Source: http://www.google.com/patents/US20020173113?dq=5579430
Timestamp: 2014-07-13 12:30:29
Document Index: 555422125

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60']

Patent US20020173113 - Vapor deposition; doping - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsAbstract of Disclosure Silicon alloys and doped silicon films are prepared by chemical vapor deposition and ion implantation processes using Si-containing chemical precursors as sources for Group III and Group V atoms. Preferred dopant precursors include (H3Si)3-xMRx, (H3Si)3N, and (H3Si)4N2, wherein...http://www.google.com/patents/US20020173113?utm_source=gb-gplus-sharePatent US20020173113 - Vapor deposition; dopingAdvanced Patent SearchPublication numberUS20020173113 A1Publication typeApplicationApplication numberUS 10/074,149Publication dateNov 21, 2002Filing dateFeb 11, 2002Priority dateFeb 12, 2001Also published asDE60223662D1, DE60223662T2, DE60227350D1, EP1374290A2, EP1374290B1, EP1374291A2, EP1374291B1, EP1421607A2, US6716713, US6716751, US6743738, US6821825, US6900115, US6958253, US6962859, US7186582, US7273799, US7285500, US7547615, US7585752, US7893433, US8067297, US8360001, US20020168868, US20020197831, US20030022528, US20030068851, US20030068869, US20030082300, US20050048745, US20050064684, US20050208740, US20050250302, US20070102790, US20080014725, US20080073645, US20100012030, WO2002064853A2, WO2002064853A3, WO2002065508A2, WO2002065508A3, WO2002065516A2, WO2002065516A3, WO2002065516A8, WO2002065517A2, WO2002065517A3, WO2002080244A2, WO2002080244A3, WO2002080244A9Publication number074149, 10074149, US 2002/0173113 A1, US 2002/173113 A1, US 20020173113 A1, US 20020173113A1, US 2002173113 A1, US 2002173113A1, US-A1-20020173113, US-A1-2002173113, US2002/0173113A1, US2002/173113A1, US20020173113 A1, US20020173113A1, US2002173113 A1, US2002173113A1InventorsMichael ToddOriginal AssigneeTodd Michael A.Export CitationBiBTeX, EndNote, RefManReferenced by (40), Classifications (121), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetVapor deposition; dopingUS 20020173113 A1Abstract Abstract of Disclosure Silicon alloys and doped silicon films are prepared by chemical vapor deposition and ion implantation processes using Si-containing chemical precursors as sources for Group III and Group V atoms. Preferred dopant precursors include (H3Si)3-xMRx, (H3Si)3N, and (H3Si)4N2, wherein R is H or D, x = 0, 1 or 2, and M is selected from the group consisting of B, P, As, and Sb. Preferred deposition methods produce non-hydrogenated silicon alloy and doped Si-containing films, including crystalline films.
Claims 1.A deposition process for making a non-hydrogenated Si-containing film, comprising:
Cross Reference to Related Applications [0001] This application claims priority to U.S. Provisional Application No. 60/268,337, filed February 12, 2001; U.S. Provisional Application No. 60/279,256, filed March 27, 2001; U.S. Provisional Application No. 60/311,609, filed August 9, 2001; U.S. Provisional Application No. 60/323,649, filed September 19, 2001; U.S. Provisional Application No. 60/332,696, filed November 13, 2001; U.S. Provisional Application No. 60/333,724, filed November 28, 2001; and U.S. Provisional Application No. 60/340,454, filed December 7, 2001; all of which are hereby incorporated by reference in their entireties. This application is related to, and incorporates by reference in their entireties, co-owned and co-pending U.S. Patent Application Serial Numbers: 10/074,563; 10/074,722; 10/074,633; 10/074,564; and 10/074,534, all of which were filed on February 11, 2002.
Background of Invention Field of the Invention [0002] This invention relates generally to silicon-containing films useful in the semiconductor industry, and more particularly to processes for making doped silicon and silicon alloy films using silicon-containing chemical precursors as sources for compound or doped films.
