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TW201817909A - 用於藉由原子層沉積在基板上形成過渡金屬氮化物膜之方法及相關的半導體裝置結構 - Google Patents

用於藉由原子層沉積在基板上形成過渡金屬氮化物膜之方法及相關的半導體裝置結構 Download PDF

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TW201817909A
TW201817909A TW106133152A TW106133152A TW201817909A TW 201817909 A TW201817909 A TW 201817909A TW 106133152 A TW106133152 A TW 106133152A TW 106133152 A TW106133152 A TW 106133152A TW 201817909 A TW201817909 A TW 201817909A
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nitride film
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派提 瑞薩能
麥可 尤金 吉凡斯
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荷蘭商Ａｓｍ智慧財產控股公司
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Abstract

本發明提供用於藉由原子層沉積在基板上形成過渡金屬氮化物膜之方法及相關的半導體裝置結構。在某些具體實例中，方法可包含使基板與包含過渡金屬前驅物的第一蒸氣相反應物接觸且使該基板與包含烷基聯胺前驅物的第二蒸氣相反應物接觸。在某些具體實例中，相關的半導體裝置結構可包含PMOS電晶體閘極結構，該PMOS電晶體閘極結構包含過渡金屬氮化物膜及在該過渡金屬氮化物膜及半導體本體間的閘極介電質。該過渡金屬氮化物膜包含顯著的(200)晶體方向。

Description

用於藉由原子層沉積在基板上形成過渡金屬氮化物膜之方法及相關的半導體裝置結構 【相關申請案之交叉參考】
本申請案主張2016年11月1日申請的名為「用於藉由原子層沉積在基板上形成過渡金屬氮化物膜之方法及相關的半導體裝置結構」之美國臨時專利申請案第62/415,842號之優先權，其以引用之方式併入本文中。
背景
本發明大體上係關於用於藉由原子層沉積在基板上形成過渡金屬氮化物膜之方法及相關的半導體裝置結構。
金屬-氧化物-半導體(MOS)技術已慣常利用n型摻雜多晶矽做為閘極電極材料。然而，經摻雜多晶矽對於先進節點應用可能並非理想的閘極電極材料。舉例來說，雖然經摻雜多晶矽為導電的，仍可能存在表面區域，其在偏置條件下可能載體空乏。此區域可做為額外閘極絕緣體厚度存在，通常稱為閘極空乏(gate depletion)，且可提供相應的氧化物厚度。 雖然閘極空乏區域可能是薄的，在幾埃(Å)的等級，其隨著閘極氧化物厚度在先進節點應用中的減小而可能變成重要的。做為另一個例子，多晶矽對於NMOS及PMOS裝置皆不展現理想的有效工作函數(eWF)。為克服經摻雜多晶矽非理想的有效工作函數，可利用植入臨限電壓調整。然而，隨著裝置幾何在先進節點應用中的減小，植入臨限電壓調整方法可變得日益複雜且不實際。
