TWI747943B - System for treatment of deposition reactor - Google Patents

Abstract

A system and method for treating a deposition reactor are disclosed. The system and method remove or mitigate formation of residue in a gas-phase reactor used to deposit doped metal films, such as aluminum-doped titanium carbide films or aluminum-doped tantalum carbide films. The method includes a step of exposing a reaction chamber to a treatment reactant that mitigates formation of species that lead to residue formation.

Description

System for processing deposition reactor [Cross reference of related applications]

This application is a partial continuation of the U.S. Patent Application No. 14/987,420 filed on January 4, 2016 and titled "METHOD AND SYSTEM FOR TREATMENT OF DEPOSITION REACTOR"; the '420 application is in January 2014 The divisional application of U.S. Patent Application No. 14/166,462 (current U.S. Patent No. 9,228,259) filed on the 28th and titled "METHOD FOR TREATMENT OF DEPOSITION REACTOR"; the '462 application claims filed on February 1, 2013 The right to apply for the U.S. Provisional Application No. 61/759,990 entitled "METHOD AND SYSTEM FOR TREATMENT OF DEPOSITION REACTOR". The disclosures of the aforementioned applications are hereby incorporated by reference.

The present invention generally relates to methods and systems for processing deposition reactors. More specifically, the illustrative examples of the present invention relate to methods and systems for reducing or removing accumulation in vapor deposition reactors.

Doped metal films (for example, doped metal carbides, metal nitrides, metal borides, and metal silicides, such as aluminum-doped metal carbides) can be used in a variety of applications. For example, aluminum-doped titanium carbide and similar materials can be used for metal oxide field effect transistors (MOSFET) or insulated gated field effect transistors (IGFET) (such as complementary metal oxide field effect transistors). The gate electrode in a complementary metal oxide semiconductor (CMOS) device is used as a barrier layer or filling material for semiconductor or similar electronic devices, or as a coating in other applications.

When the doped metal film is used as a layer of an electronic device or as a coating, it is typically deposited using a vapor deposition technique such as a chemical vapor deposition technique including atomic layer deposition. The precursors used for vapor deposition often include organometallic compounds (for example, including aluminum) and metal halide compounds (for example, including titanium or tantalum). Unfortunately, the decomposition temperature of the organometallic compound can be much lower than the temperature at which the desired doped metal film is formed (for example, lower than 200°C). Therefore, precursor decomposition products or residues may be formed in the deposition reaction chamber during the deposition process. The residue can then form particles, which lead to defects in the layers deposited using the reactor. In addition, in the presence of metal halide compounds, some decomposition products may undergo polymerization, and the polymerization products may cause additional defects in the deposited layer. The multiple defects in the deposited layer are generally related to a certain amount of material deposited in the reactor; the number of defects in the layer generally increases with multiple deposition runs or the amount of deposited material increases.

In order to reduce the number of defects in the deposited layer, after a certain amount of material has been deposited or multiple substrates have been processed, the reactor can be purged with inert gas for an extended period of time (about several hours). This prolonged purification procedure significantly reduces the output rate of the deposition reactor and increases the operating cost of the reactor.

Therefore, there is a need for improved methods and systems for treating deposition reactors to reduce or alleviate particle formation, such as particles produced by the accumulation of decomposition products of precursors of the material used to deposit the doped metal film.

Various embodiments of the present invention provide improved methods and systems for removing or reducing the formation of residues in a deposition reactor or otherwise converting the residues to produce fewer particles. More specifically, the exemplary system and method alleviate the use of doped metal films (such as metal films including carbon, boron, silicon, nitrogen, aluminum, or any combination thereof) in a vapor deposition reactor. The formation of residues resulting from the use of or multiple precursors, the conversion or removal of the residues. Although the various shortcomings of the prior art are discussed in more detail below, in general, methods and systems use gas phase reactants to reduce the formation of undesirable residues in the reaction chamber, convert or remove the residues. By mitigating the formation of undesirable residues, converting or removing the residues, fewer particles are formed in the reactor and therefore fewer defects are formed in the deposited film. In addition, the substrate yield rate of the reactor can be improved and the cost of operating the reactor can be reduced.

