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(12) United States Patent (10) Patent No.: US 6,583,048 B2 Vincent Et Al

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(12) United States Patent (10) Patent No.: US 6,583,048 B2 Vincent Et Al USOO6583048B2 (12) United States Patent (10) Patent No.: US 6,583,048 B2 Vincent et al. (45) Date of Patent: Jun. 24, 2003 (54) ORGANOSILICON PRECURSORS FOR 6,147,009 A 11/2000 Grill et al. .................. 438/780 INTERLAYER DELECTRIC FILMS WITH E. f 1328 R s al - - - - - - - - - - - - - - C. 2 - as alla C al. LOW DELECTRIC CONSTANTS 6,225,238 B1 * 5/2001 Wu ............................ 438/778 (75) Inventors: Jean Louise Vincent, Bethlehem; 64414916440.876 B1 - 8/2002: W.E". tal. ................ S2.438/778 Mark Leonard O'Neill, Allentown; 2 - - -a- Howard Paul Withers, Jr., FOREIGN PATENT DOCUMENTS Breinigsville; Scott Edward Beck, EP O469926 5/1992 .............. CO8J/7/06 Kutztown; Raymond Nicholas Vrtis, EP O935.283 8/1999 ... C23C/16/40 Allentown, all of PA (US) EP 1123991 8/2001 ... C23C/16/40 JP 1088352 4/1998 ... C23C/16/30 (73) Assignee: Air Products and Chemicals, Inc., WO 35 3.1: 'g5:6-8 Allentown, PA (US) WO 99.41423 s/1999 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 M.J. Loboda, et al., “D iti f Low-K Dielectric Fil U.S.C. 154(b)(b) by O.0 daysdavs. Using.J. Loboda, Trimethylsilane,” et al., LjepoSluon in Electrochemical OILow-K LJ1electric Soc. Proc., Films V. 98–6, pp. 145 to 152. (21) Appl. No.: 09/944,042 “Low-k Dielectrics: Will Spin-On or CVD Prevail?”, in 22) Filled: Aug. 31, 2001 Semiconductor International, Jun. 2000, pp. 1 to 10. (22) File lug. 3, Gill Yong Lee, et al., “Recent Progress in PECVD Low-k (65) Prior Publication Data Dielectrics for Advanced Metallization Schemes”, 198" Meeting of the Electrochemical Society, Oct. 2000, Section US 2002/0142579 A1 Oct. 3, 2002 H-1, Abstract No. 531. O O Patent Application Publication US 2002/0072220A1, Wang, Related U.S. Application Data et al., “Low-K Dielectric CVD Precursors and Uses (63) Continuation-in-part of application No. 09/761,269, filed on Thereof, Pub. Date: Jun. 13, 2002, filed: Oct. 5, 2001. Jan. 17, 2001, now abandoned. * cited by examiner (51) Int. Cl............................................. H01L 21f4763 Primary Examiner David Nelms (52) U.S. Cl. ....................................................... 438/623 ASSistant Examiner Thao P Le (58) Field of Search ................................. 438/623, 743, (74) Attorney, Agent, or Firm Mary E. Bongiorno 438/763, 770, 773, 622 (57) ABSTRACT (56) References Cited A method of forming a low dielectric constant interlayer U.S. PATENT DOCUMENTS dielectric film O a substrate by reacting, under chemical Vapor deposition conditions Sufficient to deposit the film on 4,988,573 A 1/1991 Nakayama et al. ......... 428/421 the Substrate, an organosilicon precursor comprising a silyl 5.948,928 A 9/1999 Siegele et al. ....... ... 556/442 ether, a silyl ether oligomer, or an organosilicon compound 5,989.998. A 11/1999 Sugahara et al. ........... 438/623 containing one or more reactive groups, to form an interlayer s: A 3.2: ki R al. ......... 4is,g dielectric film having a dielectric constant of 3.5 or less. The 6,054,3792Y- - -2 A 4/2000 YauOSle et al. .. ... 438/623 films formed by the above method. 6,072.227 A 6/2000 Yau et al. ................... 257/642 6,086,952 A 7/2000 Lang et al. ............ 427/255.29 56 Claims, 1 Drawing Sheet g i 3 Inventive exampie i3 Inventive example #2 2500 2009 Waverumbers (cm-1} U.S. Patent Jun. 24, 2003 US 6,583,048 B2 ******************************************************************IOOOZOOGZ OOG000||OOG AeNAsuequunua-ujo) -61-I| S 3 g : S 3 3 & & d o o Cd C C o d o eoueqJOSCW US 6,583,048 B2 1 2 ORGANOSILICON PRECURSORS FOR e=0.1-25%) will be referred to as F-OSG. The ratio and INTERLAYER DELECTRIC FILMS WITH Structural arrangement of carbon, Silicon, oxygen, fluorine, LOW DELECTRIC CONSTANTS and hydrogen atoms in the final ILD is dependent on the precursors chosen, the oxidant, and the CVD process CROSS REFERENCE TO RELATED conditions, Such as RF power, gas flow, residence time, and APPLICATIONS temperature. This is a continuation in part of application Ser. No. Doping the Silica with carbon atoms or organic groups 09/761,269 filed on Jan. 17, 2001 abandoned. lowers the k of the resulting dielectric film for several reasons. Organic groups, Such as methyl, are hydrophobic, BACKGROUND OF THE INVENTION thus, adding methyl or other organic groups to the compo The electronics industry utilizes dielectric materials as sition can act to protect the resulting CVD deposited film insulating layers between circuits and components of inte from contamination with moisture. The incorporation of grated circuits (IC) and associated electronic devices. Line organic groupS. Such as methyl or phenyl can also Serve to dimensions are being reduced in order to increase the Speed “open