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(12) United States Patent (10) Patent No.: US 9,048,183 B2 Ganguli Et Al

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(12) United States Patent (10) Patent No.: US 9,048,183 B2 Ganguli Et Al USOO9048183B2 (12) United States Patent (10) Patent No.: US 9,048,183 B2 Ganguli et al. (45) Date of Patent: Jun. 2, 2015 (54) NMOSMETAL GATE MATERIALS, (52) U.S. Cl. MANUFACTURING METHODS, AND CPC .......... HOIL 21/28008 (2013.01); C23C I6/06 EQUIPMENT USING CVD AND ALD (2013.01); C23C 16/32 (2013.01); PROCESSES WITH METAL BASED (Continued) PRECURSORS (58) Field of Classification Search (71) Applicant: Applied Materials, Inc., Santa Clara, None CA (US) See application file for complete search history. (56) References Cited (72) Inventors: Seshadri Ganguli, Sunnyvale, CA (US); Srinivas Gandikota, Santa Clara, CA U.S. PATENT DOCUMENTS (US); Yu Lei, Belmont, CA (US); Xinliang Lu, Fremont, CA (US); Sang 5,055,280 A 10/1991 Nakatani et al. Ho Yu, Cupertino, CA (US); Hoon Kim, 6,139,922 A 10/2000 Kaloyeros et al. Santa Clara, CA (US); Paul F. Ma, Santa (Continued) Clara, CA (US); Mei Chang, Saratoga, CA (US); Maitreyee Mahajani, FOREIGN PATENT DOCUMENTS Saratoga, CA (US); Patricia M. Liu, Saratoga, CA (US) KR 2003OOO9093. A 1, 2003 s OTHER PUBLICATIONS (73) Assignee: APPLIED MATERIALS, INC., Santa International Search Report PCT/US2011/033820 dated Jan. 5, Clara, CA (US) 2012. (*) Notice: Subject to any disclaimer, the term of this (Continued) patent is extended or adjusted under 35 Primary Examiner — Yasser A Abdelaziez U.S.C. 154(b) by 0 days. (74) Attorney, Agent, or Firm — Patterson & Sheridan, LLP (21) Appl. No.: 14/147,291 (57) ABSTRACT Embodiments provide methods for depositing metal-contain (22) Filed: Jan. 3, 2014 ing materials. The methods include deposition processes that form metal, metal carbide, metal silicide, metal nitride, and (65) Prior Publication Data metal carbide derivatives by a vapor deposition process, including thermal decomposition, CVD, pulsed-CVD, or US 2014/O12O712 A1 May 1, 2014 ALD. A method for processing a substrate is provided which Related U.S. Application Data includes depositing a dielectric material forming a feature (63) Continuation of application No. 13/093,710, filed on definition in the dielectric material, depositing a work func s ws tion material conformally on the sidewalls and bottom of the Apr. 25, 2011, now Pat. No. 8,642,468. feature definition, and depositing a metal gate fill material on (60) Provisional application No. 61/327,995, filed on Apr. the work function material to fill the feature definition, 26, 2010. wherein the work function material is deposited by reacting at least one metal-halide precursor having the formula MX (51) Int. Cl. wherein Mistantalum, hafnium, titanium, and lanthanum, X HOIL 2L/3205 (2006.01) is a halide selected from the group of fluorine, chlorine, HOIL 2L/28 (2006.01) bromine, or iodine, and y is from 3 to 5. (Continued) 18 Claims, 4 Drawing Sheets -10 HEATASUBSTRATETCAN INITIAL DEPOSITONTEMPERATURE EXPOSE THE SUBSTRATETAMETALHALIDE CONTAINNS GASAT ANNTIAL FLONRATE 0URINSAWAPOREPOST)NPR3CESS I EXPOSE THE SUBSTRATETOONE ORMORE REACTIVEGASE8ATAN INITIAL FLOWRATE DURINSAWAPOREFOSITION PROCESS 08 FRMINA META-CONTAINING MATERALONTHESUBSTRATE 2 ADJUST THE DEPOSITION TEMPERATUREANDIORTHE FLOWRATECFTHE METAL HALIDE CONTAINING THE NEORMORE REACTWE DESRED SASES AETAccNTAININGSOMPOSTION No. 14 ESRE) NOlaf-E METAccrinINGTHICKNESS OF MATERA ACHEWE YES US 9,048,183 B2 Page 2 (51) Int. C. 7,098,131 B2 8/2006 Kang et al. C23C I6/06 (2006.01) 7,105,444 B2 9, 2006 Choi et al. 7,148,100 B2 12/2006 Kim et al. C23C I6/32 (2006.01) 7,148,548 B2 12/2006 Doczy et al. C23C I6/42 (2006.01) 7,244,645 B2 7/2007 Kim et al. C23C I6/455 (2006.01) 7,452,811 B2 11/2008 Choi et al. HOIL 2L/285 (2006.01) 7,514,346 B2 4/2009 Chau et al. 7,563,701 B2 7/2009 Chang et al. His (38 ) 2004/02089947,833,855 A1*B2 11/201010, 2004 KangHarkonen et al. et al. ......... 427,249.1 HOIL 29/49 (2006.01) 2004/0259303 A1 12/2004 Lee et al. (52) U.S. C. 2005/OOO9325 A1 1/2005 Chung et al. 2006/024.0665 A1 10/2006 Kang et al. CPC .......... C2C 1642 (2013.01); CC1645 2007/0001.238 A1 1/2007 Koyama et al. (2013.01); HOIL 2L/2879 (2013.01); HOIL 2009.0035946 A1 2/2009 Pierreux et al. 21/28088 (2013.01); HOIL 21/28097 (2013.01); 2009/00789 16 A1 3/2009 Shah et al. HOIL 21/28562 (2013.01); HOIL 21/76843 2009,0081868 A1 3/2009 Shah et al. (2013.01); HOIL 21/76871 (2013.01); HOIL 2009, O149012 A1 6/2009 Brasket al. 21/823814 (2013.01); HOIL 2 1/823.842 38883. A. R388 Ma al (2013.01); HOIL 29/495 (2013.01): HOIL 2010/0129.535 A1 5, 2010 Shah et al. 29/4966 (2013.01) 2011/0081774 A1 4, 2011 Yeh et al. 2011 0115023 A1 5/2011 Cheng et al. (56) References Cited U.S. PATENT DOCUMENTS OTHER PUBLICATIONS Robert S. Chau. “Integrated CMOS Tri-Gate Transistors: Paving the 6,346,741 B1 2/2002 Van Buskirk et al. Way to Future Technology Generations.” Technology(a Intel Maga 6,815,285 B2 11/2004 Choi et al. 6,876,078 B2 4/2005 Kim et al. Zine, pp. 1-7. Aug. 2006. 