Defluorination of tungsten by high pressure treatment
阅读说明:本技术 通过高压处理的钨脱氟 (Defluorination of tungsten by high pressure treatment ) 是由 基思·塔特森·王 托马斯·琼万·权 肖恩·康 怡利·Y·叶 于 2018-05-23 设计创作,主要内容包括:与用于处理在工件上的钨膜的工艺相关的方法和系统包括:将工件支撑在腔室中;将氢气引入腔室中且建立至少5个大气压的压力;并且当腔室中的压力是至少5个大气压时,将工件上的钨膜暴露于氢气。(Methods and systems related to a process for treating a tungsten film on a workpiece include: supporting a workpiece in a chamber; introducing hydrogen gas into the chamber and establishing a pressure of at least 5 atmospheres; and exposing the tungsten film on the workpiece to hydrogen gas when the pressure in the chamber is at least 5 atmospheres.)
1. A method of treating a tungsten film on a workpiece, comprising:
supporting the workpiece in a chamber;
introducing hydrogen gas into the chamber;
establishing a pressure of at least 5 atmospheres in the chamber; and is
Exposing the tungsten film on the workpiece to the hydrogen gas when the pressure in the chamber is at least 5 atmospheres.
2. The method of claim 1, further comprising: heating the tungsten film to a temperature of about 250 ℃ to about 600 ℃.
3. The method of claim 2, wherein heating the tungsten film comprises maintaining support for the workpiece in the chamber at an elevated temperature.
4. The method of claim 3, wherein the temperature of the tungsten film is raised prior to establishing the pressure of at least 5 atmospheres in the chamber.
5. The method of claim 1, wherein establishing the pressure in the chamber comprises introducing hydrogen and an inert gas to provide a gas mixture in the chamber.
6. The method of claim 5, wherein hydrogen comprises from about 1 volume percent (vol%) to about 4 vol% of the gas mixture.
7. The method of claim 5, exposing the tungsten film to hydrogen gas when the hydrogen gas has a partial pressure of about 1 bar to about 10 bar.
8. The method of claim 5, wherein the inert gas comprises nitrogen, argon, or a combination thereof.
9. A method of forming tungsten on a workpiece, comprising:
depositing a tungsten film on the workpiece by chemical vapor deposition using a precursor gas containing tungsten and fluorine; and
exposing the tungsten film on the workpiece to hydrogen gas in a chamber when the pressure in the chamber is at least 5 atmospheres.
10. The method of claim 9, wherein the precursor gas comprises tungsten hexafluoride, and the method further comprises: heating the tungsten film to a temperature of about 250 ℃ to about 600 ℃.
11. The method of claim 9, comprising establishing pressure in the chamber by introducing hydrogen and an inert gas to provide a gas mixture in the chamber.
12. An annealing system, comprising:
a chamber body defining a chamber;
a support for holding a workpiece, wherein an outer surface of the workpiece is exposed to an environment in the chamber;
a robot for inserting the workpiece into the chamber;
a first gas source for providing hydrogen;
a pressure source coupled to the chamber to raise the pressure in the chamber to at least 5 atmospheres; and
a controller coupled to the robot, the first gas source, and the pressure source, the controller configured to cause the robot to transport a workpiece having a tungsten film thereon into the chamber, to cause the gas source to supply the hydrogen gas to the chamber, and to cause the pressure source to increase the pressure in the chamber to at least 5 atmospheres while the workpiece is held on the support in the chamber.
13. The annealing system of claim 12, wherein the heater comprises a resistive heater embedded in the support.
14. The annealing system of claim 12, wherein the heater comprises a radiant heater located in a wall of the chamber body and positioned to irradiate the workpiece on the support.
15. The annealing system of claim 12, comprising a second gas source to supply an inert gas to the chamber, and wherein the controller is coupled to the second gas source and configured to cause the first gas source to introduce hydrogen and the second gas source to introduce an inert gas to provide a gas mixture in the chamber.
Technical Field
The present invention relates to high pressure processing of tungsten films on workpieces such as semiconductor wafers.
Background
Microelectronic circuits and other microscale devices are typically fabricated by sequentially depositing and patterning multiple layers on a substrate or wafer, such as a wafer of silicon or other semiconductor material. For some applications, a metal film (e.g., tungsten) is deposited on a substrate to form microelectronic or other micro-scale features or to provide electrical interconnections.
