WO2004010467A2 - Low temperature dielectric deposition using aminosilane and ozone - Google Patents
Low temperature dielectric deposition using aminosilane and ozone Download PDFInfo
- Publication number
- WO2004010467A2 WO2004010467A2 PCT/US2003/022168 US0322168W WO2004010467A2 WO 2004010467 A2 WO2004010467 A2 WO 2004010467A2 US 0322168 W US0322168 W US 0322168W WO 2004010467 A2 WO2004010467 A2 WO 2004010467A2
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- WO
- WIPO (PCT)
- Prior art keywords
- chamber
- silicon
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- reactant
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
- H01L21/0214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/308—Oxynitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
Definitions
- the present invention relates generally to the field of semiconductors. More specifically, the present invention relates to chemical vapor deposition on semiconductor devices and wafers.
- low pressure thermal chemical vapor deposition produces premetal dielectric films with good step coverage characteristics and acceptable gapfill aspect ratio.
- Some precursors such as bis(tertiary- butylamino)silane (BTBAS) and Et SiH 2 , produce SiO 2 when reacted with O 2 at a temperature of about 400°C by chemical vapor deposition (CVD).
- Integrated circuits of future generation require lower temperature processes for premetal dielectric (PMD) and spacer applications.
- One alternative to lowering the process temperature is to use a high-density plasma (HDP) chemical vapor deposition (HDPCVD) process.
- HDP high-density plasma
- HDPCVD high-density plasma
- HDPCVD phosphorous-doped glass
- NSG non-doped silicate glass
- HDP chemical vapor deposition has drawbacks that limit its usefulness.
- the HDPCVD process limits gapfill capability to approximately 3:1 aspect ratio, while a higher temperature thermal CVD process achieves a more desirable gapfill of 6:1 or higher aspect ratios.
- the industry is in need of a method of performing chemical vapor deposition on premetal dielectrics at lower temperatures while simultaneously maintaining good step coverage.
- the present invention provides a method of depositing SiO 2 and other oxides onto a silicon substrate at a low temperature of about 400°C and below while maintaining good step coverage and gapfill capability.
- This method of the present invention can be utilized for both doped and undoped SiO 2 deposition .
- Typical applications of this process in IC fabrication are, but not limited to, premetal dielectrics (PMD), shallow trench isolation (STI), trench liner, and spacer dielectrics.
- the deposition process of the present invention carf also be performed with silicon oxynitride using a mixture of O 3 and NH 3 as the reactant gases. Additional aspects of the invention include using substrates other than silicon such as SiC, SOI, flat panels, tungsten or aluminum.
- a method of depositing a dielectric layer on the surface of a substrate in a process chamber comprising exposing the substrate to reactive gases comprised of an oxidant gas and a silicon precursor and where the oxidant gas includes ozone, and the silicon precursor includes at least one of silicon alkylamide and aminosilane.
- the method is carried out at a temperature in the range of approximately 20°C to 400°C.
- a method of depositing a silicon oxynitride layer on a substrate in a chamber comprising exposing the substrate to reactant gases comprised of an oxidant gas, ammoma and a silicon precursor where the oxidant includes ozone and the silicon precursor includes at least one of silicon alkylamide and aminosilane and the method is carried out at a temperature in the range of approximately 20°C to 400°C.
- FIG. 1 illustrates a CVD apparatus suitable for performing process of the present invention.
- the present invention provides a novel low thermal budget method that deposits dielectric layers or films on semiconductor substrates at temperatures equal to and below approximately 400°C by chemical vapor deposition (CVD).
- CVD chemical vapor deposition
- the CVD reaction is summarized by the following equation:
- the Si-N bond in aminosilane and silicon alkylamide compounds (referred to as silicon precursors) is labile and reacts with an oxidant gas at a lower temperature than will other Si-containing precursors.
- the preferred silicon precursors from these classes of compounds have smaller R groups, such as methylethylamide.
