|Publication number||USRE42887 E1|
|Application number||US 12/548,363|
|Publication date||Nov 1, 2011|
|Priority date||Nov 18, 2003|
|Also published as||CA2546081A1, CN1906735A, EP1690287A2, US7261919, US8153280, US20050106320, US20110001143, WO2005049884A2, WO2005049884A3|
|Publication number||12548363, 548363, US RE42887 E1, US RE42887E1, US-E1-RE42887, USRE42887 E1, USRE42887E1|
|Inventors||Mehran Mehregany, Christian A. Zorman, Xiao-An Fu, Jeremy Dunning|
|Original Assignee||Case Western Reserve University|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (18), Non-Patent Citations (13), Classifications (17), Legal Events (2)|
|External Links: USPTO, USPTO Assignment, Espacenet|
A part of this invention was made with government support under Contracts No. NCA3-201 awarded by NASA and DABT 63-1-0010 awarded by DARPA. The government has certain rights in this invention.
The present invention relates to silicon carbide and other films, and, more particularly, to controlled deposition of these films on a substrate.
Semiconductor, micro- and nanoelectromechanical systems (MEMS/NEMS) apply integrated circuit fabrication technology to fabricate optical, mechanical, electrochemical, and biosensor devices. One of the important steps in creating MEMS and NEMS devices is the deposition of thin films of material onto substrates. Once the films are deposited, various etching techniques may be employed to shape the deposited film.
In typical MEMS/NEMS devices, silicon is a primary material. Silicon carbide is a material that has very good physical and chemical characteristics, and is noted for these properties at temperatures above about 300° C. Silicon carbide is an advantageous material for use in films for MEMS and NEMS, particularly because of its exceptional electrical, mechanical, and chemical properties compared to silicon in normal and harsh operating environments.
One of the barriers limiting development of silicon carbide in MEMS production has been the inability to deposit uniform films of silicon carbide on large area substrates having properties that are advantageous to and required for MEMS and NEMS. Deposition of silicon carbide is conventionally subject to variations in residual stress, residual stress gradient, and electrical resistivity. These properties are important to the proper operation of MEMS and NEMS devices.
With silicon, residual stress, residual stress gradient and electrical resistivity can be controlled after the film is deposited by annealing the film at elevated temperatures. Annealing in silicon induces crystallographic changes that result in the modification of these properties. With single crystalline and polycrystalline silicon carbide, such an approach is not feasible because silicon carbide is chemically and crystallographically stable at conventional annealing temperatures. For silicon carbide films deposited on silicon substrates, annealing is completely ineffective because the non-silicon carbide substrate limits the annealing temperatures to temperatures too low for effective annealing. The present invention bypasses the need for annealing altogether by implementing control of the residual stress, residual stress gradient, and electrical resistivity in the silicon carbide films during the film formation (deposition) process.
The present invention provides methods of depositing films on a substrate that enables control of the residual stress, residual stress gradient, and electrical resistivity of the deposited film. The invention includes films of various compositions, such as ceramic films with the ceramic compound having a metallic and non-metallic component. Preferably, the film is a silicon carbide film. The silicon carbide film is deposited by chemical vapor deposition onto a substrate, such as a silicon substrate, by placing the substrate in a reaction chamber and evacuating the chamber to a pressure below about 10 mtorr. The temperature of the chamber is maintained at about 900° C. A carbon precursor, such as acetylene (5% in hydrogen) is supplied to the chamber at a flow rate of about 180 standard cubic centimeters per minute (sccm). A silicon precursor, such as dichlorosilane (DCS), is supplied to the chamber at a flow rate of about 54 sccm. As the precursors are supplied, the pressure of the reaction chamber increases and may be maintained at a fixed pressure.
Under these conditions, tensile films with appreciable stress gradients are deposited at pressures less than 2.65 torr and compressive films with appreciable stress gradients are deposited at pressures greater than 2.65 torr. At 2.65 torr, the film has a very low residual tensile stress (<20 MPa), a negligible stress gradient, and a resistivity that is less than 10 Ω·cm without intentional doping. So control of the pressure with other parameters fixed resulted in control of the residual tensile stress, stress gradient, and electrical resistivity.