7,067,420 B2 6/2006 Choi et al. 7,081409 B2 7/2006 Kang et al. * cited by examiner U.S. Patent Jun. 2, 2015 Sheet 1 of 4 US 9,048,183 B2 -10 HEATA SUBSTRATE TO AN INITIAL 102 DEPOSITION TEMPERATURE EXPOSE THE SUBSTRATE TO A METALHALDE -104 CONTAINING GAS AT AN INITIAL FLOW RATE DURING AWAPORDEPOSITION PROCESS EXPOSE THE SUBSTRATE TO ONE ORMORE 106 REACTIVEGASES AT AN INITIAL FLOW RATE DURING AWAPORDEPOSITION PROCESS 108 FORMING AMETAL-CONTAINING MATERIAL ON THE SUBSTRATE ADJUST THE DEPOSITION TEMPERATURE AND/OR THE FLOW RATE OF THE METAL HALIDE CONTAINING THE ONE ORMORE REACTIVE DESIRED GASES COMPOSITION OF HE METAL-CONTAINING MATERIAL ACHIEVED 2 114 DESIRED THICKNESS OF HE METAL-CONTAINING MATERIAL ACHIEVED YES FIG. 1 U.S. Patent Jun. 2, 2015 Sheet 2 of 4 US 9,048,183 B2 FIG. 2A FIG. 2B U.S. Patent Jun. 2, 2015 Sheet 3 of 4 US 9,048,183 B2 FIG. 3A FIG. 3B U.S. Patent Jun. 2, 2015 Sheet 4 of 4 US 9,048,183 B2 Š7 s US 9,048,183 B2 1. 2 NMOS METAL GATE MATERIALS, processes more easily deposit tantalum materials on features MANUFACTURING METHODS, AND containing undercuts than does PVD processes. Formation of EQUIPMENT USING CVD AND ALD tantalum-containing films from CVD or ALD processes using PROCESSES WITH METAL BASED TaCls as a precursor may require as many as three treatment PRECURSORS 5 cycles using various radial based chemistries (e.g., atomic hydrogen or atomic nitrogen) to form tantalum materials. CROSS-REFERENCE TO RELATED Processes using TaCls may also Suffer from chlorine contami APPLICATIONS nants within the tantalum material. While metal-organic tan talum precursors may be used to form tantalum materials This application is a continuation of co-pending U.S. 10 containing no chlorine contaminants, the deposited materials patent application Ser. No. 13/093,710, filed Apr. 25, 2011, may suffer with the undesirable characteristic of a high car which claims benefit of U.S. provisional patent application bon content. Other metal materials to be deposited for metal Ser. No. 61/327,995, filed Apr. 26, 2010. Each of the afore gate electrodes have experienced similar difficulties as the mentioned patent applications is herein incorporated by ref deposition of tantalum. CCC. 15 Therefore, there is a need for a process to deposit metal containing materials on a Substrate, including as a metal gate BACKGROUND OF THE INVENTION electrode as well as a barrier layer. 1. Field of the Invention SUMMARY OF THE INVENTION Embodiments of the invention generally relate to elec- 20 tronic device processing, and more particularly, to vapor Embodiments of the invention generally provide methods deposition processes for metal-containing materials and the for depositing a metal-containing material onto a Substrate. compositions of the metal-containing materials. The metal-containing materials may include tantalum, 2. Description of the Related Art hafnium, titanium, and lanthanum-containing materials that The electronic device industry and the semiconductor 25 may further be doped with nitrogen, carbon, silicon, and/or industry continue to strive for larger production yields while aluminum. The deposition process may include thermal increasing the uniformity of layers deposited on Substrates decomposition processes, chemical vapor deposition (CVD) having increasingly larger Surface areas. These same factors processes, pulsed CVD processes, atomic layer deposition in combination with new materials also provide higher inte (ALD) processes, as well as plasma enhanced (PE) processes, gration of circuits per unit area on the Substrate. As circuit 30 Such as PE-CVD and PE-ALD. integration increases, the need for greater uniformity and In one embodiment, a method for processing a substrate process control regarding layer characteristics rises. includes depositing a dielectric material having a dielectric Several areas of fabrication that are constantly improving constant greater than 10, forming a feature definition in the include the formation of metal gate electrodes and the depo dielectric material, depositing a work function material con sition of contact barrier layers. Gate electrodes have often 35 formally on the sidewalls and bottom of the feature definition, been made with silicon based materials, but more frequently and depositing a metal gate fill material on the work function are made with metallic materials, such as tungsten or cobalt. material to fill the feature definition, wherein the work func However, the materials used for gate electrodes have had less tion material is deposited by reacting at least one metal-halide than desirable electronic properties.
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