For some layers, to achieve the desired material properties, the substrate is typically subjected to an annealing process in which the substrate is often rapidly heated to about 200 ℃ to 500 ℃, and more typically to about 300 ℃ to 400 ℃. The substrate may be held at the temperature for a relatively short time, for example 60 to 300 seconds. The substrate can then be cooled down quickly, wherein the entire process typically takes only a few minutes. Annealing may be used to change the material properties of layers on the substrate. Annealing may also be used to activate dopants, drive dopants between films on a substrate, alter film-to-film or film-to-substrate interfaces, densify deposited films, or repair damage from ion implantation.
As feature sizes for microelectronic devices and interconnects become smaller, the allowable defect rate substantially decreases. Some defects result from contamination embedded in one or more layers.
Disclosure of Invention
In one aspect, processing a tungsten film on a workpiece comprises: supporting the workpiece in a chamber, introducing hydrogen gas into the chamber, and establishing a pressure of at least 5 atmospheres in the chamber; and exposing the tungsten film on the workpiece to hydrogen gas when the pressure in the chamber is at least 5 atmospheres.
Other embodiments of this aspect include corresponding systems, apparatus, and computer programs configured to perform the actions of the methods encoded on computer storage.
These and other embodiments may each optionally include one or more of the following features.
The temperature of the tungsten film may be raised to between 250 ℃ and 600 ℃. The temperature of the tungsten film may be increased by maintaining support for the workpiece in the chamber at an elevated temperature. The temperature of the tungsten film may be raised before a pressure of at least 5 atmospheres is established in the chamber.
Establishing pressure in the chamber may include introducing hydrogen gas and an inert gas to provide a gas mixture in the chamber. The hydrogen gas in the gas mixture in the chamber may be between 1% and 4% by volume of the gas mixture. The inert gas in the gas mixture in the chamber may include nitrogen and/or argon. The tungsten film may be exposed to hydrogen gas when the hydrogen gas has a partial pressure of 1 to 10 bar (bar).
The tungsten film may be part of a fabricated three-dimensional NAND (3D NAND) structure.
In another aspect, a method of forming tungsten on a workpiece includes: depositing a tungsten film on a workpiece by chemical vapor deposition using a precursor gas containing tungsten and fluorine; and exposing the tungsten film on the workpiece to hydrogen gas in the chamber when the pressure in the chamber is at least 5 atmospheres.
The tungsten film may be part of a three-dimensional NAND (3D NAND) in fabrication. The precursor gas may comprise tungsten hexafluoride. The tungsten film is raised to a temperature between 250 ℃ and 600 ℃. The chamber pressure may be established by introducing hydrogen and an inert gas (e.g., argon and/or nitrogen) to provide a gas mixture in the chamber.
In another aspect, an annealing system includes: a chamber body defining a chamber; a support for holding a workpiece, wherein an outer surface of the workpiece is exposed to an environment in the chamber; a robot for inserting a workpiece into the chamber; a first gas source for providing hydrogen; a pressure source coupled to the chamber to raise a pressure in the chamber to at least 5 atmospheres; and a controller coupled to the robot, the first gas source, and the pressure source. The controller is configured to cause the robot to transport the workpiece having the tungsten film thereon into the chamber, cause the gas source to supply hydrogen gas to the chamber, and cause the pressure source to increase the pressure in the chamber to at least 5 atmospheres while the workpiece is held on the support in the chamber.
The annealing system may include a heater to raise the temperature of the workpiece on the support to between 250 ℃ and 600 ℃. The heater may comprise a resistive heater embedded in the support, and/or the heater may be a radiant heater located in a wall of the chamber body, the radiant heater being positioned to irradiate the workpiece on the support. The pressure source may comprise a pump.
The annealing system can include a second gas source to supply an inert gas (e.g., argon and/or nitrogen) to the chamber, and the controller can be coupled to the second gas source and can be configured to cause the first gas source to introduce hydrogen and the second gas source to introduce the inert gas to provide a gas mixture in the chamber.
Particular implementations of the subject matter described in this specification can be implemented to realize one or more of the following advantages. Post-deposition annealing of tungsten films can improve film quality by reducing the presence of fluorine in the tungsten film. Reducing fluorine can reduce the likelihood of defects and can increase yield. The use of a defluorinated high pressure gas allows the use of low temperatures during the annealing process by increasing the diffusion of the gas into the layer, maintaining a relatively low thermal budget after treatment of the workpiece, and preserving the overall layer structure quality. In addition, the low temperature of deposition can be used to deposit tungsten films, thereby reducing layer mixing resulting from higher temperature deposition.
