Molecular layer deposition method and system

Abstract

An example processing method can include flowing a first deposition precursor into a substrate processing region to form a first portion of an initiator compound layer. The first deposition precursor can include an aldehyde reactive group. The method can include removing a first deposition effluent including the first deposition precursor from the substrate processing region. The method can include flowing a second deposition precursor into the substrate processing region. The second deposition precursor can include an amine reactive group, and the amine reactive group can react with the aldehyde reactive group to form a second portion of the initiator compound layer. The method can include removing a second deposition effluent including the second deposition precursor from the substrate processing region. The method can include annealing the initiator compound layer to form an annealed carbon-containing material on a surface of a substrate.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit and priority of U.S. Patent Application No. 16 / 935,385, filed July 22, 2020, entitled “MOLECULAR LAYER DEPOSITION METHODAND SYSTEM,” which is incorporated herein by reference in its entirety. Technical Field

[0003] This technology relates to semiconductor processing. More specifically, this technology relates to methods and systems for depositing and annealing carbon-containing materials on semiconductor substrates. Background Technology

[0004] Integrated circuits are made possible by processes that create complex patterned material layers on substrate surfaces. Creating patterned materials on a substrate requires controlled methods for forming and removing exposed material. As device sizes continue to shrink, material formation can impact subsequent operations. For example, in gap-filling operations, material can be formed or deposited to fill trenches or other features formed on a semiconductor substrate. These filling operations can be challenging because features can be characterized by high aspect ratios and reduced critical dimensions. For instance, continuous deposition can pinch off features, including between sidewalls within the feature, and can create voids within the feature, as deposition can occur at the top of the feature and along its sidewalls. This can affect device performance and subsequent processing operations.

[0005] Therefore, there is a need for improved systems and methods capable of producing high-quality devices and structures. This technology addresses these and other needs. Summary of the Invention

[0006] Embodiments of this technology include a method for forming a carbon-containing material on a substrate using molecular layer deposition (MLD). The method may include introducing a first deposition precursor into a substrate processing region to form a first portion of an initial compound layer. The first deposition precursor may include aldehyde-reactive groups. The method may include removing a first deposition effluent comprising the first deposition precursor from the substrate processing region. The method may include introducing a second deposition precursor into the substrate processing region. The second deposition precursor may include amine-reactive groups, and the amine-reactive groups may react with aldehyde-reactive groups to form a second portion of the initial compound layer. The method may include removing a second deposition effluent comprising the second deposition precursor from the substrate processing region. The method may include annealing the initial compound layer to form an annealed carbon-containing material on the surface of the substrate.

[0007] In some embodiments, the method may include depositing at least one additional compound layer on an initial compound layer. The initial compound layer and at least one additional compound layer may form an annealed carbonaceous material on the surface of a substrate. A first deposition precursor may be delivered at a temperature greater than or about 100°C. A second deposition precursor may be delivered at a temperature less than or about 100°C. The first deposition time and the second deposition time may be less than or about 5 seconds. The first deposition time may be longer than the second deposition time. The flow of the first deposition precursor may increase the pressure in the substrate processing area to a pressure range of about 1 mTorr to about 500 Torr. Removal of the first deposition effluent from the substrate processing area may include a removal time of less than or about 60 seconds. An exemplary thermal annealing temperature for annealing the compound layer may be greater than or about 100°C (e.g., about 100°C to about 600°C). In some embodiments, the initial compound layer shrinks by less than 10% by volume due to the annealing of the deposited and annealed initial compound layer. In some embodiments, the substrate may include one or more substrate features characterized by an aspect ratio greater than or about 5:1 and a width less than or about 10 nm. In some embodiments, the method may further include depositing at least one additional compound layer on the initial compound layer, wherein the initial compound layer and at least one additional compound layer form an annealed carbon-containing material on the surface of the substrate.