In another embodiment, the chamber is maintained at a pressure of about 2.0 torr. A carbon precursor, such as acetylene (5% in hydrogen), is supplied to the chamber at a flow rate of about 180 standard cubic centimeters per minute (sccm). A silicon precursor, such as DCS, is supplied to the chamber at a flow rates between 18 and 72 sccm. Under these conditions, tensile films with appreciable stress gradients are deposited at DCS flow rates below 35 sccm and compressive films with appreciable stress gradients are deposited at DCS flow rates above 35 sccm. At a DCS flow rate of 35 sccm, the film has a very low residual tensile stress (<20 MPa), a negligible stress gradient and a resistivity that is less than 10 Ω·cm without intentional doping. So control of the flow rate of the metal element precursor, in this case the silicon precursor DCS, with other parameters fixed resulted in control of the residual tensile stress, stress gradient, and electrical resistivity.
The present invention also relates to substrates having a silicon carbide film deposited thereon in which the residual stress is 0±100 MPa and the achieved electrical resistivity is less than about 10 Ω·cm, and to semiconductor, MEMS, and NEMS devices having such substrates.
The present invention relates to the deposition of film, preferably a silicon carbide (SiC) film, onto a substrate with control of various properties, such as residual stress, residual stress gradient, and electrical resistivity. The invention will be described as it relates to deposition of SiC onto a silicon substrate, particularly for use with MEMS and NEMS devices. The invention, however, is only exemplified by such description and is limited only by the claims included herein.
Silicon carbide film, particularly polycrystalline SiC film, is desirable for use in MEMS and NEMS devices, as described above. Control of key properties, such as residual tensile stress, residual tensile stress gradient, and electrical resistivity, provides SiC films that may be effectively used in MEMS and NEMS devices. Silicon carbide films having low residual stress, less than about 100 MPa, and preferably less than about 50 MPa, are highly desirable for MEMS and NEMS applications. Conventional deposition techniques have heretofore been unable to achieve such low stress values in polycrystalline silicon carbide films.
In these and other applications, control of stress properties, such as residual stress and residual stress gradient, and electrical resistivity properties also may be desired to achieve other preselected values that may not be low stress values.
These films are particularly suitable for use in devices operating in harsh environments because of the outstanding mechanical, electrical, and chemical properties of SiC. Examples of such applications include pressure sensors for internal combustion and jet engines, wind tunnel sensors and instrumentation, and instrumentation and control systems of nuclear power systems. In addition, silicon carbide can be used in device structures commonly made from silicon, such as acceleration sensors, biomedical sensors and actuators and other applications not typically characterized by harsh environments. Silicon carbide can be used as an alternative material to silicon, capitalizing on the superior mechanical and chemical properties, as well as comparable electrical properties between SiC and silicon.
Applicants have successfully produced thin polycrystalline SiC films with controlled properties on silicon and silicon dioxide substrates in which the residual tensile stress is at or near zero, the electrical resistivity is very low, and the residual tensile stress gradient is near zero. These films were produced by a low pressure chemical vapor deposition process, using dicholorosilane (SiH2Cl2) as the precursor for silicon (Si) and a mixture of 5% acetylene (C2H2) in hydrogen (H2) as the precursor for carbon. Applicants have determined that control of the silicon precursor flow rate and/or the pressure at which the deposition occurs allows for production of SiC film having the properties described above. Successful production of cantilevers, bridges, membranes, and lateral resonant structures has been completed, demonstrating the viability of the material fabricated in accordance with the present invention in micromachining applications.
It is believed that control of the flow rate of silicon precursor and/or the deposition pressure of the reaction chamber while other parameters are fixed will enable control of the residual stress, the residual stress gradient, and the electrical resistivity of silicon carbide film deposited by vapor deposition for any silicon precursor and carbon precursor. One of ordinary skill in art may determine the appropriate pressure and silicon precursor flow rate to achieve minimum residual stress, residual stress gradient, and electrical resistivity without undue experimentation, and use of alternate silicon and carbon precursors does not depart from the spirit and scope of the invention.
