure shown in the BEEM current to be analyzed by the second-derivative (SD) BEEM spectrum.
Figure 20 shows the thermal conductivity of this multi-walled carbon nanotube as a function of temperature in the range of 10°K to 350°K.
Figure 21 shows the measured thermal power of carbon nanotubes with multiple walls in the range of 10°K to 350°K.
Figure 22 shows an experimental device used to measure the mechanical movement of piezoelectric or pyroelectric nanowires, and at the same time, it can measure the electrostatic potential across the nanowires.
Figure 23 shows a nanowire growth device according to an embodiment of the present invention.
Figure 24 shows the synthesis of Si/SiGe superlattice nanowires, using a pair of
The high frequency Nd-YAG laser can produce pulse ablation of pure Ge target material and generate Ge gas
Mutually.
Figure 25 shows a nanowire array synthesized using the process described in Example 4.
Figure 26 shows that the use of energy-dispersive X-ray spectroscopy (EDS) can check the chemical composition in the darker area.
Figure 27 shows scanning a focused electron beam along the long axis of the nanowire and tracking the X-ray signal from Si and Ge atoms in this line.
Figure 28 shows the relationship between the experimentally observed growth rate and the diameter of the nanowire.
Figure 29 shows that the quantum beam system of electrons and phonons can drastically increase its ZT value.
Figure 30 shows the thermoelectric element of the present invention.
Figure 31 shows the nanowire polymer synthetic array of the present invention.
Figure 32 shows the light-emitting diode/laser diode for electron emission of the present invention.
Figure 33 shows that the present invention uses LOHN to make a single quantum dot LED.
Figure 34 shows a p-n-p LOHN with three terminals.
Figure 35 shows another three-terminal LOHN.
Figures 36~39 show the configuration of the nanowire components of the motor converter. Figures 36 and 37 show the vertical configuration, and Figures 38 and 39 show the horizontal configuration.
Figure 40 shows that <0001> can also be displayed in the X-ray diffraction pattern in a Siemens Z5000 machine experiment.
Figure 41 shows the evolution of the emission spectrum when the pump power is increased.
The 42nd shows that as the power of the pump increases, the integrated emission intensity will also increase rapidly.
Figure 43 shows a nano laser.
Figure 44 shows the time-resolved spectrum record in the double exponential decay mode.
[Field of Invention]
The present invention relates to a nanostructure, in particular to a substantially crystalline nanowire structure, which includes a diameter along a bobbin, the maximum variation of the diameter is less than 10%, and the diameter is about 200nm. This nanostructure can be made into a homogeneous structure, a heterogeneous structure, or a combination of the two.
[Background of the invention]
Figure 1 shows the technology that effectively converts different types of energy (such as heat, electronics, machinery, and optics). It is the creative foundation of modern economy and the most recognized symbol of the development of science and engineering. For example, optoelectronics is used to process the conversion between optics and electronics, which demonstrates the foundation of modern information technology. The conversion between thermal energy and electrical energy is a characteristic of the energy economy. Even if the efficiency and conversion method are only slightly improved, it will have a huge impact on financial savings, energy storage and the environment. Similarly, the energy conversion of electronic machinery has become the core technology of modern machinery and sensors, which can make it widely used in industrial technology. Based on its importance, it is natural to think about whether nano-level technology and engineering can play a role in energy conversion. Undoubtedly, under the continuous demand for miniaturization and high efficiency of components, nano-level components can play a role in energy conversion. Therefore, high-quality energy conversion devices based on one-dimensional inorganic nanostructures or nanowires are indeed necessary for their substantial development. In view of this, the technology of the present invention meets the above-mentioned needs and overcomes the shortcomings of the conventional technology.
[Summary of the invention]
The present invention provides a one-dimensional nanostructure, which includes a single crystal homogeneous structure and a heterostructure. The maximum diameter of the nanowire is less than 200nm, and on the cross-section where the diameter of the nanowire changes the most. The diameter change is less than 10%. The nanowire of the present invention includes a heterostructure, which is composed of at least one substantially crystalline material and another different material, and an interface or junction can be formed between the two materials (junction). Moreover, the heterostructure used in the nanowire of the present invention can also use two materials with the same material but different crystal directions. The nanowire of the present invention has various cross-sectional shapes, including round, square, rectangular, and hexagonal shapes.
The heterogeneous structure of the present invention can be composed of any number of axial, longitudinal or line segments of various configurations. To become a heterogeneous structure, at least two line segments are made of materials with different compositions. The so-called different composition materials refer to (i) materials with different chemical compositions (whether essential or added materials), or (ii) materials with different lattice directions (for example: the same material but With different lattice arrangements). Each line segment of the heterostructure can contain various materials, such as doped or essential semiconductor materials, which can be applied to various semiconductor devices, among which pn, pnp, npn, pin, pip and other junction surfaces can be formed by traditional doping methods .
When viewed in the longitudinal direction, the nanowire heterogeneous structure can contain materials of different composition, that is, spaced or periodic line segments are composed of different materials, or can be regarded as a multi-line segment nanowire, in which at least two line segments are made of Composition of different materials. For example, there is a longitudinal heterostructure nanowire, in which two adjacent line segments are composed of two different materials, Si and SiGe.
In the nanowire heterostructure of the present invention, the joint surface between the substantially crystalline materials has a fairly obvious outline. For example, the transition zone between materials has an outline equivalent to an atomic layer with a thickness of 20 nm. For LOHN, the tapered band will be along one end of the longitudinal axis of the first material toward the adjacent second material, and the composition of the first material at this end will decrease, and is about the size of the first material. 99% of the composition at the axial center. In particular, the composition change distance of the heterostructure is within 1 μm between the first material and the second material. For COHN, the end point of 99% of its composition is measured in a radial manner. In either case, the tapered band changes from a substantially crystalline or substantially single-crystalline material to another material with a different composition. However, because the heterogeneous structure of the present invention can contain multiple line segments in the longitudinal direction and/or axial direction, based on special applications and requirements, the joint surface of one part of the heterogeneous structure will show a very obvious outline, while the other parts will not. . Moreover, not only can the material composition of adjacent line segments change rapidly or gently, by controlling the doping of the line segment materials of the heterogeneous structure, a rapid or gentle dopant transition phenomenon can also be formed between the line segments.
Various surface configurations can be obtained by using the aforementioned structure of the present invention, some of which have been described previously. Other examples are: LOHN of single or multiple joints, COHN of single or multiple joints, a combination of LOHN and COHN, two-terminal configuration, N>2 terminal configuration, a combination of heterogeneous structure and homogeneous structure, with one or Homogeneous structure with multiple electrodes (which can be heterostructures), heterostructure with one or more electrodes, homogeneous structure with insulator, and heterostructure with insulator. The interface between a nanowire and a terminal constitutes a heterogeneous junction. Using these structures and configurations, various components can be produced, including: phononic band gap components, quantum dots that beam electrons in special regions, thermoelectric components (such as solid state air conditioners and engines), and photonic components (such as: Nano lasers), nano motor (MEM) components (such as motor brakes and inductors), various forms of energy conversion components (such as: light to mechanical energy, heat energy to light) and other components.
[Detailed description of the invention]
In order to make the above and other objects, features, and advantages of the present invention more obvious and understandable, preferred embodiments are listed below in conjunction with the accompanying drawings, which are described in detail as follows:
1 Introduction
The present invention provides a series of nanostructures, hereinafter referred to as nanowires. The nanowire of the present invention includes a heterostructure, which is composed of at least one substantially crystalline material and another different material, and an interface or junction can be formed between the two materials (junction). Moreover, the heterostructure used in the nanowire of the present invention can also use two materials with the same material but different crystal directions. In addition, the surface of the nanowire (which can be a homogeneous structure or a heterogeneous structure) of the present invention has the function of capturing special chemical or biological species. In fact, the substantive crystalline material is used to make the heterostructure, which can make the heterostructure have the same substantive crystallization effect. In a preferred embodiment, at least one material with substantial crystallinity is included in the heterostructure. In this regard, if the material exhibits long range ordering, the best option is to use a substantially crystalline material.
When the maximum diameter of the nanowire of the present invention is less than 200 nm, and in the region of the maximum change in diameter, the diameter change of the nanowire is less than 10%. Therefore, the nanowire of the present invention has various cross-sectional shapes, including circular, square, rectangular, and hexagonal shapes, but it is not limited to any shape. For example, ZnO nanowires have a hexagonal profile, SnO <sub>2</sub> Nanowires have a square profile profile, and Si or Ge nanowires have a circular profile profile.
The surface configuration of the nanowire heterostructure of the present invention contains two or more substantial single crystal materials, and their spatial arrangement can develop novel and unique quantum confinement effects. This approach is expected to open a path of scientific discovery and provide an expectation of dramatic changes in energy conversion technology.
The present invention is based on the well-known vapor-liquid-solid (VLS) chemical synthesis process. This process will be described in this article, and this process has been described in detail in the following reference publications: Wagner, RS, " VLS Mechanical of Crystal Growth";Whisker Technology,pp.47-119(1970);Wagner,etal.,"Vapor-Liquid-Solid Mechanism of Single Crystal Growth";Applied Physical Letters,Vol4.,No.5,pp.89 -90(1964); Givargizov, E., "FundamentalAspect of VLS Growth", Journal of Crystal Growth, Vol. 31, pp. 20-30 (1975). In the VLS process, if widely varying semiconductor materials (such as si, Ge, ZnO, etc.) are used, single crystal nanowires can be grown, and their diameter can be controlled below 200nm, and in the best case, the diameter can be controlled at Within the range of 5~50nm, and its length can range from 1~20μm. In addition, materials of Group III-V, Group II-IV, Group II-VI can also be used to make single crystal nanowires by the VLS process.
In addition, if the diameter of the semiconductor nanowire is shortened to 5~50nm, the quantum beam effect of electrons will allow the electron band structure to be changed. Such a beam system will also strongly affect the phonon transmission of the nanowire because it significantly modifies the sound spectrum and service life. In the synthesis of VLS nanowires, the importance of the surface energy and growth direction is that the synthesis phases of the nanowires can be in a stable state, while the synthetic phases in a main body or film will be in a stable state. . Therefore, materials with unique phases and properties can create this effect.
2. Heterostructure of nanowires
Please refer to Figures 2 and 3, which show the two nanowire heterostructures of the present invention, including (i) axial heterostructure nanowire (referred to as COHN) 10 and (ii) longitudinal heterostructure nanowire Wire (referred to as LOHN) 12, which can be used as a basic material for other heterostructures and components. As shown in the sample shown in Figure 2, the axially heterogeneous structure nanowire 10 includes a substantially crystalline axis 14 surrounded by a sheath 16 of a different composition material, and the axis 14 and the sheath 16 are A joint surface 18 is formed therebetween. The material of the sheath 16 can be substantially crystalline or amorphous, polymer, semiconductor, oxide or other similar materials. As shown in the sample shown in Figure 3, the longitudinal heterostructure nanowire 12 includes at least one line segment 20 of substantially crystalline material, which is adjacent to a line segment 22 of a different composition material, and there is a gap between the two line segments 20 and 22. A bonding surface 24 is formed.
The heterogeneous structure of the present invention can be composed of any number of axial, longitudinal or line segments of various configurations, which are as follows.
For example, the additional superlattice line segments 26, 28, and 30 as shown in Fig. 3 indicate that a heterostructure is not limited to only include two adjacent line segments. However, in order to be a heterogeneous structure, at least two line segments are made of materials with different compositions. The so-called different composition materials refer to (i) materials with different chemical compositions (whether essential or added materials), or (ii) materials with different lattice directions (for example: the same material but With different lattice arrangements). When viewed in the longitudinal direction, the nanowire heterogeneous structure can contain materials of different composition, that is, spaced or periodic line segments are composed of different materials, or can be regarded as a multi-line segment nanowire, in which at least two line segments are made of Composition of different materials. For example, there is a longitudinal heterostructure nanowire, in which two adjacent line segments are composed of two different materials, Si and SiGe.
The various samples shown in Figures 4-7 are heterostructured nanowires with added line segments in the axial direction. As shown in FIG. 4, an axial heterostructure nanowire 32 includes a shaft 34, a first section of sheath 36 and a second section of sheath 38. As shown in FIG. 5, an axial heterogeneous structure nanowire 40 includes a first section of the shaft 42, a second section of the shaft 44 and a sheath 46. As shown in FIG. 6, an axial heterogeneous structure nanowire 48 includes a first section axis 50, a second section axis 52, a first section sheath 54 and a second section sheath 56. As shown in FIG. 7, an axial heterostructure nanowire 58 includes a plurality of superlattice line segments 60, 62, 64, 66, 68, 70, which are surrounded by a sheath 72. The material of the sheath can be polycrystalline or amorphous, and can be made of the following materials, such as polymers, semiconductors, oxides or other similar materials. In addition, the axially heterostructured nanowires can include a multi-layer sheath.