為克服與經摻雜多晶矽閘極電極相關的問題，非理想的經摻雜多晶矽閘極材料可以替代材料置換，例如舉例來說，以過渡金屬氮化物置換。舉例來說，可修飾過渡金屬氮化物的性質以提供對於NMOS及PMOS裝置具有更理想的有效工作函數的閘極電極結構，其中閘極電極的有效工作函數，亦即提取一個電子所需的能量，必須與半導體材料的障壁高度相容。舉例來說，在PMOS裝置的例子中，所需的有效工作函數為大約5.0eV。
原子層沉積(ALD)可用於過渡金屬氮化物膜的沉積，該等過渡金屬氮化物膜為例如氮化鉭(TaN)、氮化鈦(TiN)、氮化鎢(WN)及氮化鈮(NbN)。然而，利用已知前驅物經由ALD所形成的過渡金屬氮化物膜之電子或結晶性質的修飾可能由於ALD方法的自我限制特性而受限。
提供本發明內容以簡化的形式引入概念的選擇。該等概念更詳細描述於下列實施例、具體實例等實施方式的揭示中。本發明內容不意欲確認所請標的的主要特徵或必要特徵，亦不意欲用來限制所請標的範圍。
在某些具體實例中，提供藉由原子層沉積在基板上形成過渡金屬氮化物膜之方法。該等方法可包含使基板與包含過渡金屬前驅物的第 一蒸氣相反應物接觸且使基板與包含烷基聯胺前驅物的第二蒸氣相反應物接觸。
在某些具體實例中，提供半導體裝置結構。該等半導體裝置結構可包含PMOS電晶體閘極結構，該PMOS電晶體閘極結構包含過渡金屬氮化物膜及在該過渡金屬氮化物膜及半導體本體間的閘極介電質。在某些具體實例中，該過渡金屬氮化物膜包含顯著的(200)晶體方向。
出於概述本發明及所達成的優於先前技術之優點的目的，已在上文中對本發明之某些目標及優點加以描述。當然，應理解，未必所有的該等目標或優點均可根據本發明之任何特定具體實例而達成。因此，舉例而言，熟習此項技術者將認識到，可以如本文中所教示或建議來達成或最佳化一個優點或一組優點而不一定達成本文中可能教示或建議的其他目標或優點的方式來實施或進行本發明。
所有此等具體實例均意欲處於本文所揭示之本發明範圍內。此等及其他具體實例將自以下參考附圖的某些具體實例之詳細描述而對熟習此項技術者變得顯而易見，但本發明並不受限於所揭示之任何特定具體實例。
雖然說明書以特別指出且清楚記載本發明的具體實例的申請專利範圍結束，當與附圖結合閱讀時可更容易從本發明具體實例的某些實施例之敘述確定本發明具體實例的優點，其中：圖1為展示根據本發明之具體實例所形成之氮化鈦膜的x-射線繞射(XRD)掃描的圖。
圖2為根據本發明之具體實例所形成之半導體裝置結構的簡化截面視圖。
圖3為展示各種閘極電極結構的有效工作函數(eWF)的圖，該等閘極電極結構包含氮化鈦膜作為氮化鈦膜厚度的函數。
圖4展示經配置以執行本發明具體實例的反應系統。
此處的說明不意欲為任何特定材料、結構或裝置的確切觀點，而僅是理想地表現用於描述本發明的具體實例。