Description of the Related Art [0003] Silicon and silicon-containing materials (e.g., silicon germanium, silicon germanium carbon, silicon carbon alloys, silicon carbide, etc.) are widely used in microelectronic devices that are manufactured today. Many of these materials serve as semiconductor films in integrated circuits with electronic band gap energies that are a function of their specific elemental composition. By incorporating dopant elements, primarily derived from the Group III and Group V families of elements, these semiconductors can be transformed into p-type (electron deficient) and n-type (electron rich) semiconductors. These doped materials are the building blocks for a number of microcircuit devices e.g., transistors.
Summary of Invention [0011] The inventors have discovered that doped Si-containing films can be made using chemical precursors that comprise at least one silicon atom and at least one Group III or Group V atom. In accordance with one aspect of the invention, a deposition process is provided for making a non-hydrogenated Si-containing film, comprising:providing a vapor deposition chamber having a substrate disposed therein,introducing a dopant precursor to the chamber, wherein the dopant precursor comprises at least one silicon atom and at least one Group III and/or Group V atom, anddepositing a non-hydrogenated Si-containing film onto the substrate.
Brief Description of Drawings [0017]Figure 1 shows a schematic diagram (not to scale) of a preferred ion implantation apparatus. Detailed Description [0018] Chemical precursors comprised of at least one silicon atom and at least one Group III and/or Group V atom are preferably employed in the disclosed CVD and ion implantation processes. The term Group III refers to elements in Group III of the periodic table and thus includes B, Al, Ga, In, and Tl. The term Group V refers to elements in Group V of the periodic table and thus includes N, P, As, Sb and Bi. Preferred chemical precursors include (H3Si)3-xMRx, (H3Si)3N, and (H3Si)4N2, wherein R is H or D, x = 0, 1 or 2, and M is selected from the group consisting of B, Al, Ga, In, P, As, and Sb. The term dopant precursor is used herein to refer to the group of chemical precursors that includes electrically active dopants, e.g., an element selected from the group consisting of boron, arsenic, phosphorous and antimony. The term dopant precursor also includes chemical precursors that comprise a nitrogen atom, in the context of making nitrogen-doped films such as nitrogen-doped SiC. Such chemical precursors may be obtained commercially or prepared by methods known to those skilled in the art. [0019] Trisilylarsine ((SiH3)3As and deuterated versions thereof) and trisilylphosphine ((SiH3)3P and deuterated versions thereof) are especially preferred dopant precursors for making the alloys and doped Si-containing films described herein. Such precursors may be made by methods known to those skilled in the art, see, e.g., Examples 12 and 13 of U.S. Patent No. 4,910,153, which is hereby incorporated be reference in its entirety and particularly for the purpose of describing the preparation of chemical precursors. Nitrogen-containing chemical precursors that are free of N-H bonds are preferred dopant sources for III-V compound semiconductor materials and for making nitrogen-doped silicon carbide (SiC) films. Examples of such preferred precursors include trisilylamine and tetrasilylhydrazine. [0020] In some embodiments, a dopant precursor is preferably used in combination with an elemental source such as a silicon source, germanium source, oxygen source, and/or carbon source. Elemental sources are sources of the particular element in question. The dopant precursors disclosed herein can serve as elemental sources but, to avoid confusion, the term elemental source as used herein does not include compounds identified above as dopant precursors.