In the production of axial heterostructure nanowires, a single-section nanowire or a partial area of a longitudinal heterostructure nanowire can be coated with a sheath. For example, as shown in FIG. 8, an axial heterostructure nanowire 74 includes a single-segment axis 76, and a sheath 78 only surrounds a part of the single-segment axis 76. As shown in FIG. 9, an axial heterogeneous structure nanowire 80 includes a first section of LOHN axis 82, a second section of LOHN axis 84, and a sheath 86 only surrounds a part of the axis. Alternatively, the axis may contain a superlattice and be surrounded by a part of the sheath. Moreover, the sheath can also be divided into sections, so that each segment of the sheath is connected or spaced apart. The above-mentioned sheath configuration method can adopt the traditional mask technology, so that the configuration method can achieve the aforementioned nanowire structure.
From the foregoing, it can be seen that each line segment of the heterostructure can contain various materials, such as doped or essential semiconductor materials, which can be applied to various semiconductor devices. Among them, pn, pnp, npn, pin, and pin can be formed by traditional doping methods. Pip and other joint surfaces. For example, traditional dopants can be selected, such as: B, Ph, AS, In, Al, etc.; materials can be selected from elements of group II, group III, group IV, group V, and group VI, and may contain quatemaries and teriaries and oxides. In essence, any type of semiconductor material and its alloy can be used to fabricate adjacent materials in the nanowire heterostructure of the present invention. For example, the nanowire heterostructure 88 shown in FIG. 10 is a pn junction element 88. The nanowire heterostructure 90 shown in Fig. 11 is a pnp, npn, pin or pip junction element. Basically, the various nanowire heterostructures of the present invention are a kind of semiconductor wire, which can control the doping and composition in the longitudinal or/and radial direction to produce a wire with different composition materials.
According to the above, at least one line segment in the heterostructure of the present invention is composed of a substantial crystalline material, such as single crystal, polycrystalline, defective crystal lattice, and so on. As long as the material has long-range ordering, it can be regarded as a substantial crystalline material used in the present invention. Preferably, at least 20% of the material from the center of the cross-section outwards is substantially single crystal. For a silicon nanowire, the best one is epitaxial growth, such as single crystal growth on a wafer by vapor deposition of silicon.
The diameter of the nanowire of the present invention is approximately less than 200 nm at its maximum diameter, and its preferred range is 5-50 nm. Except for nanowires with circular cross-sections, for nanowires with other shapes and cross-sections, the diameter is the average of the larger axis section and the smaller axis section. In addition, the diameter from one end to the other end of the nanowire of the present invention has a fairly high consistency. In particular, on the section where the diameter of the nanowire has the largest change, the amount of diameter change here (such as: (d <sub>max</sub> -d <sub>min</sub> )d <sub>min</sub> ) Is less than 10%, and the range of diameter change is 0.5% to 10%.
In the nanowire heterostructure of the present invention, the joint surface produced between the substantially crystalline materials has a fairly obvious contour. For example, the transition zone between materials has an outline equivalent to an atomic layer with a thickness of 20 nm. For LOHN, the tapered band will be along one end of the longitudinal axis of the first material toward the adjacent second material, and the composition of the first material at this end will decrease, and is about the size of the first material. 99% of the composition at the axial center. In particular, the composition change distance of the heterostructure is within 1 μm between the first material and the second material. For COHN, the end point of its 99% composition is measured in a radial manner. In either case, the tapered band changes from a substantially crystalline or substantially single-crystalline material to another material with a different composition. However, because the heterostructure of the present invention can include multiple line segments in the longitudinal direction or/and the axial direction, based on special applications and requirements, the joint surface of one part of the heterogeneous structure will show a very obvious outline, while the other parts will not. . Moreover, not only can the material composition of adjacent line segments change rapidly or gently, by controlling the doping of the line segment materials of the heterogeneous structure, a rapid or gentle dopant transition phenomenon can also be formed between the line segments.
Please refer to Figure 2 again. By selecting the band structure of the materials 14 and 16 of COHN, the dopant atoms will exist in the sheath 16 and the charge will be confined in the axis 14, which can be adjusted The effect of doping. In this way, for uncoated nanowires, it can reduce the problems of doping and interface scattering, and can provide a relatively high electron mobility. This one-dimensional view is a description of the 2-D electron gas (2-D electron gas) generated by the two-dimensional heterostructure of semiconductors. As for 1-Delectron gas (1-Delectron gas) can also be used in high-performance thermoelectronic components and photonic components, and its electron mobility plays a very important role.
3. Nanowire synthesis
Heterogeneous structures of reduced size, such as nanowires, have attracted considerable attention and are of technological importance. However, due to the difficulty of one-dimensional control, nanowire synthesis still encounters huge challenges in materials science. In the synthesis of carbon nanotubes, although the actual growth mechanism can be avoided, the arc discharge, laser ablation, or chemical vapor deposition in the gas phase encounters huge problems. challenge. Carbon nanotubes can also be made into templates for prefabricating nanorods with different compositions. At present, it is also committed to using thin film plates to make metal nanorods or semiconductor nanorods. However, most nanorods are polycrystalline, and some of their usefulness will be limited. In order to obtain well-defined structural properties in a one-dimensional system, it is necessary to develop a universal and predictable method to synthesize single crystal nanowires to achieve consistency in size and aspect ratio.
3.1 VLS mechanism
Compared with the above-mentioned synthesis technology, the vapor-liquid-solid (VLS) process is a more effective method to chemically synthesize single-crystal one-dimensional nanomaterials. The VLS process has been widely used in the manufacture of early micron-sized whiskers and nanowires of various compositions in recent years. The method is to first dissolve gaseous reactants in the nano-sized catalytic liquid, and then form single crystals by one-dimensional growth. Nano whiskers. Based on the analysis of the phase equilibrium diagram, an appropriate catalyst can be selected.
Example one
Please refer to Fig. 12, which shows the growth process of silicon nanowires on a silicon (111) substrate 100. SiH is used in this example <sub>4</sub> The gas is used as the gas phase source of silicon, and the Au nanocluster 104 is used as the catalyst. A preferred method is to perform a chemical vapor deposition (CVD) process in the range of 600 to 800°C. At this temperature, the Au nanocluster 104 forms a liquid alloy containing Si, and will immediately separate into multiple nano-sized Au-Si alloy droplets 106. Then, if the Si species are continuously deposited on the Au-Si alloy droplets 106, a Si nanowire 108 will start to grow in the supersaturated state. This process is then continued until the nanowire 108 reaches a predetermined length. Then, in the traditional chemical vapor transport (chemical vapor transport, CVT) / chemical vapor deposition (chemical vapor deposition) In the vapor deposition (CVD) mechanism, Si, Ge, ZnO and other nanowires can be produced sequentially. Observation through transmission electron microscope (TEM) and X-ray diffractometer (XRD) shows that inorganic nanowires are single crystalline and contain a better growth direction. For example, the orientation of Ge is [111]. For nano-clusters (such as Au, Co, Ni, Fe) that use monodisperse catalysts of different sizes (such as 2-100nm), the diameter of the nanowires can be controlled within the range of 5-200nm. These catalysts can be dispersed on the silicon substrate or on the top surface of the meso-porous silicon oxide film. Moreover, by observing different growth times, we can see that the aspect ratio of nanowires varies from 10 to 1000.
The position of the nanowire on the substrate 100 can be controlled by using any traditional technology or yellow light lithography or deposition process for the catalyst. Moreover, in order to make the array of nanowires, the yellow light process can be used to define the pattern of the thin film catalyst on the substrate, and then heat treatment is performed to dissolve the thin film into a plurality of droplets. Each droplet can be used as each droplet. The catalyst for a nanowire.
In addition, the material of the substrate is not limited to Si, and insulating materials (such as sapphire) can also be used to make the substrate. The metal catalyst can also be made of materials other than Au. For example: the production of GaN nanowires is based on a C-sapphire substrate using Ni catalyst and Ga and NH <sub>3</sub> For gas, the best growth direction is (002). Moreover, MnO can be used <sub>2</sub> Mixture with C to dope Mn into this nanowire. Similarly, for the growth of Ga(Co)N nanowires, the following conditions can be used: Ni catalyst, C-sapphire substrate, Ga+NH <sub>3</sub> Co, Go <sub>3</sub> O <sub>4</sub> The mixture of +C is doped. The following conditions can be used for the growth of GaN nanowires: Ni catalyst, C-sapphire substrate, Ga <sub>2</sub> O <sub>3</sub> +C mixture.
The following conditions can be used for the growth of alloy Ga-N-Zn-O nanowires: Ni catalyst, C-sapphire substrate, Ga+NH <sub>3</sub> , a mixture of ZnO+C.
Example two
Using high temperature TEM to observe the growth of Ge nanowires in the same environment, there will be a small amount of Ge particles and Au nanoclusters scattered on the TEM grid, which is provided as a Ge gas source for the heating step in the vacuum chamber . It was also discovered that when the Ge-Au alloy is formed, Au nanoclusters will begin to melt. In the subsequent Ge vapor phase condensation process, the size of the droplets will increase. When the droplet containing Ge is supersaturated, the Ge nanowire will be ejected from the droplet and start to grow. In Figure 12, the actual observation time of nanowire growth can reflect the VLS mechanism.
Based on these observations, it is obvious that the following views on the growth of nanowires are:
(1) With different compositions (such as: Si, Ge, GaAs, CdSe, GaN, AlN, Bi <sub>2</sub> Te <sub>3</sub> , ZnO, etc.) In the synthesis of inorganic nanowires, suitable metal catalysts, gas preforms and reaction temperatures can be used. The subsequent decision can be made by checking the binary phase diagram or the ternary phase diagram.
(2) Traditional dopants such as B, Ph, As, In and Al can be used.
(3) The material can be selected from elements of group 2, group 3, group 4, group 5, and group 6, and can include quatemaries, teriaries, and oxides. In essence, any type of semiconductor material and its alloy can be used to fabricate adjacent materials in the nanowire heterostructure of the present invention.
(4) To the first order approximation, the catalyst system defines the diameter of the nanowire. Smaller nanoclusters will form thinner nanowires. This has also been successfully demonstrated in GaP and Si nanowire systems.
Synthesized by the VLS mechanism, it is characterized by intervening surfactants that cause epitaxial growth. By preventing the restoration of the semiconductor growth surface, intervening materials (such as molten metal nanoparticles or monolayers) will catalyze epitaxial growth. . Since there is no stable recovery (because recovery requires continuous dismantling and reconstruction), compared to the traditional epitaxial growth technology, VLS growth technology can be performed under selective and low-temperature conditions. At low temperatures, it can provide more opportunities to reach a new phase state, and can produce obvious interface contours, which can prevent the morphological evolution of the nanowire material in the growth process (for example: Rayleigh breakup).
3.2 Changed phase balance
The geometry of the nanowire allows the unstable phases in the bulk or thin film to have a chance to synthesize. A high surface-to-volume ratio can increase the importance of free energy surface energy, especially for crystalline phases with high anisotropic surface energy. For example, in the semiconductor polytypes of the three, five, and twenty-six groups, compared to a monolithic equilibrium boundary, the difference between sphalerite (cubic crystal system) and wurtzite (hexagonal crystal system) The equilibrium phase boundary will shift due to pressure and temperature. For example, for nanowires with the same composition, compare the sphalerite nanowires with the <111> configuration and the wurtzite nanowires with the <0001> configuration. The cylindrical wurtzite nanowires will be more similar to Wuer. Wullf balanced shape, which exposes the rhomboidal cut surface with low surface energy. In previous studies on nanowires, it can be observed with OMCVD that the wurtzite phase is indeed the better phase of GaAs. Moreover, the epitaxial relationship between the substrate and the nanowire can be used to capture the rate stable phase of the nanowire pattern. This strategy has been successfully used in film growth.
3.3 Heterogeneous epitaxy in nanowires
Semiconductor heterostructures can confine electrons and holes, guide light, and can be selectively doped. However, if the heterostructures exist in the effective area of the device, no displacement phenomenon can occur at the interface. The required range of materials is that coherent epitaxial crystals must be grown on the substrate to reach a sufficient thickness, and the height is limited by lattice misfit. For a lattice misalignment, the equilibrium critical thickness of coherent epitaxy can be estimated by the elasticity of the film, the core energy of misalignment and the crystallography (such as the composition of the plane endpoint of the Berger vector). . Although the coherent heteroepitaxial film can grow properly and exceed the equilibrium critical thickness, the film will become a rate-steady state, and the displacement mechanism will cause it to become a loose state. The shape of the VLS nanowire can change the interface, thereby significantly increasing the balance critical thickness and dynamic critical thickness.
The two main effects are described below. The first effect is that the state of the flexible interface perpendicular to the growth direction becomes loose. In an ideal film morphology, strain energy will exist in the coherent film per unit area, and this strain energy will increase linearly as the film thickness changes. In the heterostructure of nanowires, the thin film will only be horizontally bound at the interface. When the thickness of the nanowire increases, lateral relaxation will occur, which will saturate the stored elastic strain energy. In fact, when the material undergoes lateral relaxation, part of the strain energy will be stored on one side of the substrate. This result, for the equilibrium critical thickness due to lattice mismatch, increases with the value of the film. The difference is that since the stored elastic strain energy will reach saturation, the lattice mismatch has a certain limit. The fact that refutes this first effect is that due to the decrease in the volume of the nanowire, the strain energy loss associated with the mismatched differential strain field will be reduced. However, the central energy project will remain, allowing the first effect to be controlled as expected.