[0008] Embodiments of this technology also include a processing method, the processing method comprising flowing a first deposition precursor into a substrate processing region. The first deposition precursor can be characterized by a first formula, the first formula comprising: Y1-R1-Y2, Wherein R1 includes one or more of alkyl, aryl, or cycloalkyl groups, and Y1 and Y2 independently include hydroxyl (hydroxide group), aldehyde (aldehyde group), ketone (ketone group), acid (acid group), amino (amino group), isocyanate (isocyanate group), thiocyanate (thiocyanate group), or acyl chloride (acyl chloride group).

[0009] A first deposition precursor may react with reactive groups on the surface of the substrate in the substrate processing region to form a first portion of an initial compound layer on the surface of the substrate. The method may further include removing a first deposition effluent comprising the first deposition precursor from the substrate processing region and allowing a second deposition precursor to flow into the substrate processing region. The second deposition precursor may be characterized by a second formula, which includes: Z1-R2-Z2, Wherein R2 includes one or more of alkyl, aryl, or cycloalkyl groups, and Z1 and Z2 independently include hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, or acyl chloride groups. The second deposition precursor may react with a first portion of the initial compound layer to form a second portion of the initial compound layer. The method may further include removing a second deposition effluent comprising the second deposition precursor from a substrate processing area. The method may also include annealing the initial compound layer to form an annealed carbonaceous material on the surface of the substrate.

[0010] In additional embodiments, exemplary R1 may be an aryl group, exemplary Y1 and Y2 may be independently aldehyde or isocyanate groups, exemplary R2 may be an alkyl group, and exemplary Z1 and Z2 may be amino groups. An exemplary first deposition precursor may include terephthalaldehyde or 1,4-phenylenediisocyanate, and an exemplary second deposition precursor may include ethylenediamine. In a further embodiment, removing the first deposition precursor may include infusing a purge gas into the substrate processing area and removing the mixture of the first deposition effluent and the purge gas from the substrate processing area. An exemplary purge gas may include helium.

[0011] Embodiments of this technology further include a process method of performing two or more cycles to form a carbon-containing composite layer on a substrate. Each of the two or more cycles of forming the carbon-containing composite layer may include forming a first portion of a compound layer on the surface of the substrate, wherein the first portion of the compound layer is formed by introducing a first deposition precursor into a substrate processing region, wherein the first deposition precursor reacts with reactive groups on the surface of the substrate in the substrate processing region to form the first portion of the compound layer. Each of the two or more cycles may further include forming a second portion of the compound layer on at least a portion of the first compound layer, wherein the second portion of the compound layer is formed by introducing a second deposition precursor into the substrate processing region, and the second deposition precursor reacts with the first portion of the initial compound layer to form the second portion of the compound layer. The two or more carbon-containing composite layers on the substrate may be annealed to form an annealed carbon-containing material on the surface of the substrate.

[0012] In an additional embodiment, the first deposition precursor may include terephthalaldehyde or 1,4-phenyl diisocyanate, and the second deposition precursor may include ethylenediamine. In a further embodiment, the compound layers shrink by less than 10% by volume due to the annealing of two or more carbon-containing compound layers.

[0013] Such techniques offer numerous advantages over conventional systems and methods. For example, embodiments of this technique produce carbon-containing layers with significantly fewer voids, cracks, and other physical defects compared to carbon-containing materials formed by conventional methods. This technique can also form carbon-containing materials with higher density and lower porosity than materials formed by conventional methods. Further details regarding embodiments of this technique, along with many of their advantages and features, are described below in conjunction with the accompanying drawings. Attached Figure Description

[0014] A further understanding of the nature and advantages of the disclosed technology can be achieved by referring to the remainder of the specification and the accompanying drawings.

[0015] Figure 1 The illustrations depict various stages in the formation of a portion of a compound layer deposited by a molecular layer deposition process according to some embodiments of the present technology.

[0016] Figure 2 A schematic cross-sectional view of an exemplary processing chamber according to some embodiments of the present technology is illustrated.

[0017] Figure 3 The illustrations depict exemplary operations in processing methods according to some embodiments of the present technology.