According to various specific examples of the present invention, the method for treating the reactor includes the following steps: providing a metal halide chemical substance to the reaction chamber of the deposition reactor, and selecting a chemical substance selected from the group consisting of an organometallic compound chemical substance and an aluminum CVD compound chemical substance. The metal CVD precursor is provided to the reaction chamber to form a doped metal film, the processing reactant chemical substance is provided to the reaction chamber, and the reaction chamber is exposed to the processing reactant chemical substance to reduce the particles containing the decomposition product of the metal CVD precursor Particle formation (e.g., by reducing the accumulation of residues or by converting the residues into materials that are less likely to form particles in the reactor), and cleaning the reaction chamber. The deposition step of the method can be repeated to deposit a desired amount of doped metal film or process a desired number of substrates before treating the reactor with a treatment reactant. According to exemplary aspects of these specific examples, the processing reactant source includes a compound selected from the group consisting of a compound containing one or more hydrogen atoms and a compound containing a halogen (eg, chlorine, HCl). According to various aspects, the processing reactant source includes a compound selected from the group consisting of ammonia, hydrogen, silane (for example, silane, disilane, or higher-order silane), methane, silane hydride, borohydride, halogenated silane, Halogenated boranes, alkenes (for example, ethylene), alkynes, hydrazine and their derivatives (such as alkylhydrazine) and the like. And according to other aspects, the processing reactant source includes a compound having the same chemical formula as the decomposition product of the metal CVD source. The treatment reactant can be exposed remotely or directly thermally activated or plasma activated to form an activated substance.

According to other illustrative specific examples of the present invention, a system for processing a deposition reactor includes: a reactor containing a reaction chamber; a metal halide source fluidly coupled to the reactor; A metal CVD source consisting of one or more of an organometallic compound and an aluminum CVD compound; a processing reactant source coupled to the reactor; configured to before or during the introduction of the metal CVD precursor into the reaction chamber A controller that executes the reaction chamber processing using the processing reactant from the processing reactant source; and a vacuum pump coupled to the reactor. The system may include direct or remote plasma and/or thermal excitation devices to provide activated reactant materials to the reaction chamber. According to exemplary aspects of these specific examples, the processing reactant source includes a compound selected from the group consisting of a compound containing one or more hydrogen atoms and a compound containing a halogen (eg, chlorine, HCl). According to various aspects, the processing reactant source includes a compound selected from the group consisting of ammonia, hydrogen, one or more silanes, methane, silane hydrides, borohydrides, halogenated silanes, halogenated boranes, olefins (such as , Ethylene), alkynes and hydrazine and their derivatives (such as alkylhydrazine) and the like. According to other aspects, the processing reactant source includes a material having the same chemical formula as the decomposition product of the metal CVD source (for example, the β-hydride elimination product of the metal CVD source).

According to other specific examples of the present invention, the method for processing a deposition reactor includes the following steps: providing a metal halide chemical substance to the reaction chamber for a period of time; after the step of providing the metal halide chemical substance to the reaction chamber for a period of time, processing The reactant chemical substance is provided to the reaction chamber for a period of time; and during or after the processing reactant chemical substance is provided to the reaction chamber for a period of time, the metal CVD precursor chemical substance is provided to the reaction chamber to form a layer of doped metal. In this case, particle formation is reduced during the deposition step (for example, through reduction in residue formation or through densification of residue) and any residue formed can be removed during the deposition process and optionally after the deposition process Things. The process reactants can be introduced with the metal CVD precursor chemistry or before the metal CVD precursor is introduced. According to the illustrative aspects of these specific examples, the processing reactant chemicals include one or more of the following: hydrogen compounds including one or more hydrogen atoms (for example, hydrogen, HCl, one or more silanes, methane , Ethylene and the like) and compounds including halogens (e.g., chlorine, HCl). The treatment reactant can be exposed remotely or directly thermally activated or plasma activated to form an activated substance. According to an additional aspect of these specific examples, the step of providing the processing reactant chemical substance to the reaction chamber includes providing a source of the compound having the same chemical composition as the decomposition product of the organometallic compound or the aluminum CVD compound.

According to other illustrative specific examples, the system includes a controller to execute the steps in the methods disclosed herein.

The foregoing summary of the invention and the following embodiments are only illustrative and explanatory, and do not limit the present invention or the claimed invention.

