CN1643674A - Low temperature dielectric deposition using aminosilane and ozone - Google Patents

Low temperature dielectric deposition using aminosilane and ozone Download PDF

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CN1643674A
CN1643674A CN 03805832 CN03805832A CN1643674A CN 1643674 A CN1643674 A CN 1643674A CN 03805832 CN03805832 CN 03805832 CN 03805832 A CN03805832 A CN 03805832A CN 1643674 A CN1643674 A CN 1643674A
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gas
chamber
silicon
substrate
reactant
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千崎佳秀
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ASML US Inc
Aviza Technology Inc
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ASML US Inc
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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
    • 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]

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Abstract

This invention describes a method of depositing dielectric layers or films with good step coverage and ability to fill high-aspect ratio device structures at low temperature (20 - 400 C) by CVD processes through the use of aminosilane or silicon alkylamide compounds as the silicon precursor with an oxidizerthat includes ozone. The present invention further provides a method of depositing silicon oxynitride (SiO<x>N<y>) films at low temperatures using aminosilane or silicon alkylamide compounds as a silicon precursor, with an oxidizer that includes ozone, and ammonia (NH<3>).

Description

Low temperature dielectric deposition using aminosilane and ozone
Cross reference to related applications
The present invention relates to and claims priority from U.S. provisional patent application 60/396,746 entitled "Low temperature direct dispensing Using amino silanes and Ozone", filed on 7/19/2002, the entire disclosure of which is incorporated herein by reference.
Technical Field
The present invention generally relates to the field of semiconductors. More particularly, the present invention relates to chemical vapor deposition on semiconductor devices and wafers.
Background
In the manufacture of semiconductor devices, low pressure thermal Chemical Vapor Deposition (CVD) produces a premetal dielectric film (premetal dielectric film) with good step coverage (step coverage) characteristics and acceptable gap fill (gapfill) aspect ratio (aspect ratio). Some precursors, such as bis (tetrabutylammonium) silane (BTBAS) and Et2SiH2, produce SiO2 when reacted with oxygen O2 by Chemical Vapor Deposition (CVD) at about 400 ℃. However, future integrated circuits require lower temperature pre-Process Metal Dielectric (PMD) and spacer application (spacer application). Alternative methods of reducing the processing temperature are: a High Density Plasma (HDP) chemical vapor deposition (HDPCVD) process is used. Depositing phosphorus doped glass (PSG) or undoped silicate glass (NSG) at a temperature in a range of 300-500 ℃ by using an HDPCVD process. However, HDP chemical vapor deposition has drawbacks that limit its usefulness. The HDPCVD process limits the gap filling capability to an aspect ratio of about 3: 1, while the higher temperature thermal CVD process achieves a more suitable 6: 1 gap filling or higher aspect ratio. Therefore, there is a need in the art for a method of performing chemical vapor deposition on pre-metal dielectrics at lower temperatures while retaining good step coverage.
Summary of The Invention
The present invention provides a method of depositing SiO on a silicon substrate at a low temperature of about 400 deg.C2And other oxides while maintaining good step coverage and gap fill capability.
The method of the invention can be used for doped and undoped SiO2And (6) depositing. The classical applications of this method in IC fabrication are, but are not limited to, pre-metal dielectrics (PMD), Shallow Trench Isolation (STI), trench liners (trench liners) and spacer dielectrics.
By using O3And NH3The deposition process of the present invention can also be carried out with silicon oxynitride (silicon oxynitride) as the reactant gas. Other aspects of the invention include substrates other than silicon, such as SiC, SOI, flat panels (plates), tungsten, or aluminum.
One aspect of the invention provides a method of depositing a dielectric layer on a surface of a substrate within a processing chamber, the method comprising: the substrate is exposed to a reactant gas comprising an oxidant gas comprising ozone and a silicon precursor comprising at least one of silicon alkylamide (silicon alkylamide) and aminosilane. The process may be carried out at a temperature in the range of about 20 to 400 ℃.
Another aspect of the invention provides a method of depositing a silicon oxynitride layer on a substrate in a process chamber, the method comprising: the substrate is exposed to a reactant gas comprising an oxidant gas, an ammonia gas, and a silicon precursor, wherein the oxidant comprises ozone and the silicon precursor comprises at least one of a silicon alkylamide and an aminosilane. The process may be carried out at a temperature of about 20 to 400 ℃.
Drawings
The invention is described in detailbelow with reference to the attached drawing figures, wherein:
FIG. 1 illustrates a CVD apparatus suitable for operating the method of the present invention.
Detailed Description
The present invention provides a novel low thermal budget method, i.e., a method of depositing dielectric layers or films on a semiconductor substrate by Chemical Vapor Deposition (CVD) at a temperature less than or equal to about 400 ℃. In one embodiment of the invention, the CVD reaction can be summarized by the following equation:
(1)
wherein the silicon precursor is Si (NR)1R2)4，R1Or R2Is H, C1-C6Alkyl, cycloalkyl, F-substituted alkyl, or Si (NR)1R2)4-xLx(X ═ 1, 2, or 3), wherein L ═ H or Cl.
