TWI751158B - Structures and devices including germanium-tin films and methods of forming same - Google Patents

Structures and devices including germanium-tin films and methods of forming same Download PDF

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TWI751158B
TWI751158B TW106115126A TW106115126A TWI751158B TW I751158 B TWI751158 B TW I751158B TW 106115126 A TW106115126 A TW 106115126A TW 106115126 A TW106115126 A TW 106115126A TW I751158 B TWI751158 B TW I751158B
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TW201821657A (en
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約翰 托勒
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荷蘭商Ａｓｍ智慧財產控股公司
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Abstract

Methods of forming germanium-tin films using germane as a precursor are disclosed. Exemplary methods include growing films including germanium and tin in an epitaxial chemical vapor deposition reactor, wherein a ratio of a tin precursor to germane is less than 0.1. Also disclosed are structures and devices including germanium-tin films formed using the methods described herein.

Description

包括鍺-錫膜之結構與裝置及該膜之形成方法 Structure and device including germanium-tin film and method of forming the film 【相關申請的交叉參考】[Cross-reference to related applications]

本申請案係為2013年8月14日提出名稱為「形成包括鍺錫之膜之方法及包括該等膜之結構與裝置(Methods of Forming Films Including Germanium Tin and Structures and Devices Including the Films)」的美國申請案第13/966,782號的部分連續申請案，其內容以引用方式併入本文中。 This application is filed on August 14, 2013 and entitled "Methods of Forming Films Including Germanium Tin and Structures and Devices Including the Films" Part of the continuation-in-part of US Application No. 13/966,782, the contents of which are incorporated herein by reference.

本發明通常係關於用於沉積包括鍺及錫之膜之技術以及包括此等膜之結構與裝置。更具體地說，本發明係關於使用鍺烷作為前驅物形成包含鍺及錫之膜之方法，形成包括該等膜之結構與裝置之方法，以及包括該等膜之結構與裝置。 The present invention generally relates to techniques for depositing films including germanium and tin, and structures and devices including such films. More specifically, the present invention relates to methods of forming films comprising germanium and tin using germane as a precursor, methods of forming structures and devices including such films, and structures and devices including such films.

各種電子裝置(諸如半導體裝置)以及光子裝置(諸如雷射及太陽能裝置)可包括或可所欲地包括諸如GeSn、GeSiSn等的鍺-錫層。例如，可使用GeSn層來形成直接能帶間隙(band gap)裝置及/或可用於在相鄰鍺層中提供應變(strain)以增加鍺層中的遷移率。同樣地，可使用GeSiSn層來形成可調能帶間隙裝置以及具有可調光學性質的光學裝置。為了獲得所欲的裝置性質，鍺-錫膜通常具有結晶結構，其通常遵循下伏層的結晶結 構。 Various electronic devices, such as semiconductor devices, and photonic devices, such as lasers and solar devices, may or may desirably include germanium-tin layers such as GeSn, GeSiSn, and the like. For example, GeSn layers can be used to form direct band gap devices and/or can be used to provide strain in adjacent germanium layers to increase mobility in germanium layers. Likewise, GeSiSn layers can be used to form tunable bandgap devices as well as optical devices with tunable optical properties. In order to obtain desired device properties, germanium-tin films generally have a crystalline structure, which generally follows the crystalline structure of the underlying layer.

GeSn層可使用各種技術沉積或生長。例如，使用包括分子束磊晶及超高真空化學氣相沉積的真空製程來形成GeSn膜。用於此種製程的鍺前驅物典型地包括二鍺烷(Ge2H6)或三鍺烷(Ge3H8)。當膜包括矽時，矽前驅物可包括二矽烷、三矽烷、或其它更高階矽烷化合物、或具有通式(H3Ge)xSiH4-x(x=1-4)、(H3Si)xGeH4-x(x=1-4)的雜核Si-Ge化合物。 The GeSn layer can be deposited or grown using various techniques. For example, the GeSn film is formed using a vacuum process including molecular beam epitaxy and ultra-high vacuum chemical vapor deposition. Germanium precursors for such processes typically include digermane (Ge 2 H 6 ) or trigermane (Ge 3 H 8 ). When the film includes silicon, the silicon precursor may include disilane, trisilane, or other higher order silane compounds, or have the general formula (H 3 Ge) x SiH 4-x (x=1-4), (H 3 Si ) x GeH 4-x (x=1-4) heteronuclear Si-Ge compound.

儘管使用此種製程沉積或生長結晶GeSn及GeSiSn層，但使用二鍺烷、三鍺烷、或更高階鍺烷前驅物在若干方面上係為有問題的。例如，當某些載體氣體(例如，氫)及/或摻雜劑(例如，p型摻雜劑)與前驅物一起使用時，使用二鍺烷或更高階鍺烷前驅物(諸如三鍺烷)形成包括GeSn之膜或層沒有選擇性。再者，二鍺烷在濃縮形式上係為相對不穩定(爆炸性)；因此，容器中所含之前驅物之量可被限制，典型地小於154克，此又導致使用此種前驅物之製程之生產量相對較低。此外，二鍺烷及更高階鍺烷相對昂貴。因此，需要形成包括GeSn之結晶膜之改良方法。 Although crystalline GeSn and GeSiSn layers are deposited or grown using this process, the use of digermane, trigermane, or higher order germane precursors is problematic in several respects. For example, when certain carrier gases (eg, hydrogen) and/or dopants (eg, p-type dopants) are used with the precursor, digermane or higher order germane precursors such as trigermane are used ) has no selectivity to form a film or layer comprising GeSn. Furthermore, digermane is relatively unstable (explosive) in concentrated form; therefore, the amount of precursor contained in the container can be limited, typically less than 154 grams, which in turn leads to processes using this precursor production is relatively low. Furthermore, digermanes and higher order germanes are relatively expensive. Therefore, there is a need for an improved method of forming a crystalline film including GeSn.

本發明各種具體實例係關於形成GeSn膜之方法以及包括該等膜之結構與裝置。使用本文描述之方法形成的膜可用於例如半導體、直接能帶間隙、光子或任何包括該膜之裝置。僅管在下文中更詳細地討論了本發明各種具體實例解決先前技術方法之缺點的方式，通常，本發明提供使用鍺烷(GeH4)前驅物在基板表面上形成鍺-錫層(例如，結晶)之方法以及包括此等膜之結構與裝置。 Various embodiments of the present invention relate to methods of forming GeSn films and structures and devices including such films. Films formed using the methods described herein can be used, for example, in semiconductors, direct bandgap, photonics, or any device that includes the films. Tube only be discussed in more detail below, various specific examples of the present invention is to solve the disadvantages of the prior art methods of way, generally, the present invention provides the use of germane (GeH 4) precursor is formed of germanium on the substrate surface - tin layer (e.g., crystalline ) and structures and devices including such membranes.

如本文所用，鍺-錫(GeSn)層(本文亦稱為膜)或包括鍺 及錫之層係為包括元素鍺及錫之層。此等層可例如包括額外元素，諸如矽(例如，GeSnSi)或碳(例如，GeSnSiC)，或摻雜劑，諸如硼、鎵、磷、砷或銻，舉例而言。 As used herein, a germanium-tin (GeSn) layer (also referred to herein as a film) or a layer comprising germanium and tin is a layer comprising the elements germanium and tin. Such layers may, for example, include additional elements such as silicon (eg, GeSnSi) or carbon (eg, GeSnSiC), or dopants such as boron, gallium, phosphorus, arsenic or antimony, for example.