[0026] A suitable manifold may be used to supply feed gas(es) to the CVD chamber. In a preferred embodiment, the gas flow in the CVD chamber is horizontal, most preferably the chamber is a single-wafer, horizontal gas flow reactor, preferably radiatively heated. Suitable reactors of this type are commercially available, and preferred models include the Epsilon� series of single wafer reactors commercially available from ASM America, Inc. of Phoenix, Arizona. While the methods described herein can also be employed in alternative reactors, such as a showerhead arrangement, benefits in increased uniformity and deposition rates have been found particularly effective in the horizontal, single-pass laminar gas flow arrangement of the Epsilon� chambers, employing a rotating substrate, particularly with low process gas residence times (e.g., less than about 100 seconds) within the chamber during processing. [0027] For PECVD, suitable deposition conditions can be created by coupling energy to a gas mixture including a dopant precursor in order to ionize the dopant precursor and create radicals. A preferred plasma can be generated by applying high- or low-radio frequency power to the dopant precursor. The plasma may be generated remotely, e.g., outside of the CVD chamber, then the activated atoms and/or molecules can be introduced to the CVD chamber, or the activated atoms and/or molecules can be introduced to the chamber by generating the plasma within the chamber. In a preferred embodiment, an in situ plasma is created within the deposition chamber in the presence of the dopant precursor. A preferred PECVD chamber is an Eagle-10� reactor, available commercially from ASM Japan K.K., of Tokyo, Japan. Preferred power levels may range up to about 5 kW. [0028] PECVD is preferably conducted at a substrate temperature of about 0�C or greater, more preferably about 50�C or greater, even more preferably about 100�C or greater. Preferably, such deposition takes place at a temperature of about 650�C or less, more preferably about 550�C or less, most preferably about 450�C or less. As in the thermal CVD techniques discussed above, preferred deposition temperatures depend on the desired application. Typical PECVD deposition temperatures are in the range of about 0�C to about 650�C, preferably about 50�C to about 550�C, more preferably about 100�C to about 450�C. [0029] In the preferred in situ plasma embodiment, the dopant precursor is preferably introduced to the PECVD chamber in the form of a gas or as a component of a feed gas, using a suitable manifold and/or bubbler where appropriate. The total pressure in the PECVD chamber is preferably in the range of about 0.1 torr to about 10 torr, more preferably in the range of about 0.5 torr to about 8 torr, most preferably in the range of about 1 torr to about 5 torr. The partial pressure of the dopant precursor is preferably in the range of about 0.0001% to about 100% of the total pressure, more preferably about 0.001% to about 50% of the total pressure. The feed gas can include a gas or gases other than the dopant precursor, such as inert carrier gases. Helium and argon are preferred carrier gases for PECVD. [0030] Atomic layer deposition (ALD) may also be used to deposit Si-containing films using chemical precursors described herein. ALD, as used herein, refers to a process in which very thin layers are deposited sequentially on a surface. ALD generally proceeds differently from conventional CVD techniques. In conventional CVD, when two or more reactant gases are introduced to the deposition chamber, they react together on the substrate and form a deposit on the substrate surface. In ALD, the reactant gases are introduced one at a time, without substantial mixing in the gas phase. Films deposited by ALD are built up in cycles by introducing short, alternating pulses of each reactant. The pulses may optionally comprise inert gases e.g. carrier gases such as helium, hydrogen, argon and/or nitrogen. Such inert gases also preferably serve to aid removal of reactants between pulses by purging.
[0032] In a preferred embodiment, ALD is conducted by alternately introducing a dopant precursor and a second reactant, each optionally in the presence of a carrier gas. The dopant precursor is provided in the absence of the second reactant. Preferred dopant precursors include trisilylarsine, trisilylphosphine, trisilylamine, and tetrasilylhydrazine, most preferably trisilylamine. A preferred second reactant is an oxygen source, more preferably water, water vapor, or ozone. Deposition temperatures are preferably selected to be above the condensation temperatures and below the thermal decomposition temperatures of the reactants used. Preferably, temperatures are in the range of about 50�C to about 350�C, more preferably about 65�C to about 300�C. Preferably, films deposited by ALD are non-hydrogenated. ALD is preferably conducted using commercially available equipment. Particularly preferred tools for these purposes are the line of Atomic Layer CVD� equipment available commercially from ASM International N.V., Bilthoven, the Netherlands. The Pulsar 2000�reactor is particularly designed for single wafer ALD processing.