如本文所用，術語「原子層沉積」(ALD)可意指蒸氣沉積製程，其中在製程腔室中執行沉積循環，較佳地為複數個連續的沉積循環。典型地，在每個循環中，前驅物係經化學吸附至沉積表面(例如基板表面或先前沉積的底層表面，諸如從先前ALD循環而來的材料)，形成不會直接與額外前驅物反應的單層或次單層(亦即，自限制反應)。然後，若需要，可接續將反應物(例如，另一前驅物或反應氣體)引入該製程腔室以用於在沉積表面將經化學吸附的前驅物轉換成所欲的材料。典型地，此反應物可與該前驅物進一步反應。此外，亦可在每個循環期間利用沖洗步驟自製程腔室中移除過量前驅物及/或移除過量反應物及/或在經化學吸附的前驅物轉化後自製程腔室移除反應副產物。此外，本文所用術語「原子層沉積」意欲包括相關術語所指定的製程，例如「化學氣相原子層沉積」、「原子層磊晶」(ALE)、分子束磊晶(MBE)、氣體源MBE或有機金屬MBE、及當執行交替前驅物組成物、反應氣體及沖洗(例如惰性載體)氣體脈衝時的化學束磊晶。
如本文所用，術語「基板」可意指任何底層材料或可使用的 材料，或在其上可形成裝置、電路或膜。
如本文所用，術語「烷基聯胺」可意指聯胺(N2H4)衍生物，其可包含烷基官能基團且亦可包含額外官能基團。
本發明包括可用來形成過渡金屬氮化物膜或包含過渡金屬氮化物膜的方法及裝置結構。現有可用在過渡金屬氮化物膜的ALD的前驅物由於其無法調控ALD過渡金屬氮化物膜的某些特性可能有所限制；該等特徵可包括有效工作函數及晶體方向。舉例來說，已知閘極電極的有效工作函數可作為其厚度的函數改變，亦即，閘極電極的有效工作函數可隨包含閘極電極的材料的厚度減小而減小或增加。由於裝置幾何在先進節點應用中的減小，相應裝置膜的厚度(例如閘極電極)亦可隨該膜的有效工作函數之相應改變而減小。此閘極電極在減小的厚度的有效工作函數的改變可導致NMOS及PMOS裝置結構不理想的有效工作函數。因此，需要方法及結構以提供更想要的過渡金屬氮化物膜。此方法及結構的實例於下文詳述。
ALD基於典型自我限制反應，藉此使用反應物的依續及交替脈衝以沉積約每沉積循環一原子(或一分子)的材料單層。典型地選擇沉積條件及前驅物以提供自飽和反應，如此一種反應物的吸附層產生對相同反應物的氣相反應物不具反應性的表面終止。接著使基板與不同反應物接觸，該反應物與先前的終止反應俾使持續進行沉積。因此，交替脈衝的每個循環典型地不產生超過所欲材料的約一個單層。然而，如上所述，熟悉技術者會瞭解在一或多個ALD循環中可沉積超過一個材料的單層，例如，如果某些氣相反應不顧該製程的交替特性地發生。
在一用於沉積過渡金屬氮化物膜的ALD型製程中，一個沉 積循環包含使基板暴露於第一反應物，自反應空間移除任何未反應第一反應物及反應副產物，使該基板暴露於第二反應物，接著進行第二移除步驟。該第一反應物可包含金屬前驅物，特別是過渡金屬前驅物，例如鈦前驅物，及該第二反應物可包含烷基聯胺前驅物，例如舉例來說第三丁基聯胺(C4H9N2H3)、甲基聯胺(CH3NHNH2)、二甲基聯胺((CH3)2N2H2)之至少一者。
該過渡金屬前驅物或化合物可包含至少一種選自包含下列之群的過渡金屬：鈧(Sc)、釔(Y)、鈦(Ti)、鋯(Zr)、鉿(Hf)、釩(V)、鈮(Nb)、鉭(Ta)、鉻(Cr)、鉬(Mo)、鎢(W)、錳(Mn)、鎝(Tc)、錸(Re)、鐵(Fe)、釕(Ru)、鋨(Os)、鈷(Co)、銠(Rh)、銥(Ir)、鎳(Ni)、鈀(Pd)、鉑(Pt)、銅(Cu)、銀(Ag)、金(Au)、鋅(Zn)、鎘(Cd)或汞(Hg)。然而，由於本文例示氮化鈦膜，在此等具體實例中，金屬化合物可包含鈦。
在一個非限制具體實例中，可在ALD製程中使用過渡金屬鹵化物反應物，例如四氯化鈦(TiCl4)作為過渡金屬前驅物。