100‧‧‧System

102‧‧‧Reactor

104‧‧‧Reaction Chamber

105‧‧‧Reaction Space

106‧‧‧Substrate holder

108‧‧‧Gas Distribution System

110‧‧‧Metal halide source

112‧‧‧Metal Chemical Vapor Deposition (CVD) Source

114‧‧‧Handle reactant source

Line 116‧‧‧

Line 118‧‧‧

120‧‧‧line

122‧‧‧Valve

124‧‧‧Valve

126‧‧‧Valve

128‧‧‧Vacuum pump

130‧‧‧Carrier gas and/or purification gas source

Line 132‧‧‧

134‧‧‧Valve

136‧‧‧Substrate or workpiece

138‧‧‧controller

140‧‧‧Remote plasma source

142‧‧‧Thermal excitation source

200‧‧‧Method

202‧‧‧Step

204‧‧‧Step

206‧‧‧Step

208‧‧‧Step

210‧‧‧Step

212‧‧‧Step

214‧‧‧Step

216‧‧‧Step

300‧‧‧Method

302‧‧‧Step

304‧‧‧Step

306‧‧‧Step

308‧‧‧Step

310‧‧‧Step

312‧‧‧Step

600‧‧‧controller

602‧‧‧Bus

604‧‧‧Processor

606‧‧‧Memory

608‧‧‧Optional communication interface depending on the situation

610‧‧‧Input device

612‧‧‧Output device

A more complete understanding of the specific examples of the present invention can be obtained when considering the embodiments and the scope of patent application in conjunction with the following illustrative drawings.

Figure 1 illustrates a system according to various illustrative embodiments of the present invention.

Figure 2 illustrates a method according to an illustrative specific example of the present invention.

Figure 3 illustrates another method according to an illustrative embodiment of the present invention.

Figure 4 illustrates multiple defects on a substrate based on multiple substrates processed without processing.

Figure 5 illustrates multiple defects on a substrate based on multiple substrates processed using the processes described herein.

Fig. 6 schematically illustrates a controller according to an illustrative specific example of the present invention.

It should be understood that the elements in the drawings are explained for simplicity and clarity, and the elements are not necessarily drawn to scale. For example, the size of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the specific examples of the present invention described.

The description of illustrative specific examples of the method and system provided below is only illustrative and intended for illustrative purposes only; the following description is not intended to limit the scope of the present invention or the scope of the patent application. In addition, the description of multiple specific examples with the stated features is not intended to exclude other specific examples with additional features or other specific examples with different combinations of stated features.

The methods and systems described herein can be used to alleviate the formation, removal and/or conversion of residues in reactors used to deposit doped metal films (for example, films including carbon, boron, silicon, and/or nitrogen) The residue, if these operations are not performed, will accumulate and/or produce particles during the deposition process. The use of the method and system described herein results in a reduction in particle formation from residues and therefore in higher yields and a reduction in the operating cost of the deposition reactor compared to a reactor that is only cleaned after a similar deposition procedure .

Turning now to FIG. 1, it illustrates a system 100 for mitigating the accumulation of deposit residues as described herein. The system 100 includes: a reactor 102, which includes a reaction chamber 104 (including a reaction space 105, a substrate holder 106, and a gas distribution system 108); a metal halide source 110; and a metal chemical vapor deposition (CVD) source 112 Process the reactant source 114; connect the source 110 to the source 114 to the lines 116, 118, 120 of the reactor 102; insert the valves 122, 124, and 126 between the source 110 to the source 114 and the reactor 102; the controller 138 A vacuum pump 128; a carrier gas and/or purge gas source 130 coupled to the reactor 102 via a line 132 and a valve 134 as appropriate; a remote plasma source 140 as appropriate; and a thermal excitation source 142 as appropriate.

The reactor 102 may be a stand-alone reactor or part of a cluster tool. In addition, the reactor 102 may be dedicated to doped metal deposition and processing procedures as described herein, or the reactor 102 may be used in other procedures, such as for other layer deposition and/or etching processes. For example, the reactor 102 may include processes typically used for physical vapor deposition (PVD), chemical vapor deposition (CVD), and/or atomic layer deposition (ALD). The reactor can include remote or direct thermal excitation, direct plasma and/or remote plasma equipment (for example, remote plasma source 140 and/or remote thermal excitation source 142). During the deposition or processing procedure, thermal or plasma activation equipment is used to generate excitation molecules or substances from one or more of the source 110 to the source 114 to enhance the reactivity of the reactants from the source 110 to the source 114. Although all the reactants sent to the optional remote plasma source 140 are used for illustration, this need not be the case. For example, gas from a processing reactant source with or without carrier gas can be sent to the remote plasma source 140. By way of an example, the reactor 102 includes a reactor suitable for ALD deposition. An exemplary ALD reactor suitable for use in the system 100 is described in US Patent No. 8,152,922, the content of which is hereby incorporated by reference, and does not conflict with the present invention in content.