The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
Drawings
Fig. 1 is a block diagram of a high pressure substrate processing system.
Fig. 2 is a flow diagram of an exemplary process flow for tungsten defluorination by high pressure processing in a high pressure substrate processing system.
Fig. 3 illustrates an exemplary high pressure substrate processing system.
Fig. 4 illustrates another example of a high pressure substrate processing system.
Like reference symbols in the various drawings indicate like elements.
Detailed Description
Introduction to
In general, it is desirable to reduce the defect density of layers deposited on a workpiece, for example, a tungsten film deposited on a semiconductor wafer (e.g., a semiconductor wafer used to fabricate 3D NAND structures). The defect density may occur in various ways, including residues from precursor gases (e.g., tungsten hexafluoride) used in the deposition process of the tungsten film. Reducing residual fluorine in the deposited tungsten film can reduce deleterious effects such as unintentional oxide etching leading to defects in adjacent layers and reduced k-values in gate oxides deposited adjacent to the tungsten film.
Systems and methods for high pressure processing are described below to defluorinate tungsten films using high pressure annealing. The tungsten film deposited on the workpiece is exposed to a high pressure (e.g., at least 5 atmospheres) of a forming gas (e.g., 4% hydrogen gas mixed with an inert gas) while being held at a high temperature (e.g., 200 ℃ to 500 ℃) for several minutes to one hour.
System for controlling a power supply
Fig. 1 is a block diagram of a high pressure
A robot (not shown in fig. 1) including a robotic arm may be used to transfer workpieces into and out of the high pressure chamber 102, for example, between chambers of a multi-chamber substrate processing tool.
The high pressure chamber 102 includes a support, such as a pedestal 106 for supporting a workpiece in the high pressure chamber 102. The pedestal 106 may use various support mechanisms to support one or more workpieces, for example, the pedestal 106 may use locking pins (lockingpins) and springs to support the workpiece, and/or the workpiece may be placed directly on top of the pedestal 106.
In some embodiments, the high pressure chamber 102 includes one or more heating elements 108. For example, the heating element 108a is a resistive heater and is integrated into the pedestal 106 for heating the workpiece. In some embodiments, the high pressure chamber 102 includes a heating element 108b, wherein the heating element 108b can heat and maintain a selected temperature within the high pressure chamber 102. The heating element 108b may be a radiant heater embedded in the wall of the high pressure chamber body and positioned to illuminate the workpiece on the pedestal 106. When the workpiece is supported on the pedestal 106 and gas (if used) has been introduced into the high pressure chamber 102, the heat from the heating element 108 may be sufficient to anneal the workpiece. The heating element 108 may be a resistive heating element and may conductively and/or radiatively heat the workpiece. Additionally, the heating element 108 may include discrete heating coils, or radiant heaters (e.g., infrared lamps).
The
The pumping system 114 includes one or more pumps for reducing the pressure in the high pressure chamber 102 and/or the vacuum chamber 104. The pump may include a rotary pump, a scroll pump, and/or a progressive cavity pump. For example, the pumping system 114 may be used to reduce the pressure in the vacuum chamber 104 to at or near vacuum pressure, e.g., less than 1 milliTorr (milliTorr). In another example, the pumping system 114 may be used during pumping and purging cycles of the high pressure chamber 102 to reduce the presence of contaminants in the high pressure chamber 102 prior to process operations.
In some embodiments, the
In some embodiments, the high pressure
One or more operations of the high pressure
High pressure treatment of tungsten films
Fig. 2 is a flow diagram of an
The workpiece is inserted into the chamber, such as by a robot, and then supported in the chamber, such as on the pedestal 106 within the high pressure chamber 102 (202). In some embodiments, the high pressure chamber 102 and/or the susceptor 106 are maintained at a particular temperature (e.g., 300 ℃ to 500 ℃) using one or more heating elements 108. The temperature of the high pressure chamber 102 and/or the pedestal 106 may be established prior to introducing the workpiece into the high pressure chamber 102. Further, the temperature of the workpiece (e.g., a tungsten film on a substrate) may be established at a particular temperature (e.g., 250 ℃ to 600 ℃) by using one or more heating elements 108 when the workpiece is supported by the pedestal 106 in the high pressure chamber 102. In some embodiments, the temperature of the workpiece (e.g., a tungsten film on a substrate) is raised prior to establishing a pressure of at least 5 atmospheres in the high pressure chamber 102.