根據本發明各種具體實例，形成包括GeSn之層之方法包括以下步驟：提供氣相反應器，提供耦合至氣相反應器的鍺烷前驅物源，提供耦合至氣相反應器的錫前驅物源，在氣相反應器的反應腔室內提供基板，提供鍺烷前驅物及錫前驅物至反應腔室，以及在基板表面上形成(例如，磊晶生長)鍺錫結晶層。根據此等具體實例的各個方面，提供鍺烷前驅物及錫前驅物至反應腔室的步驟包括提供具有體積比為約0.001至約0.1、約0.005至約0.05、小於約0.1、或小於約0.05之錫前驅物及鍺烷前驅物之混合物。在形成鍺錫結晶層的步驟期間的反應腔室溫度及壓力可根據各種因素而變化。例示性反應腔室溫度範圍為約200℃至約500℃、約250℃至約450℃、或約300℃至約420℃。在此步驟中例示性反應腔室壓力範圍為約300托至約850托、約400托至約800托、約500托至約760托、環境大氣壓±約20托、環境大氣壓±約10托、或環境大氣壓±約5托。根據此等具體實例的另外方面，鍺-錫層包括矽。在此等情況下，方法進一步包含提供矽源前驅物至反應腔室的步驟。例示性矽源前驅物包括二矽烷、三矽烷、四矽烷、新戊矽烷(neopentasilane)及更高階矽烷化合物。併入結晶鍺-錫層中之錫之量可為約大於1at%、大於2at%、或大於5at%、或範圍為約0at%至約15at%錫、約2at%至約15at%錫、約0.2at%至約5at%錫、或約0.2at%至約15at%錫。當結晶鍺錫層包括矽時，該層可包括大於0at%矽、大於約1at%矽、或約1at%矽至約20at%矽之間、約2at%矽至約16at%矽 之間、或約4at%矽至約12at%矽之間。根據此等具體實例的另外方面，基板包括矽。根據其它方面，基板包括例如覆蓋矽之鍺層。根據此等具體實例之例示性方法額外包括以下步驟：形成覆蓋基板之絕緣層，在絕緣層內形成導通孔(via)，以及在導通孔內形成(例如，選擇性地)(例如，結晶)鍺-錫層且覆蓋基板，該基板可包括一或多個先前形成的層。 According to various embodiments of the present invention, a method of forming a layer comprising GeSn includes the steps of: providing a gas phase reactor, providing a source of germane precursor coupled to the gas phase reactor, providing a source of tin precursor coupled to the gas phase reactor , providing a substrate in a reaction chamber of a gas phase reactor, providing germane precursors and tin precursors to the reaction chamber, and forming (eg, epitaxially grown) a germanium-tin crystalline layer on the surface of the substrate. According to various aspects of these specific examples, the step of providing the germane precursor and the tin precursor to the reaction chamber includes providing a volume ratio of about 0.001 to about 0.1, about 0.005 to about 0.05, less than about 0.1, or less than about 0.05 A mixture of tin precursor and germane precursor. The reaction chamber temperature and pressure during the step of forming the germanium tin crystalline layer may vary according to various factors. Exemplary reaction chamber temperature ranges are from about 200°C to about 500°C, from about 250°C to about 450°C, or from about 300°C to about 420°C. Exemplary reaction chamber pressure ranges in this step are about 300 Torr to about 850 Torr, about 400 Torr to about 800 Torr, about 500 Torr to about 760 Torr, ambient atmospheric pressure ± about 20 Torr, ambient atmospheric pressure ± about 10 Torr, or ambient atmospheric pressure ± about 5 Torr. According to further aspects of these specific examples, the germanium-tin layer includes silicon. In such cases, the method further includes the step of providing a silicon source precursor to the reaction chamber. Exemplary silicon source precursors include disilane, trisilane, tetrasilane, neopentasilane, and higher order silane compounds. The amount of tin incorporated into the crystalline germanium-tin layer may be about greater than 1 at%, greater than 2 at%, or greater than 5 at%, or in the range of about 0 at% to about 15 at% tin, about 2 at% to about 15 at% tin, about 0.2 at % to about 5 at % tin, or about 0.2 at % to about 15 at % tin. When the crystalline germanium tin layer includes silicon, the layer may include greater than 0 at% silicon, greater than about 1 at% silicon, or between about 1 at% silicon and about 20 at% silicon, between about 2 at% silicon and about 16 at% silicon, or Between about 4 at% silicon and about 12 at% silicon. According to further aspects of these specific examples, the substrate includes silicon. According to other aspects, the substrate includes, for example, a germanium layer overlying silicon. Illustrative methods according to these specific examples additionally include the steps of forming an insulating layer overlying the substrate, forming vias within the insulating layer, and forming (eg, selectively) (eg, crystallizing) within the vias The germanium-tin layer also covers the substrate, which may include one or more previously formed layers.

根據本發明另外的例示性具體實例，形成包含鍺-錫(例如，結晶)層之結構之方法包括以下步驟：提供氣相反應器，在氣相反應器的反應腔室內提供基板，以及使用一或多種包含鍺烷(GeH4)之前驅物在基板表面上形成包含鍺及錫(例如，結晶)之層。根據此等具體實例的各個方面，形成包含鍺及錫之層的步驟包括提供具有體積比為約0.001至約0.1、約0.005至約0.05、小於約0.1、或小於約0.05之錫前驅物及鍺烷之混合物。根據另外的方面，在形成包含鍺錫之結晶層的步驟期間的反應腔室溫度範圍為約200℃至約500℃、約250℃至約450℃、或約300℃至約420℃。根據又另外的方面，在形成包含鍺錫之層的步驟期間的反應腔室壓力範圍為約300托至約850托、約400托至約800托、約500托至約760托、環境大氣壓±約20托、環境大氣壓±約10托、或環境大氣壓±約5托。根據此等具體實例的又另外的方面，形成包含鍺及錫之層的步驟包括形成包含矽鍺錫之層。在此等情況下，提供矽前驅物至反應腔室。例示性矽源前驅物包括二矽烷、三矽烷、四矽烷、新戊矽烷及更高階矽烷化合物。併入鍺-錫層中之錫之量可為約大於1at%、大於2at%、或大於5at%、或範圍為約0at%至約15at%錫、約2at%至約15at%錫、約0.2at%至約5at%錫、或約0.2at%至約15at%錫。當結晶鍺-錫層之層包括矽時，該層可包括大於0at%矽、大 於約1at%矽、或約1at%矽至約20at%矽之間、約2at%矽至約16at%矽之間、或約4at%矽至約12at%矽之間。根據此等具體實例的各個方面，基板包括矽。根據其它方面，基板包括例如覆蓋矽之鍺層。根據此等具體實例的例示性方法額外包括以下步驟：形成覆蓋基板之絕緣層，在絕緣層內形成導通孔，以及在導通孔內形成(例如，選擇性地)鍺錫層且覆蓋基板。 According to further illustrative embodiments of the present invention, a method of forming a structure comprising a germanium-tin (eg, crystalline) layer includes the steps of providing a gas phase reactor, providing a substrate within a reaction chamber of the gas phase reactor, and using a or comprising more germane (GeH 4) of the precursor-forming layer comprises germanium, and tin (e.g., crystalline) on the surface of the substrate. According to various aspects of these embodiments, forming a layer comprising germanium and tin includes providing a tin precursor and germanium having a volume ratio of about 0.001 to about 0.1, about 0.005 to about 0.05, less than about 0.1, or less than about 0.05 A mixture of alkanes. According to further aspects, the temperature of the reaction chamber during the step of forming the crystalline layer comprising germanium tin ranges from about 200°C to about 500°C, about 250°C to about 450°C, or about 300°C to about 420°C. According to yet further aspects, the reaction chamber pressure during the step of forming the layer comprising germanium tin is in the range of about 300 Torr to about 850 Torr, about 400 Torr to about 800 Torr, about 500 Torr to about 760 Torr, ambient atmospheric pressure ± About 20 Torr, ambient atmospheric pressure ± about 10 Torr, or ambient atmospheric pressure ± about 5 Torr. According to yet further aspects of these embodiments, the step of forming a layer comprising germanium and tin includes forming a layer comprising silicon germanium tin. In these cases, a silicon precursor is provided to the reaction chamber. Exemplary silicon source precursors include disilane, trisilane, tetrasilane, neopentasilane, and higher order silane compounds. The amount of tin incorporated into the germanium-tin layer may be about greater than 1 at%, greater than 2 at%, or greater than 5 at%, or in the range of about 0 at% to about 15 at% tin, about 2 at% to about 15 at% tin, about 0.2 at % to about 5 at % tin, or about 0.2 at % to about 15 at % tin. When the layer of the crystalline germanium-tin layer includes silicon, the layer may include greater than 0 at% silicon, greater than about 1 at% silicon, or between about 1 at% silicon to about 20 at% silicon, about 2 at% silicon to about 16 at% silicon between about 4 at% silicon and about 12 at% silicon. According to various aspects of these specific examples, the substrate includes silicon. According to other aspects, the substrate includes, for example, a germanium layer overlying silicon. Illustrative methods according to these embodiments additionally include the steps of forming an insulating layer overlying the substrate, forming vias within the insulating layer, and forming (eg, selectively) a germanium tin layer within the vias and overlying the substrate.