The substrate holder 106 is designed to hold the substrate or workpiece 136 in place during processing. According to various illustrative specific examples, the holder 106 may form part of a direct plasma circuit. Additionally or alternatively, the holder 106 may be heated, cooled, or at ambient processing temperature during processing.

Although the gas distribution system 108 is illustrated in the form of blocks, the gas distribution system 108 may be relatively complex and designed to mix vapor or gas from the source 110 and/or the source 112 and from one or more sources such as the gas source 130 The carrier gas/purification gas is then distributed to the remainder of the reactor 102. Additionally, the system 108 can be configured to provide a vertical (as illustrated) or horizontal flow of gas to the chamber 104. An exemplary gas distribution system is described in U.S. Patent No. 8,152,922. By way of example, the distribution system 108 may include shower heads. The gas distribution system can form part of the direct plasma source.

The metal halide source 110 includes one or more gases or materials that become gaseous (including metals and halides). Exemplary metals include titanium, tantalum, and niobium. Exemplary halides include chlorine and bromine. For example, the source 110 may include _{one or more of titanium chloride (e.g., TiCl 4} ), tantalum chloride (e.g., TaCl ₅ ), and niobium chloride (e.g., NbCl 5 ). The gas from the source 110 may be exposed to heat and/or remote plasma and/or direct plasma sources to form activated or excited species, such as ions and/or one or more of chlorine, titanium, tantalum, and niobium. Or free radicals. The term "activated species" includes precursors and any ions and/or free radicals that can be formed during exposure of the precursor to any thermal and/or plasma process. In addition, when the term "chemical substance" is used in conjunction with a compound, regardless of whether the compound (eg, reactant) has been exposed to heat or plasma activation, the term includes the compound and any activating substance.

The metal CVD source 112 includes one or more gases or substances that react with a reactive substance or form a reactive substance or become a gaseous substance, and the reactive substance reacts with a compound or substance from the metal halide source 110 to form a doped metal. The deposited layer of the film, such as a layer of aluminum-doped titanium carbide or aluminum-doped tantalum carbide, other carbyne, nitride, silicide, or boride. For example, the metal CVD source 112 may include organometallic compounds and/or aluminum CVD compounds, such as aluminum hydride compounds. Exemplary suitable organometallic compounds include trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), diethylaluminum chloride (DEACL) ), diethylaluminum hydride (DMAH) and tritertiarybutylaluminum (TTBA). Exemplary aluminum CVD aluminum hydride compounds include trimethylamine aluminum hydride (trimethylamine alane; TMAA), triethylamine aluminum hydride (triethylamine alane; TEAA), dimethyl ethylamine alane (DMEAA), and trimethylamine aluminum hydride Borane (trimethylaminealane borane; TMAAB) and methylpyrrolidine alane (MPA).

The use of organometallic compounds and aluminum hydride compounds can be advantageous because these compounds allow atomic layer deposition, which allows precise, conformal, self-limiting deposition of layers of desired materials. However, organic precursors are easily decomposed at or below the film deposition temperature. In fact, some precursors decompose at a temperature of 200°C (or more) below the temperature at which the film is formed. Therefore, the compound may decompose into undesirable products before reaching the substrate 136, causing residues to form within the chamber 104 (e.g., within the reaction space 105), for example at or near a gas distribution system 108 such as a shower head. As described above, residue formation can later cause the formation of particles that cause defects in the deposited metal film.

For example, many organometallic compounds can undergo β-hydride elimination reactions, in which alkyl groups bonded to the metal center are converted into corresponding metal hydrides and olefin compounds. The formation of olefin compounds (especially at or near the gas distribution system 108) can result in the accumulation of residues including organic and inorganic materials. In addition, the decomposition products may polymerize (e.g., in the presence of material from the metal halide source 110), which may cause the formation of additional or alternative residues.

The gas from the source 112 may be exposed to a direct and/or remote thermal excitation source (for example, the remote excitation source 142) and/or a direct plasma source (for example, using the gas distribution system 108 and parts of the substrate holder 106 as electrodes ) And/or remote plasma source 140 to form activated species, such as ions and/or free radicals.

