TW201004863A - Super lattice/quantum well nanowires - Google Patents

Super lattice/quantum well nanowires Download PDF

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TW201004863A
TW201004863A TW98109050A TW98109050A TW201004863A TW 201004863 A TW201004863 A TW 201004863A TW 98109050 A TW98109050 A TW 98109050A TW 98109050 A TW98109050 A TW 98109050A TW 201004863 A TW201004863 A TW 201004863A
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nanowire
layer
segmented
segment
segmented nanowire
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TW98109050A
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Harold J Hovel
Qiang Huang
xiao-yan Shao
James Vichiconti
George F Walker
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Description

201004863 ' 六、發明說明： 【發明所屬之技術領域】 本發明之揭露係_包含不辭導體材料片段之奈米線及製 造此類奈米線之方法，特別是關於包含内建超晶格/量子井結構之 奈米線。 【先前技術】 由於微尺度及奈米尺度裴置組件之創新電子及光學性質（包含 源自奈米限量子機械面向之勒新物理領域），半導體奈米線逐漸引 © 起關注。材料如巨大型態(bulk form)之鍺化矽(SiGe)、應變石夕 (strained Si)、超晶格、及量子井具有獨特之性質，使此類材料可 應用於許多光學及電子裝置。 習知技術係使用化學氣相澱積法將矽奈米線於石夕基座上方晶 膜生成，如專利申請案公開號第US2〇〇7/〇222〇74 A1號所述，或 將石夕奈米線於矽基座上方之二塊狀共聚物(dibl〇ckc〇p〇lymer)所界 定之圖案樣板生成。專利申請案公開號第US2〇〇6/〇〇987〇5 A1號 〇所述之方法係藉化學氣相澱積(CVD)法於圖案矽基座上方生成矽 奈米線及量子點。專利申請案公開號第US2〇〇5/〇248〇〇3 A1號所 述之方法係藉化學氣相法形成異質接面(heter〇juncti〇n)奈米線。專 利申請案公開號第US2007/0235738 A1號所述之方法係藉化學氣 相殿積法形成具有内嵌量子之p矽/n矽奈米線接面。
钱刻均勻摻雜矽基座以形成矽奈米線之化學方法已於K Q
Peng 等人(Adv. Mater. 14(2002) 1164 ; J. Electroanal. Chem. 558(2003) 35 ; Adv. Func· Mates. 13(2003) 127。）之公開案(published 3 201004863 WWk)t有所論述。® 1顯示之示意圖係關於Peng等人如何獲得 石夕奈米線之方法。 【發明内容】 ★本發明揭露分段奈米線及製造此類分段奈雜之方法。此處 揭露^奈米線藉由於奈祕形式結合超晶格及量子絲構、創造 二維篁子井結構㈣—般二維量子井結構，具有展現更鑛物理 性質之高度可能性。 形成二或多半導體材料層之基座後，基座係藉化學蝕刻部分 移除而不使用樣板(template)。最初’化學侧始於基座表面之某 二位置。半導體材料可由特定晶面(crystal plane)而向表面定位，如 平面(111)或(110)。化學蝕刻優先沿半導體材料之晶軸 (crystallographic axis)持續’就矽而言係方向[1〇〇]，致使具有不同 材料片段(其對應不同層之材料)之奈米線保持位於極少化學蝕刻 或無化學蝕刻之位置。