根據本發明又另外的具體實例，結構包括根據本發明之方法所形成的結晶鍺-錫層。該結構可用於形成電子(例如，半導體)或光子(例如，太陽能或發光)裝置。 According to yet further embodiments of the present invention, structures include crystalline germanium-tin layers formed according to the methods of the present invention. The structures can be used to form electronic (eg, semiconductor) or photonic (eg, solar or light emitting) devices.

並且根據本發明又額外的例示性具體實例，裝置包括根據本發明之方法所形成的結晶鍺-錫層。 And according to yet additional illustrative embodiments of the present invention, a device includes a crystalline germanium-tin layer formed according to the method of the present invention.

100:系統 100: System

102:反應器 102: Reactor

104:鍺烷前驅物源 104: Germane precursor source

106:錫前驅物源 106: Tin precursor source

108:前驅物源 108: Precursor Source

110:吹掃及/或載體氣體源/氣體源 110: Purge and/or carrier gas source/gas source

112:混合器 112: Mixer

114:增壓室 114: plenum

116:真空源 116: Vacuum source

118:管線 118: Pipeline

120:管線 120: Pipeline

122:管線 122: Pipeline

124:管線 124: Pipeline

126:管線 126: Pipeline

128:管線 128: Pipeline

130:管線 130: Pipeline

132:管線 132: Pipeline

134:閥 134: Valve

136:閥 136: Valve

138:閥 138: Valve

140:閥 140: Valve

142:基板 142: Substrate

144:反應腔室 144: Reaction Chamber

200:方法 200: Method

202:步驟 202: Steps

204:步驟 204: Steps

206:步驟 206: Steps

208:步驟 208: Steps

210:步驟 210: Steps

212:步驟 212: Steps

300:方法 300: Method

302:步驟 302: Step

304:步驟 304: Step

306:步驟 306: Steps

308:步驟 308: Steps

310:步驟 310: Steps

400:結構 400: Structure

402:矽基板 402: Silicon substrate

404:鍺緩衝層 404: germanium buffer layer

406:鍺-錫層 406: germanium-tin layer

500:搖擺掃描 500: Swing Scan

600:結構 600: Structure

602:基板 602: Substrate

604:絕緣層 604: Insulation layer

606:導通孔(via) 606: Via (via)

608:鍺層 608: germanium layer

610:鍺-錫層 610: germanium-tin layer

700:結構 700: Structure

702:基板 702: Substrate

704:第一層 704: first floor

706:鍺-錫層 706: germanium-tin layer

708:第二層 708: Second Floor

可藉由參考關於以下圖式的詳細說明及申請專利範圍而更完整的了解本發明之例示性具體實例。 Illustrative embodiments of the present invention may be more fully understood by reference to the detailed description of the following drawings and the scope of the claims.

圖1說明根據本發明例示性具體實例的用於形成結晶鍺錫層之系統。 1 illustrates a system for forming a crystalline germanium tin layer according to an illustrative embodiment of the present invention.

圖2說明根據本發明另外的例示性具體實例的形成包含鍺錫層之方法。 2 illustrates a method of forming a germanium-tin-containing layer according to a further illustrative embodiment of the present invention.

圖3說明根據本發明例示性具體實例的形成包含鍺錫層之另一種方法。 3 illustrates another method of forming a germanium-tin-containing layer according to an illustrative embodiment of the present invention.

圖4說明根據本發明例示性具體實例的結構。 Figure 4 illustrates a structure according to an illustrative embodiment of the present invention.

圖5說明根據本發明例示性具體實例的結構的搖擺掃描(rocking scan)。 5 illustrates a rocking scan of a structure according to an illustrative embodiment of the present invention.

圖6說明根據本發明又額外的例示性具體實例的另一結構。 6 illustrates another structure in accordance with yet additional illustrative embodiments of the present invention.

圖7說明根據本發明額外的例示性具體實例的又另一結構。 7 illustrates yet another structure according to an additional illustrative embodiment of the present invention.

應當理解，圖式中的元件係為了簡明及清楚起見而所示，並且不一定按比例繪製。例如，圖式中的一些元件的尺寸可以相對於其它元件被放大以幫助了解本發明的所示具體實例。 It should be understood that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to assist in understanding the illustrated embodiments of the invention.

以下提供的方法、結構及裝置之例示性具體實例之描述僅為例示性的且僅用於說明目的；以下描述並不旨在限制本發明或申請專利範圍之範圍。再者，具有所述特徵之多個具體實例之敘述不旨在排除具有額外特徵之其它具體實例或併入所述特徵之不同組合之其它具體實例。 The following descriptions of illustrative specific examples of methods, structures, and devices are provided for illustration and for purposes of illustration only; the following descriptions are not intended to limit the scope of the invention or claims. Furthermore, the recitation of multiple specific examples having a stated feature is not intended to exclude other specific examples having additional features or other specific examples incorporating different combinations of the stated features.

本發明通常係關於形成覆蓋基板之包括鍺及錫之層(諸如結晶層)之方法。鍺-錫層可包括額外元素(諸如矽及/或碳)，其與鍺-錫層形成晶格之部分。 The present invention generally relates to a method of forming a layer including germanium and tin, such as a crystalline layer, overlying a substrate. The germanium-tin layer may include additional elements, such as silicon and/or carbon, which form part of the lattice with the germanium-tin layer.

如本文所用，「基板」係指具有任何具有其上可沉積材料之表面的材料。基板可包括諸如矽(例如，單晶矽、單晶鍺或其它半導體晶圓)的塊材(bulk material)，或可包括覆蓋塊材之一或多個層。此外，基板可包括形成在基板之層之至少一部分內或之上的各種拓撲(topology)，諸如溝槽、導通孔、線等。例示性基板包括矽晶圓、包含覆蓋矽之鍺之層，以及包含覆蓋矽之鍺矽錫之層。 As used herein, "substrate" refers to any material having a surface on which material can be deposited. The substrate may include a bulk material such as silicon (eg, single crystal silicon, single crystal germanium, or other semiconductor wafers), or may include one or more layers overlying the bulk material. In addition, the substrate may include various topologies, such as trenches, vias, lines, etc., formed in or on at least a portion of the layers of the substrate. Exemplary substrates include silicon wafers, layers including germanium overlying silicon, and layers including germanium-silicon-tin overlying silicon.

圖1說明適用於使用本文所述方法形成鍺錫之系統100。在所示實施例中，系統100包括反應器102、鍺烷前驅物源104、錫前驅物源106、視需要選用之第三前驅物源108(例如，用於在成形層中包括矽或其它元素)、吹掃及/或載體氣體源110、視需要選用之混合器112、視需要選用之進氣增壓室(plenum)114及真空源116。源104-110可使用管線118-132及閥134-140耦合至混合器112或反應器102。雖未出示，但系統(諸如系統100)可包括用於摻雜劑(例如，諸如磷或砷之n型摻雜劑，或諸如硼之p型摻雜劑)的額外源及相應的輸送線。另外或或者，摻雜劑可包含於一或多個前驅物源104-108中。 FIG. 1 illustrates a system 100 suitable for forming germanium tin using the methods described herein. In the illustrated embodiment, the system 100 includes a reactor 102, a germane precursor source 104, a tin precursor source 106, an optional third precursor source 108 (eg, for including silicon or other elements), a source of purge and/or carrier gas 110, an optional mixer 112, an optional inlet plenum 114, and a vacuum source 116. Sources 104-110 may be coupled to mixer 112 or reactor 102 using lines 118-132 and valves 134-140. Although not shown, systems such as system 100 may include additional sources for dopants (eg, n-type dopants such as phosphorus or arsenic, or p-type dopants such as boron) and corresponding delivery lines . Additionally or alternatively, dopants may be included in one or more of the precursor sources 104-108.