3.4 Longitudinal heterostructure nanowire (LOHN)
Most of the success of semiconductor integrated circuits depends on the defect engineering capability shown by doping control. Because defect engineering can provide doping to make new components, and has a strong impact on electron scattering, it is very important for Chennai. Rice noodles will have a profound effect.
According to the basic mechanistic knowledge of the growth of VLS nanowires, Nos. 10, 11, and 13 show the composition profile that grows along the spool by sequentially supplying different dopant gases. For example: the LOHN shown in Figure 13 contains p with Si <sup>-</sup> n Bonding surface, B can be used for subsequent nanowire growth <sub>2</sub> H <sub>6</sub> And PH <sub>3</sub> . Using the cVD process enables accurate growth control of the component profile, and an obvious component interface can be made. Figure 14 shows a one-dimensional superlattice l30 composed of Si/Ge, which can also use various III-V, II-VI, II-IV, tertiary and quaternary materials . Therefore, by sequentially changing the gas used in the VLS process, various types of LOHN can be synthesized immediately. Generally speaking, this process allows one-dimensional bandgap engineering (bandgap engineering), which can produce a series of diverse quantum dots. In thin film growth, quantum dots are usually grown in solution or by forming islands. Since the location of these quantum dots cannot be known in advance, it is very difficult to contact individual quantum dots. By accurately integrating quantum dots in a single nanowire, difficulties in connection can be avoided. This is the so-called "system on an nanowire)". This new type of one-dimensional nanostructure provides more opportunities to explore new physical phenomena in low-dimensional systems. This is very likely to be applied to active nanoelectronics, nano-optical nanothermal electrons and Nanoelectronic machinery, etc. Moreover, this can be used to synthesize nanowires with different lattice structures, such as: zinc blende, wurtzite, CdSe, GaN and other nanowires. The production method can be used for epitaxial growth In the relationship between the substrate and the nanowire, different substrates are used to cover certain rate stable phases.
3.5 Axial heterostructure nanowire (referred to as COHN)
Using the fabricated nanowire as a physical model, the axial nanostructure shown in Figure 2 can also be synthesized. For example, the organic molecules on the surface of the decomposition wire can form a conformal and uniform carbon coating on the Ge nanowire, which can be stretched immediately to form a COHN with a strong electron beam effect. For example: GaAs nanowires produced by the VLS method can be subsequently coated with a thin layer of A1 by low-temperature chemical vapor deposition <sub>1-x</sub> Ga <sub>x</sub> The As layer can effectively prevent the VLS lattice from growing along the spool and can promote A1 <sub>1-x</sub> Ga <sub>x</sub> The surface of the As layer is excessively grown. However, it should be noted that the sheath can be crystalline or amorphous, and can contain polymers, semiconductors, oxides or similar materials. In order to form COHN, a single-segment nanowire or a LOHN must be made in any of the methods described above. A single piece of nanowire or a LOHN will become the axis of COHN, and then will be used as a model for making sheaths. For example, in the manufacture of sheath, monomer polymerization can be carried out on the surface of a single-stage nanowire or a LOHN. Alternatively, any physical vapor deposition (PVD) or chemical vapor deposition (CVD) process is used to coat the nanowire or LOHN surface. The material of the shaft/sheath is not limited, it can be a combination of the following, such as: Si/ZnO, Ge/C, Si/SiO <sub>2</sub> , SnO <sub>2</sub> /TiO <sub>2</sub> , GaN/ZnO, GaAlN/GaN, etc. It is important that the number of configurations of the shaft/sheath material is not limited. Even oxides, such as Zn0, can also be used as shaft materials. The following is the material combination of the shaft/sheath, and the material of the shaft and the sheath is single crystal, for example: TiO <sub>2</sub> /Sn0 <sub>2</sub> , M: TiO <sub>2</sub> /SnO <sub>2</sub> (M=Mn, Fe, Co, Cr, etc.), PbTiO <sub>3</sub> /SnO <sub>2</sub> , BaTiO <sub>3</sub> /SnO <sub>2</sub> , LaMnO <sub>3</sub> /SnO <sub>2</sub> , HTSC (High Temperature Semiconductor)/SnO <sub>2</sub> 。
This method can also be used to synthesize a nanotube. For example: a layer of organic molecular material can be coated on a Ga nanowire axis. After pyrolysis under vacuum, the surface of the organic material will be carbonized. Then, at a temperature of 800~1000°C, the Ga nanowire axis will be melted or evaporated to become a carbon nanotube.
In order to understand the structural characteristics of these nanowires, one must rely on TEM and XRD. Both TEM and XRD can determine the structure and phase of the nanowire. Moreover, TEM can also provide defect structures within individual nanowires, regional microstructures at the interface, growth direction, overall crystallinity, etc.
4. Nanowire properties 4.1 Electronic structure and properties 4.1.1 Model
The role of interface thickness and position in nanowires has been widely studied in quantum wires. The definition of quantum wires is the use of electron beam yellow light or a separate gate electrode static beam method. The transition from ballistic transmission to diffuse transmission, positive or negative magnetoresistance, conduction quantization, and general fluctuations have been detected at low temperatures. Using the VLS process to make nanowires provides a special opportunity to study the variability of electron transport in one-dimensional electronic materials. Moreover, doped nanowires are similar to CVD thin film deposition, so they can provide additional opportunities to study the dominant scattering mechanism at various electron densities. Please refer to Figures 2 and 15. In COHN, adjusting the doping of materials with a wide band gap can separate the ionized dopants 140 and free carriers 142 in space, thereby achieving a higher mobility. Confining free carriers within the axial region of the nanowire sheath will reduce the surface scattering effect. When electrons occupy the cylindrical area adjacent to the heterostructure interface of the coaxial nanowire, a new quantized whispering gallery electronic state can be formed. Please refer to Figure 16. The heterostructure along the LOHN nanowire will form a quantum dot state 144. These states will obviously affect the electronic properties of nanowires. One of them can be found as the phenomenon of Coulomb's lock-up, which is the same-dimensional resonance tunneling effect.
A better model is established in the following two stages. First, using a simple one-dimensional band structure model and Songta time approximation, the electron mobility is measured along the nanowire at high temperature. Then, use refined models (such as: variable range jump model) to illustrate surface/interface scattering, and calculate the dependence of temperature and conductivity. For other applications, such as modification of phonon spectrum and scattering time, electronic phonon reaction, etc., Monte Carlo simulation of Boltzmann equation can be used. Note that heterostructure nanowires can include several beam-system interface phonon models, which can scatter electrons in different ways from any of the bulk semiconductors.
4.1.2 Features
In order to describe the electronic properties of bulk heterostructured nanowires, it is very important to measure the doping concentration profile, electron mobility, and voltage energy barrier at the heterogeneous interface of the nanowires. Before providing the nanowire material, it must be carefully checked by the traditional method of characterizing the bulk or film. The electronic conductivity along the nanowire is an important coefficient, and its characteristics must be defined within a large temperature range. In addition, the measurement of electromagnetic resistance can provide more information about how surface scattering affects electron transport. The measurement of thermoelectric properties, such as Seebeck coefficient, can provide more information about the electron density state and scattering mechanism near the Fermi surface. The measurement of thermionic emission current can be used to determine the energy barrier of heterostructures along the nanowire.
Ballistic electron emission microscopy (BEEM) is an ideal technique that can measure the regional electronic properties of nanowire structures and can describe the characteristics of axial heterostructures. BEEM is an effective low-energy electron microscope for profile and spectroscopy. It can provide nm-level resolution for substrates embedded below 30nm on the surface. BEEM has been applied to the study of the self-aggregation quantum dot structure grown on GaAs.
Example three
GaSb quantum dots grown on GaAs can be observed by STM and BEEM images. In the STM image, a rough round appearance (about 50nm in diameter and about 5nm in height) marks the side position of an embedded point. In the BEEM image, the area aligned with the outline of this point of the STM image is darker than the periphery, which implies that the electron reflection deviates from the voltage barrier at this point, and therefore the BEEM current passing through this point is reduced. The energy barrier height (eg: region-band offset) can be opened and closed between a spectral change BEEM acquires self. Among the many points in the BEEM spectrum, the opening and closing points are configured by a modified Bell-Kaiser planar tunneling model, which can provide the GaSb point on GaAs with a regional conduction band deviation. The displacement is about 0.08±0.02eV. Figures 17 and 18 show the BEEM spectral characteristics of individual quantum dots automatically polymerized by GaSb/GaAs.
. In addition to measuring the nature of the offset of the direct contact zone of the liquid, this technique has also been used to study GaAS <sub>1-x</sub> N <sub>x</sub> The electronic band structure of the alloy material, the sequence effect on the GaInP band structure, and the resonance tunneling of the InP quantum dots beamed between the AlInP energy barrier.
It can be seen from the above that BEEM can not only be used to describe the electronic properties of individual nanowires, but also the variability of longitudinal heterostructures, such as the structure 150 shown in Figure 19. The limiting effect will make the structure shown in the BEEM current can be analyzed by the second-derivative (SD) BEEM spectrum.
4.2 Optical properties
Due to the role played by the surface state and the non-radiative recombination on the surface state, the observation of light emission phenomena from nanowires encounters considerable challenges. In the use of COHN, electrons will be beamed at the central area inside the nanowire, thereby reducing the effect of the free surface. The photoluminescence spectrum in a large temperature range can be used to study the light emission phenomenon of nanowires, which can be provided as a super-resolution technology to obtain images with sub-wavelength spatial resolution. In addition, scanning solid immersion lenses can be used to define the light emission characteristics of individual nanowires. The fabrication and characteristics of the pn junction surface of nanowires is a key basic material for optoelectronic devices. The DC method, pulse electronic method, and optical method can all be used to measure the photocurrent, recombination life, and photoluminescence in the nanowire.
4.3 Thermal properties
Generally speaking, the thermal properties in semiconductors are dominated by the transmission of voice phonons. The thermal conductivity produced by phonons is related to the following two basic characteristics: (i) phonon dispersion relationship; (ii) phonon lifetime. Its value can be calculated from the following relationship:
<maths><img file="TW554388B_D0001.tif" /></maths>
Among them, p represents phonon polarization, ν(p,ε) represents the function of the group rate of polarization and energy, ε=hω represents phonon energy, f <sub>BE</sub> (ε,T) stands for Bose-Einstein equilibrium distribution, T stands for temperature, D(p,ε) stands for state density, <img file="TW554388B_D0002.tif" /> (r, p, ε) represents the function of the position, polarization and energy of the phonon lifetime. At room temperature (T=0.1θ <sub>D</sub> , Θ <sub>D</sub> Stands for Debye temperature), the thermal conductivity of most bulk semiconductors is limited by phonon inverse scattering.
The transmission of phonons in the heterostructure of nanowires will change dramatically along with the transmission of phonons in the entire semiconductor. The main reason is that the imposed restrictions in the two directions will cause significant changes in the distribution relationship. Secondly, the existence of a heterostructured interface will induce a variety of phonon patterns, and these phonon forms will be formed on the interface. In this way, in addition to two lateral acoustic branches and one vertical acoustic branch, a variety of different phonon polarizations will be generated in the entire semiconductor. The phonon temperature changes due to the following two reasons: first, the phonon-phonon interface will change, this is due to the selection rule based on the energy immortality and the wave vector relationship that changes with the distribution relationship; second, the phase Compared with the overall semiconductor, the boundary scattering of the 5-50nm diameter nanowire will become stronger. Finally, because the nanowire beam system allows us to enter a new crystalline phase, it can completely modify the phonon dispersion relationship.
The thermal and thermoelectric properties of the nanowire of the present invention can be measured using a microfabricated structure, which has two suspended heaters, and this heater includes a coil made by an electron beam lithography system. In the test, a carbon nanotube bundle with multiple walls was placed across the two heaters to bridge the two heaters. By monitoring the heat input of one heater and the temperature of two heaters, the thermal conductivity of the nanotube can be obtained. Figure 20 shows the thermal conductivity of this multi-walled carbon nanotube as a function of temperature in the range of 10°K~350°K, where T <sup>2</sup> Represents the associative change of the phonon beam system in two-dimensional materials. The monotonous increase in thermal conductivity shows suppression of phonon-phonon scattering and a very long mean free path (about 1μm). This study can also be used to measure the thermal conductivity of the COHN and LOHN of the present invention. Moreover, by using batch-made atomic force microscopes (AFM) and scanning thermal microscopes (SThM) with temperature sensors on the top, the regional thermal properties and thermal conductivity characteristics of COHN and LOHN can be obtained.
The calculation of the characteristics of nanowires focuses on the following three viewpoints: (i) calculation of phonon dispersion relationship; (ii) calculation of phonon lifetime based on dopant scattering, nanowire size and boundary scattering; (iii) ) Calculation of phonon transport. Because the wave effect (phonon band gap) has been considered in the dispersion relationship, Monte-Carlo simulation can be used to solve the Boltzmann transport equation, which can easily calculate the nanowire The density state of the different polarization branches, the frequency-dependent group velocity, and the phonon lifetime.