Hydrogen gas is introduced into the high pressure chamber 102 (204). The hydrogen gas may be H2Or deuterium (D)2) In the form of (1). The hydrogen gas may be part of a forming gas that includes one or more inert gases (e.g., nitrogen and/or argon). In some embodiments, the percentage of hydrogen in the forming gas is at least 1%, and at most 4.5% by volume. The inert gas may be mixed with the hydrogen gas prior to delivery into the high pressure chamber 102 by the
The
After the desired pressure is established in the high pressure chamber 102, the tungsten film on the workpiece is exposed to hydrogen while the high pressure chamber 102 is maintained at an elevated pressure (208). The exposure time includes a few minutes to a few hours (e.g., at least 5 minutes, and no more than an hour). In some embodiments, the annealing temperature (temperature of the workpiece during the annealing process), the partial pressure of hydrogen in the high pressure chamber 102, and the exposure time to the defluorination process may be correlated so that the optimum operating parameters may be found by adjusting the above (and other) variables.
Without being bound to any particular theory, molecular hydrogen gas cracks to atomic hydrogen on the surface of the heated tungsten film and then diffuses along the grain boundaries of the tungsten film. Diffusion of reactants (e.g., cracked hydrogen) into the tungsten film may be a limiting factor in the rate at which the defluorination process occurs. As the cracked hydrogen diffuses into the tungsten film, the cracked hydrogen bonds with fluorine on the surface of the tungsten film or embedded within the tungsten film. The bonded hydrogen and fluorine form hydrogen fluoride which can then diffuse out of the tungsten film. Atomic hydrogen can additionally be used to weaken and break the bonds between fluorine and tungsten in tungsten films.
In some embodiments, hydrogen gas is introduced into the high pressure chamber 102 through the
In some embodiments, the workpieces may be heated to a particular temperature while in the vacuum chamber 104 and then transferred by a robot (not shown) to the high pressure chamber 102, into which hydrogen gas may be introduced.
In some embodiments, a tungsten film is deposited on a workpiece that is subsequently subjected to the high pressure processing described herein. For example, a tungsten film may be deposited on a workpiece by Chemical Vapor Deposition (CVD) using a precursor gas containing tungsten and fluorine (e.g., tungsten hexafluoride). In some embodiments, tungsten hexafluoride may be used as a precursor gas to deposit a tungsten film. The amount of residual fluorine trapped within the deposited tungsten film may depend in part on the deposition temperature (e.g., lower deposition produces higher concentrations of residual fluorine). The tungsten film may then be exposed to hydrogen gas in the high pressure chamber 102 when the pressure in the high pressure chamber 102 is at least 5 atmospheres.
Embodiments of high pressure substrate processing systems
Fig. 3 and 4 illustrate two embodiments of a high pressure substrate processing system. Fig. 3 illustrates an exemplary high pressure
The
The high pressure
The high pressure
When the
When the
Because the
In some embodiments, the high pressure
However, the one or
A controller is operatively connected to the pumping system, the
In a process for performing high pressure processing of a material layer on the
The
After the
The hydrogen gas and appropriate temperature and pressure conditions in the
When the high pressure processing is complete, the
To enable the
Fig. 4 illustrates another example of a high pressure
For example, the gas delivery system and pumping system of the high pressure
The high pressure
The one or
The high pressure
Specifically, the valve assembly 416 includes a slit valve 423 located between the
The
The
Similar to
When the valve assembly 416 is in the open position, the distal ends 425b of the
The controller may operate the high pressure
The configuration shown in fig. 4 has the advantages that: the pressure within the
The controller and other computing device portions of the systems described herein may be implemented in digital electronic circuitry, or in computer software, firmware, or hardware. For example, the controller may include a processor executing a computer program as stored in a computer program product (e.g., in a non-transitory machine-readable storage medium). Such a computer program (also known as a program, software application, or code) can be written in any form of programming language, including compiled or interpreted languages, and it can be deployed in any form, including as a stand-alone program or as a module, component, subroutine, or other unit suitable for use in a computing environment.
While this document contains many specific implementation details, these should not be construed as limitations on the scope of any inventions or of what may be claimed, but rather as descriptions of features specific to particular implementations of particular inventions. Certain features that are described in this document in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Furthermore, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.
Accordingly, other implementations are within the scope of the following claims.
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