反應器102可為獨立(standalone)的反應器或集群工具(cluster tool)之部分。此外，反應器102可專用於特別製程，諸如沉積製程，或反應器102可用於其它製程，例如用於層鈍化及/或蝕刻製程。例如，反應器102可包括典型地用於磊晶化學氣相沉積(CVD)處理的反應器，諸如可自ASM獲得的Epsilon® 2000 Plus或IntrepidTM XP，並且可包括直接電漿及/或遠端電漿裝置(未出示)及/或各種加熱系統，諸如輻射、電感及/或電阻加熱系統(亦未出示)。使用電漿可增強一或多種前驅物的反應性。所示之反應器為單基板水平流動反應器，其使反應物能夠在基板142上層流，且具有低停留時間，此反過來又促進了相對快速的循序的基板處理。2009年1月13日公告之Pomarede等人的美國專利第7,476,627號中描述了適用於系統100的例示性CVD反應器，其內容於此藉由引用以該等內容不與本發明衝突之範圍併入本文中。儘管所示為水平流動反應器，根據替代具體實例之反應器102可包括垂直流動，例如自噴頭噴出並且實質上向下流動至基板上之流。 Reactor 102 may be a standalone reactor or part of a cluster tool. Furthermore, the reactor 102 may be dedicated to a particular process, such as a deposition process, or the reactor 102 may be used for other processes, such as for layer passivation and/or etching processes. For example, reactor 102 may typically comprise an epitaxial reactor for the chemical vapor deposition (CVD) process, such as may be obtained from ASM Epsilon ® 2000 Plus or Intrepid TM XP, and may comprise a direct plasma and / or far A terminal plasma device (not shown) and/or various heating systems such as radiant, inductive and/or resistive heating systems (also not shown). The use of plasma can enhance the reactivity of one or more precursors. The reactor shown is a single substrate horizontal flow reactor that enables laminar flow of reactants over substrate 142 with low residence time, which in turn facilitates relatively fast sequential substrate processing. An exemplary CVD reactor suitable for use with the system 100 is described in US Patent No. 7,476,627 to Pomarede et al., issued January 13, 2009, the contents of which are hereby incorporated by reference to the extent that they do not conflict with the present invention. into this article. Although shown as a horizontal flow reactor, reactor 102 according to an alternate embodiment may include vertical flow, such as a flow that exits a showerhead and flows substantially down onto the substrate.

反應器102之反應腔室144之操作壓力可根據各種因素而變化。反應器102可經組態以在接近環境大氣壓力下操作。接近環境大氣壓 力之操作允許相對快的成膜。作為實施例，在層形成步驟期間反應器102之操作壓力範圍為約300托至約850托、約400托至約800托、約500托至約760托、環境大氣壓力±約20托、環境大氣大氣壓力±約10托或環境大氣壓±約5托。 The operating pressure of the reaction chamber 144 of the reactor 102 may vary depending on various factors. Reactor 102 may be configured to operate near ambient atmospheric pressure. close to ambient pressure Manipulation of force allows relatively fast film formation. As an example, the operating pressure of the reactor 102 during the layer formation step is in the range of about 300 Torr to about 850 Torr, about 400 Torr to about 800 Torr, about 500 Torr to about 760 Torr, ambient atmospheric pressure ± about 20 Torr, ambient Atmospheric pressure ± about 10 Torr or ambient atmospheric pressure ± about 5 Torr.

源104包括鍺烷(GeH4)，並且可視需要包括一或多種摻雜劑化合物，諸如典型地用於製造光子及/或半導體裝置之化合物。例示性p型摻雜劑化合物包括B2H6，以及例示性n型摻雜劑化合物包括AsH3。 Source 104 comprises germane (GeH 4), and optionally comprises one or more dopant compound, producing photons and / or a semiconductor device such as typically used. Exemplary compounds include p-type dopants B 2 H 6, and exemplary n-type dopant compound comprises AsH 3.

相較於其他前驅物(諸如二鍺烷、三鍺烷、或其它更高階鍺烷)，將鍺烷使用於形成鍺-錫層上係為有利的，其係因為當與各種載體氣體(例如氫、氮等)混和時鍺烷係相對具選擇性的，且即使當摻雜劑(例如，p型摻雜劑)與前驅物一起使用時亦可相對具選擇性的(例如，使用如本文所述的各種製程條件)。此外，鍺烷與更高階二鍺烷相比相對安全，因此與更高階鍺烷相比可以更高之量使用及/或運輸。此外，與更高階鍺烷化合物相比，鍺烷用作用於其它層(諸如鍺)之前驅物，且更容易獲得以及更便宜。 The use of germane in the formation of germanium-tin layers is advantageous over other precursors such as digermane, trigermane, or other higher order germanes because of its advantages when used with various carrier gases such as Germanes are relatively selective when mixed with hydrogen, nitrogen, etc., and can be relatively selective even when dopants (eg, p-type dopants) are used with precursors (eg, using as described herein) the various process conditions described). In addition, germane is relatively safe compared to higher order digermanes and thus can be used and/or transported in higher amounts than higher order germanes. Furthermore, germane is used as a precursor for other layers, such as germanium, and is more readily available and less expensive than higher order germane compounds.

錫前驅物源106包括任何適於提供錫至鍺-錫層之化合物。例示性錫前驅物包括氯化錫(SnCl4)、氘代錫烷(SnD4)以及經甲基及/或鹵化物取代的錫烷，諸如具有式Sn(CH3)4-nXn的化合物，其中X為H、D(氘)、Cl或Br，及n為0、1、2或3；ZSn(CH3)3-nXn，其中Z為H或D，X為Cl或Br，及n為0、1或2；Z2Sn(CH3)2-nXn，其中Z為H或D，X為Cl或Br，及n為0或1；或SnBr4。2013年3月4日提交之名稱為「用於蒸氣沉積之錫前驅物及沉積製程(TIN PRECURSORS FOR VAPOR DEPOSITION AND DEPOSITION PROCESSES)」之申請案第13/783,762號更詳細地討論了適用於本發明之一些例示性錫前驅體，其內容於此藉由引用以該等內容不與本發明衝突之範圍併入本文中。 Tin precursor source 106 includes any compound suitable for providing a tin to germanium-tin layer. Exemplary tin precursors include tin chloride (SnCl 4 ), deuterated stannane (SnD 4 ), and methyl- and/or halide-substituted stannanes, such as those having the formula Sn(CH 3 ) 4-n X n compounds, wherein X is H, D (deuterium), Cl or Br, and n is 2 or 3; ZSn (CH 3) 3 -n X n, where Z is H or D, X is Cl or Br , and n is 0, 1, or 2; Z 2 Sn(CH 3 ) 2-n X n , where Z is H or D, X is Cl or Br, and n is 0 or 1; or SnBr 4 . Application No. 13/783,762, filed March 4, 2013, entitled "TIN PRECURSORS FOR VAPOR DEPOSITION AND DEPOSITION PROCESSES," discusses in more detail the application to the present invention of some exemplary tin precursors, the contents of which are hereby incorporated by reference to the extent that they do not conflict with the present invention.