4.4 Thermoelectric properties
The thermal power of semiconductors is dependent on the following three properties: (i) the density of electronic states close to the Fermi level; (ii) the effective mass of electrons; (iii) the carrier scattering rate. Because the electrons in the nanowire are produced by quantum beams, the electron band structure (state density and scattering rate) can be significantly changed, so the band structure and the position of the Fermi level can be constructed to modify the thermal power. The aforementioned suspended heating element can traverse a nanowire to measure its temperature and position difference. For example: Figure 21 shows the thermal power measurement value of carbon nanotubes with multiple walls in the range of 10°K~350°K. The positive thermal power shown here means that the electric hole is used as the dominant load in the nanowire. son. Therefore, this device can be used to measure the thermoelectric properties of nanowire heterostructures, such as the aforementioned COHN and LOHN.
4.5 Piezoelectric properties
Wurtzite-type structure provides a spontaneouselectric dipole moment, so materials with this structure will produce pyroelectricity and piezoelectricity. These properties can allow strong linear coupling to form between mechanical stress and polarization. Between (direct piezoelectric effect) and a temperature change and polarization change (pyroelectric effect). Wurtzite-type nanowires (such as GaAs, InAs, GaN, AlN, ZnO, etc.) and nanowire heterostructures can therefore be applied to nano-sized sensors and manipulators. Potential applications include: integrated atomic force microscope probes, resonant mass sensors with single-molecule sensitivity, thermal sensors with nanometer specifications, filters with adjustable electric field GHz, large-displacement nanobeam manipulators, and nanometers Meter specification flow sensor.
In the <0001> wurtzite type nanowire, the orientation of spontaneous polarization is along the spool, so the electric field and metal mechanical stress provided along the spool will produce the greatest piezoelectric response. The simplest electrode configuration is applied to the joint between the base and the top, and the axial stress provided by the joint between the base and the top can be sensed through the direct piezoelectric effect. Since the cross-sectional area of the wire is small, a large stress can be generated with a small force. For nanowires used in resonance sensors, one end of the nanowire must not be mechanically controlled, and a conductive surface that is very close to the nanowire is used to detect the charge on the top of the nanowire, and to pass it through. Remove or add charge.
Figure 22 shows an experimental device that uses an AFM cantilever probe 164 to measure the mechanical movement of a piezoelectric or pyroelectric nanowire 160 placed on a conductive substrate 162, and a voltage sensor 166 can be used at the same time To measure the electrostatic potential across the nanowire. In order to achieve electrical and mechanical measurements, the end of the AFM cantilever probe 164 is in contact with a metal catalyst cover 168 on the nanowire.
5. Block-by-block growth of monocrystalline SiSiGe
For a variety of potential semiconductor nanowire applications, the heterojunction of nanoscale optoelectronics and the formation of superlattices are very important. In view of this, a hybrid pulsed laser/chemical vapor deposition (HPL-CVD) process has been developed to synthesize a semiconductor nanowire with an axial sequence heterostructure. The laser ablation process generates a programmable pulse gas source, and the nanowire growth can be formed block by block with a clear composite contour on the bobbin. Single crystal nanowires with axial Si/SiGe superlattice structure have been successfully synthesized. This unique heterogeneous one-dimensional nanostructure has the potential to be used in light-emitting devices and thermoelectrics.
Most of the success of semiconductor integrated circuits depends on the ability to carefully control doping and interfaces to produce heterostructures. In fact, two-dimensional semiconductor interfaces are commonly found in optoelectronic devices, such as: light-emitting diodes, laser diodes, quantum string lasers, and transistors. The production of heterostructures of one-dimensional nanostructures (nanowires) is also very important for potential products (such as effective light emitting sources and better thermostats). Although there are many well-developed technologies (such as molecular beam epitaxy) that can be used to fabricate thin-film heterostructures and superlattices, there is still a lack of a general synthesis scheme to fabricate one-dimensional heterostructures with a clear coherent interface. Heterojunction and superlattice. Early research on semiconductor nanowires or nanotubes always dealt with homogeneous systems, which formed a few exceptions of heterostructures, including: heterogeneous junctions formed between carbon nanotubes and silicon/carbon nanowires , Formed on individual carbon nanotubes or GaAs/Ga <sub>1-x</sub> In <sub>x</sub> The pn junction on the As nanowire. Recently, a continuous electrochemical method has been reported that can be used to synthesize metal bar code micro-rods, but this method has forced fewer ideal interfaces for polycrystalline products. Here, we use the PLA-CVD process to synthesize semiconductor nanowires with periodic axial heterostructures, including the production of single crystal nanowires with Si/SiGe superlattice structure, and its characteristics can be completely defined by electron microscopy .
Example Four
Please refer to FIG. 23, which shows a nanowire growth apparatus 170 according to an embodiment of the present invention, which includes a reaction furnace 172 and a quartz reaction tube 174. A (111) silicon wafer 176 coated with an aluminum film is placed in the quartz reaction tube 174 to serve as a substrate. Mixed with SiCl <sub>4</sub> With H <sub>2</sub> The gas system is continuously introduced into the reaction tube 174 through an inlet 178. A computer-programmed laser pulse 180 is focused on a pure Ge target 182. The remaining gas can be led out of the reaction tube 174 through an outlet 184.
Please refer to Figures 23 and 24 at the same time. The nanowire growth is based on VLS, which uses Au as a metal solvent at high temperature, as shown in the previous and Figure 12. The process starts with the decomposition of the gaseous reactants in the nano droplets of the metal solvent, and then the nucleation and growth of the single crystal wire. The concept of heterojunction nanowires is that to maintain a highly crystalline and coherent interface along the spool, precise composite contours and interface control in nano or even atomic specifications are required. Based on the understanding of the important mechanism of VLS nanowire growth, it is possible to control its specifications by continuously feeding different gas phase sources.
Please refer to Figure 24 of the gate. In the example of synthesizing Si/SiGe superlattice nanowires, a dual-frequency Nd-YAG laser (wavelength 532nm, 6Hz, power density 10J/cm <sup>2</sup> .Unit pulse) can cause the pure Ge target 182 to generate pulse ablation, and then generate a pulse type Ge gas phase. H <sub>2</sub> The flow rate is about 100sccm, SiCl <sub>4</sub> With H <sub>2</sub> The ratio of is about 0.02, the system pressure is about one atmosphere, and the reaction temperature is about 850°C~950°C. At this temperature, the Au thin film 186 forms a liquid alloy containing Si, and spontaneously collapses into a nano-sized droplet type Au-Si alloy 188. Then, the Si species are continuously deposited into the Au-Si alloy droplets, where the Si nanowire 190 will begin to grow to close to supersaturation. When the laser is turned off, only Si species will be deposited in the alloy droplets and a pure Si block will grow. However, if the laser is turned on during the growth process, Ge gas phase will be generated, and both Ge and Si species will be deposited in the alloy droplets. When the laser is turned on, SiGe alloy 192 will precipitate from the solid/liquid interface. By periodically turning the laser on and off (this sequence is easy to program), a block-by-block Si/SiGe superlattice 194 can be formed on each nanowire. The entire growth process is similar to the living polymerization synthesis of bulk copolymers.
Different gases and targets can be used for the growth of various other different nanowire structures. For example, PbSe growth can perform laser ablation on PbSe/Au targets in Ar gas. Moreover, the growth of the nanowire superlattice of the present invention is not limited to the aforementioned synthesis process. Another way is to use multiple targets and use a computer to manipulate the laser to select the target. Therefore, physical or chemical vapor deposition processes that need to provide vapor can be used, and are not limited to PLD, CVD, and MBE. For example, the gas-phase supply source can be equipped with a computer-controlled valve to pulse the flow of a predetermined gas.
Example 5
Figure 25 shows a nanowire array 200 synthesized using the process described in Example 4, and a scanning electron microscopy (scanning electron microscopy, SEM) image. In Example 5, an Au thin film with a thickness of 20nm is placed on the Si(111) substrate 202, and the pattern of the Au thin film is defined into four regions by the yellow light process, and then each thin film region is reduced to four Droplets, each droplet is used as a catalyst for a related nanowire. During the growth process, the laser is periodically turned on for 5 seconds and turned off for 25 seconds, and this cycle must be repeated for up to 15 minutes. As shown previously, the Si nanowires will grow along the [111] direction, and the growth of the qualitative epitaxial nanowire array will be completed on the Si(111) substrate. When the alloy droplets solidify, they will appear as a bright spot on the top 204 of each nanowire 206. A close inspection of the nanowires revealed that the tip was shaped like a flower, which was formed during the solidification of liquid alloy droplets. The diameter range of nanowires is about 50nm~300nm. Operate the PhilipCM200 TEM at 200KeV to obtain STEM images of two nanowires. In the bright domain mode, dark bars appearing periodically along the spool can be seen, which are periodically stacked by the SiGe alloy and Si line segments. Become. The cross-sectional electronic scanning of Ge atoms is larger than that of Si, so the apparent SiGe alloy bulk will be darker than the pure Si bulk. Use energy-dispersive X-ray spectroscopy (energy-dispersive X-ray spectroscopy, EDS) can check the chemical composition in the darker area. As shown in Figure 26, a strong Si spike and obvious Ge doping (~12% Ge by weight) are found. To further adjust the periodicity of Ge doping, scan a focused electron beam along the long axis of the nanowire, and track the changes in the X-ray signal from Si and Ge atoms in this line, as shown in Figure 27 . The X-ray signals of Si and Ge show periodic adjustments and uncorrelated intensities. In other words, when the X-ray signal of Ge reaches a maximum value, the X-ray signal of Si reaches a minimum value, which proves that the Si/SiGe superlattice is formed along the bobbin. What we have noticed is that at this stage, the steepness of the Si/SiGe interface of the nanowire is not ideal, but we believe this can be improved by an accurate and fast gas-phase batching/switching system (such as molecular beam process) .
It must be emphasized that the elastic boundary state of heteroepitaxial growth of VLS nanowires can be used for superlattice nanowires to create a seamless interface by growing epitaxial thin films on a flat substrate. The non-difference interface is unstable in the conventional two-dimensional configuration. Although the coherent heteroepitaxial film grows well and can exceed the equilibrium critical thickness, the differential displacement mechanism causes the film to change from a quasi-steady state to a loose state. The type of VLS nanowires provides an opportunity to significantly extend the balance and dynamic critical thickness, or equivalently, changing the boundary conditions under a thickness condition can make the lattice mismatch become compatible with each other.
A selected area electron diffraction (SAED) and a high-resolution transmission electron microscopy (HRTEM) can be used to define the highly crystalline nature of the superlattice nanowire. Record the SAED pattern perpendicular to the axis of the nanowire, and index the pattern as the diffraction along the [110] area axis of crystalline Si, and suggest that the nanowire growth does indeed occur along the [111] direction. It can be further confirmed in the HRTEM image that it clearly shows that the (111) atomic plane (interval 0.314nm) is perpendicular to the nanowire axis. If the interface ratio cannot be seen immediately in the STEM image, the interface of the HRTEM mode cannot be distinguished because the doping ratio in the SiGe block is too low. However, these HRTEM images clearly confirm the highly crystalline nature of Si/SiGe superlattice nanowires. A large number of HRTEM images indicate that the single crystallinity of Si/SiGe superlattice nanowires can be maintained over the entire line length, and there are only a few line or surface defects.
According to the data of structure and chemical composition, the nanowire prepared according to the PLA-CVD process in the present invention has a high degree of crystallinity in the Si/SiGe superlattice structure along the axis of the nanowire, and the reaction conditions can be adjusted. You can immediately control the diameter of the nanowire, the concentration of Ge, and the chemical adjustment cycle. The diameter of the nanowire is affected by the thickness of the Au layer on the substrate. For example, for a 20nm thick Au film, the average diameter of the nanowire is about 100nm. If the thickness of the Au layer is reduced by 1nm, the average diameter of the nanowire is about Reduce by 20nm. Moreover, the diameter of the nanowire is also affected by the reaction temperature. The lower the reaction temperature, the thinner the nanowire. The Ge concentration in the superlattice is controlled by the ratio of Ge atoms to Si atoms in the alloy droplets, increasing laser intensity or reducing SiCl <sub>4</sub> The flow rate can increase the Ge concentration. In addition, the period (L) of the superlattice is the product of the growth rate (V) and the laser switching period (T). The formula is: L=V×T. Therefore, reducing the growth rate or the laser switching period can reduce Superlattice period. Similarly, by changing the ratio of the laser switch, the ratio of different constituent blocks can be adjusted at any time.