- the reaction is carried out in a reactor or chamber in which a substrate is present.
- the SiO 2 CVD process temperature can be reduced to below 400°C while maintaining a good step coverage characteristic and gapfill capability of a low pressure thermal CVD process.
- Ozone gas provides atomic oxygen at lower temperature than can be achieved with other oxidizers such as water or O 2 .
- Oxidation of the silicon precursor in this reaction gives good results at temperatures of about 200°C or lower, with a temperature range of 20°C to 300°C being the preferred range.
- Process gas flow rates are in the range of about 1 seem to 1000 seem for the precursor gas flow, preferably in the range of about 10 to 500 seem.
- Oxidizer gas flow rates are in the range of about 10 to 2000 seem, preferably in the range of about 100-2000 seem.
- Diluent gas flow may also be used in some cases to improve uniformity but is not required.
- Inert gases such as nitrogen, helium, neon, argon, xenon and combinations thereof can be used as the diluent gas. Nitrogen and argon are preferred diluent gases for cost reasons.
- Diluent gas flow rates are in the range of about 1 seem to 1000 seem. In all cases the gas flow rates depend on the size of the chamber and pumping capability, as the pressure must be within the required range, and such variables can be determined by those of ordinary skill in the art with routine experimentation.
- the formation of silicon oxynitride is provided.
- a substrate placed in a chamber is exposed to the following reactants and the CVDreaction is summarized by the following equation:
- silicon oxynitride SiO x N y
- SiO x N y is deposited at a low temperature using a mixture of NH 3 and O 3 gases.
- SiO x N y is an important material for optical application due to the variable refractive index between 1.45 for SiO 2 and 2.0 for silicon nitride.
- the Si-N bond in aminosilane or silicon alkylamide compounds is quite labile and reacts with the ozone at a low temperature allowing for a low temperature CVD method that occurs below 400°C.
- the gas flow rate of ammonia (NH 3 ) is in the range of about 10 seem to 2000 seem, and preferrably in the range of aboutlOO to 2000 seem.
- This novel method can be utilized for both doped and undoped SiO 2 formation.
- Applications of this method in IC fabrication include, but not limited to, premetal dialectics (PMD), shallow trench isolation (STI), trench liner, and spacer dielectrics.
- the pressure is varied to optimize the process for different applications.
- the reactions can be performed at atmospheric pressure with good results, or the reactions can be performed at a, pressure in the range of about 1 milliTorr up to about 800 Torr.
- the reaction can be performed at decreased pressure for an increased improvement in step coverage on non-planar substrates.
- a higher pressure can be used in PMD applications with less stringent step coverage requirements.
- the higher the pressure the faster the rate of reaction and resulting deposition rate.
- the substrate used in the present invention is typically silicon. However, alternate substrates such as SiC, SOI, flat panels, tungsten or aluminum may be used instead of silicon and are within the scope and spirit of the invention. The choice of substrate is dependent on the specific application.
- the present invention may be carried out in known deposition systems such as commonly used CVD, PECVD, spray pyrolysis, arc jet deposition, or ALD systems.
- FIG. 1 a simplified cross sectional view of a CVD system 10 suitable for carrying out the method of the present invention is shown.
- a silicon wafer 100 is loaded into the deposition chamber 101 and supported by a wafer support or chuck 102.
- the process may be conducted at low or near atmospheric pressure.
- the wafer 100 is heated to deposition temperature by a heater preferably located within the support 102.
- the process pressure is established by introducing a diluent gas 103 into the chamber 101 via an injector 110.
- the silicon precursor 104 and the oxidizer 105 (and also NH 3 106 if SiO x N y is to be deposited) gases are introduced into the chamber using conventional gas delivery methods used in the semiconductor and thin films industries.
- the reactant gases are conveyed proximate the wafer.
- the reactant gases mix and react to form a desired layer of material on the surface of the wafer.