In equation (1), the Si-N bond in aminosilane and alkylamidosilicon compounds (hereinafter referred to as "silicon precursors") is unstable. This bond reacts with the oxidant gas at a lower temperature than other silicon-containing precursors. Preferred silicon precursors in compounds of this type have a relatively small R group, such as a methyl ethyl amide group. The reaction is carried out in a reactor or chamber containing the substrate. In combination with ozone as a component of the oxidant gas, SiO2The CVD process temperature can be reduced to below 400 deg.C while maintaining low pressure thermal CVDGood step coverage and slot fill capability of the process. The ozone gas provides atomic oxygen at a lower temperature than gaseous oxidants such as oxygen gas or water. In this reaction, the oxidation of the silicon precursor provides good results at temperatures of about 200 ℃ or less, with a temperature range of 20 ℃ to 300 ℃ being a preferred range. For the precursor gas flow, the process gas flow rate is in the range of about 1sccm to 1000sccm, preferably in the range of about 10 to 500 sccm. The oxidant gas flow rate is in the range of about 10sccm to 2000sccm, preferably in the range of about 100 sccm to 2000 sccm.
In some cases, a diluent gas flow may also be used to improve uniformity, but is not required. Inert gases such as nitrogen, helium, neon, argon, xenon, and combinations thereof may be used as the diluent gas. In view of cost, nitrogen and argon are preferred diluent gases. The dilution gas flow rate is in the range of about 1sccm to 1000 sccm. The gas flow rate depends in all cases on the size of the chamber and the pumping capacity, since the pressure must be in the desired range, and a person skilled in the art can determine these variations with routine experimentation.
In another aspect of the invention, the formation of silicon oxynitride is provided. The substrate placed in the chamber was exposed to the following reactants and the CVD reaction was summarized using the following equation:
(2)
wherein the silicon precursor is Si (NR)1R2)4，R1Or R2Is H, C1-C6Alkyl, cycloalkyl, F-substituted alkyl or Si (NR)1R2)4-xLx(X ═ 1, 2, or 3), wherein L is H or Cl.
In equation (2), NH is used3And O3Gas mixture, low temperature deposition of silicon oxynitride (SiO)xNy). In addition to semiconductor applications, SiOxNyIs an important material for optical applications because of the SiOxNyHaving a refractive index of 1.45 (to SiO)2Say) and 2.0 (for silicon nitride). As shown by the reaction of equation (1), the Si — N bond in aminosilane or silicon alkylamide compounds is rather unstable and reacts with ozone at low temperatures, which allows low temperature CVD processes to be carried out at temperatures below 400 ℃. In this aspect of the invention, ammonia (NH)3) The gas flow rate of (a) is in the range of about 10sccm to 2000sccm, preferably in the range of about 100 to 2000 sccm. The novel method can be used to form doped or undoped SiO2. Applications of the method in IC fabrication include, but are not limited to, front metal dielectrics (PMD), Shallow Trench Isolation (STI), trench liners, and spacer dielectrics.
In another aspect of the invention, the pressure may be varied to optimize the process for different applications. Referring to equations (1) and (2), these reactions can be carried out at atmospheric pressure with good results, or they can be carried out in the range of about 1 millitorr (milliToor) to 800 Torr. For example, to obtain improved step coverage on a non-planar substrate, the reaction may be carried out under reduced pressure. Alternatively, higher pressures may be used in PMD applications where step coverage requirements are not the most stringent. Generally, the higher the pressure, the faster the reaction rate and ultimately the deposition rate.
The substrate used in the present invention is typically silicon. However, alternative substrates such as SiC, SOI, flat plate, tungsten, or aluminum may be used in place of silicon and are within the scope and spirit of the present invention. The choice of substrate depends on the particular application.
The present invention may be carried out in known deposition systems such as commonly used CVD, PECVD, spray pyrolysis (spray pyrolysis), arcjet deposition (arc jet deposition), or ALD systems 10. Referring to fig. 1, fig. 1 shows a simplified cross-sectional view of a CVD system that performs a method suitable for the present invention. A silicon wafer 100 is placed within a deposition chamber 101 and supported by a wafer support or chuck 102. The process can be carried out at sub-or near-atmospheric pressure. In the process chamber 101, the wafer 100 is heated to a deposition temperature with a heater, preferably located within the support 102. For a CVD process, the process pressure is established by introducing a dilution gas 103 into the chamber 101 through the injector 110. Next, a silicon precursor 104 and an oxidizing agent 105 (if SiO is to be deposited) are introduced using gas delivery methods common in the semiconductor and thin film industriesxNyAlso includes NH3106) A gas. Near the wafer, a reactant gas is delivered. The reactant gases mix and react to form the desired layer of material on the wafer surface. After a suitable period of time required to achieve the target film thickness, the silicon precursor and oxidizer/NH are turned off3A flow of gas and preferably a diluent inert gas is fed into the chamber to purge residual reactants to an exhaust (exhaust) 112. After a suitable purge time, the process is completed and the wafer is then removed from the process chamber.
Although the exemplary embodiment of the present invention is a CVD deposition, the reactions and methods described herein are also advantageous for depositing dielectric films using other deposition techniques, including plasma enhanced CVD (pecvd), spray pyrolysis, arc spray or cathodic arc spray deposition, and spin-on-glass (wet chemical) deposition. The invention is also useful in Atomic Layer Deposition (ALD) where the reactants can be delivered independently.
Having thus described the invention with the details and particularity required by the patentlaws, what is claimed and desired protected by letters patent is set forth in the appended claims.