不同片段間之介面可與分段奈米線之縱向 垂直或與其形成一角度。 揭路之化學钮刻方法係一減去(subtractive)做法，由具有二或 多不同半導體層之平面基座產生具有鍺化矽(SiGe)、鍺(Ge)量子井 結構、及石夕奈米線内之垂直接面。 【實施方式】 包含不同選替半導體層如石夕/鍺化石夕(SiGe)/石夕/鍺化石夕、石夕/緒/ 石夕/錯、或η-矽/p-石夕/η->δ夕選替層之多層基座可進行化學蝕刻處理。 蝕刻基座以形成具有内嵌量子井或超晶格結構之半導體奈米線。 4 201004863 較佳半導體為矽。尤以η摻雜及p亨雜矽為佳。特別是，此處揭 露之奈米線包含具有量子尺寸之多^選替材料。例如，以堆疊幾 何(stacked geometry)具有鍺或鍺化矽層之矽奈米線。量子井藉7吉合 矽(Si)、錯化矽(SiGe)、石夕、鍺化石夕等之選替層而獲得。結構不限 於錯化石夕；錯奈米線可結合砰化鎵(GaAs)層，石夕奈米線可結合破 化鎵(GaP)、砷磷化鎵(GaAsP)、或其他πΐ_ν或u-yj族元辛 如此幕多之料枝祕細絲_之紅，如帶 structure)修正及修正之f子性f所引起之魏增加。在某些實施例 中，奈米線-維之橫截面較另一維之橫截面小，即橫截面係姻 ❹㈣棚形。可㈣奈樣Μ段之三維允浦賴㈣子 性質。以下將列舉特定範例。 于 平線3 :包t或多層基座上之層對應自基座所獲得之奈 未線片。因此，此處使用之「分層奈米線」—詞可* 米線」-詞錢使H步，某些實施地含 ς 施例包含複數個片段。揭露草意又、實 線不可包含額外=段某數1之片段不應視為意謂分段奈米 基座上之層厚度係決定最終奈米線#段 2可依據晶膜生成參數或晶體生成參數而。已製造出 度同樣可介於丨。奈米及方料。錯切及錯層之厚 ㈣===;線形成係使用相同物基座_之化學 基座之上表面。貧又保4之邊緣以指㉘奈米線之形成乃始自 5 201004863 已透枣氟化氫-氮氧化銀(HF-AgN03)溶液蝕刻矽晶圓表面之 平面(100)而獲得矽奈米線。澱積於表面上之銀微小粒子導致某些 位置餘刻之增加；然而，在未出現銀粒子之位置上蝕刻則大大減 少。結果產生如圖3所示矽基座上眾多垂直奈米線。稍後藉酸钱 刻移除銀粒子。銀粒子移除以硝鹽酸(王水，aquaregia)為較佳。另 一較佳之酸為硝酸(nitric acid)。奈米線及基座表面不殘留反應副產 物’反應副產物會危害其他製造奈米線之方法。 在較佳實施例中’化學姓刻劑係石肖酸銀，AgN〇3) ❹及氣化氫(Mrogen fluoride，HF)水溶液之混合。氟化氫對硝酸銀 之較佳克分子比(molarratio)係120至480，而以範圍約240為更 佳。用於獲得圖3中奈米線之姓刻溶液包含1 :丨混合之3 4克/ 毫升(0.02M)确酸銀加1 : 5(4.8M)氟化氫溶液，因此氟化氫/確酸銀 水溶液之克分子比等於240。1 : 1混合之硝酸銀/氟化氫尚可稀釋 或濃縮至尚達5至10倍，且雖姓刻速率實質不同但仍形成半導體 奈米線。若溶液包含過量之硝酸銀，如氟化氫/硝’酸銀克分子比為 24，則钱刻變為平面而不導致奈米線之形成。溶液中過量之氟化 _ 氫，如氟化氫/確酸銀克分子比為2400，則不導致奈米線之形成且 矽幾乎不受蝕刻。 / 〇°C至90°C範圍之溶液溫度為較佳，而以約室溫之溫度為更 佳。溶液溫度對奈米線形成之主要影響係蝕刻速率隨溫度之增加 而增加。於溫度2(TC之標準溶液(3.4克/毫升(0.02M)硝酸銀加 5(4·8Μ)氟化氫)钱刻1〇分鐘後’可獲得長度介於〖〇至丨5微米門 201004863 奈米線之橫截面(dimension)尺寸範圍自1 〇奈米至500奈米， 且係多面而非圓形。通常一橫截面較另一橫截面小，且在某些條 件下奈米線係奈米帶(nano-ribbon)狀。#刻速率依溶液濃度、溶液 溫度、及攪動(agitation)而定。矽基座(1〇〇)於溫度2〇t：之標準溶液 (3.4克/毫升(0.02M)确酸銀加1 : 5(4.8M)氟化氫)浸入30分鐘後， 導致約3微米長之奈米線。相同之基座於溫度35。〇之標準溶液浸 入30分鐘產生約6微米長之奈米線，而相同之基座溫度5〇〇c於相 同之溶液浸入30分鐘則產生約16微米長之奈米線。當於超音波 處理槽(其提供強烈攪動)執行相同實驗’則與靜止蝕刻溶液相比之 〇餘刻速率倍升。 