視需要選用之第三前驅物源108在使用時包括可包含於沉積層中的額外元素或化合物之前驅物。例如，前驅物源108可包括矽前驅物，諸如二矽烷、三矽烷、四矽烷、新戊矽烷及更高階矽烷化合物，碳前驅物，諸如H3SiCH3、(H3Si)4C、CH4、H3GeCH3及(H3Ge)2CH2，及/或可包括一或多種適合作為摻雜劑前驅物/化合物的化合物。若源108包括矽前驅物，則如上所述，系統100可包括額外的摻雜劑源及相應的輸送線。 The optional third precursor source 108, in use, includes additional elemental or compound precursors that may be included in the deposited layer. For example, precursor source 108 may include a silicon precursor, such as titanium Silane, tris Silane, four Silane, neopentyl Silane and higher order Silane compound, a carbon precursor, such as H 3 SiCH 3, (H 3 Si) 4 C, CH 4, H 3 GeCH 3 and (H 3 Ge) 2 CH 2 , and / or may comprise one or more suitable compounds as a dopant precursor / compound. If the source 108 includes a silicon precursor, the system 100 may include additional dopant sources and corresponding delivery lines, as described above.

氣體源110可包括任何適合的吹掃或載體氣體。適用作載體及吹掃氣體的例示性氣體包括氮、氬、氦及氫。 Gas source 110 may include any suitable purge or carrier gas. Exemplary gases suitable for use as carrier and purge gases include nitrogen, argon, helium, and hydrogen.

系統100可包括氣體分配系統。2012年4月10日公告之Schmidt等人提交名稱為「用於ALD反應器的氣體混合器及歧管組件(Gas Mixer and Manifold Assembly for ALD Reactor，)」之美國專利第8,152,922號列示了允許在氣體(例如，源104-110)之間快速切換的例示性氣體分配系統，其內容於此藉由引用以該等內容不與本發明衝突之範圍併入本文中。氣體分配系統可用於例如在氣體到達增壓室114或反應器102之前混合一或多種前驅物氣體及載體氣體(其可與氣體源110之吹掃氣體相同或不同)。 System 100 may include a gas distribution system. U.S. Patent No. 8,152,922, entitled "Gas Mixer and Manifold Assembly for ALD Reactor," issued April 10, 2012 by Schmidt et al. Exemplary gas distribution systems that rapidly switch between gases (eg, sources 104-110), the contents of which are incorporated herein by reference to the extent that they do not conflict with the present invention. A gas distribution system may be used, for example, to mix one or more precursor gases and a carrier gas (which may or may not be the same as the purge gas of gas source 110 ) before the gases reach plenum 114 or reactor 102 .

現在轉向圖2，圖2說明形成結晶鍺-錫層之例示性方法200。方法200包含以下步驟、基本上由以下步驟組成、或由以下步驟組成：提供氣相反應器(步驟202)，提供耦合至氣相反應器之鍺烷源(步驟204)，提供耦合至氣相反應器之錫前驅物源(步驟206)，在氣相反應器之反應腔 室內提供基板(步驟208)，提供鍺烷及錫前驅物至反應腔室，其中錫前驅物與鍺烷之比例小於0.1(步驟210)，以及在基板表面上形成鍺錫之結晶層(步驟212)。方法200可用於在步驟212之在基板表面上形成鍺錫之結晶層期間及/或之前形成(例如，選擇性地生長)鍺-錫膜，而不需要蝕刻劑。 Turning now to FIG. 2, FIG. 2 illustrates an exemplary method 200 of forming a crystalline germanium-tin layer. The method 200 comprises, consists essentially of, or consists of the steps of: providing a gas phase reactor (step 202), providing a source of germane coupled to the gas phase reactor (step 204), providing a gas phase reactor coupled to tin precursor source for the reactor (step 206), in the reaction chamber of the gas phase reactor A substrate is provided in the chamber (step 208 ), germane and tin precursors are provided to the reaction chamber, wherein the ratio of the tin precursor to germane is less than 0.1 (step 210 ), and a crystalline layer of germanium-tin is formed on the surface of the substrate (step 212 ) ). Method 200 can be used to form (eg, selectively grow) a germanium-tin film during and/or before forming a crystalline layer of germanium-tin on the surface of the substrate in step 212 without the need for an etchant.

在步驟202期間，提供適於磊晶生長的氣相反應器，諸如CVD反應器。反應器可為單基板層流反應器。此等反應器可自ASM獲得，諸如Epsilon® 2000 Plus及IntrepidTM XP。 During step 202, a gas phase reactor suitable for epitaxial growth, such as a CVD reactor, is provided. The reactor may be a single substrate laminar flow reactor. These reactors can be obtained from ASM, such as Epsilon ® 2000 Plus and Intrepid TM XP.

在步驟204及206期間，將適合的鍺烷(GeH4)及錫前驅物源耦合至反應器。如上所述，鍺烷源可包括摻雜劑化合物，諸如p型摻雜劑化合物。或者，可自額外源(未出示)提供摻雜劑。錫前驅物源可包括例如氯化錫及/或錫氘化物及/或本文所述之其它錫前驅物。 In step 204 and 206 during the appropriate germane (GeH 4), and tin precursor source is coupled to the reactor. As mentioned above, the germane source may include a dopant compound, such as a p-type dopant compound. Alternatively, the dopant may be provided from an additional source (not shown). The source of tin precursors may include, for example, tin chloride and/or tin deuterides and/or other tin precursors described herein.

在步驟208期間，將基板裝載於反應器之反應腔室中。基板可自反應器系統之裝載負載鎖(loading load lock)接收並且使用適合的轉運機構輸送至反應腔室。 During step 208, the substrate is loaded into the reaction chamber of the reactor. The substrate can be received from a loading load lock of the reactor system and delivered to the reaction chamber using a suitable transfer mechanism.

在步驟210下，將錫前驅物及鍺烷提供至反應器之反應腔室中。錫前驅物及鍺烷可在進入腔室之前混合(例如，在混合器112中)。此外，鍺烷及錫前驅物可單獨或結合與一或多種載體氣體混合。鍺烷及/或錫前驅物可與反應腔室上游(諸如在混合器或混合器上游)的載體混合。 At step 210, the tin precursor and germane are provided into the reaction chamber of the reactor. The tin precursor and germane may be mixed (eg, in mixer 112) prior to entering the chamber. Additionally, germane and tin precursors can be mixed with one or more carrier gases, alone or in combination. The germane and/or tin precursor can be mixed with the carrier upstream of the reaction chamber, such as in a mixer or mixer.

如上所述，相較於使用典型前驅物，使用鍺烷於形成包括鍺及錫之層上具有許多優點。令人驚訝地及出人意料地發現，使用相對於錫前驅物相對高的鍺烷分壓形成高質量的結晶鍺-錫層。根據本發明例示性具體實例的各個方面，提供鍺烷及錫前驅物至反應腔室的步驟包括提供錫前驅物及鍺烷之混合物，錫前驅物與鍺烷之體積比為約0.001至約0.1、約0.005至約0.05、小於約0.1、或小於約0.05。 As mentioned above, the use of germane in forming layers including germanium and tin has many advantages over the use of typical precursors. Surprisingly and unexpectedly, it was found that high quality crystalline germanium-tin layers are formed using a relatively high partial pressure of germane relative to the tin precursor. According to various aspects of the illustrative embodiments of the present invention, the step of providing germane and tin precursors to the reaction chamber includes providing a mixture of tin precursor and germane in a volume ratio of tin precursor to germane of about 0.001 to about 0.1 , about 0.005 to about 0.05, less than about 0.1, or less than about 0.05.

在步驟212期間，結晶層(例如，磊晶層)係形成覆蓋基板。步驟212期間的例示性反應腔室溫度範圍可在約200℃至約500℃、約250℃至約450℃、或約300℃至約420℃。並且，此步驟期間的例示性反應腔室壓力範圍可在約300托至約850托、約400托至約800托、約500托至約760托、環境大氣壓力±約20托、環境大氣壓力±約10托或環境大氣壓力±5托。在相對高的壓力下操作允許快速生產包括鍺-錫膜之結構。 During step 212, a crystalline layer (eg, an epitaxial layer) is formed overlying the substrate. Exemplary reaction chamber temperatures during step 212 may range from about 200°C to about 500°C, about 250°C to about 450°C, or about 300°C to about 420°C. Also, exemplary reaction chamber pressure ranges during this step may range from about 300 Torr to about 850 Torr, about 400 Torr to about 800 Torr, about 500 Torr to about 760 Torr, ambient atmospheric pressure ± about 20 Torr, ambient atmospheric pressure ± about 10 Torr or ambient atmospheric pressure ± 5 Torr. Operating at relatively high pressures allows for the rapid production of structures including germanium-tin films.