前驅物可藉由惰性氣體分離，例如氬(Af)或氮氣(N2)，以防止反應物間的氣相反應且使自飽和表面反應發生。然而在某些具體實例中，可移動基板以分別接觸第一金屬反應物及第二烷基聯胺反應物。因為該等反應為自飽和的，基板嚴格的溫度控制及前驅物精準的給量控制通常係不必須的。然而，該基板溫度較佳為使得入射氣體種類不會凝結進入單層亦不會在表面分解。在該基板與下一反應性化學品接觸前，例如藉由沖洗反應空間或藉由移動基板自該基板表面移除過剩的化學品及反應副產物(若有的話)。非所欲氣相分子可藉由惰性沖洗氣體的幫助有效地自反應空間排除。可使用真空泵協助沖洗。
根據某些具體實例，使用ALD型製程以在基板上(例如積體電路工件)形成過渡金屬氮化物膜，例如氮化鈦膜。較佳地，每個ALD循環包含兩個不同的沉積步驟或階段。在沉積循環(「金屬階段」)的第一階段中，其上欲沉積的基板表面係與第一反應物接觸，該第一反應物包含過渡金屬，例如鈦(亦即，鈦源材料或化學品)，其化學吸附至該基板表面上，在該基板的表面上形成不超過反應物種類的約一個單層。
在某些具體實例中，該過渡金屬(例如鈦)源化學品，本文亦指稱為「過渡金屬化合物」(或在某些具體實例中指稱為「鈦化合物」)，為鹵化物且經吸附單層藉由鹵素配位體終結。在某些具體實例中，鈦鹵化物可為四氯化鈦(TiCl4)。
過量的過渡金屬(例如鈦)源材料及反應副產物(若有的話)可藉由例如以惰性氣體沖洗而自該基板表面移除。過量的過渡金屬源材料及任何反應副產物可在泵系統產生的真空的幫助下移除。
在沉積循環的第二階段中(「氮氣階段」)，基板係與烷基聯胺接觸。在某些具體實例中，該烷基聯胺可包含第三丁基聯胺、甲基聯胺、二甲基聯胺之至少一者。第二烷基聯胺反應物可與留在基板表面的含鈦分子反應。較佳地，在第二階段中，氮氣係藉由該第二烷基聯胺反應物與該過渡金屬(例如鈦)源材料產生的單層交互作用而併入該膜。在某些具體實例中，該第二烷基聯胺反應物與該經化學吸附的過渡金屬種類間的反應在該基板上產生過渡金屬氮化物薄膜。
過量的第二源化學品及反應副產物(若有的話)係藉由例如沖洗氣體脈衝及/或由泵系統產生的真空而自該基板表面移除。沖洗氣體較 佳地為任何惰性氣體，例如(非限制性)氬氣(Ar)、氮氣(N2)或氦氣(He)。若有沖洗(亦即，沖洗氣體脈衝)或其他反應物移除步驟的介入，一階段通常會視為立即接在另一階段之後。
圖1為展示根據本發明之具體實例所形成之氮化鈦膜的2θ之x-射線繞射(XRD)掃描的圖，其藉由本發明所載利用過渡金屬前驅物及烷基聯胺前驅物的ALD方法所形成。舉例來說，符號100所標示的XRD掃描係得自利用四氯化鈦及烷基聯胺在基板溫度為350℃下的ALD所形成的氮化鈦膜。符號100所標示的該XRD掃描指示藉由本發明方法所形成的過渡金屬氮化物膜(例如氮化鈦)可包含一些晶體方向包括(111)、(200)、(220)、(311)及(420)方向，其中(200)晶體方向為主要的。因此，在本發明的某些具體實例中，藉由本文描述之ALD製程所形成的過渡金屬氮化物膜包含(200)晶體方向，且在某些具體實例中，該過渡金屬氮化物膜主要包含(200)晶體方向。
在本發明某些具體實例中，形成過渡金屬氮化物膜可包含形成過渡金屬氮化物膜至小於50埃的厚度、或小於30埃的厚度、或小於20埃的厚度。作為本發明一個非限制具體實例，形成過渡金屬氮化物膜可包含形成過渡金屬氮化物膜至小於30埃的厚度。