The processing reactant source 114 includes one or more gases or materials that become gaseous. The gases and materials include reducing the formation of residues in the reactor and/or in a manner that produces fewer particles (for example, by making the residues dense Chemical) A compound or substance that converts the residue. Exemplary compounds and substances can react with halogens (e.g., on deposited films) on halogen (e.g., Cl) terminal molecules to reduce the formation of undesirable decomposition products. For example, the processing reactant source 114 may include a compound selected from the group consisting of a compound containing one or more hydrogen atoms and a compound containing a halogen (eg, chlorine, HCl). According to various aspects, the processing reactant source includes a compound selected from the group consisting of ammonia, hydrogen, one or more silanes (for example, silane), methane, silicon hydride, borohydride, halogenated silane, halogenated boron Alkanes, alkenes (for example, ethylene), alkynes, hydrazine and their derivatives (such as alkylhydrazine), etc. And according to other aspects, the processing reactant source includes a material having the same chemical formula as the decomposition product of the metal CVD source (for example, the same chemical formula as the chemical formula of the β-hydride elimination product of the metal CVD source).

The gas from the source 114 may be exposed to heat and/or remote plasma and/or direct plasma sources to form an activated or excited substance, such as one or more of hydrogen and/or chlorine and/or other activated substances Ions and/or free radicals.

The carrier gas or inert source 130 includes one or more gases or materials that become gaseous that are relatively unreactive in the reactor 102. Exemplary carrier gases and inert gases include nitrogen, argon, helium, and any combination thereof.

The remote plasma source 140 may include any suitable remote plasma unit. Similarly, the remote thermal excitation source 142 and the direct thermal excitation source may include any suitable thermal excitation equipment, such as lamps, heaters, lasers, other light sources, and the like.

As illustrated in FIG. 1, the controller 138 may be coupled to one or more of the valves 122, 124, 126, and 134; the vacuum source 128; the remote plasma source 140; and/or the remote thermal excitation source 142. According to various examples of the present invention, the controller 138 is configured to perform one or more operations of the reaction chamber processing using the processing reactant from the processing reactant source. The treatment can occur before or during the introduction of the metal CVD precursor into the reaction chamber. By means of an illustrative example, the controller 138 is configured to provide metal halide chemistry from the metal halide source 110 to the reaction space 105, adding a metal selected from the group consisting of organometallic compound chemistry and aluminum CVD compound chemistry. The CVD precursor is provided from the metal CVD source 112 to the reaction space 105 to form a deposited doped metal film including one or more of B, C, Si, and N overlying substrate 136. The substrate is removed as appropriate, and the The processing reactant chemical substance is provided from the processing reactant source 114 to the reaction space 105, and the reaction space 105 is exposed to the processing reactant chemical substance to reduce the formation of particles containing the decomposition products of the metal CVD precursor, and to purify the reaction chamber 104.

FIG. 6 schematically illustrates a controller 600 according to at least one specific example of the present invention, which is suitable for use as the controller 138. The controller 600 may be configured to perform one or more or all method steps of the methods described herein. The controller 600 includes a bus 602 interconnecting a processor 604, a memory 606, an optional communication interface 608, an input device 610, and an output device 612. The bus 602 allows communication between the components of the controller 600. The processor 604 may include one or more processing units or microprocessors that interpret and execute encoded instructions. In other implementations, the processor 604 can be implemented by one or more application-specific integrated circuits (ASIC), field programmable gate array (FPGA), or the like. Including these devices.

The memory 606 may include random access memory (RAM) or another type of dynamic storage device that stores information and instructions for execution by the processor 604. The memory 606 may also include a read-only memory (ROM) or another type of static storage device that stores static information and instructions for the processor 604. The memory 606 may additionally or alternatively include other types of magnetic or optical recording media and their corresponding drives for storing information and/or commands. As used herein, the term "memory" broadly includes registers, buffers, and other data structures configured to store data.

The communication interface 608 may include a protocol stack for processing data transmitted via currently known or to-be-developed data protocols. The communication interface 608 may include a transceiver type device and an antenna that allows the controller 600 to communicate with other devices and/or systems via radio frequency. The communication interface 608 may additionally or alternatively include interfaces, ports, or connectors to other devices.

The input 610 may include one or more devices that allow the operator to enter information into the controller 600, such as a keyboard, keypad, mouse, pen, touch sensitive pad or touch sensitive screen, microphone, one or more biometric mechanisms, and the like By. The output 612 may include one or more devices that output information to the operator, such as a display, printer port, speakers, or the like.