步驟212可包括形成包含鍺矽錫之層。在此等情況下，提供矽前驅物至反應腔室。例示性矽源前驅物包括二矽烷、三矽烷、四矽烷、新戊矽烷及更高階矽烷化合物。另外或或者，步驟212包括形成包括碳之層。在此等情況下，碳源可包括H3SiCH3、(H3Si)4C、CH4、H3GeCH3及(H3Ge)2CH2中之一或多種。矽及/或碳前驅物或其它適合的前驅物可與載體氣體混合且視需要與一或多種如本文所述之其它前驅物混合。步驟212可包括在步驟212期間或之前不使用蝕刻劑的選擇性沉積。 Step 212 may include forming a layer comprising germanium silicon tin. In these cases, a silicon precursor is provided to the reaction chamber. Exemplary silicon source precursors include disilane, trisilane, tetrasilane, neopentasilane, and higher order silane compounds. Additionally or alternatively, step 212 includes forming a layer comprising carbon. In such cases, the carbon source may include H 3 SiCH 3, (H 3 Si) 4 C, CH 4, H 3 GeCH 3 and (H 3 Ge) 2 CH 2, one or more. Silicon and/or carbon precursors or other suitable precursors can be mixed with the carrier gas and optionally with one or more other precursors as described herein. Step 212 may include selective deposition without the use of an etchant during or before step 212 .

方法200亦可包括形成覆蓋基板之絕緣層及在絕緣層內形成導通孔之步驟。以下更詳細地描述形成絕緣層及在絕緣層內形成導通孔之例示性技術。在此等情況下，鍺-錫層可選擇性地於導通孔內在基板上形成，如下所述-例如，不使用將基板暴露於蝕刻劑以便能夠選擇性地沉積鍺-錫膜的額外步驟。 The method 200 may also include the steps of forming an insulating layer overlying the substrate and forming vias in the insulating layer. Exemplary techniques for forming insulating layers and forming vias within the insulating layers are described in greater detail below. In such cases, a germanium-tin layer can be selectively formed on the substrate within the vias, as described below - eg, without the additional step of exposing the substrate to an etchant to enable selective deposition of the germanium-tin film.

圖3說明根據本發明額外具體實例之另一方法300。方法300包含以下步驟、基本上由以下步驟組成、或由以下步驟組成：提供氣相反 應器(步驟302)，在氣相反應器之反應腔室內提供基板(步驟304)，以及使用一或多種包含鍺烷之前驅物在基板表面上形成包含鍺錫之結晶層(步驟306)。類似於方法200，方法300可用於在形成包含鍺錫之結晶層的步驟期間或之前形成(例如，選擇性地)鍺-錫層，而不需要蝕刻劑。 FIG. 3 illustrates another method 300 according to an additional embodiment of the present invention. Method 300 comprises, consists essentially of, or consists of providing a gas phase reactor (step 302), providing a substrate within a reaction chamber of the gas phase reactor (step 304), and using one or more A germane containing precursor forms a crystalline layer containing germanium tin on the surface of the substrate (step 306). Similar to method 200, method 300 can be used to form (eg, selectively) a germanium-tin layer without the need for an etchant during or before the step of forming a crystalline layer comprising germanium-tin.

在步驟302期間，提供適用於生長包含鍺錫之結晶層的反應器。反應器可包括任何本文所述之反應器，諸如水平流動磊晶CVD反應器。 During step 302, a reactor suitable for growing a crystalline layer comprising germanium tin is provided. The reactor may include any of the reactors described herein, such as a horizontal flow epitaxial CVD reactor.

在步驟304期間，在反應器之反應腔室內提供基板。步驟304可與方法200的步驟208相同或類似。 During step 304, a substrate is provided within the reaction chamber of the reactor. Step 304 may be the same as or similar to step 208 of method 200 .

在步驟308下，形成包含鍺錫之結晶層。根據本發明例示性具體實例的各個方面，形成包含鍺錫之層的步驟包括提供錫前驅物及鍺烷之混合物，錫前驅物與鍺烷之體積比為約0.001至約0.1、約0.005至約0.05、小於約0.1、或小於約0.05。根據另外的方面，在形成包含鍺錫之結晶層的步驟期間的反應腔室溫度範圍為約200℃至約500℃、約250℃至約450℃、或約300℃至約420℃。並且，根據又另外的方面，在形成包含鍺錫之層的步驟期間的反應腔室壓力範圍為約300托至約850托、約400托至約800托、約500托至約760托，環境溫度大氣壓力±約20托，環境大氣壓力±約10托，或環境大氣壓力±約5托。 At step 308, a crystalline layer comprising germanium and tin is formed. According to various aspects of the illustrative embodiments of the present invention, the step of forming a layer comprising germanium tin includes providing a mixture of a tin precursor and germane in a volume ratio of the tin precursor to the germane of about 0.001 to about 0.1, about 0.005 to about 0.005 to about 0.05, less than about 0.1, or less than about 0.05. According to further aspects, the temperature of the reaction chamber during the step of forming the crystalline layer comprising germanium tin ranges from about 200°C to about 500°C, about 250°C to about 450°C, or about 300°C to about 420°C. And, according to yet further aspects, the reaction chamber pressure during the step of forming the layer comprising germanium tin is in the range of about 300 Torr to about 850 Torr, about 400 Torr to about 800 Torr, about 500 Torr to about 760 Torr, ambient Temperature atmospheric pressure ± about 20 Torr, ambient atmospheric pressure ± about 10 Torr, or ambient atmospheric pressure ± about 5 Torr.

步驟306可包括形成包含矽鍺錫之層。在此等情況下，提供矽前驅物至反應腔室。例示性矽源前驅物包括二矽烷、三矽烷、四矽烷、新戊矽烷及更高階矽烷化合物。另外或或者，步驟306包括形成包含碳之鍺錫層。例示性碳前驅物包括H3SiCH3、(H3Si)4C、CH4、H3GeCH3及(H3Ge)2CH2中之一或多種。 Step 306 may include forming a layer comprising silicon germanium tin. In these cases, a silicon precursor is provided to the reaction chamber. Exemplary silicon source precursors include disilane, trisilane, tetrasilane, neopentasilane, and higher order silane compounds. Additionally or alternatively, step 306 includes forming a germanium tin layer including carbon. Exemplary carbon precursor comprising H 3 SiCH 3, (H 3 Si) 4 C, CH 4, H 3 GeCH 3 and (H 3 Ge) 2 CH 2, one or more.

方法300亦可包括視需要選用之步驟308和310：形成覆蓋基板之絕緣層(步驟308)及在絕緣層內形成導通孔。在步驟308期間，可將任何適合的絕緣層(諸如氧化矽或氮化矽)沉積至基板上。然後，在步驟310期間，可在絕緣層內形成一或多個導通孔。可使用反應離子蝕刻或其它適合的技術來形成一或多個導通孔。 Method 300 may also include optional steps 308 and 310 of forming an insulating layer overlying the substrate (step 308 ) and forming vias in the insulating layer. During step 308, any suitable insulating layer, such as silicon oxide or silicon nitride, may be deposited onto the substrate. Then, during step 310, one or more vias may be formed in the insulating layer. The one or more vias may be formed using reactive ion etching or other suitable techniques.

在執行步驟308及310的情況下，可在導通孔內選擇性地形成在步驟306期間形成的結晶層。如上所述，由於當使用各種載體氣體(諸如氫)時以及當該層包括一或多種摻雜劑(諸如p型摻雜劑)時，鍺烷前驅物係相對選擇性的，因此使用鍺烷前驅物係為有利的。如上所述，方法300可用於選擇性地沉積鍺-錫膜，而不需要使用蝕刻劑。 With steps 308 and 310 performed, the crystalline layer formed during step 306 may be selectively formed within the via. As discussed above, germane is used because the germane precursor is relatively selective when various carrier gases (such as hydrogen) are used and when the layer includes one or more dopants (such as p-type dopants) Precursors are advantageous. As described above, method 300 can be used to selectively deposit germanium-tin films without the use of an etchant.