[0018] Several figures in the accompanying drawings are included as schematic diagrams. It should be understood that the drawings are for illustrative purposes and should not be considered to be to scale unless specifically stated otherwise. Furthermore, as schematic diagrams, the drawings are provided to aid understanding, and may not include all aspects or information compared to a realistic representation, and may include exaggerated material for illustrative purposes.

[0019] In the accompanying drawings, similar parts and / or features may have the same reference numerals. Furthermore, various parts of the same type may be distinguished by adding a letter after the reference numeral to differentiate between similar parts. If only the first reference numeral is used in the specification, the description applies to any one of the similar parts having the same first reference numeral, regardless of the lettering. Detailed Implementation

[0020] Carbon-containing materials can be used in the fabrication of semiconductor devices with many structures and processes, including as mask materials, etch-resistant materials, and trench-filling materials, among other applications. More specific examples of applications for carbon-containing materials include forming hot-injection hard molds, metal gate (MG) dicing hard molds, metal gate fabrication, and inverted-tone patterning. This technique involves forming these carbon-containing materials on semiconductor substrates using molecular layer deposition (MLD).

[0021] Embodiments of this technology include molecular layer deposition (MLD) methods and systems for forming a carbon-containing material on a semiconductor substrate. An exemplary MLD method may include providing a first deposition precursor to a surface of a semiconductor substrate, wherein the precursor forms a first layer (e.g., a first monolayer) on the substrate surface. During or after the formation of the first layer, unbound deposition effluent, which may include unbound molecules of the first deposition precursor, is removed from a processing area exposing the semiconductor substrate. A second deposition precursor may then be introduced into the semiconductor substrate, wherein molecules of the second deposition precursor bind to reactive portions on the first layer to form a second layer (e.g., a second monolayer). During or after the formation of the second layer, unbound deposition effluent, which may include unbound molecules of the second deposition precursor, is removed from the processing area. The semiconductor substrate now has a first compound layer made of a first layer bonded to the semiconductor substrate and a second layer bonded to the first layer. Additional compound layers having the first and second layers may be deposited on the deposited layers until the number of deposited compound layers reaches a desired thickness of the carbon-containing material on the semiconductor substrate. The compound layers may then be annealed to form the carbon-containing material on the semiconductor substrate.

[0022] This technology provides a solution to the problems of conventional methods for forming carbon-containing materials on semiconductor substrates. For example, the carbon-containing materials formed by this technology have significantly fewer voids, cracks, and other physical defects than those formed using spin-on carbon (SOC) and flowable chemical vapor deposition (FCVD) methods. This technology can also form carbon-containing materials with higher density and lower porosity than those formed using SOC and FCVD.

[0023] When processing as-deposited materials to form the final material, the high levels of hydrogen found in many SOC and FCVD precursors lead to high levels of shrinkage. Shrinkage up to 50% by volume is not uncommon for processed as-deposited SOC and FCVD materials, resulting in gaps, cracks, and voids in the processed material, as well as stress on substrate features in contact with the material. The processed carbonaceous material produced by this technique exhibits a shrinkage rate of less than 10% by volume compared to the as-deposited material (e.g., 5-10% by volume, less than about 5% by volume).

[0024] This technology also provides a solution to the problems of conventional plasma deposition methods for forming carbon-containing materials on semiconductor substrates. Conventional plasma deposition methods, such as plasma-enhanced chemical vapor deposition (PECVD) and high-density plasma-enhanced chemical vapor deposition (HDPCVD), tend to produce ion sputtering that can damage substrate features on the semiconductor substrate. They can also generate resputtered ions and other substances that can create defects in the deposited carbon-containing material. Furthermore, they tend to deposit material unevenly in and around substrate features, creating voids in and around substrate trenches and steps, and producing inhomogeneous surfaces in flat substrate regions. This technology can form carbon-containing materials with a high level of consistency and narrow substrate features (e.g., a width of less than about 25 nm) and a high aspect ratio (e.g., an AR of 10:1 or greater), without requiring plasma that can damage substrate features during deposition.