蝕刻速率對於半導體基座之摻雜物形式或摻雜物密度並非特 別靈敏’除對未摻雜石夕(内部石夕)外。與磷(P)、硼⑼、或砷(As)摻 雜而導致體電阻率(resistivity)0.01歐姆-公分(ohm_cm)之p型摻雜 物及體電阻率(resistivity)lOO歐姆-公分⑽取㈣之n型摻雜物，產 生之半導體奈米線具有類似長度及幾何。然而，内部石夕之活動相 當不同。内部矽(體電阻率9999歐姆-公分)之蝕刻速率較摻雜矽範 ❹例之速率慢20倍。 " 具有鍺化矽量子井之矽奈米線可藉晶膜生成矽基座上之石夕及 鍺化石夕選替層而製造。可藉晶膜生成過程(epipr_s)將層變薄， 致使鍺化石夕厚度低於臨界厚度且不發生鬆弛/缺陷。執行銀增強 (Ag-enhanced)姓刻同時，製造包含鍺化矽/石夕量子井之奈米^，如 圖3所示。已發現石夕上方之鍺化石夕層尚可以相同方式ϋ圖如 及4b分別顯不之橫截面及由上而下掃描式電子顯微鏡(聰)影 像，係使衫層基座之内嵌鍺化⑦量子點之糊⑪奈米線範^ 201004863 具有内建垂直p-n接面之矽奈米線可藉p及n摻雜物摻雜石夕基 座接著以確酸銀-狀化風溶液之化學敍刻而產生。圖5顯示具有 P:n接面矽奈米線之產生流程，而圖6顯示此範例蝕刻後之橫截面 掃描式電子顯微鏡(SEM)影像。 、 材料之選擇僅依據生成晶膜層之能力而定，且晶體生成層亦 可能有所影響。可製造此類量子奈米線之材料配對範例係石夕 鍺化矽(SiGe)、石夕 (GaAsP)、矽/硫化鋅(ZnS)、錯(Ge)/神化嫁(GaAs)、錯/石夕、錯/姻砷 霸化鎵(GalNAs)、細化鋅(驗)等。細見可於晶膜生成期間將 不同之層傳導性摻雜(c〇nductivity_d〇ped)，於奈米線及量子井内產 生雷揚1。 進一步，可使用兩種以上不同材料作為絲層之材料，產生 甚至更多新的物理/材料效應。在一實施例中， 之矽/鍺化矽(SiGe)/坤化鎵(G，三片段量子層。另一；施例中, 層間提供絕緣層。限制結構本質之唯一因素係 ❹ΪΪϊΐΖ，始生成過程。再者’已藉石肖酸鹽化學侧顯 不導致不未線及1子井奈米線之增強铜，而其他化學物可展顯 類似之效應，且不同之化學物可優化以用於不同之材料組合。” 圖7顯示以平面⑽)朝向表面定位之残座。基座係以化學 蝕刻方法處理。掃描式電子顯微鏡(SEM)影 '土 _發生，即於朝向表面之60度角。辟满,優先义軸 八於尤η η人 ++ 方法獲传之奈米線具有 ”於不冋队間之“，其定位於朝向奈米線縱向之⑻度角。 201004863 ffl 8顯示以平面(ill)朝向表面定位之兩層⑦基座。基座係以 化學蝕刻方法處理。 —· 圖9顯不之掃描式電子顯微鏡(SEM)影像揭示賴優先沿軸 [1〇〇]發生’即奈米線定也於朝向表面之547度角。藉此方法獲得 之奈米線具有介於不同片段間之介面，其定餘朝向奈米線縱向 之54.7度角。 ® 10顯示之上下圖式係自平面(111)侧之基座所獲得之石夕 β ί倍放*。侧係使用原始之標準溶液於溫度耽執 圖11顯示之側視圖式係自平面(111)钱刻之基座所獲得之石夕 奈米線5_倍放大，奈米線與基座形成—54J度角。 之詞係概括複數及單數 此處所使用「包含」-詞(及其文法上之變異)係敘述「具有 (或「包含(induding)」之函括意思，轉「僅包含(咖㈣ ❹〇'y 〇f)」之排除意思。應了解此處所使用「一⑻」及「該(㈣」 而法H 有公開文件、專觀專利申請案藉引用 各之Γ部，且因任何及所有目的’如嚼红個別指定 t開文件、翻及專利申請絲個而成為本文之—部。 不—致之處，則以本發明之揭露為主。 9 201004863 一巧，露之詳猶示並_本發明之揭露。另外，揭露僅顯 不並說明錄實施例’但如上所述，應了解揭露可驗不同之其 他組合、修正、及魏，且财於此處所麻概紅細内加^ 改變或Ljl ’ #合上列揭示及/或相關技術之技術或知識。 ，上述實施例進-步欲_執行之已知最佳模式，且欲致使此 =領域具有通常知識者以此類或其他實補及特定應用或用途 所^不哪正*實簡露。因此，詳述不欲_於此處所揭露 之形式。再者’應轉峨之申請專繼_包含觀之實施例。 【圖式簡單說明】 ^顯示_技術方法於發晶圓上製造經蝴、未分段梦奈 未線之不意圖。 圖2顯示藉化學餘刻石夕基座⑽)而形成石夕奈米線之掃描 子顯微鏡(SEM)橫截面圖。 面示=顯不具餘合(⑻卿㈣好井之分縣米線之橫截