使用方法200或方法300(例如，在步驟212或306期間)所形成之層可包括例如大於1at%、大於2at%、或大於5at%、或約0at%至約15at%之間錫、約2at%至約15at%之間錫、約0.2at%至約5at%之間錫、或約0.2at%至約15at%之間錫。當結晶鍺錫層包括矽時，該層可包括大於0at%矽、大於約1at%矽、或約1at%矽至約20at%之間矽、約2at%的矽至約16at%之間矽、或約4at%矽至約12at%之間矽。當該膜包含碳時，該膜可包括額外的錫。包括碳的例示性鍺錫膜可包括約0.2至約20at%錫、約0至約20at%矽及約0至約10at%碳。 Layers formed using method 200 or method 300 (eg, during steps 212 or 306 ) may include, for example, greater than 1 at %, greater than 2 at %, or greater than 5 at %, or between about 0 at % and about 15 at % tin, about 2 at % % to about 15 at% tin, between about 0.2 at% to about 5 at% tin, or between about 0.2 at% to about 15 at% tin. When the crystalline germanium tin layer includes silicon, the layer may include greater than 0 at % silicon, greater than about 1 at % silicon, or between about 1 at % silicon and about 20 at % silicon, between about 2 at % silicon and about 16 at % silicon, Or about 4at% silicon to about 12at% silicon. When the film includes carbon, the film may include additional tin. Exemplary germanium tin films including carbon may include about 0.2 to about 20 at% tin, about 0 to about 20 at% silicon, and about 0 to about 10 at% carbon.

圖4說明根據本發明各種具體實例(諸如方法200或方法300)所形成之結構400之穿透式電子顯微鏡圖像。結構400包括矽基板402、覆蓋基板402之鍺緩衝層404及使用鍺烷作為前驅物所形成的鍺-錫層406。在所示實施例中，層406包括約8at%錫。在所示結構中沒有觀察到穿線缺 陷(threading defect)。 4 illustrates a transmission electron microscope image of a structure 400 formed in accordance with various embodiments of the present invention, such as method 200 or method 300. The structure 400 includes a silicon substrate 402, a germanium buffer layer 404 overlying the substrate 402, and a germanium-tin layer 406 formed using germane as a precursor. In the embodiment shown, layer 406 includes about 8 at% tin. No threading defects were observed in the structures shown Threading defect.

圖5說明結構(諸如結構400)的(004)搖擺掃描500。掃描說明與鍺-錫層、鍺層及矽基板相關聯的離散峰。如圖所示，鍺-錫峰與Pendellosung條紋相關聯，其指出鍺-錫層中的高結晶度。 FIG. 5 illustrates a (004) wobble scan 500 of a structure, such as structure 400 . The scans illustrate discrete peaks associated with the germanium-tin layer, germanium layer, and silicon substrate. As shown, germanium-tin peaks are associated with Pendellosung fringes, which indicate high crystallinity in the germanium-tin layer.

現在轉向圖6，圖6說明根據本發明額外的例示性具體實例之結構600。結構600包括基板602、絕緣層604、在層604內所形成之導通孔606、鍺層608(例如，在基板602上所磊晶形成)，以及鍺-錫層610(例如，在層608上所磊晶形成)。可將層608及/或610選擇性地於導通孔606內形成-例如使用方法200或方法300。 Turning now to FIG. 6, FIG. 6 illustrates a structure 600 in accordance with an additional illustrative embodiment of the present invention. Structure 600 includes substrate 602, insulating layer 604, vias 606 formed in layer 604, germanium layer 608 (eg, epitaxially formed on substrate 602), and germanium-tin layer 610 (eg, on layer 608) formed by epitaxy). Layers 608 and/or 610 may be selectively formed within via 606 - eg, using method 200 or method 300 .

圖7說明根據本發明額外具體實例之另一結構700。結構700包括基板702、第一層(例如，鍺-矽-錫層、鍺-矽-碳-錫層、鍺錫層、鍺-矽層或鍺層中之一或多者)704、鍺-錫層706以及第二層(例如，鍺-矽-錫層、鍺-矽-碳-錫層、鍺錫層、鍺-矽層、或鍺層中之一或多者)708。在所示實施例中，鍺-錫層706位於第一層704與第二層708之間；層704及708可包含相同材料(具有相同或不同組成物)或不同材料。下面表1說明層704及層708材料之例示性組合。 FIG. 7 illustrates another structure 700 according to an additional embodiment of the present invention. Structure 700 includes a substrate 702, a first layer (eg, one or more of a germanium-silicon-tin layer, germanium-silicon-carbon-tin layer, germanium-tin layer, germanium-silicon layer, or germanium layer) 704, germanium- Tin layer 706 and second layer (eg, one or more of germanium-silicon-tin layer, germanium-silicon-carbon-tin layer, germanium-tin layer, germanium-silicon layer, or germanium layer) 708 . In the illustrated embodiment, germanium-tin layer 706 is located between first layer 704 and second layer 708; layers 704 and 708 may comprise the same material (of the same or different compositions) or different materials. Table 1 below illustrates exemplary combinations of layer 704 and layer 708 materials.

Figure 106115126-A0305-02-0017-1
Figure 106115126-A0305-02-0017-1

層704-708可根據本文所述之方法形成。此外，儘管未出示，但如上文結合圖6所述，可在絕緣材料之導通孔內形成一或多個層704-708。作為實施例，第一層704可包含GeSnx，以及第二層708可包含GeSny，其中x及y不相等。 Layers 704-708 can be formed according to the methods described herein. Additionally, although not shown, as described above in connection with FIG. 6, one or more layers 704-708 may be formed within the vias of insulating material. As an example, the first layer 704 may comprise the GeSn x, and the second layer 708 may comprise the GeSn y, wherein x and y are not equal.

應當理解，本文描述的配置及/或方法本質上係為例示性的，並且此等特定的具體實例或實施例不應被認為是限制性的。本文描述的特定例程或方法可表示任何數量中一或多個的處理策略。因此，所示的各種動作可以所示的順序執行、以其它順序執行、同時執行，或在一些情況下省略。 It is to be understood that the configurations and/or methods described herein are exemplary in nature and that these particular specific examples or embodiments are not to be considered limiting. The particular routines or methods described herein may represent one or more of any number of processing strategies. Accordingly, the various actions shown may be performed in the order shown, in other orders, concurrently, or in some cases omitted.

本發明的標的包括本文揭示的各種製程、系統及配置，以及其它特徵、功能、動作及/或性質的所有新穎的及非顯而易見的組合及子組合，以及其任何及所有等同物。 The subject matter of the present invention includes all novel and non-obvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts, and/or properties disclosed herein, and any and all equivalents thereof.