As described herein, the controller 600 may perform certain operations in response to the processor 604 executing software instructions contained in a computer-readable medium such as the memory 606. Computer-readable media can be defined as physical memory devices or logical memory devices. The logical memory device may include a single physical memory device or a memory space dispersed among multiple physical memory devices. The software instructions can be read into the memory 606 from another computer-readable medium or from another device via the communication interface 608. The software instructions contained in the memory 606 enable the processor 604 to execute the processing procedures/methods described herein. Alternatively, a fixed-wire circuit can be used in place of or combined with software instructions to implement the processing procedures described herein. Therefore, the implementation described herein is not limited to any specific combination of hardware circuits and software.

Figure 2 illustrates a method 200 of treating a reactor according to an illustrative embodiment of the present invention. The method 200 includes the following steps: providing a metal halide chemical substance (Step 202), providing a metal CVD precursor chemical substance (Step 204), forming a doped metal film (Step 206), and providing a processing reactant chemical substance (Step 208) , Exposing the reaction chamber to processing reactant chemicals (step 210), purifying the reactor as appropriate (step 212) and if the required amount of material has not yet been deposited (step 214), repeat steps 202 to step 212, and if required The amount of material has been deposited (step 214), and the procedure is complete (step 216). Although not separately illustrated, the substrate or workpiece can be removed from the reaction chamber before the processing step 210 so that the film on the workpiece is not exposed to the processing reactant chemicals. Alternatively, the substrate may be exposed to processing reactant chemicals.

Step 202 includes providing a metal halide chemical to the reaction chamber, and step 204 includes providing a metal CVD precursor chemical to the reaction chamber. Step 202 and step 204 can be performed in any order or simultaneously. In addition, although illustrated with only two reactant sources, exemplary methods may include the use of more than two reactants.

The metal halide chemical substance may include any of the above-described compounds related to the metal halide source 110. During step 202, the metal halide source may be exposed to a thermal activation process and/or a remote and/or direct plasma source to produce a metal halide chemical species including an activated species. Similarly, the metal CVD precursor may include any of the compounds described above in relation to the metal CVD source 112. And during step 204, the metal CVD precursor may be exposed to a thermal activation process and/or a remote and/or direct plasma source to generate a metal CVD precursor chemical substance including an activated substance.

During step 206, a metal film is formed. For example, the metal film may include aluminum-doped, silicon-doped and/or boron-doped titanium carbide, aluminum-doped, silicon-doped and/or boron-doped tantalum carbide and/or aluminum-doped, silicon-doped and/or boron-doped carbide Niobium or other metal films including one or more of C, Si, B, or N.

During step 208, in order to reduce the formation of residues and/or to densify the residues and/or convert the residues to form fewer particles in the reaction chamber, processing reactant chemicals are introduced into the reaction chamber. The reactant chemistry can include any of the above-mentioned compounds related to the treatment of the reactant source 114, and the reactant from the source can be exposed to heat and/or plasma activation as described herein to form Process reactant chemicals including activated substances.

By way of example, the processing reactant chemicals may include hydrogen, and the hydrogen may be introduced into the reaction chamber (for example, reaction chamber 104) or reaction space (for example, reaction space 105) via a gas distribution system (for example, system 108). Additionally or alternatively, hydrogen gas may be exposed to the remote plasma to form processing reactant chemicals that include activated species such as hydrogen radicals. According to an exemplary aspect, the remote plasma is configured so that the activated substance can reach the surface of the gas distribution system (such as a shower head) and the pores of the system close to the surface, and react with the material therein. Additionally or alternatively, step 208 may include providing a halogen such as chlorine or a halogen activating substance such as a chlorine radical to the reaction chamber/reaction space to reduce the formation of residues in the reaction chamber/reaction space.

According to other specific examples, the treatment reactant chemical includes ammonia, which may or may not be subjected to direct and/or remote thermal and/or direct and/or remote plasma activation as described herein. Ammonia is believed to react with the halogen (e.g., chlorine) end group surface of the deposited material and reduce the formation of decomposition products in the reaction chamber/reaction space.

Exemplary conditions for the ammonium residue reactant treatment procedure include deposition of approximately 1250Å carbide, followed by exposure to NH _{3 for} 10 minutes, followed by purification (removal of residual NH ₃ ) for 20 minutes, followed by deposition of approximately 1250Å carbide, followed by exposure to NH ₃ About 10 minutes, followed by purification (removal of residue NH ₃ ) for about 20 minutes. For example, 1250Å carbide can be deposited on 25 wafers (a batch of wafers) at 50Å each.

It is believed that this procedure transforms the residue in the reactor to provide better adhesion, reduce stress or even make it difficult to oxidize to prevent the residual film from falling off the surface of the reactor and falling on the wafer, thereby reducing the wafer defect level .

