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(12) Patent Application Publication (10) Pub. No.: US 2004/0194703 A1 Shenai-Khatkhate Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2004/0194703 A1 Shenai-Khatkhate Et Al US 2004O194703A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2004/0194703 A1 Shenai-Khatkhate et al. (43) Pub. Date: Oct. 7, 2004 (54) ORGANOMETALLIC COMPOUNDS Related U.S. Application Data (75) Inventors: Deodatta Vinayak Shenai-Khatkhate, (60) Provisional application No. 60/460,791, filed on Apr. Danvers, MA (US); Michael Brendan 5, 2003. Provisional application No. 60/513,476, filed Power, Newburyport, MA (US) on Oct. 22, 2003. Correspondence Address: Publication Classification S. Matthew Cairns (51) Int. Cl." .............................. C23C 16/00; CO8F 4/44 EDWARDS & ANGELL, LLP U.S. Cl. ....................... 118/715; 427/252; 427/248.1 P.O. BOX 55874 (52) Boston, MA 02205 (US) (57) ABSTRACT (73) Assignee: Rohm and Haas Electronic Materials, Organometallic compounds Suitable for use as vapor phase L.L.C., Marlborough, MA deposition precursors for Group IV metal-containing films are provided. Methods of depositing Group IV metal-con (21) Appl. No.: 10/817,618 taining films using certain organometallic precursors are also provided. Such Group IV metal-containing films are (22) Filed: Apr. 2, 2004 particularly useful in the manufacture of electronic devices. US 2004/O194703 A1 Oct. 7, 2004 ORGANOMETALLIC COMPOUNDS Sition. These precursors are difficult to handle and have high Vapor preSSures. For example, germane decomposes Vio BACKGROUND OF THE INVENTION lently at 280 C., which is below the temperature used to grow germanium films. Accordingly, processes employing 0001. The present invention relates generally to the field either germane or Silane require extensive Safety procedures of organometallic compounds. In particular, the present and equipment. Germane typically requires film growth invention relates to the certain organometallic compounds temperatures of approximately 500 C. or higher for thermal Suitable for use in vapor deposition processes. CVD applications. Such decomposition temperatures are not 0002 Metal films may be deposited on Surfaces, such as always Suitable, Such as in mass production applications non-conductive Surfaces, by a variety of means Such as where there is a need for lower temperatures, e.g. 200 C. chemical vapor deposition (“CVD”), physical vapor depo Other CVD applications require higher growth temperatures sition (“PVD”), and other epitaxial techniques such as liquid which cause conventional precursors to break up prema phase epitaxy (“LPE'), molecular beam epitaxy ("MBE”), turely which, in turn, leads to the formation of particles and chemical beam epitaxy (“CBE”) and atomic layer deposition a reduction in metal film growth rates. A further problem (“ALD). Chemical vapor deposition processes, Such as with conventional Silicon and germanium precursors is that metalorganic chemical vapor deposition (“MOCVD”), when a relatively stable Silicon precursor and a relatively deposit a metal layer by decomposing organometallic pre unstable germanium precursor are used to deposit a Silicon cursor compounds at elevated temperatures, i.e., above room germanium film, the differences in precursor Stability makes temperature, either atmospheric preSSure or at reduced pres control of the Silicon-germanium composition difficult. Sures. A wide variety of metals may be deposited using Such There is a need for precursors for Silicon and germanium CVD or MOCVD processes. Vapor phase deposition that are Safer to handle and have 0.003 For semiconductor and electronic device applica decomposition temperatures tailored to Specific conditions. tions, these organometallic precursor compounds must be There is also a desire for Silicon and germanium precursors highly pure and be substantially free of detectable levels of that have matched Stability characteristics. both metallic impurities, Such as Silicon and Zinc, as well as oxygenated impurities. Oxygenated impurities are typically SUMMARY OF THE INVENTION present from the Solvents used to prepare Such organome tallic compounds, and are also present from other adventi 0007. The present inventors have surprisingly found that tious Sources of moisture or oxygen. the above deficiencies can be remedied. The present inven 0004 For certain applications where high speed and tion provides a method of depositing a metal-containing film frequency response of an electronic device is desired, sili on a Substrate including the steps of: a) conveying one or con-only devices, e.g. Silicon bipolar transistors, have not more of the organometallic compounds of formula I in a been competitive. In a heterojunction bipolar transistor gaseous phase to a deposition chamber containing the Sub (“HBT), a thin silicon-germanium layer is grown as the Strate, base of a bipolar transistor on a Silicon wafer. The Silicon germanium HBT has significant advantages in Speed, fre quency response, and gain when compared to a conventional (I) Silicon bipolar transistor. The Speed and frequency response of a Silicon-germanium