[0050] With respect to nitrogen doping, trisilylamine and tetrasilylhydrazine are advantageously free of N-H bonds that are difficult to eliminate at low deposition temperatures and the Si atoms present in the dopant precursors may also facilitate higher growth rates for low temperature SiC. Use of trisilylamine and/or tetrasilylhydrazine as nitrogen sources for CVD deposition of SiC deposited at low temperatures may provide an advantage over current doping techniques that require the use of ion implantation, molecular nitrogen or ammonia by providing alternative ways to incorporate nitrogen atoms into SiC. Examples 1-3 [0051] A tube furnace having an inlet and outlet was equipped with a pre-mix chamber and mass flow controller. Three Si <100> substrates were placed along the length of the furnace. The furnace was evacuated and heated to a temperature of about 575�C. Trisilylphosphine gas was introduced into the furnace at a flow rate of about 5-10 standard cubic centimeters per minute (sccm) and a pressure of about 0.001 torr, and continued for about 15 minutes. The trisilylphosphine flowed along the length of the furnace to the outlet, thereby depositing Si-containing films on each of the three substrates. The substrate of Example 1 was closest to the inlet and the substrate of Example 3 was closest to the outlet. [0052] All three films were polycrystalline and had a thickness in the range of about 500 �to about 1000 �. The approximate composition (�1 atomic %) of each of the deposited films was measured by Rutherford backscattering spectroscopy (RBS). Hydrogen concentration was measured using RBS elastic recoil detection (ERD) and confirmed qualitatively by Fourier-transform infrared spectroscopy (FTIR). The results are shown below in Table 1. No oxygen or hydrogen was detected in any of the films. These examples demonstrate the deposition of non-hydrogenated Si-containing films by thermal CVD using trisilylphosphine.
TABLE 1 Example No. Si P 1 68 32 2 80 20 3 89 11 [0053]
Example 4 [0054] A Si <100> wafer substrate is etched in a solution of dilute hydrofluoric acid, rinsed and dried, then loaded into an Epsilon E2500�reactor system (available commercially from ASM America, Inc. of Phoenix, Arizona) and subjected to a hydrogen bake at 900�C at atmospheric pressure under a flow of 80 standard liters per minute (slm) of ultra-pure hydrogen for 2 minutes. The substrate is then allowed to reach thermal equilibrium at 600�C at 40 Torr pressure under a flow of 20 slm of ultra-pure hydrogen gas. The steps of etching, drying, rinsing, and baking render the single crystal surface active for epitaxial film growth.
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H01L21/02529, Y02E10/546, H01L21/3185, H01L21/2257, H01L21/28194, H01L29/66181, H01L21/0262, H01L21/02532, C23C16/308, H01L29/127, H01L29/66242, C23C16/24, C23C16/345, H01L21/28525, C30B25/02, H01L29/518, H01L21/02592, H01L21/02667, H01L21/02576, H01L21/02595, C23C16/30, H01L21/02598, H01L21/02579, H01L21/0251, H01L21/02422, C30B29/06, H01L21/0245, C23C16/0272, B82Y30/00, B82Y10/00European ClassificationC23C16/30, H01L29/12W4, C23C16/56, C23C16/36, H01L21/225A4F, H01L21/318B, C23C16/24, C23C16/34C, C23C16/32B, C30B25/02, H01L29/51, C23C16/30E, C23C16/22, H01L21/3205N, H01L21/28E2C2D, H01L29/51M, C30B29/06, H01L21/28E2B2P, H01L21/02K4C1A3, H01L21/02K4C3C1, H01L21/02K4C5M2, H01L21/02K4E3C, H01L21/02K4A1K, H01L21/02K4C3C2, H01L21/02K4B1A3, H01L21/02K4B5L7, H01L21/02K4C1A2, H01L21/02K4C5M1, H01L21/02K4C5M3, H01L21/02K4A5S, B82Y30/00, B82Y10/00, H01L28/84, H01L29/66M6D6, H01L29/66M6T2H, H01L21/20B, H01L31/20B, H01L21/285B4B, H01L31/18C, C23C16/02H, H01L21/285B4H, H01L21/20C, H01L21/28E2B2, H01L31/18C5, H01L21/205B, H01L21/205Legal EventsDateCodeEventDescriptionSep 7, 2011FPAYFee paymentYear of fee payment: 8Sep 21, 2007FPAYFee paymentYear of fee payment: 4May 23, 2002ASAssignmentOwner name: ASM AMERICA, INC., ARIZONAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TODD, MICHAEL A.;REEL/FRAME:012908/0591Effective date: 20020422Owner name: ASM AMERICA, INC. 3440 E. 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