Claims (17)

1. A method of depositing a dielectric layer on a substrate within a chamber, the method comprising:
exposing the substrate to a reactant gas comprising an oxidant gas and a silicon precursor,
wherein the oxidant gas comprises ozone and the silicon precursor comprises at least one of a silicon alkyl amide and an aminosilane, wherein the temperature of the chamber is between about 20 ℃ and 400 ℃ when the set of reactant gases is present in the chamber.
2. The method of claim 1, wherein a pressure within the chamber is between about 1 mtorr and 760 torr when the set of reactant gases is present within the chamber.
3. The method of claim 1, wherein the substrate is exposed to a reactant gas by flowing a set of reactant gases over the substrate within the chamber.
4. The method of claim 3, wherein the silicon precursor gas has a flow rate of between about 1sccm to 1000sccm and the ozone flow rate is between about 10sccm to 2000 sccm.
5. The method of claim 4, further comprising flowing a diluent gas in conjunction with the reactant gas.
6. The method of claim 1, wherein the reactant gas further comprises ammonia.
7. A method of depositing silicon oxynitride on a substrate within a chamber, the method comprising:
exposing the substrate to the reactant gas, the reactant gas comprising an oxidant gas, ammonia, and a silicon precursor,
wherein the oxidant gas comprises ozone and the silicon precursor comprises at least one of a silicon alkyl amide and an aminosilane, wherein the temperature of the chamber is between about 20 ℃ and 400 ℃ when the set of reactant gases is present in the chamber.
8. The method of claim 7, wherein the pressure within the chamber is between about 1 mtorr and 760 torr while the set of reactant gases is present within the chamber.
9. The method of claim 8, wherein the substrate is exposed to a reactant gas by flowing a set of reactant gases over the substrate within the chamber.
10. The method of claim 9, wherein the silicon precursor gas is flowed at a rate of between about 1 seem and about 1000 seem and the ozone is flowed at a rate of between about 10 seem and about 2000 seem.
11. The method of claim 10, further comprising flowing a diluent gas in conjunction with the reactant gas.
12. The method of claim 11, wherein the diluent gas is an inert gas.
13. The method of claim 12 wherein the inert gas is argon or nitrogen.
14. A method of depositing silicon oxide on a substrate in a chamber, the method comprising:
reacting ozone and a silicon precursor in the presence of a substrate in a chamber, wherein the chamber hasa temperature of 400 ℃, the silicon precursor comprises at least one of a silicon alkylamide and an aminosilane, and the oxidant gas comprises ozone.
15. The method of claim 14, further comprising reacting ammonia with the oxidant gas and the silicon precursor.
16. The method of claim 14, further comprising flowing a dilution gas through the chamber during the step of reacting the oxidant gas and the silicon precursor in the presence of the substrate in the chamber.
17. The method of claim 14, wherein the temperature is in the range of 20 to 400 ℃.
CN 03805832 2002-07-19 2003-07-15 Low temperature dielectric deposition using aminosilane and ozone Pending CN1643674A (en)

Applications Claiming Priority (2)

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US39674602P 2002-07-19 2002-07-19
US60/396,746 2002-07-19

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CN1643674A true CN1643674A (en) 2005-07-20

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AU (1) AU2003256559A1 (en)
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WO (1) WO2004010467A2 (en)

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