本文所描述的利用烷基聯胺作為ALD製程中的氮源可允許具有增加的碳及氫原子百分比的過渡金屬氮化物膜(例如氮化鈦)的形成。將增加的碳及氫原子百分比併入過渡金屬氮化物膜的能力可允許修飾該ALD過渡金屬氮化物膜之性質的能力。舉例來說，在某些具體實例中，方法可包含形成過渡金屬氮化物膜以具有大於0.1%、或大於0.5%、或大於1%、 或甚至大於10%的碳原子濃度。此外，在某些具體實例中，方法可包含形成過渡金屬氮化物膜以具有大於0.1%、或大於1%、或大於2%、或甚至大於10%的氫原子濃度。在本文列出的某些具體實例中，元素的原子濃度可利用拉塞福背散射(RBS)來決定。
本文所描述的利用過渡金屬前驅物及烷基聯胺前驅物的ALD方法可在含有經加熱基板的ALD沉積系統中執行。舉例來說，在某些具體實例中，方法可包含加熱基板至大於300℃的溫度。在某些具體實例中，方法可包含加熱基板至大於350℃的溫度。在其他具體實例中，方法可包含加熱基板至大於450℃的溫度。
薄膜藉由ALD的沉積速率(典型地以Å/脈衝循環表示)取決於一些因素，包括(例如)可得反應性表面位置的數目或表面上的活性位置及化學吸附分子的龐大程度(bulkiness)。在某些具體實例中，此等膜的沉積速率可從約0.1至約5.0Å/脈衝循環。在某些具體實例中，沉積速率可為約0.1、0.2、0.3、0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0、4.5或5.0Å/脈衝循環。
藉由本文所揭示的ALD方法形成的過渡金屬氮化物薄膜(例如氮化鈦薄膜)可在各種脈絡中被使用，例如在閘極電極結構的形成中。所屬技術領域中具有通常知識者會認知到本文所描述的方法可應用在許多脈絡，包括含有平面裝置及多閘極電晶體(例如FinFETs)之PMOS電晶體的製造。
作為非限制性實例且關於圖2，半導體裝置結構300可包含電晶體結構且可包括源極區域302、汲極區域304、介於其間的通道區域 306。電晶體閘極結構308可包含閘極電極310，其可藉由閘極介電質312與該通道區域306分隔。根據本發明內容的教示，該閘極電極310可包含過渡金屬氮化物膜，例如氮化鈦，其藉由利用過渡金屬前驅物及烷基聯胺前驅物的原子層沉積所形成。如圖2所示，在某些具體實例中，該電晶體閘極結構308可另外包含形成於該閘極電極310上的一或多個額外導電層314。該一或多個額外導電層314可包含多晶矽、耐火金屬、過渡金屬碳化物及過渡金屬氮化物的至少一者。
在某些具體實例中，該半導體裝置結構300可包含PMOS電晶體。該PMOS電晶體可另外包含該電晶體閘極結構308。該PMOS電晶體閘極結構308可包含閘極電極310，該閘極電極310包含過渡金屬氮化物膜及介於該過渡金屬氮化物膜及半導體本體316間的閘極介電質312。在某些具體實例中，該半導體裝置結構300可包含NMOS電晶體。該NMOS電晶體可另外包含該電晶體閘極結構308。該NMOS電晶體閘極結構308可包含閘極電極310，該閘極電極310包含過渡金屬氮化物膜及介於該過渡金屬氮化物膜及半導體本體316間的閘極介電質312。
在某些具體實例中，該閘極電極310可包含過渡金屬氮化物膜，例如氮化鈦、氮化鉭、氮化鎢及氮化鈮。在某些具體實例中，該閘極電極310可包含過渡金屬氮化物膜，例如氮化鈦，且可主要包含(200)晶體方向。