Although the method 200 is illustrated as including a decision or decision step 214, it can be configured to automatically run a predetermined number of loops of step 202 to step 212. For example, the method 200 may be configured to run 1, 2, 3, 4, 5, or 50 cycles of steps 202 to 212 and complete when step 208 of the last cycle ends (step 216). Alternatively, step 202 to step 212 may be repeated based on the deposition of the doped metal film up to a predetermined amount. For example, steps 202 to 212 may be executed until a cumulative film thickness of about 20 Å to about 1250 Å or about 5 Å to about 5000 Å is reached.

Figures 4 and 5 illustrate when the reactor is untreated (Figure 4) and when ammonia is used as a processing reactant chemical substance according to the method 200 when the reactor is processed under the above conditions (Figure 5) the surface of the substrate Multiple defects counted by the particle size analyzer.

Figure 3 illustrates another method 300 according to an additional illustrative embodiment of the present invention. The method 300 includes the following steps: providing a metal halide chemical substance (step 302), providing a metal CVD precursor chemical substance (step 304), providing a processing reactant chemical substance (step 306), and forming a doped metal film (step 308) , It is determined whether the required amount of material has been deposited (step 310), and if the required amount of material has been deposited, the procedure is completed (step 312), and if the required amount of material has not been deposited, step 302 to step 310 are repeated. Although the method 300 is not illustrated, it may include a purification step before step 312 (e.g., similar to step 212).

Step 302 and step 304 may be the same as step 202 and step 204, except that step 302 is executed before step 304 according to the illustrative aspects of these specific examples. And according to other aspects, step 306 is executed after step 302 and before step 304 or at the same time. By way of example, the metal halide chemistry can be introduced into the reaction chamber from the metal halide source for a period of time (e.g., a pulse of about 800 ms) during step 302. Then, during step 306, processing reactants such as hydrogen, activated hydrogen, one or more silanes, activated silanes, ethylene, and/or activated ethylene are introduced into the reaction chamber for a period of time. After or during step 306, a metal CVD reactant chemical is introduced into the reaction chamber (e.g., exposed for about 3.5 seconds) to form a doped metal film. The use of the pulse of processing reactant chemistry during step 306 before or during step 304 is believed to reduce multiple halide end-group species on the surface of the deposited material and thus reduce or eliminate residue formation.

Although illustrative specific examples of the present invention are set forth herein, it should be understood that the present invention is not limited thereto. For example, although the system and method are described in conjunction with various specific chemical substances, the present invention is not necessarily limited to these chemical substances. Various modifications, changes and improvements can be made to the system and method described in this text without departing from the spirit and scope of the present invention.

100‧‧‧System

102‧‧‧Reactor

104‧‧‧Reaction Chamber

105‧‧‧Reaction Space

106‧‧‧Substrate holder

108‧‧‧Gas Distribution System

110‧‧‧Metal halide source

112‧‧‧Metal Chemical Vapor Deposition (CVD) Source

114‧‧‧Handle reactant source

Line 116‧‧‧

Line 118‧‧‧

120‧‧‧line

122‧‧‧Valve

124‧‧‧Valve

126‧‧‧Valve

128‧‧‧Vacuum pump

130‧‧‧Carrier gas and/or purification gas source

Line 132‧‧‧

134‧‧‧Valve

136‧‧‧Substrate or workpiece

138‧‧‧controller

140‧‧‧Remote plasma source

142‧‧‧Thermal excitation source

Claims (19)