Examples of possible alternate silicon precursors include silane, trichlorosilane, and tetrachlorosilane, among others. Possible alternate carbon precursors include carbon-containing gases, methane, propane, ethylene, xylene, butane, carbon tetrabromide, and other hydrocarbons.
Possible alternate silicon and/or carbon precursors may include single-source precursors for both silicon and carbon. Examples of possible single-source precursors for both silane and carbon include halosilane, trimethylsilane, tetramethylsilane, dimethyldimethoxysilane, tetramethylcyclotetrasiloxane, bis-trimethylsilylmethane, methyltrichlorosilane, tetraethylsilane, silacyclobutane, disilabutane, and any other material suitable for use as a single source precursor, as can be determined by one of ordinary skill in the art.
If a single-source precursor is used, then either a separate carbon precursor or silicon precursor may be provided to the chamber in order to correctly control the ratio of carbon to silicon in the reactor. In this, event, the flow rate of the single source of the silicon or the single source of the carbon may be varied to achieve the proper ratio of carbon gas to silicon gas within the chamber so that the appropriate reaction occurs at the appropriate rate to deposit the silicon carbide film with the properties described above.
Other silicon-based films, such as silicon nitride (Si3N4), silicon dioxide (SiO2), silicon oxynitride (SiOxNy) and silicon carbon nitride (SiCxNy) may also be deposited with the method of the present invention using the appropriate precursors. In the case of silicon nitride, appropriate precursors may include silane (SiH4) or DCS for a silicon precursor, and ammonia (NH3) for a nitrogen precursor. The silicon precursor flow rate or the deposition pressure may be varied to achieve a deposited film having the properties described above. The optimal range of deposition pressure and silicon precursor flow rate may be determined without undue experimentation in accordance with this invention.
Other ceramic films based on a non-silicon ceramic may also be deposited with the method of the present invention to achieve the properties described above. Use of the term “ceramic” herein is defined as inorganic, nonmetallic materials, typically crystalline in nature (but could be amorphous), and generally are compounds formed between metallic and nonmetallic elements, such as aluminum and oxygen (alumina—Al2O3), calcium and oxygen (calcia—CaO), silicon and oxygen (silica—SiO2), and other analogous oxides, nitrides, borides, sulfides, and carbides. The flow rate of the nonmetallic precursor is held fixed and the deposition pressure or the flow rate of the metallic precursor would be varied to achieve the properties described above. The optimal range of deposition pressure and metallic precursor flow rate may be determined without undue experimentation using the procedures provided herein.
Other compound semiconducting films based on materials other than silicon may also be deposited with the method of the present invention to achieve the properties described above. These materials include, but are not limited to, GaN, GaAs, InP, and other analogous semiconductor materials deposited by chemical vapor deposition.
The examples described herein use silicon as the substrate material. The method described herein is not limited to use of silicon and silicon derivative substrates, such as silicon carbide and silicon dioxide, but rather can be applied to the deposition on any substrate material where the resultant film is subjected to a residual stress.
In the configuration illustrated in
In a second configuration illustrated in
The vacuum system 28, 128 consisted of a roots blower and mechanical pump combination (not shown) that can reach a base pressure of less than 1 mtorr in a fully loaded system, regardless of configuration. Pressure was controlled through pressure control system 36, 136. A butterfly valve 37, 137 was provided to assist with the pressure control. The gas flow rates and pressure control systems 36, 136 were controlled by a conventional furnace control computer system (not shown). The temperature in the reaction chamber 10, 110 was controlled via resistive heating coils 38, 138.
Each load consisted of 25 Si wafers evenly distributed in a single, 50-slot SiC boat. The first and last five wafers were designated as baffling wafers to stabilize gas flow. Wafers in slots 6, 10, 13, 16, and 20 from the loading end were designated for study.
Following each deposition, the thickness of the films was measured optically using a Nanospec 4000 AFT spectrophotometer. The film residual stresses were determined by measuring the curvature of the silicon wafers before and after film deposition, using a laser-based curvature measuring system (Frontier Semiconductor measurement, FSM 120). Silicon carbide films were deposited on both sides of the wafer, and reactive etching in a CHF3/O2 mixture was used to remove the film deposited on the backside of the wafers.