What is important is that the label is marked on the online growth axis. The PLA-CVD process provides a quantitative method to measure the growth rate of the nanowire (V=L/T), which is related to the growth supersaturation. When the laser switching period T is displayed and the superlattice period L is known, the growth rate V can be calculated. We found that under the same reaction conditions, the growth rate is correlated with the diameter. As shown in Figure 28, the relationship between the growth rate and the diameter of the nanowire observed from experiments shows that the smaller the diameter of the nanowire, the smaller the growth rate. The Gibbs-Thomson effect (Gibbs-Thomson effect) can quantify this trend. For example, increasing the pressure of the Si gas phase can reduce the supersaturation when the diameter of the nanowire is smaller. The function of the supersaturation reduction value and the diameter of the nanowire (d) is:
<maths><img file="TW554388B_D0003.tif" /></maths>
Among them, μ is the effective difference between the chemical potential energy of Si in the nutrient (gas or liquid) phase; μ. Is the same difference on a flat interface; α <sub>vs</sub> Is the special free energy on the surface of the nanowire; Ω is the atomic volume of Si. The correlation between the superlattice and the growth rate V of the lattice is not linear, and most of the cases are as follows:
<maths><img file="TW554388B_D0004.tif" /></maths>
Among them, b is a coefficient not related to supersaturation. Can be deduced into V <sup>l/n</sup> Linear correlation function proportional to 1d:
<maths><img file="TW554388B_D0005.tif" /></maths>
Among them, dC represents the critical diameter.
In Givargizov's observation of the typical CVD lattice growth of micron-sized Si, he agreed that the growth data of Si/SiGe nanowires can meet n=2.
The hybrid PLA-CVD method used in our experiment can also be used to prepare various other heterostructures on individual nanowires to meet the production requirements of customers, because a part of the vapor source provider (laser ablation) can be programmed and modified . In this way, various functional elements can be created on a single nanowire, such as p-n junctions, coupled quantum dot structures, and heterostructure bipolar transistors. This nanowire can be used as an important building block to construct nano-sized current devices and light-emitting devices, such as superlattice nanowires with low phonon transmission and high electron mobility. It is considered to have better thermoelectric properties.
6. Energy conversion elements using nanowires
The technology in this field will realize that the nanowire of the present invention can be used in a wide range of applications, including but not limited to: (a) thermoelectric coolers; (b) light-emitting diodes; (c) motor induction Device. The design of these components is based on the understanding of the various physical properties of the one-dimensional binding effect based on basic science. Although this kind of scientific understanding can rely on single nanowire research, it is better for these components to integrate multiple nanowires into a system, so nanowire arrays have become a representative use.
In order to achieve the above discussion, the above three components can be the center, but there is no other way, only the use of nanowires can be achieved. The primary purpose of centering on the above three components is to design and produce simple components that can be used as the basis for more delicate components.
6.1 Thermoelectric cooling and power generation
The Peltier effect can be used to achieve solid-state cooling and power generation, in which a cooling (or heating) phenomenon can occur when an electric current passes through the thermoelectric junction. Conversely, when a temperature difference passes through the thermoelectric material, a current is generated to pass a potential drop, thereby generating electricity. Compared with current gas-phase compression refrigerators and gas-based engines, solid-state components are extremely promising because: (i) contain any moving parts; (ii) are good for the environment; (iii) allow for downsizing. The reason why this graphic element is not widely used today is that its performance (engine efficiency and coefficient of performance (COP)) is far lower than that of systems using gas/gas phase. However, if the performance can be improved to be comparable to or better than that of the gas phase system, it is conceivable that how to use or convert energy will show a dramatic change. This powerful and compelling reason can prompt the use of nanowires to develop thermoelectric power. element. It can be seen from the following that it has recently been possible to use the nanowire of the present invention.
The material characteristics of thermoelectric coolers and generators used in the pattern must have the following advantages: ZT=S <sup>2</sup> σTk, where S represents thermal power, k represents thermal conductivity, σ represents electrical conductivity, and T represents absolute temperature. Bi <sub>2</sub> Te <sub>3</sub> Its alloy is currently the most widely used material, and its ZT=1. Theoretically, when ZT=3, the performance of the thermoelectric cooler and engine can be compared to a gas-phase compression system. In fact, if the thermoelectric material has a nanostructure, the quantum beam system of electrons and phonons can drastically increase its ZT value, as shown in Figure 29. Especially for one-dimensional nanowires, if the diameter of the wire is 5~10nm, ZT=2~5.
6.1.1 Nanowire design
Because high electron mobility is required to achieve a high ZT value, the better choice is to use COHN, because it can greatly reduce the doping and interface scattering. Because the thermal conductivity of general materials is inversely proportional to the atomic mass (ζ), the selected material must have a high ζ value, which is why Bi or Bi <sub>2</sub> Te <sub>3</sub> Nanowires will be good candidates for thermoelectric applications. Reducing the diameter of the nanowire will further reduce its thermal conductivity. This is because it is expected that the boundary scattering of nanowires with a diameter of less than 20nm can be controlled at room temperature. Except Bi <sub>2</sub> Te <sub>3</sub> In addition, other materials can also be used, such as: SiGe, InGaAs, whose alloy scattering can reduce photon transport.
6.1.2 Component design
Since nanowires are very fragile, they must be embedded in a matrix to provide mechanical strength. For example: Bi <sub>2</sub> Te <sub>3</sub> Or the SeGe COHN nanowire array can be embedded in a polymer or dielectric material, such as the thermoelectric element 210 shown in FIG. 30. The thermoelectric element 210 includes a pair of upper and lower insulating substrates 212 and 214, in which an n-doped nanowire array 216 and a p-doped nanowire array 224 are disposed. Among them, the n-doped nanowire array 216 is grown on a substrate 218, and the nanowire 220 is embedded in a polymer matrix 222; the p-doped nanowire array 224 is grown on a substrate 226 , The nanowire 228 is embedded in a polymer matrix 230. The n-doped and p-doped nanowire array wafers are joined together using serial electrical connection and parallel thermal connection to form a thermoelectric cooler and generator. These connections are made of metal contact pads 232, 234, 236, 238, 240. After the nanowire is made, a polymer solution can be poured into the nanowire array to embed the nanowire array in a polymer matrix, and then it can be hardened by heating or UV irradiation. In order to make the upper contact pads 234, 240 (located on top of the nanowires), the polymer should be etched until the nanowires are exposed first, and then the metal contact pads are deposited.
The design parameters of this composite are: (a) the surface density of the nanowire; (b) the element thickness. This idea is to develop a polymer with ultra-low thermal conductivity (k=0.lWmk) and high power factor (S <sup>2</sup> σ) nanowires to achieve high ZT values. The characteristics of component performance can be obtained through the following measurements: (a) the effective conductivity of the component; (b) the effective thermal conductivity of the component; (c) the effective Seebeck coefficient; (d) reflects the current passing through the component (E) Electric power reflecting the temperature difference and heat flow rate.
6.2 Component design
Nanowire composite materials have two different properties and can be applied to light-emitting devices. On the one hand, the low-dimensional beam system of electrons and the quantification of energy levels can be used to adjust the absorption and emission wavelengths. The one-dimensional lattice growth along the nanowire allows the lattice mismatch between different materials to be highly elastic. , Which broadens the range of absorption and emission spectra. On the other hand, the refractive index of Si and III-V semiconductors (3~4) is much higher than that of air or silica fibers (1~1.5), which creates a kind of size mismatch, which becomes the difference between fiber and semiconductor. One of the main problems of light connection. This will also limit the external quantum efficiency of the light-emitting diode, because most of the emitted photons will be absorbed again in the material.
Based on the scientific knowledge of the electric band structure of various III-V and IIVI nanowires, nanowires can be designed in order to achieve effective absorption and emission of photons. For example, as shown in Figure 31, a nanowire polymer synthetic array 250 is fabricated by integrating a plurality of nanowires 252 into a polymer matrix 254 according to the aforementioned method to provide a low effective coefficient Optically effective materials. The change in refractive index of polymers is one order of magnitude higher than that of traditional semiconductors. Combining the large thermal-optical coefficient and the photoelectric properties of semiconductor nanowires, a new energy conversion element can be provided.
Preferably, the nanowires with the highest radiation efficiency are embedded in the polymer matrix to produce photovoltaic power generation elements. Moreover, by using a mixture of nanowires made of different materials, a wider emission spectrum and white light can be obtained.
Please refer to FIG. 32. An electron-emitting light-emitting diode/laser diode 260 includes a nanowire 262, and the formation of the pn junction 264 is due to the growth of the n-type semiconductor 266 and the p-type semiconductor 268. A positive electrode 270 and a negative electrode 272 are connected to the n-type material and the p-type material, respectively. The ejection of electrons will provide a potential energy across the electrode to cause the phenomenon of light emission. The excessive dopants of this structure can be ZnO, Si/Ge, and GaN.
Please refer to Figure 33, the use of LOHN280 can make a single quantum dot LED, and the effect of quantum dot size and material can be read in the emission spectrum. The unique geometric shape of the quantum wire allows electrons and holes to be directly transmitted to the dots 282, thereby preventing the recombination of electrons and holes in other places. The production of quantum dots can use: SiGe, PbSePbTe, Bi <sub>2</sub> Te <sub>3</sub> Sb <sub>2</sub> Te <sub>3</sub> . It is even possible to put the synthetic nanowire polymer medium into a vertical hole and distribute it into a dielectric mirror, which can provide optical feedback and can read out the laser emission and react with the laser.
In addition, exquisite T-shaped, V-groove, ridge quantum wire lasers and quantum dot lasers can also be produced and defined. The electron density state of these components has 1D~0D characteristics, so it has unique properties. In particular, increasing its differential value can improve the high-speed change characteristics, and the size change can also be used to change the electron energy state and emission spectrum. It is expected that the light emission phenomenon in COHN and LOHN can create a new level of energy conversion element whose photoelectric properties can be modified to surpass the results obtained by current methods.
6.3 Nanowire element elasticity
The nanowires of the present invention can be used to make various devices. In addition to the foregoing, they also include but are not limited to the following devices: (a) Nanowires with high electron mobility (using COHN) (b) High electron mobility High-speed nanowire field effect transistor (using COHN and providing an external bias to deplete/add a channel) (C) Nanowire for infrared detector (using LOHN and embedded quantum dots) (d ) Nanowires for 1D resonance tunneling diodes (using LOHN and embedded quantum dots) (e) Nanowires for single-electron transistors (using LOHN and embedded quantum dots, which can also be combined COHN) (f) Nanowires for infrared detectors (using COHN and electronic mode of quantized whispering gallery) (g) Nanowires for magnetic detectors (using COHN and for a while Quantized whispering gallery (electron mode) influenced by magnetic field) (h) polymer-nanowire composite light-emitting element (high applied quantum efficiency, broad spectrum, good coupling with fiber) (i) polymer -Optical regulator of nanowire composite (because the speed of electronic signal matches with optical signal, it can be a regulator with very high-speed wave propagation) (j) Optical probe of polymer-nanowire composite; ( k) Waveguides and couplers of polymer-nanowire composites (nanowires are grown in directional channels between nanowires); (l) Optical switches for polymer-nanowire composites; And (m) lasers for polymer-nanowire composites (end-point emission, distributed feedback or vertical opening structure).
It is better to use LOHN to make multi-terminal devices (such as: N>2), such as pnp devices. Figure 34 shows a pnp LOHN290 with three terminals, which contains a P-type material 292, an N-type material 294, a P-type material 296, and three terminals T <sub>1</sub> , T <sub>2</sub> , T <sub>3</sub> . Figure 35 shows another three-terminal LOHN300.
6.4 Nano Electromechanical Components
In theory, the pyroelectric and piezoelectric elements of VLS nanowires have the following inherent characteristics, which can be distinguished from thin-film or bulk elements:
(a) High quality factor: The lack of extended defects can make the nanowire resonator have a high mechanical quality factor, and low defect density can be regarded as a low loss tangential, so it can have many advantages of high thermoelectric coupling (proportional to (tanδ) <sup>-1</sup> )。
(b) High surface/volume ratio: Combining the small mass per unit length and the nanowire volume with high absorption ratio allows the resonance detection of the mass increase to reach the single-molecule level.
(c) Variable length without changing the quality of the material: The longitudinal resonator of the nanowire can be made into various lengths, from sub-micron to tens to hundreds of microns, so that it can be used to make sensors with a wide resonance frequency or Actuator.
(d) Nano-scale diameter: The smaller diameter allows piezoelectric or pyroelectric nanowires to be used as direct probes under atomic or molecular forces, and nanoscale temperature. Moreover, the bending of the nano-beam unit model has longitudinal electrodes and elastic layers manufactured by projection evaporation, which can provide a very large deflection zone because the ratio of length to thickness is 1000:1, and it has excessive voltage. The large cross-sectional electric field (for 1V, 100MV/m passes through a nanobeam with a thickness of 10nm).
Refer to Figures 36~39, which show the configuration of the nanowire components of the motor converter. Figures 36 and 37 show the vertical configuration, and Figures 38 and 39 show the horizontal configuration.