A system for processing a reaction chamber, the system comprising: a reactor containing the reaction chamber; a metal halide source fluidly coupled to the reactor; selected from one or more of organometallic compounds and aluminum CVD compounds A group of metal CVD sources, which are fluidly coupled to the reactor; a source of processing reactants coupled to the reactor; a vacuum pump coupled to the reactor; and a controller, which is configured to Before or during the introduction of the metal CVD precursor into the reaction chamber, the processing reactant from the processing reactant source is used to perform the reaction chamber processing, wherein the processing reactant source includes a material having the same chemical formula as the decomposition product of the metal CVD source. For example, the system of claim 1, further comprising a plasma source, wherein the treatment reactant from the treatment reactant source is exposed to the plasma source to form one or more activation treatment reactant substances. For example, the system of item 1 of the scope of the patent application further includes a thermal excitation source, wherein the processing reactant from the processing reactant source is exposed to the thermal excitation source to form one or more excitation processing reactant substances. Such as the system of any one of items 1 to 3 in the scope of the patent application, wherein the processing reactant source comprises one or more compounds selected from the group consisting of compounds containing one or more hydrogen atoms and compounds containing halogen. For example, the system of any one of items 1 to 3 in the scope of patent application, wherein the processing reactant The source includes one or more of ammonia, hydrogen, one or more of silanes, methane, silane hydrides, borohydrides, halogenated silanes, halogenated boranes, alkenes, alkynes, and hydrazine and derivatives thereof. Such as the system of the first item in the scope of patent application, wherein the material comprises a material having the same chemical formula as the β-hydride elimination product of the metal CVD source. For example, the system of any one of items 1 to 3 in the scope of the patent application further includes a remote plasma source. For example, the system of any one of items 1 to 3 of the scope of patent application further includes a remote thermal excitation source. For example, the system of any one of items 1 to 3 in the scope of patent application, wherein the controller is further configured to perform the following operations: provide the metal halide chemical substance to the reaction chamber for a period of time; After the step of providing the halide chemical substance to the reaction chamber for a period of time, the processing reactant chemical substance is provided to the reaction chamber for a period of time; and during or during the period of providing the processing reactant chemical substance to the reaction chamber for a period of time After that, the metal CVD precursor chemical substance is provided to the reaction chamber. A system for processing a reaction chamber, the system comprising: a reactor including a reaction chamber with a reaction space; a metal halide source fluidly coupled to the reactor; selected from one of organometallic compounds and aluminum CVD compounds Or a group consisting of a metal CVD source, which is fluidly coupled to the reactor; a processing reactant source coupled to the reactor, wherein the processing reactant source contains the same decomposition product as the metal CVD source Chemical formula material; A vacuum pump coupled to the reactor; and a controller configured to perform the following operations: provide metal halide chemicals from the metal halide source to the reaction space; select from the group consisting of organometallic chemicals and aluminum The metal CVD precursor of the group consisting of CVD compound chemical substances is provided from the metal CVD source to the reaction space; forming a deposited doped compound containing one or more of B, C, Si, and N overlying the substrate Metal film; before or during the introduction of the metal CVD precursor into the reaction chamber, processing reactant chemicals are provided to the reaction space from the processing reactant source; exposing the reaction space to the processing reactant chemicals To reduce the formation of particles containing the decomposition products of the metal CVD precursor; and to purify the reaction chamber. For example, the system of claim 10, which further includes a plasma source, wherein the processing reactant chemical substance is exposed to the plasma source. For example, the system of claim 10, which further includes a thermal excitation source, wherein the processing reactant chemical substance is exposed to the thermal excitation source. Such as the system of any one of items 10 to 12 in the scope of the patent application, wherein the processing reactant source comprises one or more compounds selected from the group consisting of a compound containing one or more hydrogen atoms and a compound containing halogen. For example, the system of any one of items 10 to 12 in the scope of the patent application, wherein the source of the processing reactant comprises ammonia, hydrogen, one or more silanes, methane, silane hydrides, borohydrides, halogenated silanes, halogenated One or more of borane, alkenes, alkynes, hydrazine and their derivatives. For example, the system according to any one of items 10 to 12 in the scope of patent application, wherein the processing reactant source is provided before the introduction of the metal CVD precursor. Such as the system of any one of items 10 to 12 in the scope of the patent application, wherein the material comprises a material having the same chemical formula as the β-hydride elimination product of the metal CVD source. For example, the system of any one of items 10 to 12 in the scope of the patent application further includes a remote plasma source. For example, the system of any one of items 10 to 12 in the scope of the patent application further includes a remote thermal excitation source. A system for processing a reaction chamber, the system comprising: a reactor containing the reaction chamber; a metal halide source fluidly coupled to the reactor; selected from one or more of organometallic compounds and aluminum CVD compounds The metal CVD source of the group, which is fluidly coupled to the reactor; is coupled to a processing reactant source of the reactor, the processing reactant source includes a processing gas, and the processing gas is configured to perform lightening in the reaction chamber The formation and conversion of the residues formed in the reaction chamber is one or more of the residues, so that the residues will form fewer particles on the substrate processed in the reaction chamber, wherein the processing reactant source includes the metal CVD The decomposition product of the source has a material of the same chemical formula; and a vacuum pump coupled to the reactor, wherein the system is configured to use the processing gas to perform the reaction chamber before or during the introduction of the metal CVD precursor into the reaction chamber deal with.

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