在本發明某些具體實例中，該等額外導電層314可具有固有地較低的有效工作函數，且該閘極電極310的其中一個目的係調節該電晶體閘極結構308的有效工作函數。舉例來說，該等額外導電層314的有效 工作函數可為約4.2eV，且可利用該閘極電極310來調節該電晶體閘極結構308的有效工作函數。在某些具體實例中，該閘極電極310的性質(例如組成及厚度)可經調整以可控制地將該電晶體閘極結構308的有效工作函數調節至約4.2eV及約4.8eV間。作為非限制性實例具體實例，該閘極電極308的厚度及碳含量可經調整以提供對於NMOS電晶體結構的最佳化有效工作函數。舉例來說，在本發明某些具體實例中，該閘極電極310可具有小於10埃的厚度及小於10%的碳含量，其可致使該電晶體閘極結構308的有效工作函數為約4.6eV。
在本發明的某些具體實例中，該閘極電極310的性質可經調整以可控制地調節該電晶體閘極結構308的有效工作函數以有效地調控PMOS電晶體及/或NMOS電晶體的臨限電壓(Vth)。舉例來說，該電晶體閘極結構的有效工作函數可變化以製造互補性金屬氧化半導體(CMOS)積體電路，其包含複數個NMOS電晶體及PMOS電晶體，具有多個臨限電壓(Vth)，通常稱為多臨限電壓CMOS(MTCMOS)。
作為非限制性實例，圖3展示各種閘極電極結構的有效工作函數(eWF)的圖，該等閘極電極結構包含氮化鈦膜作為氮化鈦膜厚度的函數。在此等非限制性實例中，該閘極電極結構308包含鉿氧化物閘極氧化物312、氮化鈦閘極電極310及一或多個包含碳化鈦鋁及氮化鈦的額外導電層314。
標示為200的該eWF線指示閘極電極結構的eWF，該閘極電極結構包含藉由利用常用先前技術前驅物氨(NH3)作為氮源的ALD所形成的氮化鈦膜。標示為210的該eWF線指示閘極電極結構的eWF，該閘極 電極結構包含藉由根據本發明內容教示之ALD方法利用烷基聯胺作為氮源且在350℃的基板溫度所形成的氮化鈦膜。標示為220的該eWF線指示閘極電極結構的eWF，該閘極電極結構包含藉由根據本發明內容教示之ALD方法利用烷基聯胺作為氮源且在400℃的基板溫度所形成的氮化鈦膜。如圖3所示，包含藉由根據本發明內容教示之ALD方法(亦即，利用烷基聯胺前驅物)所形成的氮化鈦膜的該等閘極電極結構展現在減少的氮化鈦膜厚度下顯著的eWF增加。舉例來說，在氮化鈦膜厚度為大約等於或小於20埃時，包含利用烷基聯胺前驅物所形成的氮化鈦膜的該等閘極電極結構展現相較於包含利用先前技術的氨前驅物所形成的氮化鈦膜的該閘極電極結構大於200meV的eWF增加。
因此，在本發明某些具體實例中，藉由利用過渡金屬前驅物及烷基聯胺前驅物的ALD以形成過渡金屬氮化物膜可包含形成包含該過渡金屬氮化物膜的閘極電極結構以具有大於4.2eV的有效工作函數，或甚至大於4.4eV的有效工作函數。應注意本發明的具體實例允許形成包含薄金屬氮化物膜的閘極電極結構，其具有增加的有效工作函數，舉例來說，在某些具體實例中，方法可包含形成包含具有厚度小於50埃的過渡金屬氮化物膜的閘極電極結構，其具有大於4.8eV的有效工作函數。在其他具體實例中，方法可包含形成包含具有厚度小於30埃的過渡金屬氮化物膜的閘極電極結構，其具有大於4.7eV的有效工作函數。在甚至其他具體實例中，方法可包含形成包含具有厚度小於20埃的過渡金屬氮化物膜的閘極電極結構，其具有大於4.4eV的有效工作函數。
作為非限制性實例，包含該閘極電極310的該過渡金屬氮化 物膜在某些具體實例中可具有小於50埃的厚度，或在某些具體實例中小於30埃的厚度，或甚至在某些具體實例中小於20埃的厚度。