圖4a及4b顯示由化學餘刻所形成之石夕/錯化石夕/石夕奈米線之橫 截面及由上而下掃描式電子顯微鏡(SEM)影像。 圖5顯示具有垂直p_n接面之奈米線處理之示意圖。 截面=顯示根據圖5示意圖處理之具有垂直Ρ·η接面奈米線之橫 圖7 及Ρ摻雜 方向。 顯示自平面(110)触刻之基座所獲得之石夕奈米線，η摻雜 片段與奈米線縱向形成—60度角，賊應於⑪⑽)晶體 圖δ顯示之上至下圖式係自平面(1丨丨)蝴之基座所獲得之石夕 201004863 ’ 奈米線500倍放大。 ’ 圖9顯示之側視掃描式電子顯微鏡(SEM)影像係自平面(lu) 蝕刻之基座所獲得之碎奈米線1〇,〇〇〇倍放大’奈米線與基座形成 一 54.7度角。 圖10顯示之上至下圖式係自平面(111)餘刻之基座所獲得之 碎奈米線1，000倍放大。 圖11顯示之侧視圖式係自平面(111)蚀刻所獲得之矽奈来線 5,000倍放大掃描式電子顯微鏡(SEM)影像，奈米線與基座形成— 54.7度角。 Φ 【主要元件符號說明】

Claims (1)

  1. 201004863 七、申請專利範圍： 1. 一種獲得一分段奈米線之方法，其包含： ’ 一 …自-層狀結構部分移除-第—材料及與該第—材料不同之一 第二材料’其中該層狀結構係包含該第—材料及該第二材料 以獲得具有該第—材料—片段及該第二材料—片段之該分段奈^ 線。 、 2. 如申請專利範圍第丨項所述之方法，其中該部分移除包含化學钱 刻。 3·如申請專繼圍第2項職之方法，其巾該辨侧包含施加— 氟化氫/硝酸銀溶液。 4. 如申請專利範圍第2項所述之方法，其中該化學蝕刻主要沿該第 材料或该第一材料之一晶軸(cryStau〇graphic狀的方向發生。 5. 如申請專利範圍第4項所述之方法，其中該化學蝕刻主要沿晶軸 ❹方向[100]發生。 6. 如申請專利範圍第1項所述之方法，其中該第一材料係n摻雜矽 且該第二材料係ρ摻雜矽，或該第一材料係ρ摻雜矽且該第二材 料係η摻雜矽。 7·如申請專利範圍第1項所述之方法，其中該層狀結構包含至少二 不同材料之複數層。 12 201004863 8. 如中請專祕S1第1項所述之方法，其中該分段奈米線係一分段 奈米帶(nano-ribbon) 〇 、 9. 如申請專舰®帛1酬叙料，其t該分段奈錄具有一多 面表面。 10.如申請專利範圍第1項所述之方法，其中該第—材料及該第二 材料係選自包含石夕、鍺化石夕(siGe)、填化錄(Gap)、神填化嫁 (GaAsP)、硫化鋅(ZnS)、錯(Ge)、魏錯(Ge岭辦化鎵(GainAs) ^ 及硒化鋅(ZnSe)之群組。 包含獲得根據 11.一種製造-電子、光學、及熱電子裝置之方法 申明專利範圍第1項之一分段奈米線。 I2.一種獲得一分段奈米線之方法，其包含： 形成一第一材料之一第一層； 1成與該第-材料不同且與該第—材料相鄰之—第二材料之 〇 —第二層；以及 一=分移除該第一材料及第二材料，藉以獲得具有該第一材料 片段及該第二材料一片段之一分段奈米線。 請專利範圍第12項所述之方法，其中該® —層或該第二層 係包含晶膜生成(epitaxial growth)。 請專利範圍第12項所述之方法，其中該第一層或該第二層 ^成係包含澱積一多晶態材料。 13 201004863 ’其進一步包含於該部分移 15.如申請免利範圍第12項所述之方法 除前形成至少二不同材料之複數層。 16.如申請專利範圍第12項所述之方法，其中該第一材料及該第二 材料係選自包含矽(si)、鍺化矽(SiGe)、磷化鎵(GaP)、砷磷化鎵 (GaAsP)、硫化鋅(ZnS)、鍺(Ge)、砷化鍺(GeAs)、銦砷化鎵(GaInAs) 及砸化鋅(ZnSe)之群組。 Π.—種製造一電子、光學、或熱電子裝置之方法，係包含獲得根 ® 據申請專利範圍第12項之一分段奈米線。 18.—種包含一第一材料第一片段、及一第二材料第二片段之分段 奈米線，其中該第一片段及該第二片段間之一介面係定位於朝向 該分段奈米線縱向之一角度。 19.一種包含根據申請專利範圍第18項之分段奈米線之太陽能電 池。 20·—種包含根據申請專利範圍第18項之分段奈米線之垂直空腔 表面發光雷射、一發光二極體、或一光電裝置。 14
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