[0025] Figure 1 The illustration shows a simplified cross-section of a substrate surface during six stages of an exemplary MLD process for forming a compound layer on a substrate surface. The first cross-section 102 illustrates a portion of the substrate having a reactive surface material "-X" that can be used to bond with a first deposition precursor having the following formula:

[0026] Here, "-Y" represents a reactive group that can form a covalent bond with "-X" groups on the substrate surface under suitable reaction conditions. The next cross-section 104 illustrates the first deposition precursor being introduced onto the substrate surface and some molecules of the precursor forming covalent bonds with the -X groups on the surface. A subsequent cross-section 106 illustrates the molecules of the first deposition precursor saturating the available -X groups to form a first portion of the compound layer (e.g., a first monolayer) and leaving additional precursor molecules suspended in the gas phase as part of the first deposition precursor effluent. A subsequent cross-section 108 illustrates unreacted molecules in the first deposition precursor being removed from near the substrate surface in preparation for the introduction of a second deposition precursor.

[0027] In some embodiments, -X groups may have a greater number density (e.g., -X groups / unit area) on some portions of the substrate than on other portions. For example, a greater number of -X groups per unit area may be present on the bottom surface of substrate gaps, trenches, or other substrate features than on the sidewalls (e.g., vertical surfaces) of a substrate feature. For example, in some embodiments, the base of a feature may more readily form reactive ligands of the first deposition precursor, and thus, the base of the substrate may produce at least 1.1 times the number of reactive ligands per unit area compared to the number of reactive ligands on the sidewalls, and may produce at least 1.2 times, at least 1.4 times, at least 1.6 times, at least 1.8 times, at least 2.0 times, at least 2.5 times, at least 3.0 times, at least 5.0 times, at least 10.0 times, or more of the reactive ligands. In these embodiments, the MLD process can form a compound layer on the bottom surface of a substrate feature where the -X group number density is high, and form little or no compound layer on the sidewall surface of a substrate feature where the -X group number density is low or zero. These embodiments facilitate bottom-up gap filling of the compound layer in the substrate feature, which significantly reduces the likelihood of voids or seams formed by MLD deposited material deposited on the sidewalls of the substrate feature.

[0028] The second depositional precursor shown in this example is represented by the following formula:

[0029] Wherein “-Z” represents a reactive group, which can form covalent bonds with unreacted “-Y” groups on the layer formed by the reaction of the first deposition precursor with available “-X” groups on the substrate surface. Cross section 110 illustrates the introduction of a second deposition precursor onto the substrate surface, with some molecules of the second precursor forming covalent bonds with available –Y groups in the layer formed by the first precursor. The next cross section 112 illustrates the molecules of the second deposition precursor saturating the available –Y groups to form a second portion of the compound layer (e.g., a second monolayer) and leaving additional precursor molecules suspended in the gas phase as part of the first deposition precursor effluent. Unreacted second precursor molecules in the second deposition precursor effluent can be removed from the substrate surface to prepare for the formation of additional compound layers or to treat the compound layers for the formation of carbon-containing materials on the substrate.

[0030] exist Figure 1In the illustrated embodiments, the first deposition precursor may include two reactive groups "-Y" arranged at the para position around a central aromatic ring. Exemplary -Y groups may include hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, or acyl chloride groups, as well as other reactive groups. In other embodiments, two or more, three or more, four or more, or five or more -Y groups may be present around the aromatic ring. Further embodiments include each -Y group being the same reactive group, at least two -Y groups being different reactive groups, and all -Y groups being different reactive groups, as well as other combinations of -Y groups in the first deposition precursor. Specific examples of the first deposition precursor include hydroquinone, terephthalaldehyde, terephthaloyl chloride, and p-phenylenediamine.

[0031] Figure 1 The second deposition precursor in the illustrated embodiment comprises two reactive "-Z" groups disposed on the opposite carbon of the ethyl group. The reactive "-Z" groups are selected to react with the "-Y" groups at the substrate surface near the first portion of the compound layer under processing conditions. Exemplary -Z groups may include hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, or acyl chloride groups, as well as other reactive groups. Specific examples of the second deposition precursor include ethylene glycol and ethylenediamine, etc.