該閘極電極310的性質亦可進一步藉由將增加的碳及氫原子百分比併入包含該閘極電極310的該過渡金屬氮化物膜的能力來修飾。舉例來說，在某些具體實例中，包含該閘極電極310的該過渡金屬氮化物膜可具有大於0.1%、或大於1%或甚至大於10%的碳的原子濃度。此外，在某些具體實例中，包含該閘極電極100的該過渡金屬氮化物膜可具有大於0.1%、或大於1%或甚至大於10%的氫的原子濃度。在本文指出的某些具體實例中，元素的原子濃度可利用拉塞福逆散射(RBS)決定。
本發明的具體實例亦可包括經配置以執行本發明方法的反應系統。更詳細地說，圖4綱要式地描繪了包括反應腔室402的反應系統400，該反應腔室402另外包括在先決的壓力、溫度及環境條件下保留基板(未顯示)及選擇性地使基板暴露於各種氣體的機制。前驅物反應物源404可藉由導管或其他合適的構件404A耦合至該反應腔室402，且可進一步耦合至歧管、閥控制系統、質量流控制系統，或控制源自該前驅物反應物源404的氣體前驅物的機制。由該前驅物反應物源404供給的前驅物(未顯示)及該反應物(未顯示)在室溫及標準大氣壓力條件下可為液體或固體。此前驅物可在反應物源真空容器中汽化，該真空容器在前驅物源腔室中可維持在汽化溫度或高於汽化溫度。在此等具體實例中，經汽化前驅物可藉由載體氣體(例如非活性或惰性氣體)運輸且然後經由導管404A饋入該反應腔室402。在其他具體實例中，該前驅物在標準條件下可為氣體。在此等具體實例中，該前驅物不須經汽化且可不需要載體氣體。舉例來說，在一個具體實例中， 該前驅物可儲存在汽缸中。該反應系統400亦可包括額外前驅物反應物源，例如前驅物反應物源406，其亦可如上述經由導管406A耦合至該反應腔室。
沖洗氣體源408亦可經由導管408A耦合至該反應腔室402，且選擇性地供給各種惰性或高貴氣體至反應腔室402，以協助前驅物氣體或廢氣自該反應腔室的移除。可供給的該等各種惰性或高貴氣體可源自固體、液體或儲存的氣體形式。
圖4的該反應系統400亦可包含系統操作及控制機制410，其提供電子電路及機械組件以選擇性地操作閥、歧管、泵及其他包括在該反應系統400中的設備。操作此電路及組件以自相應的前驅物源404、406及沖洗氣體源408提供前驅物及沖洗氣體。該系統操作及控制機制410亦控制氣體脈衝次序的時間選擇、該基板及反應腔室的溫度、該反應腔室的壓力及各種其他為提供該反應系統400適當操作的必要操作。該操作及控制機制410可包括控制軟體及經電子或氣壓控制的閥以控制進入及流出該反應腔室402的前驅物流、反應物流及沖洗氣體流。該控制系統可包括如軟體或硬體組件的模組，例如FPGA或ASIC，其係執行某些任務。模組可有利地經配置以駐於該控制系統的可定址儲存介質上且經配置以執行一或多種製程。
相關技術領域中具有通常知識者會認知到本發明反應系統的其他組態係可能的，包括不同數目及類型的前驅物反應物源及沖洗氣體源。此外，該具有通常知識者亦會認知到可用於完成選擇性地將氣體饋入反應胺室402的目標的閥、導管、前驅物源及沖洗氣體源可以有許多種配置。此外，作為反應系統的示意表現，已省略許多組件以簡化闡釋，且該 等組件可包括例如各種閥、歧管、純化器、加熱器、容器、通氣孔及/或旁通管。
上述所描述的本發明之實例具體實例並不限制本發明的範圍，因為此等具體實例僅為本發明具體實例的例子，其由所附申請專利範圍及其合法等效範圍界定。任何等效具體實例皆意欲在本發明範圍內。事實上，除所示及描述者外，各種本發明的修飾，例如其他有用的所述元素結合，自說明書中對具有通常知識者可變得顯見。此等修飾及具體實例亦意欲在所述的申請專利範圍內。