Single layer cantilever beams were fabricated from about 500 nm-thick polycrystalline SiC films made in accordance with this example to characterize the stress gradient at various deposition pressures. The stress gradient is the change in the magnitude of residual stress as a function of film thickness. Stress gradients can cause cantilever beams to bend, whereas beams made from films with little or no stress gradient remain flat. For MEMS and NEMS devices, a stress gradient near zero is desirable when the planarity of device structures is required. A residual stress gradient in the structural layers of MEMS/NEMS devices is desirable in applications where curved or strained structures are needed. In such structures, precise control of residual stress gradient is required. Control of stress gradients requires precision control of residual stresses.
The same procedure described above was used, except that the low pressure chemical vapor deposition apparatus 112 illustrated in
As above, the films were characterized for residual stress, residual stress gradient, and electrical resistivity.
While the present invention has been illustrated by the above description of embodiments, and while the embodiments have been described in some detail, it is not the intent of the applicants to restrict or in any way limit the scope of the invention to such detail. Additional advantages and modifications will readily appear to those skilled in the art, such as the use of alternate precursors or the deposition of alternate films. Therefore, the invention in its broader aspects is not limited to the specific details, representative apparatus and methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of the applicants' general or inventive concept.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US4532150 *||Dec 22, 1983||Jul 30, 1985||Shin-Etsu Chemical Co., Ltd.||Method for providing a coating layer of silicon carbide on the surface of a substrate|
|US4560589 *||Sep 19, 1983||Dec 24, 1985||Shin-Etsu Chemical Co., Ltd.||Method for providing a coating layer of silicon carbide on substrate surface|
|US4855254 *||Dec 13, 1988||Aug 8, 1989||Fujitsu Limited||Method of growing a single crystalline β-SiC layer on a silicon substrate|
|US4971851||Nov 18, 1985||Nov 20, 1990||Hewlett-Packard Company||Silicon carbide film for X-ray masks and vacuum windows|
|US5162133||Dec 20, 1990||Nov 10, 1992||International Business Machines Corporation||Process for fabricating silicon carbide films with a predetermined stress|
|US5188706 *||Mar 16, 1990||Feb 23, 1993||Kabushiki Kaisha Toshiba||Method of manufacturing an x-ray exposure mask and device for controlling the internal stress of thin films|
|US5254370 *||Jun 19, 1992||Oct 19, 1993||Hoya Corporation||Method for forming a silicon carbide film|
|US5296258 *||Sep 30, 1992||Mar 22, 1994||Northern Telecom Limited||Method of forming silicon carbide|
|US5390626 *||Mar 26, 1993||Feb 21, 1995||Hoya Corporation||Process for formation of silicon carbide film|
|US5415126 *||Aug 16, 1993||May 16, 1995||Dow Corning Corporation||Method of forming crystalline silicon carbide coatings at low temperatures|
|US5541023 *||May 28, 1993||Jul 30, 1996||Fujitsu Limited||X-ray mask, method of manufacturing the x-ray mask and exposure method using the x-ray mask|
|US5616426||Sep 29, 1995||Apr 1, 1997||The Carborundum Company||Ceramic substrate with silicon carbide smoothing layer|
|US5698261 *||Aug 15, 1994||Dec 16, 1997||Aktsionernoe Obschestvo Russkoe Obschestvo Prikladnoi Elektroniki||Process for producing silicon carbide layers and an article|
|US5800878||Oct 24, 1996||Sep 1, 1998||Applied Materials, Inc.||Reducing hydrogen concentration in pecvd amorphous silicon carbide films|