As shown in Figures 36 and 37, in <0001> wurtzite, its spontaneous polarization is in the longitudinal direction, which is arranged along the spool. Therefore, the electric field and mechanical stress along the spool will produce the largest spontaneous polarization. In the axial configuration 310, the simplest electrode configuration is to use contact electrodes 312 and 314 at the bottom and top, respectively, and the longitudinal stress provided in the bottom and top contact is detected by direct piezoelectric effect. Since the current cross-sectional area is small, a small external force can generate a large stress. For example: for a cross-sectional area of 10nm <sup>2</sup> For the line, a uniaxial tensile stress of 10nN can produce a uniaxial stress of 100Pa, so the piezoelectric coefficient of 5nCN can produce 0.5Cm <sup>2</sup> The piezoelectric change, this value can usually be detected. For nanowires used in resonance sensors, one end of the nanowire must be non-mechanical, and a conductive surface needs to be provided to detect the charge near the end of the nanowire, and by Tunneling method to remove or increase the charge.
As shown in Figures 38 and 39, completely separated induction and actuation can be obtained from the <hkiO> arrangement of wurtzite nanowires, that is, the spontaneous polarization will be perpendicular to the direction of line growth. For such nanowires, the growth method can be performed at the appropriate surface arrangement of the single crystal substrate, such as the (0001), (hkiO) arrangement of the sapphire substrate. In the lateral configuration 320, the electrode can be placed at the end of the wire to activate the piezoelectric shear mode d <sub>15</sub> , Or set along the length of the line to use d <sub>31</sub> . Figure 38 shows d <sub>31</sub> Mode, the electrodes 322 and 324 are placed along the length of the wire, which can provide large electrical breakdown strength (>300MV/m) and high breaking strength to defect-free AlN nanowires, which can then be used to make high-displacement nanowires. Line unit mold bending and external force sensor. Assuming that a suitable elastic layer is formed by projection deposition on one side of the nanowire, relative to the electrode on the other side, the end point displacement δ of the nanowire will be approximately d <sub>31</sub> L <sup>2</sup> V/t <sup>2</sup> . For lateral voltage 1V, thickness 10nm, length 5μm and d <sub>31</sub> If it is 3pm/V, the end point displacement is about 0.75μm.
The challenges encountered in the synthesis and process of the horizontal configuration far exceed those of the vertical configuration. For example, nanowires must be nucleated in the horizontal arrangement, and their nucleation needs to be on the substrate or seed layer of crystalline wurtzite. Once nucleated, the isotropy of the surface energy will produce nanowires with rectangular cross-sections, which is quite ideal for projection deposition. Based on the experimental data of lateral growth of GaN, the growth rate of horizontal nanowires will greatly exceed that of vertical nanowires. Once synthesized, multiple metal layers can be fabricated using projection deposition methods to become the curved objects of the nanobeam unit mode. A thin compliant metal layer (such as Cr/Au) can be used as an electrode, and a pair of compliant metal layers ( Such as Ti/Pt) can be used as an electrode or an elastic layer, which can be used to control the optimal position of the central axis of the bending mode actuation. Alternatively, a solution process can be used to selectively deposit metals with different surface properties on the two surfaces.
6.5 Nano laser for room temperature UV nanowire
The development of short-wavelength semiconductor lasers is currently a subject of considerable interest. A room temperature green-blue diode laser structure has been developed, which uses ZnSe and In <sub>x</sub> Ga <sub>1-x</sub> N is the active layer. ZnO is another wide band gap (3.37eV) compound semiconductor, suitable for blue photoelectric applications. In fact, ultraviolet laser action has been reported on disordered ZnO particles and films. For wide-bandgap semiconductor materials, it is necessary to provide a high carrier concentration in order to achieve sufficient light to generate a laser effect in the electron-hole plasma (EHP) process. This kind of EHP mechanism is usually used in early laser diodes, and basically requires a high nodal band critical value. On the other side of EHP, the excitons in the semiconductor recombine, and the boton properties can provide a low critical value stimulated emission. In order to achieve effective exciton laser action at room temperature, the exciton connection energy (E <sup>b</sup> ex) Must be greater than the heat energy at room temperature (26meV). Under this consideration, ZnO becomes a good choice because of its E <sup>b</sup> ex is equivalent to 60meV, which is significantly larger than ZnSe (22meV) and GaN (25meV).
In order to further reduce the critical value, a low-dimensional compound semiconductor nanostructure was produced, whose quantum size effect can provide a substantial density state at the end of the band, and its carrier beam system can increase the recombination of radiation. The use of semiconductor quantum well structure as a medium for obtaining low-critical optics can show significant progress in semiconductor laser technology. The phenomena of excitation emission and optical acquisition can be confirmed by Si and CdSe nanoclusters and their overall structure.
Another point of view of the present invention, at the critical value of 40kWcm <sup>2</sup> Under the optical excitation, it is confirmed that the first exciton laser effect is generated in the ZnO nanowire. The chemical elasticity of nanowires is like its one-dimensional characteristics, which can make its laser light source reach the ideal miniaturization. These small-wavelength nanolasers can be widely used in optical calculations, data storage, and nanoanalysis.
Example 6
The synthesis of Zn0 nanowires uses a vapor transmission process to catalyze epitaxial growth on a sapphire (110) substrate, which uses patterned Al thin film as the catalyst for nanowire growth. In the growth of nanowires, a layer of gold film with a thickness of 10~35 is first coated on a clean sapphire (110) substrate, which can use or not use a TEM grid as a shadow mask (this Au pattern is also made You can use the micron contact printing method before selective etching). Then transfer the same amount of ZnO powder and graphite powder to an aluminum boat, and place the sapphire substrate coated with Au pattern at a distance of 0.5 to 0.25 cm from the center of the aluminum boat. Then it is heated to 880~950 in an Ar atmosphere. C, the carbothermic reduction of ZnO will generate Zn gas phase and transfer it to the substrate, enabling ZnO nanowire growth. This growth usually takes 2-10 minutes.
After epitaxial growth on the substrate, a highly arrayed nanowire can be formed. When an Au patterned film is used, selective nanowire growth can be performed immediately, while ZnO nanowires only grow on the area coated with Au. This is because the catalytic properties of the Au film can provide excellent selectivity, and The area of the nanowire array can be extended to cm <sup>2</sup> . Generally speaking, the diameter range of nanowires is 20~150nm, and the main diameter range is 70~100nm. The factor affecting the diameter distribution is the uneven size of the Au nanobeam catalyst during the annealing process of growth. By adjusting the growth time, the length of the nanowire can be controlled within 2~10μm. This patternable nanowire growth technology can be applied to the manufacture of nano-level light emitters.
We found that almost all nanowires grow perpendicular to the substrate. This is because there is a good epitaxial interface between the (0001) plane of the ZnO nanowire and the (110) plane of the substrate. The ideal a-plane (110) of sapphire is two-fold symmetrical, while the c-plane of ZnO is six-fold symmetrical, which does not match, except that the correlation factor between the a-axis of ZnO and the c-axis of sapphire is 4 ( Its mismatch at room temperature is less than 0.08%). This kind of matching makes it grow on the c arrangement along the sapphire [0001] direction and the strong trend direction of ZnO, which is equivalent to a discontinuous interface outside the sapphire [0001] direction, and a special vertical epitaxial growth configuration will be produced. For the growth of high-quality c-array ZnO nanowire arrays, the anisotropy of the a-plane of sapphire is very critical.
The SEM image of the nanowire array can clearly define the plane of the six endpoints of the nanowire. The strong evidence is that the nanowire grows along the <0001> direction and is indeed between the ends and the sides. There are obvious cut surfaces on the surface, which suggests that nanowires can be used as an effective laser medium. Using TEM, a structural characteristic of ZnO nanowires can be defined. According to the high-resolution TEM image, the distance between two adjacent lattice planes is 2.56±0.05, which is equivalent to the distance between two lattice planes (0002), and <0001> is the maximum of ZnO nanowires. Good growth direction. In particular, as shown in Figure 40, in a Siemens Z5000 machine experiment, <0001> can also be displayed in the X-ray diffraction pattern, only the (0001) front is found, which means that the The nanowire array has an excellent C-axis arrangement.
Using He-Cd laser (325nm) as an excitation source, the optical luminescence spectrum of nanowires can be measured, and it is found that near the end of the band gap, strong luminescence can be generated at about 377nm. In order to know the possibility of exciting light from the arranged nanowires, the emission of energy dependence was tested. The sample adopts a Nd-YAG laser (266nm, 3ns pulse) which is the fourth harmonic at room temperature. width). Focusing on the light beam absorbed by the nanocue, the incident angle relative to the symmetry axis of the nanowire is 10°, and the emitted light is collected in the direction perpendicular to the end face of the nanowire (along the symmetry axis), and can be used Monochromator (ISA) and Perle cooled CCD (EG&G) collect the light excited by the nanowire. All experiments were done at room temperature, and the laser reaction in ZnO nanowires can be found.
Figure 41 shows the evolution of the emission spectrum when the pump power is increased. At low excitation density (below the laser critical value), the spectrum contains a single and main self-emission peak (curve a), its FWHM is 17nm, and its spontaneous emission is 140meV, which is lower than the band gap 3.37eV, generally Photons are produced due to recombination during exciton impact. As the pump power increases, the emission peak becomes narrower because the amplitude is close to the maximum value of the spectrum. When the exciton density exceeds the laser critical value (40kw/cm <sup>2</sup> ), sharp peaks will appear in the spectrum (curve b and inset). The pump powers of these spectra are 20, 100, and 150kw/cm respectively <sup>2</sup> . Below the critical value, the line width of these peaks is less than 0.3 nm, which is less than 50 times the line width of the self-emission peak. Above the critical value, as the pump power increases, the integrated emission intensity will also increase rapidly, as shown in Figure 42. Here, the narrow line width and the rapidly increasing emission intensity mean that excited emission will occur in the nanowire. The observed single or multiple sharp peaks (curve b in Figure 41 and inset) show that different laser modes will appear within the wavelength of 370~400nm. Moreover, compared to the previously reported laser critical value (300kWcm <sup>2</sup> ), its laser critical value is quite low. Obviously, the shortwave nanowire nanolaser can be operated at room temperature, and its actual nanolaser density can reach 1.lx10 <sup>10</sup> cm <sup>-2</sup> 。
In fact, without making a mirror, by observing the laser effect of the nanowire, it is possible to think of using a single crystal nanowire with a cut surface as a resonance opening to enhance the excitation emission. Figure 43 shows a nano laser 330, which is made by growing a ZnO nanowire 332 with multiple cut edges (such as six sides) on a sapphire substrate 334. Note that the nanowire 332 is not Different straight structure, but homogeneous structure. The nanowire is suitable as a resonance opening, which contains two hexagonal sections 336 and 338, which is suitable as a reflector. The huge oscillating intensity effect can be used, which occurs when the size of the high-quality nanowire lattice is larger than the size of the exciton wave but smaller than the optical wavelength, which can cause excitation and emission in the nanowire array. For group II-VI semiconductors, the split edge can be used as a mirror. For nanowires, one end between the sapphire substrate 334 and ZnO is an epitaxial interface 336, and the other end is the sharp surface (0001) of the ZnO nanolattice, both of which can be used as laser openings Mirror, this is because the reflection coefficients of sapphire, ZnO, and air are 1.8, 2.45, and 1.0 respectively. This is very important for the nature of the nanowire, that is, because it is very easy to be adjacent to a waveguide. The production of natural openings/waveguides in nanowires reminds people of a simple chemical method that can form a nanowire laser opening without using cracking and etching. In fact, as shown in Figure 41, for the various laser modes found in these nanowires, the distance between the lines of about 5μm length is 5nm, and the number is quite consistent with the calculated distance v of adjacent resonance frequencies. <sub>F</sub> =c2nl, where v <sub>F</sub> Represents the emission mode spacing, c represents the speed of light, n represents the refractive index, and 1 represents the length of the resonance opening. Another way to make a waveguide is to coat a layer of polymer on the nanowire.
Using the Ti: Sapphire laser (pulse excitation, 200fs pulse length) and a fringe camera with a pre-analysis function for detection, it can study the luminescence decay phenomenon of Zn0 nanowires by using the Ti: Sapphire laser (pulse excitation, 200fs pulse length) in the tri-band blocking mode. Please refer to Figure 44, assuming that in a fast and a slow process, the time is fixed at 70ps and 350ps. At room temperature, good phenomena (straight lines) and experimental data can be observed in the obtained double exponential decay mode. (Dotted line), the time-resolved spectrum was recorded under the excitation power condition of 6.39mw. These lifetime measurement results show that the radiation recombination of excitons is an overlapping phenomenon of fast and slow processes, and the luminescence lifetime is mainly determined by the concentration of defects, which trap electrons and/or holes and lead to non-radioactive Recombination phenomenon. Although the actual cause of the luminescence decline is still unclear at this stage, the high-quality crystals obtained by the nanowire growth process can have an extremely long service life. At the same time, the record here also partially explains the low laser threshold.
All in all, we have confirmed that the ultraviolet laser in an ordered array of Zn0 nanowires can have a capacity of 40kW/cm at room temperature. <sup>2</sup> Laser critical value. Moreover, the actual density of the nano laser on the substrate can reach 1.1×10 <sup>10</sup> cm- <sup>2</sup> . It is expected to use Zn0Cd0 alloy nanowire to adjust the laser wavelength to the blue region. In addition, the p-n junction created in the nanowire can test the possibility of electrons emitting blue laser light from the nanowire. The above-mentioned miniaturized nanowire and nanolaser can be applied to nanophotonics and microanalysis.