HBT are comparable to more expen sive gallium-arsenide HBTs. 0005 The higher gain, speeds, and frequency response of silicon-germanium HBTs have been achieved as a result of certain advantages of Silicon-germanium not available with 0008 wherein M is Sior Ge; R and Rare independently pure Silicon, for example, narrower band gap and reduced chosen from H, alkyl, alkenyl, alkynyl and aryl; each R is resistivity. Silicon-germanium may be epitaxially grown on independently chosen from (C-C)alkyl, alkenyl, alkynyl a Silicon Substrate using conventional Silicon processing and and aryl, provided that R is not cyclopentadienyl; each R' tools. This technique allows one to engineer device proper is independently chosen from (C-C)alkyl, X is halogen; ties Such as the energy band structure and carrier mobility. a=0-3; b=0-3; c=0-3; d=0-3; e=0-4; and a+b+c+d+e=4; For example, it is known in the art that grading the concen wherein RzR"; wherein the sums of a+b and a--dare each tration of germanium in the Silicon-germanium base builds s3; provided that when M=Si the sum of b+c is s3; b) into the HBT device an electric field or potential gradient, decomposing the one or more organometallic compounds in which accelerates the carriers across the base, thereby the deposition chamber; and c) depositing the metal film on increasing the Speed of the HBT device compared to a the Substrate. Silicon-only device. A common method for fabricating sili 0009. Also, the present invention provides a device for con and Silicon-germanium devices is by CVD. A reduced feeding a fluid Stream Saturated with an organometallic pressure chemical vapor deposition technique (“RPCVD') compound Suitable for depositing a metal film containing used to fabricate the HBT device allows for a controlled Silicon, germanium and combinations thereof to a chemical grading of germanium concentration across the base layer as Vapor deposition System including a vessel having an elon well as precise control over the doping profile. gated cylindrical shaped portion having an inner Surface 0006 Germane (GeH) is the conventional precursor for having a croSS-Section, a top closure portion and a bottom germanium deposition while Silane (SiH), and dichlorosi closure portion, the top closure portion having an inlet lane (SiHCl) are conventional precursors for Silicon depo opening for the introduction of a carrier gas and an outlet US 2004/O194703 A1 Oct. 7, 2004 opening, the elongated cylindrical shaped portion having a 0015. Further, the present invention provides a method of chamber containing one or more organometallic compounds manufacturing an electronic device including the Step of of formula I depositing a germanium-containing film on a Substrate wherein the film is deposited by the steps of: a) conveying (I) one or more of the organogermanium compounds described R above in a gaseous phase to a deposition chamber containing the Substrate; b) decomposing the one or more organoger Ran M -(NR'R''). A V manium compounds in the deposition chamber; and c) X Hb depositing the germanium-containing film on the Substrate. DETAILED DESCRIPTION OF THE 0010 wherein M is Sior Ge; R and Rare independently INVENTION chosen from H, alkyl, alkenyl, alkynyl and aryl; each R is independently chosen from (C-C)alkyl, alkenyl, alkynyl 0016. As used throughout this specification, the follow and aryl, provided that R is not cyclopentadienyl; each R' ing abbreviations shall have the following meanings, unless is independently chosen from (C-C)alkyl, X is halogen; the context clearly indicates otherwise: C=degrees centi a=0-3, b=0-3; c=0-3; d=0-3; e=0-4; and a+b+c+d+e=4; grade; NMR=nuclear magnetic resonance; mol=moles, wherein RzR"; wherein the sums of a+b and a+d are each b.p. =boiling point, g=gram; L=liter, M=molar; ca.=approxi s3; provided that when M=Si the sum of b+c is s3; the inlet mately; um=micron=micrometer; cm=centimeter, ppm= opening being in fluid communication with the chamber and parts per million; and mL=milliliter. the chamber being in fluid communication with the outlet opening. 0017 “Halogen” refers to fluorine, chlorine, bromine and iodine and "halo” refers to fluoro, chloro, bromo and iodo. 0.011) Another embodiment of the present invention is an Likewise, "halogenated” refers to fluorinated, chlorinated, apparatus for vapor deposition of metal films including one brominated and iodinated. “Alkyl” includes linear, branched or more devices for feeding a fluid Stream including one or and cyclic alkyl. Likewise, “alkenyl' and “alkynyl' include more organometallic compounds described above. linear, branched and cyclic alkenyl and alkynyl, respec 0012. The present invention further provides an organ tively. The term “SiGe” refers to silicon-germanium. The ogermanium compound of formula IIA or IIB: articles “a” and “an” refer to the singular and the plural. As used herein, “CVD' is intended to include all forms of chemical vapor deposition such as MOCVD, MOVPE, (IIA) OMVPE, OMCVD and RPCVD. R’ NRR2) 0018. Unless otherwise noted, all amounts are percent by Ge. weight and all ratioS are molar ratioS.
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