- the silicon precursor and oxidizer/NH 3 gas flows are turned off, and preferably diluent inert gas flow is conveyed to the chamber to purge the chamber of remaining reactants through exhaust 112. After an appropriate purge time, the process is complete and the wafer is removed from of the process chamber.
- the reactions and methods described herein are also beneficial for depositing dielectric films by other deposition techniques, including Plasma Enhanced CVD (PECVD), spray pyrolysis, arc jet or cathodic arc spray deposition, and spin-on glass (wet chemical) deposition.
- PECVD Plasma Enhanced CVD
- spray pyrolysis arc jet or cathodic arc spray deposition
- spin-on glass wet chemical deposition
- This invention can also be applied to atomic layer deposition (ALD), where the reactants may be conveyed independently.
- ALD atomic layer deposition
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Formation Of Insulating Films (AREA)
- Chemical Vapour Deposition (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
Claims
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004523447A JP2005534179A (en) | 2002-07-19 | 2003-07-15 | Low temperature dielectric deposition using aminosilane and ozone. |
| AU2003256559A AU2003256559A1 (en) | 2002-07-19 | 2003-07-15 | Low temperature dielectric deposition using aminosilane and ozone |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39674602P | 2002-07-19 | 2002-07-19 | |
| US60/396,746 | 2002-07-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2004010467A2 true WO2004010467A2 (en) | 2004-01-29 |
| WO2004010467A3 WO2004010467A3 (en) | 2004-06-03 |
Family
ID=30770945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2003/022168 Ceased WO2004010467A2 (en) | 2002-07-19 | 2003-07-15 | Low temperature dielectric deposition using aminosilane and ozone |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2005534179A (en) |
| CN (1) | CN1643674A (en) |
| AU (1) | AU2003256559A1 (en) |
| TW (1) | TW200403726A (en) |
| WO (1) | WO2004010467A2 (en) |
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| EP1601011A1 (en) * | 2004-05-25 | 2005-11-30 | Applied Materials, Inc. | A method for forming a sidewall spacer for a metal oxide semi-conductor device |
| KR100888186B1 (en) * | 2007-08-31 | 2009-03-10 | 주식회사 테스 | Insulation Formation Method |
| US7875312B2 (en) | 2006-05-23 | 2011-01-25 | Air Products And Chemicals, Inc. | Process for producing silicon oxide films for organoaminosilane precursors |
| US7875556B2 (en) | 2005-05-16 | 2011-01-25 | Air Products And Chemicals, Inc. | Precursors for CVD silicon carbo-nitride and silicon nitride films |
| US8197915B2 (en) * | 2009-04-01 | 2012-06-12 | Asm Japan K.K. | Method of depositing silicon oxide film by plasma enhanced atomic layer deposition at low temperature |
| US8357619B2 (en) | 2008-02-01 | 2013-01-22 | Tokyo Electron Limited | Film formation method for forming silicon-containing insulating film |
| US8530361B2 (en) | 2006-05-23 | 2013-09-10 | Air Products And Chemicals, Inc. | Process for producing silicon and oxide films from organoaminosilane precursors |
| US8771807B2 (en) | 2011-05-24 | 2014-07-08 | Air Products And Chemicals, Inc. | Organoaminosilane precursors and methods for making and using same |
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| US6235650B1 (en) * | 1997-12-29 | 2001-05-22 | Vanguard International Semiconductor Corporation | Method for improved semiconductor device reliability |
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- 2003-07-15 CN CN 03805832 patent/CN1643674A/en active Pending
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- 2003-07-17 TW TW92119580A patent/TW200403726A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| AU2003256559A8 (en) | 2004-02-09 |
| WO2004010467A3 (en) | 2004-06-03 |
| JP2005534179A (en) | 2005-11-10 |
| CN1643674A (en) | 2005-07-20 |
| AU2003256559A1 (en) | 2004-02-09 |
| TW200403726A (en) | 2004-03-01 |
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