It can be seen from the above that the nanowire of the present invention can be used as an optical aperture. Another way to make an optical opening is to make a dielectric at one end of the wire. Moreover, one part of the nanowire can contain one form of energy conversion, and the other part can contain a different form of energy conversion, as in a distribution feedback laser. It is also possible not to cover one end of the optical opening, like a laser or optical amplifier. In addition, this opening can also be a part of the aforementioned nanowire, and this opening can also be added to the nanowire. In essence, the production of lasers or optical amplifiers can use nanowires, pump sources, and openings, and the openings can be part of the nanowires or separate from the nanowires. Even if the traditional excitation light emission technology is used, this opening is not required.
The nanowire of the present invention can be used as a functional element of a quantum dot laser, such as the US Patent No. 5,260,957 mentioned in the reference, in which quantum dots can be integrated into the nanowire, and the pump source can be It is installed to stimulate population inversion in quantum dots. However, in order to generate a laser, the nanowire can push and pull itself to reverse the population of the nanowire. The nanowire can be integrated into a polymer matrix as described above to become a unit in a matrix (such as a laser element). The pump source can be an optical pump source (such as a pump laser) or an electronic pump source, the cathode and anode of which are connected to the nanowire in direct contact or ohmic contact. If a pump laser is used, the wavelength of the pump should preferably be more than leV more than the wavelength of the nanowire. The nanowire can be placed in an opening, or the end point can be made into a reflective surface, so that the nanowire can be used as an opening.
6.6 Other components
It can be seen from the foregoing that a large number of devices can be produced using nanowires and their synthesis methods. Other components are not limited to include:
6.6.1 Field Effect Transistor (TEF)
This is a three-terminal device that can be made using COHN, and its gate voltage can control the current flowing from the source to the drain. The source and the drain can be any two points of the nanowire and are in contact with the axis of the nanowire, and the gate is located between the source and the drain and will be in contact with the sheath of the nanowire. The gate voltage controls the conductivity of the channel between the source and drain. This performance can provide at least two forms of TEF. The first type is a junction FET, which includes a pn junction with a reverse bias and is located at the gate. At this time, the axis of the nanowire is an N-type semiconductor, and the sheath is a P-type semiconductor (and vice versa). When a reverse bias is provided on the bonding surface, the depletion zone at the axis can be increased, and the current flowing from the source to the drain can be displayed. The second type of FET uses metal oxide (MOSFET) or metal insulation (MISFET) to contact the gate. The sheath of the nanowire contains two secondary sheaths, and the axis of the nanowire is sequentially covered with an oxide Layer or insulating layer and a conductive layer. Provide a voltage between the conductive sheath and the axis of the nanowire to remove the channel between the source and the drain (it becomes a depleted form of MOSFET/MISFET). If there is no channel formed at the axis of the nanowire, when the gate voltage is zero, a channel can be created (it becomes an increased form of MOSFET/MISFET).
6.6.2 Infrared (IR) Detector
The IR detector can be made using nanowires, which are made of semiconductor materials and have a band gap at the IR wavelength (1-20 microns). This detector is a two-terminal element, and two connection points are made on both ends of the nanowire. It can be measured by providing a bias voltage between the two ends. The presence of light will change the conductivity of the nanowire (becoming a light conductor). Or, when no applied bias voltage is provided, the light will create a voltage across the nanowire (which becomes a photovoltaic operation). Its operation requires an internal electric field in the nanowire. The pn junction or the metal/semiconductor junction at the contact points at both ends of the nanowire can be understood. When the diameter of the nanowire is smaller than the electron De Broglie wavelength of the electron, the quantum beaming effect will change the effective band gap of the material and the region sensitive to IR radiation. Another type of IR detector can be made by LOHN, which is similar to the optical detector of quantum well IR inserted into the subband. A series of heterostructures along the direction of the nanowire creates quantization in the conductive band or valence band of the material. The electronic state is not limited to the band gap of the material. In any IR wavelength (1-20 microns), the optical absorption can be adjusted between the electronic states. The contact of the two ends of the nanowire can understand the photoconductor or photovoltaic IR detector.
6.6.3 Single electron infrared detector
This device is similar to the aforementioned LOHN-based IR detector. The difference is that the parameters (length, nanowire diameter, composition) of the heterostructure layer can be selected so that the large number of free electrons created in the special layer can be changed. With electrostatic energy, no other electrons can be transmitted from this layer until the free electrons leave (known as the Coulomb blockade). In this way, the single electron situation can be detected, and then the single photon situation can be detected.
6.6.4 Resonant tunneling diode
This is a two-terminal element made by LOHN. The basic idea is to divide a LOHN into five segments (transmitting, blocking 1, well, blocking 2, collector). The well layer must be short enough to quantize the electrical energy state while blocking The band structure of the layer needs to be selected so that the electron wave function gradually disappears, but the probability of electron transport across this layer is not zero. Under a bias voltage, electrons are emitted from the emitter contact to a collector contact. Under a special bias, when the energy of incident electrons from the emission layer is equivalent to the quantization energy level in the well layer, the transmission phenomenon across the entire structure will increase (resonance tunneling), so that the current-voltage characteristic can be negatively differentiated The increased resistance value can be used to make high-speed oscillators or logic circuits.
6.6.5 Light Emitting Diode (LED)
A single nanowire light-emitting diode can be fabricated using the pn junction surface of the nanowire. In the heterostructure close to the depletion region (where electrons and holes will recombine), a higher efficiency LEDO can be provided by beaming carriers. LEDs are made using nanowire arrays. It is important to mix an appropriate Fillers (such as polymers) have low absorption and scattering loss. In the completed element, a nanowire composite is placed between the two electrodes.
6.6.6 Electronic pump laser
This is composed of nanowire composite LEDs and optical openings. The optical openings are arranged vertically (along the sides of the nanowire composite) or horizontally (similar to scattered Bragg reflection lasers). Composed of electric mirrors.
6.6.7 Optical waveguide/inner connection
In terms of its surface configuration, nanowires can be used as part of the composition of the material (nanowires plus filling materials), or used to guide the light of the nanowires themselves. In the subsequent examples, the main design parameters are the optical loss along the line and the number of lateral modes. The typical design is based on COHN, and a special number of guiding modes or group dispersion values can be obtained by selecting the index of the axis and the sheath layer (similar to the design of the silicon-based optical fiber). In the previous example (synthetic nanowire material), it can be regarded as a new engineering material, and the wave guide can be fabricated (in the form of a bump or a flat layer) in the traditional way.
6.6.8 Optical coupler/adjuster/switch
In the example of nanowire synthetic material, basically a filling material (such as polymer) can be obtained, and its photoelectricity, photothermal property or photomagnetism can be adjusted through the mixed nanowire array. Therefore, different materials and various wire diameters can be selected to adjust to the required properties (such as: increasing the photoelectric coefficient, incorporating the nanowire p-n junction surface into the optical gain). When the nanowire synthetic material is finished, it can be used as a new thin film material, and can be made into guided wave switches, regulators, and couplers using traditional methods. The main advantage is that for thin film devices, the properties of passive and active heterostructure nanowires can be combined with simple polymer manufacturing processes.
6.6.9 Motor/heat engine components
Nanowires made of piezoelectric or piezoresistive materials can be used as motor inductors. Under uniaxial strain, piezoelectric (AlN, ZnO) nanowires can generate a voltage signal along the spool axis, and piezoresistive (Si) nanowires can change the resistance, which can be measured by measuring the current passing through. The amount is known. When these nanowires are mixed into a polymer matrix, an elastic/compliant material is essentially obtained, which can be used to detect uniaxial strain. Piezoelectric elements can also provide uniaxial motion. If the nanowire heterostructure is made by coating another material on one side of the single crystal nanowire (such as a part of COHN), it can be used to provide a bending action, such as the same coupling part (bimorph). For example, when two materials have different thermal expansion coefficients, it can be used to detect temperature changes and any factors that change temperature (such as radiation absorption, electrical dispersion). In addition, by changing the temperature, this element can be used as a thermal actuator. Coupling components based on nanowires can be used to detect any amount of strain perpendicular to the axis of the nanowire.
6.6.10 Chemical sensing element
When the nanowire can exhibit the function of a chemical sensor, the nanowire can also be used as a chemical logic. For example: Consider a LOHN whose sections are composed of materials A, B, and C. Assuming that when chemical A is adsorbed, material A can be made conductive (the same situation also occurs in materials B and C), then only if The presence of chemistry A', B', and C'makes the nanowires highly conductive. This is a chemical logic. For example, when A'and B'and C'=1, then A'and B'are not C'=0. If these structures are placed in a series/parallel network structure, AND or OR logic can be generated. This of course can be extended to biosensing. In fact, since the bioreceptor is a high-level species, biosensing will be simpler.
7. Conclusion
From the foregoing, it can be seen that when the size of the semiconductor is limited to less than 200 nm in a two-dimensional, one-dimensional or zero-dimensional structure, especially when the size is between 5 and 50 nm, its properties can be manipulated in novel ways. VLS and other chemical synthesis techniques can be used to grow nanowires and extremely heterogeneous structures. These structures include COHN, LOHN, and combinations of these two. COHN can allow adjustment of doping so that the nanowire has a relatively high charge carrier mobility, while LOHN can allow one-dimensional band gap engineering to integrate multiple quantum dots or pn junctions into a single nanowire. The belt structure engineering close to the Fermi level can also allow adjustment of its thermoelectric properties. The one-dimensional beam system has a strong influence on the phonon spectrum and service life, and can dramatically change its thermal properties. Moreover, the heterogeneous structure of nanowires offers promising prospects for integrating semiconductor nanowires into piezoelectric nanostructures to make nanomotor converters. Moreover, the elastic interface conditions of COHN and LOHN can form an undifferentiated interface, which is unstable in a two-dimensional state (quantum well and heterostructure) or in a thin film form, and at the same time, it can be used in a bulk or thin film form. The quasi-stable phase becomes a stable phase.
COHN and LOHN also provide their own development of energy conversion components, including thermoelectric air conditioners or generators, light-emitting components, and nanomotor converters. The effective materials in these devices include a composite of unidirectional nanowire arrays synthesized by VLS, embedded in a polymer matrix, and can become a nanosystem through pattern definition and integration.
Semiconductor nanowires with a diameter of 5~10nm provide a unique opportunity to develop thermoelectric air conditioners and generators, which perform better than gas-based components. This kind of solid-state components can have a huge impact on the use of energy in the environment. Impact. The use of nanowires with quantum dots can be applied as an efficient and size-adjustable photoelectric converter.
Furthermore, embedding nanowires in a polymer matrix can form a luminescent elastic medium, which has a lower effective index than semiconductors and can efficiently couple with optical fibers, thereby greatly improving the added quantum efficiency. When combined with single electrons, this quantum dot nanowire can be used as a single photon element to significantly affect information storage and manufacturing processes. Piezoelectric transducers using nanowires can become a component with high quality factor and high resonant frequency, which can be used in applications between molecular induction/nanoactuators and high-frequency signal processors. Finally, single-crystal nanowires that use the end of the section as a mirror can be applied to nano-cluster elements.
LOHN contains heterostructures along the length of the nanowire, which can also be designed or have the following interesting properties, but not limited to: (a) pn, pnp or other various bonding surfaces that can be used for photonic components; (b) With adjustable size optical absorption/emission quantum dots and single electron tunneling properties, photonic devices can be fabricated; (c) Nanowire superlattices with high electron mobility and low phonon transmission, then It can be applied to thermoelectric elements; (d) Piezoelectric and electronic heterogeneous elements can be applied to Naimi motor converters. It is worth noting that the elastic boundary conditions for heteroepitaxial growth of VLS nanowires can create a seamless interface in superlattice nanowires. Because the epitaxial film grows on a flat substrate, it is traditional The two-dimensional configuration will show an unstable state. On the other hand, in other examples, the existence of the difference is allowed, and the defects can be controlled by the method of the present invention.
Although considerable efforts have been made in the past on synthesis technology and research on zero-dimensional (quantum dots) and two-dimensional (quantum wells and heterostructures) nanostructures, little attention has been paid to semiconductor nanowires other than carbon nanotubes. However, compared to quantum dots, nanowires with a length of 1~10μm offer unique opportunities to integrate lithographic microfabrication features into nanostructures, which are usually 1μm in length. Moreover, the two-dimensional structure of nanowires can further provide beam system, which has been widely studied and used. Due to these advantageous contributions, various types of elements based on the heterostructure of nanowires can be designed as: (i) high-efficiency thermoelectric air conditioners or generators; (ii) adjustable light-emitting diodes; (iii) Piezoelectric nanomechanical sensors and actuators. In these components, the use of heterostructures of nanowires is essential because they can greatly improve conversion efficiency or open up new conversion methods. These simple components can also be used as the basis for other more complex components.