up' the Structure of the Silica, possibly leading to and storage capability of microelectronic devices (e.g. com 15 lower density through space-filling with bulky CH bonds. puter chips). Microchip dimensions have undergone a sig Organic groups are also useful because Some functionalities nificant decrease in the past decade Such that line widths can be incorporated into the OSG, and then later “burned previously about 1 micron are being decreased to 0.18 out' or oxidized to produce a more porous material which micron with forecasts for as low as 0.10-0.05 in the next will inherently have a lower k. The incorporation of voids or 5-10 years. AS the line dimensions decrease, the require pores in a low dielectric constant material will result in ments for preventing signal crossover (crosstalk) between reductions in the dielectric constant proportional to the chip components become much more rigorous. These amount of porosity. While this is beneficial, the amount of requirements can be Summarized by the expression RC, porosity incorporated into the film must be balanced with the where R is the resistance of the conductive line and C is the deleterious effects that the introduction of pores will have on capacitance of the insulating dielectric interlayer. C is 25 the mechanical properties of the film. Thus the optimum inversely proportional to Spacing and proportional to the amount of porosity will be material dependant. dielectric constant (k) of the interlayer dielectric (ILD). Doping the ILD with fluorine provides low polarizability, Thus, shrinking the Spacing requires a lower k to maintain thus leading to lower k. Fluorine-containing organic groups an acceptable RC. Such as CF are very hydrophobic, so their presence will also Historically, silica (SiO) with a dielectric constant of Serve to protect the Silica from contamination with moisture. 4.2–4.5 has been employed as the ILD. However, at line While fluorinated silica materials have the requisite ther dimensions less than 0.18 microns, Silica is no longer mal and mechanical Stability to withstand very high tem acceptable and an ILD with a k of 2.4-3.3 and below is peratures (up to 500 C), the materials' properties (e.g., low needed. 35 water Sorption, mechanical properties) are Susceptible to Two general approaches to making a low k ILD are being compromised when large amounts of fluorine are spin-on and chemical vapor deposition (CVD). Although incorporated into the material. Fluorinated organic both methods are capable of generating a low k ILD, CVD materials, Such as poly(tetrafluoroethylene) despite having processes have the advantage of being able to utilize existing very low k values down to 2.0 or less, have not shown Sufficient Stability to the temperatures experienced during toolsets. Another advantage to CVD is simpler integration 40 due to the silica-like structure of CVD-produced films Subsequent processing Steps involved in the manufacture of compared to organic polymer films produced by Some an integrated circuit. Organic polymers in general do not spin-on processes. CVD is also thought to have better possess Sufficient mechanical Strength for processing under conformality and gap filling capability than the spin-on current conditions. Also, fluorocarbon polymers can have method. 45 other drawbackS Such as poor adhesion, potential reaction The current method of choice for dissociating or activat with metals at high temperature, and poor rigidity at high ing the reactive gases in a CVD chamber is by using a RF temperature in Some cases. coupled plasma in a reaction Zone above the Substrate, Such One way to incorporate carbon into an ILD is by using an as that described in WO9941423. In plasma enhanced organosilane Such as methylsilanes (CH),SiH as a Silicon Source in the PECVD reaction. WO9941423 and U.S. Pat. chemical vapor deposition (PECVD) the temperature 50 required for the dissociation and deposition is typically No. 6,054,379 describe the reaction of a silicon compound between 100 and 400 C., which is generally lower than containing methyl groups and Si-H bonds with nitrous temperatures required for thermal CVD. oxide (N2O) oxidant to give an SiOC film with a carbon content of 1-50% by atomic weight and a low dielectric Conventional silica (SiO) CVD dielectric films produced COnStant. from SiH4 or TEOS (Si(OCH2CH), tetraethylorthosilicate) 55 and O. have a dielectric constant k greater than 4.0. There U.S. Pat. No. 6,159,871 disclose methylsilanes (CH), are Several ways in which industry has attempted to produce SiH (X is 1-4) as Suitable CVD organosilane precursors to silica-based CVD films with lower dielectric constants, the OSG low k films. Materials with 10–33% carbon content, by most Successful being the doping of the insulating film with weight, and k leSS than 3.6 are reported. carbon atoms, fluorine atoms, or organic groups containing 60 An article by M.
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