Claims (20)

  1. 一種用於藉由原子層沉積在基板上形成過渡金屬氮化物膜之方法，該方法包含：使該基板與包含過渡金屬前驅物的第一蒸氣相反應物接觸；且使該基板與包含烷基聯胺前驅物的第二蒸氣相反應物接觸。
  2. 如申請專利範圍第1項之方法，其另外包含選擇該烷基聯胺前驅物以包含第三丁基聯胺(C 4H 9N 2H 3)、甲基聯胺(CH 3NHNH 2)、二甲基聯胺((CH 3) 2N 2H 2)之至少一者。
  3. 如申請專利範圍第1-2項中任一項之方法，其另外包含選擇該過渡金屬前驅物以包含鈦前驅物、鉭前驅物、鎢前驅物或鈮前驅物之一者。
  4. 如申請專利範圍第3項之方法，其另外包含選擇該鈦前驅物以包含鈦鹵化物。
  5. 如申請專利範圍第4項之方法，其另外包含選擇該鈦鹵化物以包含四氯化鈦(TiCl 4)。
  6. 如申請專利範圍第1-2項中任一項之方法，其中該方法包含至少一沉積循環，其中該基板交替地且依續地與該第一蒸氣相反應物及該第二蒸氣相反應物接觸。
  7. 如申請專利範圍第6項之方法，其中重複該沉積循環兩次或更多次。
  8. 如申請專利範圍第1-2項中任一項之方法，其另外包含形成該過渡金屬氮化物膜以包含顯著的(200)晶體方向。
  9. 如申請專利範圍第1-2項中任一項之方法，其另外包含形成該過渡金屬氮化物膜至大約小於50埃的厚度。
  10. 如申請專利範圍第1-2項中任一項之方法，其另外包含形成包含該過渡金屬氮化物膜的閘極電極結構，該閘極電極結構具有大於4.2eV的有效工作函數。
  11. 如申請專利範圍第1-2項中任一項之方法，其另外包含形成該過渡金屬氮化物膜以具有大於0.5%的碳原子濃度。
  12. 如申請專利範圍第1-2項中任一項之方法，其另外包含加熱該基板至大約大於約350℃的溫度。
  13. 一種反應系統，其經配置以執行如申請專利範圍第1-2項中任一項之方法。
  14. 一種半導體裝置結構，其包含PMOS電晶體閘極結構，該PMOS電晶體閘極結構包含：過渡金屬氮化物膜；半導體本體；配置在該過渡金屬氮化物膜及該半導體本體間的閘極介電質；其中該過渡金屬氮化物膜包含顯著的(200)晶體方向。
  15. 如申請專利範圍第14項之半導體裝置結構，其中該過渡金屬氮化物膜包含氮化鈦。
  16. 如申請專利範圍第地14-15項中任一項之半導體裝置結構，其中該過渡金屬氮化物膜具有小於大約50埃的厚度。
  17. 如申請專利範圍第地14-15項中任一項之半導體裝置結構，其中該PMOS閘極結構具有大於4.2eV的有效工作函數。
  18. 如申請專利範圍第地14-15項中任一項之半導體裝置結構，其中該過渡 金屬氮化物膜具有大於0.5%的碳原子濃度。
  19. 一種半導體裝置結構，其包含：NMOS電晶體閘極結構，該NMOS閘極結構包含：過渡金屬氮化物膜；半導體本體；及配置在該過渡金屬氮化物膜及該半導體本體間的閘極介電質；其中該過渡金屬氮化物膜包含顯著的(200)晶體方向。
  20. 如申請專利範圍第19項之半導體裝置結構，其中該過渡金屬氮化物膜包含氮化鈦。
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