Various surface configurations can be obtained by using the aforementioned structure of the present invention, some of which have been described previously. Other examples are: LOHN of single or multiple joints, COHN of single or multiple joints, a combination of LOHN and COHN, two-terminal configuration, N>2 terminal configuration, a combination of heterogeneous structure and homogeneous structure, with one or Homogeneous structure with multiple electrodes (which can be heterostructures), heterostructure with one or more electrodes, homogeneous structure with insulator, and heterostructure with insulator. The interface between a nanowire and a terminal constitutes a heterogeneous junction. Using these structures and configurations, various components can be produced, including: phononic band gap components, quantum dots that beam electrons in special regions, thermoelectric components (such as solid state air conditioners and engines), and photonic components (such as: Nano lasers), nano motor (MEM) components (such as motor brakes and inductors), various forms of energy conversion components (such as: light to mechanical energy, heat energy to light) and other components.
Although the present invention has been disclosed in a preferred embodiment as above, it is not intended to limit the present invention. Anyone who is familiar with this technique can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, this The scope of protection of the invention shall be subject to the scope of the attached patent application.
Schematic description
Figure 1 shows the technology for efficiently converting different types of energy.
Figure 2 shows that the COHN heterostructure of the present invention has a sheath on the shaft.
Figure 3 shows that the LOHN of the present invention has five line segments.
Figure 4 shows that the COHN of the present invention has a shaft and two sections of sheath.
Figure 5 shows that the COHN of the present invention has a two-axis center and a section of sheath.
Figure 6 shows that the COHN of the present invention has a two-axis center and two-stage sheath.
Figure 7 shows that the COHN of the present invention has multiple superlattice line segments and a sheath.
Figure 8 shows that the COHN of the present invention has a single-segment axis and a sheath only surrounds a part of the single-segment axis.
Figure 9 shows that the COHN of the present invention has two sections of LOHN axis and a sheath only surrounds a part of the axis.
Figure 10 shows that the nanowire heterostructure of the present invention is a pn junction device.
Figure 11 shows that the nanowire heterostructure of the present invention is a pnp, npn, pin or pip junction device.
Figure 12 shows that the actual observation time of nanowire growth can reflect the VLS mechanism.
Figure 13 shows the pn junction of LOHN of the present invention containing Si.
Figure 14 shows a one-dimensional superlattice composed of SiGe.
Figure 15 shows the conductive band gap of the COHN of the present invention.
Figure 16 shows the conductive band gap of the LOHN of the present invention.
Figures 17 and 18 show the BEEM spectral characteristics of individual quantum dots automatically polymerized by GaSb/GaAs.
Figure 19 shows that the confinement effect will enable the structure shown in the BEEM current to be analyzed by the second-derivative (SD) BEEM spectrum.
Figure 20 shows the thermal conductivity of this multi-walled carbon nanotube as a function of temperature in the range of 10°K to 350°K.
Figure 21 shows the measured thermal power of carbon nanotubes with multiple walls in the range of 10°K to 350°K.
Figure 22 shows an experimental device used to measure the mechanical movement of piezoelectric or pyroelectric nanowires, and at the same time, it can measure the electrostatic potential across the nanowires.
Figure 23 shows a nanowire growth device according to an embodiment of the present invention.
Figure 24 shows the synthesis of Si/SiGe superlattice nanowires, using a pair of
The high frequency Nd-YAG laser can produce pulse ablation of pure Ge target material and generate Ge gas
Mutually.
Figure 25 shows a nanowire array synthesized using the process described in Example 4.
Figure 26 shows that the use of energy-dispersive X-ray spectroscopy (EDS) can check the chemical composition in the darker area.
Figure 27 shows scanning a focused electron beam along the long axis of the nanowire and tracking the X-ray signal from Si and Ge atoms in this line.
Figure 28 shows the relationship between the experimentally observed growth rate and the diameter of the nanowire.
Figure 29 shows that the quantum beam system of electrons and phonons can drastically increase its ZT value.
Figure 30 shows the thermoelectric element of the present invention.
Figure 31 shows the nanowire polymer synthetic array of the present invention.
Figure 32 shows the light-emitting diode/laser diode for electron emission of the present invention.
Figure 33 shows that the present invention uses LOHN to make a single quantum dot LED.
Figure 34 shows a p-n-p LOHN with three terminals.
Figure 35 shows another three-terminal LOHN.
Figures 36~39 show the configuration of the nanowire components of the motor converter. Figures 36 and 37 show the vertical configuration, and Figures 38 and 39 show the horizontal configuration.
Figure 40 shows that <0001> can also be displayed in the X-ray diffraction pattern in a Siemens Z5000 machine experiment.
Figure 41 shows the evolution of the emission spectrum when the pump power is increased.
The 42nd shows that as the power of the pump increases, the integrated emission intensity will also increase rapidly.
Figure 43 shows a nano laser.
Figure 44 shows the time-resolved spectrum record in the double exponential decay mode.
Symbol description of main components
Heterostructure nanowires. . . 10
Longitudinal heterostructure nanowires. . . 12
Axis. . . 14
jacket. . . 16
Joint surface. . . 18
Line segment. . . 20
Line segment. . . twenty two
Joint surface. . . twenty four
Superlattice line segment. . . 26, 28, 30
Axial heterostructure nanowires. . . 32
Axis. . . 34
The first section of the sheath. . . 36
The second section of the sheath. . . 38
Axial heterostructure nanowires. . . 40
The first section of the axis. . . 42
The second section of the axis. . . 44
jacket. . . 46
Axial heterostructure nanowires. . . 48
The first section of the axis. . . 50
The second section of the axis. . . 52
The first section of the sheath. . . 54
The second section of the sheath. . . 56
Axial heterostructure nanowires. . . 58
Superlattice line segment. . . 60, 62, 64, 66, 68, 70
jacket. . . 72
Axial heterostructure nanowires. . . 74
Single section axis. . 76
jacket. . . 78
Axial heterostructure nanowires. . . 80
The first segment of the LOHN axis. . . 82
The second section of LOHN axis. . . 84
jacket. . . 86
p-n junction element. . . 88
Heterogeneous structure of nanowires. . . 90
Silicon substrate. . . 100
Au nanoclusters. . . 104
Au-Si alloy droplets. . . 106
Si nanowire. . . 108
One-dimensional superlattice. . . 130
Doping. . . 140
Free carriers. . . 142
Quantum dot state. . . 144
structure. . . 150
Piezoelectric or thermoelectric nanowires. . . 160
Conductive substrate. . . 162
AFM cantilever probe. . . 164
Voltage sensor. . . 166
Metal catalyst cover. . . 168
Nanowire growth equipment. . . 170
Reaction furnace. . . 172
Quartz reaction tube. . . 174
Silicon wafer. . . 176
Entrance. . . 178
Computer program laser pulse. . . 180
Pure Ge target. . . 182
exit. . . 184
Au film. . . 186
Au-Si alloy. . . 188
Si nanowire. . . 190
SiGe alloy. . . 192
SiSiGe superlattice. . . 194
Nanowire array. . . 200
Si substrate. . . 202
Nanowires. . . 206
top. . . 204
Thermoelectric elements. . . 210
Upper and lower insulating substrates. . . 212, 214
n-doped nanowire array. . . 216
Base. . . 218
p-doped nanowire arrays. . . 224
Polymer matrix. . . 222
Nanowire array. . . 224
Base. . . 226
Nanowires. . . 228
Polymer matrix. . . 230
Metal contact pads. . . 232, 234, 236, 238, 240
Nanowire polymer synthesis array. . . 250
Nanowires. . . 252
Polymer matrix. . . 254
Light emitting diode/laser diode emitted by electrons. . . 260
Nanowires. . . 262
p-n junction surface. . . 264
n-type semiconductor. . . 266
p-type semiconductor. . . 268
Positive electrode. . . 270
Negative electrode. . . 272
LOHN. . . 280
point. . . 282
Three terminal pn-pLOHN. . . 290
P-type material. . . 292
N-type material. . . 294
P-type material. . . 296
Three-terminal LOHN. . . 300
Axial configuration. . . 310
Contact electrode. . . 312, 314
Horizontal configuration. . . 320
electrode. . . 322, 324
Nano laser. . . 330
ZnO nanowires. . . 332
Sapphire substrate. . . 334
section. . . 336, 338
88 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63 Sheet 64 Sheet 65 Sheet 66 Sheet 67 Sheet 68 Sheet 69 Sheet 70 Sheet 71 Sheet 72 Sheet 73 Sheet 74 Sheet 75 Sheet 76 Sheet 77 Sheet 78 Sheet 79 Sheet 80 Sheet 81 Sheet 82 Sheet 83 Sheet 84 Sheet 85 Sheet 86 Sheet 87 Sheet 88
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| TWI416859B | Cited by | Taiwan Province of China | Examiner |
| CN115312640A | Cited by | China | Search report |
| TWI412153B | Cited by | Taiwan Province of China | Examiner |
| TWI482299B | Cited by | Taiwan Province of China | Examiner |
| TWI768872B | Cited by | Taiwan Province of China | Examiner |
| TWI427781B | Cited by | Taiwan Province of China | Examiner |
38 members in 10 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 60280676 | United States of America | – | |
| 28067601 | United States of America | P | |
| 60349206 | United States of America | – | |
| 34920602 | United States of America | P |
Members38
| Document | Office | Kind | |
|---|---|---|---|
| CA2442985A1 | Canada | A1 | |
| WO02080280A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2002172820A1 | United States of America | A1 | |
| US2002175408A1 | United States of America | A1 | |
| TW554388BThis record | Taiwan Province of China | B | |
| EP1374309A1 | European Patent Office (EPO) | A1 | |
| KR20040000418A | Republic of Korea | A | |
| CN1507661A | China | A | |
| MXPA03008935A | Mexico | A | |
| JP2004532133A | Japan | A | |
| US6882051B2 | United States of America | B2 | |
| US2005161662A1 | United States of America | A1 | |
| US6996147B2 | United States of America | B2 | |
| CN1306619C | China | C | |
| US2007164270A1 | United States of America | A1 | |
| CN101009214A | China | A | |
| AU2008200507A1 | Australia | A1 | |
| AU2002307008B2 | Australia | B2 | |
| US2008092938A1 | United States of America | A1 | |
| AU2008201551A1 | Australia | A1 | |
| AU2002307008C1 | Australia | C1 | |
| US7569847B2 | United States of America | B2 | |
| US7569941B2 | United States of America | B2 | |
| JP2009269170A | Japan | A | |
| KR20090127194A | Republic of Korea | A | |
| US2010003516A1 | United States of America | A1 | |
| CN101638216A | China | A | |
| AU2008200507B2 | Australia | B2 | |
| CN101009214B | China | B | |
| JP2010167560A | Japan | A | |
| US7834264B2 | United States of America | B2 | |
| EP2273552A2 | European Patent Office (EPO) | A2 | |
| KR101008294B1 | Republic of Korea | B1 | |
| JP2011093090A | Japan | A | |
| CN101638216B | China | B | |
| EP2273552A3 | European Patent Office (EPO) | A3 | |
| CA2442985C | Canada | C | |
| US9881999B2 | United States of America | B2 |
2 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Annulment or lapse of patent due to non-payment of feesLapsedMM4A | MM4A | |
| Issue of patent certificate for granted invention patentGrantedGD4A | GD4A |
Numbers
- Publication
- 554388
- Application
- 91106432
Titles5
- Chinese
- 奈米結構及奈米線之製造方法及其製造裝置
- English
- Nano structure and nano wire manufacturing method and manufacturing device
- Unlabeled
- 奈米結構及奈米線之製造方法及其製造裝置
- Unlabeled
- METHODS OF FABRICATING NANOSTRUCTURES AND NANOWIRESAND DEvICES FABRICATED THEREFROM
- Unlabeled
- Nano structure and nano wire manufacturing method and manufacturing device
Classification
- CPC, 45
- H10D62/118
- B82Y10/00
- B82Y20/00
- G02B6/107
- H01S5/341
- H01S5/3412
- Y10S977/762
- Y10S977/763
- Y10S977/951
- Y10S977/765
- Y10S977/764
- Y10T428/2933
- Y10T428/298
- Y10T428/2958
- Y10T428/2973
- Y10T428/292
- Y10T428/29
- Y10T428/2913
- Y10T428/2916
- Y10T428/24994
- Y10T428/249949
- H10N10/00
- H10N30/2042
- H10N30/852
- H10H20/818
- H10H20/821
- H10H20/812
- H10F77/14
- H10D62/123
- H10D62/122
- H10D62/121
- H10D62/813
- H10P14/2901
- H10P14/3211
- H10P14/2905
- H10P14/3402
- H10P14/3426
- H10P14/3462
- H10P14/3411
- H10P14/274
- H10P14/279
- H10W72/522
- H10W72/555
- H10W72/551
- H10D62/81
- IPC, 16
- B82B1 00
- H10N99 00
- B82B3 00
- G02B6 10
- H01L21 20
- H01L23 49
- H01L29 06
- H01L29 12
- H01L33 06
- H01L33 24
- H01S5 34
- H10N10 00
- H10N10 80
- H10N10 85
- H10N30 20
- H10N30 85