|US6103590 *||Dec 9, 1998||Aug 15, 2000||Texas Instruments Incorporated||SiC patterning of porous silicon|
|US6127068 *||Mar 31, 1998||Oct 3, 2000||Hoya Corporation||X-ray membrane for x-ray mask, x-ray mask blank, x-ray mask, manufacturing method thereof and method of polishing silicon carbide film|
|US6189766||Jul 10, 1998||Feb 20, 2001||Northrop Grumman Corporation||Zero stress bonding of silicon carbide to diamond|
|EP0445319A1||Mar 5, 1990||Sep 11, 1991||International Business Machines Corporation||Process for fabricating silicon carbide films with a predetermined stress|
|1||Hurtos et al., "Residual stress and texture in poly-SiC films grown by low-pressure organometallic chemical-vapor deposition", "Journal of Applied Physics", Feb. 15, 2000, pp. 1748-1758, vol. 87, No. 4, Publisher: American Institute of Physics, Published in: US.|
|2||Hwang, J-D et al, "Epitaxial Growth and Electrical Characteristics of Beta-SiC on Si by Low-Pressure Rapid Thermal Chemical Vapor Deposition." Japanese Journal of Applied Physics. Tokyo, JP, vol. 34, No. 3, Part 1, Mar. 1995, pp. 1447-1450. XP-000703002.|
|3||Kobayashi et al., "SiC Mask Membrane for Synchrotron Radiation Lithography", "Microelectronic Engineering ", 1990, pp. 237-240, vol. 11, Publisher: Elsevier Science Publishers B.V.|
|4||Sarro et al., "Low-stress PECVD SiC thin films for IC-compatible microstructures", "Sensors and Actuators A: Physical", 1998, pp. 175-180, Publisher: Elsevier Science S.A.|
|5||Sarro, P.M. et al,.; "Low-Stress PECVD SiC thin films for IC-compatible microstructures." Sensors and Actuators A, Elsevier Sequoia S.A., Lausane, CH, vol. 67, No. 1-3, May 15, 1998, pp. 175-180.|
|6||Search Report for PCT/US2004/037064, published Sep. 12, 2005.|
|7||Sekimoto et al., "Silicon nitride single-layer x-ray mask", "Journal of Vacuum Science Technology", Nov./ Dec. 1982, pp. 1017-1021, vol. 21, No. 4, Publisher: American Vacuum Society, Published in: US.|
|8||Temple-Boyer et al., "Residual stress in low pressure chemical vapor deposition SiNx films deposited from silane and ammonia", "Journal of Vacuum Science Technology", Jul./Aug. 1998, pp. 2003-2007, vol. 16, No. 4, Publisher: American Vacuum Society, Published in: US.|
|9||Toal et al., "Structural analysis of nanocrystalline SiC thin films grown on silicon by ECR plasma CVD", "Thin Solid Films 343-344", 1999, pp. 292-294, Publisher: Elsevier Science S.A.|
|10||Yamaguchi et al., "Properties of heteroepitaxial 3C-SiC films grown by LPCVD", "Science Direct Sensors and Actuators A", Jun. 1996, pp. 695-699, vol. 54, No. 1-3, Publisher: Elsevier B.V.|
|11||Zorman et al., "6.2: Silicon Carbide for MEMS and NEMS-An Overview", "Sensors, 2002, Proceedings of IEEE", 2002, pp. 1109-1114, vol. 2, Publisher: IEEE, Published in: US.|
|12||Zorman et al., "Deposition of Polycrystalline 3C-SiC Films on 100 mm Diameter Si(100) Wafers in a Large-Volume LPCVD Furnace", "Electrochemical and Solid-State Letters", 2002, pp. G99-G101, vol. 5, No. 10, Publisher: The Electrochemical Society, Inc., Published in: US.|
|13||Zorman et al., "6.2: Silicon Carbide for MEMS and NEMS—An Overview", "Sensors, 2002, Proceedings of IEEE", 2002, pp. 1109-1114, vol. 2, Publisher: IEEE, Published in: US.|
|U.S. Classification||427/255.11, 427/577, 427/255.17, 427/255.23, 427/249.15, 427/255.18, 427/255.26, 427/255.393, 427/249.1|
|International Classification||C23C16/00, C23C16/52, B81B3/00, G02B26/08, H01L21/04, C23C16/32|
|May 25, 2010||AS||Assignment|
Owner name: CASE WESTERN RESERVE UNIVERSITY, OHIO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MEHREGANY, MEHRAN;ZORMAN, CHRISTIAN A.;FU, XIAO-AN;AND OTHERS;SIGNING DATES FROM 20100428 TO 20100524;REEL/FRAME:024433/0262
|Feb 26, 2015||FPAY||Fee payment|
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