100‧‧‧系統 100‧‧‧System

102‧‧‧反應器 102‧‧‧Reactor

104‧‧‧鍺烷前驅物源 104‧‧‧Germane precursor source

106‧‧‧錫前驅物源 106‧‧‧Tin precursor sources

108‧‧‧前驅物源 108‧‧‧Precursors

110‧‧‧吹掃及/或載體氣體源/氣體源 110‧‧‧Purge and/or carrier gas source/gas source

112‧‧‧混合器 112‧‧‧Mixers

114‧‧‧進氣增壓室 114‧‧‧Intake plenum

116‧‧‧真空源 116‧‧‧Vacuum Source

118‧‧‧管線 118‧‧‧Pipeline

120‧‧‧管線 120‧‧‧Pipeline

122‧‧‧管線 122‧‧‧Pipeline

124‧‧‧管線 124‧‧‧Pipeline

126‧‧‧管線 126‧‧‧Pipeline

128‧‧‧管線 128‧‧‧Pipeline

130‧‧‧管線 130‧‧‧Pipeline

132‧‧‧管線 132‧‧‧Pipeline

134‧‧‧閥 134‧‧‧valve

136‧‧‧閥 136‧‧‧valve

138‧‧‧閥 138‧‧‧Valve

140‧‧‧閥 140‧‧‧valve

142‧‧‧基板 142‧‧‧Substrate

144‧‧‧反應腔室 144‧‧‧Reaction chamber

Claims (20)

一種形成結晶鍺-錫層之方法，該方法包含以下步驟：提供氣相反應器；提供耦合至該氣相反應器之鍺烷源；提供耦合至該氣相反應器之錫前驅物源；在該氣相反應器之反應腔室內提供基板；提供鍺烷及錫前驅物至該反應腔室，其中該錫前驅物與該鍺烷之體積比大於0.001且小於0.1；以及在約300托至約850托之間的壓力下在該反應腔室中在該基板表面上形成鍺錫之結晶層，在形成結晶層之步驟期間不使用蝕刻劑。 A method of forming a crystalline germanium-tin layer, the method comprising the steps of: providing a gas phase reactor; providing a source of germane coupled to the gas phase reactor; providing a source of tin precursor coupled to the gas phase reactor; providing a substrate within the reaction chamber of the gas phase reactor; providing germane and tin precursors to the reaction chamber, wherein the volume ratio of the tin precursor to the germane is greater than 0.001 and less than 0.1; and between about 300 torr and about A crystalline layer of germanium tin is formed on the surface of the substrate in the reaction chamber at a pressure between 850 Torr, no etchant is used during the step of forming the crystalline layer. 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中該鍺錫之結晶層包含矽，以及該方法進一步包含：提供矽源前驅物。 The method for forming a crystalline germanium-tin layer according to claim 1, wherein the crystalline germanium-tin layer comprises silicon, and the method further comprises: providing a silicon source precursor. 根據申請專利範圍第2項之形成結晶鍺-錫層之方法，其中提供矽源前驅物之該步驟包含提供選自以下組成之群之前驅物：二矽烷、三矽烷、四矽烷、以及新戊矽烷(neopentasilane)。 The method of forming a crystalline germanium-tin layer according to claim 2, wherein the step of providing a silicon source precursor comprises providing a precursor selected from the group consisting of disilane, trisilane, tetrasilane, and neopentyl Silane (neopentasilane). 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中，在該基板表面上生長鍺錫之結晶層之該步驟期間，該反應腔室之操作壓力為約400托至約800托。 The method of forming a crystalline germanium-tin layer according to claim 1, wherein during the step of growing the crystalline layer of germanium-tin on the surface of the substrate, the operating pressure of the reaction chamber is about 400 torr to about 800 torr . 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中，在該基板表面上生長鍺錫之結晶層之該步驟期間，該反應腔室之操作壓力為約500托至約760托。 The method for forming a crystalline germanium-tin layer according to claim 1, wherein during the step of growing the crystalline layer of germanium-tin on the surface of the substrate, the operating pressure of the reaction chamber is about 500 torr to about 760 torr . 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中，在該基板 表面上生長鍺錫之結晶層之該步驟期間，該反應腔室之操作壓力為環境大氣壓±約20托範圍內。 The method for forming a crystalline germanium-tin layer according to claim 1, wherein on the substrate During this step of growing a crystalline layer of germanium tin on the surface, the operating pressure of the reaction chamber is within the range of ambient atmospheric pressure ± about 20 Torr. 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中該錫前驅物與該鍺烷之體積比為約0.005至約0.05。 The method for forming a crystalline germanium-tin layer according to claim 1, wherein the volume ratio of the tin precursor to the germane is about 0.005 to about 0.05. 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中，在該基板表面上生長鍺錫之結晶層之該步驟期間，該反應腔室內之操作溫度為約200℃至約500℃。 The method for forming a crystalline germanium-tin layer according to claim 1, wherein during the step of growing the crystalline layer of germanium-tin on the surface of the substrate, the operating temperature in the reaction chamber is about 200°C to about 500°C . 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中，在該基板表面上生長鍺錫之結晶層之該步驟期間，該反應腔室內之操作溫度為約250℃至約450℃。 The method for forming a crystalline germanium-tin layer according to claim 1, wherein during the step of growing the crystalline layer of germanium-tin on the surface of the substrate, the operating temperature in the reaction chamber is about 250°C to about 450°C . 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中提供錫前驅物源之該步驟包含提供選自以下組成之群之錫源：SnCl4、SnD4以及經甲基及鹵化物取代的錫烷。 A method of forming a crystalline germanium-tin layer according to claim 1, wherein the step of providing a source of a tin precursor comprises providing a source of tin selected from the group consisting of SnCl 4 , SnD 4 , and methyl and halide Substituted stannanes. 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中在該基板表面上生長鍺錫之結晶層之該步驟包含生長包含約2at%至約15at%錫之結晶層。 The method for forming a crystalline germanium-tin layer according to claim 1, wherein the step of growing a crystalline layer of germanium tin on the surface of the substrate comprises growing a crystalline layer comprising about 2 at % to about 15 at % tin. 根據申請專利範圍第1項之形成結晶鍺-錫層之方法，其中該錫前驅物與該鍺烷前驅物之體積比小於0.05。 According to the method for forming a crystalline germanium-tin layer of claim 1, the volume ratio of the tin precursor to the germane precursor is less than 0.05. 一種形成包含鍺-錫層之結構之方法，該方法包含以下步驟：提供氣相反應器；在該氣相反應器之反應腔室內提供基板，該基板包含絕緣層及在該絕緣層內之導通孔(via)；以及 使用一或多種包含鍺烷之前驅物在該導通孔內選擇性地形成包含鍺錫之結晶層，其中該反應腔室內之壓力為約300托至約850托之間。 A method of forming a structure comprising a germanium-tin layer, the method comprising the steps of: providing a gas phase reactor; providing a substrate in a reaction chamber of the gas phase reactor, the substrate comprising an insulating layer and conduction within the insulating layer a hole (via); and A crystalline layer comprising germanium tin is selectively formed in the via hole using one or more precursors comprising germane, wherein the pressure in the reaction chamber is between about 300 torr and about 850 torr. 根據申請專利範圍第13項之形成包含鍺-錫層之結構之方法，其中該基板包含包含覆蓋矽之鍺之層。 The method of forming a structure comprising a germanium-tin layer according to claim 13, wherein the substrate comprises a layer comprising germanium overlying silicon. 根據申請專利範圍第13項之形成包含鍺-錫層之結構之方法，其中該鍺-錫層包含約2at%錫至約15at%錫。 A method of forming a structure comprising a germanium-tin layer according to claim 13, wherein the germanium-tin layer comprises about 2 at % tin to about 15 at % tin. 根據申請專利範圍第13項之形成包含鍺-錫層之結構之方法，其中該形成步驟不包括將該基板暴露於蝕刻劑。 A method of forming a structure comprising a germanium-tin layer according to claim 13, wherein the forming step does not include exposing the substrate to an etchant. 根據申請專利範圍第13項之形成包含鍺-錫層之結構之方法，其中該基板包含包含覆蓋矽之鍺矽錫之層。 The method of forming a structure comprising a germanium-tin layer according to claim 13, wherein the substrate comprises a layer comprising germanium-silicon-tin overlying silicon. 根據申請專利範圍第13項之形成包含鍺-錫層之結構之方法，其進一步包含以下步驟：形成覆蓋該基板之該絕緣層；以及在該絕緣層內形成該導通孔。 The method for forming a structure including a germanium-tin layer according to claim 13, further comprising the steps of: forming the insulating layer covering the substrate; and forming the via hole in the insulating layer. 一種包含鍺錫之結晶層之結構，其係根據申請專利範圍第13項之方法所形成。 A structure comprising a crystalline layer of germanium and tin, which is formed according to the method of claim 13 of the claimed scope. 根據申請專利範圍第19項之包含鍺錫之結晶層之結構，其中該結構包含在兩層鍺矽錫之間的鍺錫層。 According to claim 19 of the claimed scope, the structure comprising a crystalline layer of germanium-tin, wherein the structure comprises a germanium-tin layer between two layers of germanium-silicon-tin.
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