[0032] When the -Y and -Z groups contact near the substrate surface, these groups can be selectively configured to form covalent bonds. Exemplary combinations of -Y and -Z groups in the first and second deposition precursors may include acyl chloride -Y groups and hydroxyl -Z groups, aldehyde -Y groups and amino -Z groups, and other combinations of -Y and -Z groups. Specific combinations of the first and second deposition precursors may include terephthaloyl chloride and ethylene glycol, terephthalaldehyde and ethylenediamine, p-phenylenediamine and succinal, and other combinations.

[0033] In a further embodiment, the first deposition precursor may contain a central linking group other than a phenyl group, and the second deposition precursor may contain a central linking group other than a methine group. For example, the first and second deposition precursors may be represented by the following formula: Y-R1-Y; and Z-R2-Z, The -Y group can be as described above, and the -R1- and -R2- groups can independently represent alkyl, aryl, or cycloalkyl groups, as well as other types of hydrocarbon groups.

[0034] Figure 2A cross-sectional view of an exemplary processing chamber 100 according to some embodiments of the present technology is illustrated. The figure provides an overview of a system incorporating one or more aspects of the present technology and / or capable of performing one or more deposition or other processing operations according to embodiments of the present technology. Additional details of the chamber 200 or the performed methods are described further below. The chamber 200 can be used to form composite layers according to some embodiments of the present technology; however, it should be understood that the methods can be similarly performed in any chamber in which composite film formation may occur.

[0035] refer to Figure 2 The chamber 200 includes a chamber body 202 having a slit valve 208 formed in its sidewall 204 and a substrate support 212 disposed within the chamber body 202. The substrate support 212 is mounted to a lifting motor 214 to raise and lower the substrate support 212 and the substrate 210 disposed on the substrate support. The substrate support 212 may also include a vacuum chuck, an electrostatic chuck, or a clamping ring to secure the substrate 210 to the substrate support 212 during processing. Furthermore, the substrate support 212 may be heated using an embedded heating element (such as a resistance heater) or radiant heat (such as a heating lamp disposed above the substrate support 212). A purification ring 222 may be disposed on the substrate support 212 to define a purification channel 224 that provides purification gas to prevent deposition on the peripheral portion of the substrate 210.

[0036] A precursor delivery device 230 is disposed in the upper portion of the chamber body 202 to supply precursors, such as deposition precursors, carrier gases, and / or purge gases, to the chamber 200. A vacuum system 278 communicates with a pumping channel 279 to evacuate deposition effluents and / or other gases from the chamber 200 and to help maintain a desired pressure or desired pressure range within the pumping zone 266 of the chamber 200.

[0037] The precursor delivery device 230 includes a chamber cover 232 having an expansion channel 234 formed within its central portion. The chamber cover 232 also includes a bottom surface 260 extending from the expansion channel 234 to a peripheral portion of the chamber cover 232. The bottom surface 260 is sized and shaped to substantially cover the substrate 210 disposed on the substrate support 212. The inner diameter of the expansion channel 234 gradually increases from an upper portion 237 to a lower portion 235 adjacent to the bottom surface 260 of the chamber cover 232. Due to the expansion of the precursor, the velocity of the precursor flowing through the expansion channel 234 decreases as the precursor flows through it. The reduced precursor velocity decreases the likelihood of blowing away reactants adsorbed on the surface of the substrate 210.

[0038] The precursor delivery device 230 also includes at least two high-speed actuated valves 242 having one or more ports. At least one valve 242 can be dedicated to a specific deposition precursor. For example, a first valve can be dedicated to a first deposition precursor, such as a dialdehyde-containing precursor or a diisocyanate-containing precursor, and a second valve can be dedicated to a second deposition precursor, such as a diamine-containing precursor. When a third deposition precursor is required, a third valve can be dedicated to the third deposition precursor. For example, if the MLD process involves exposing a substrate to both a dialdehyde-containing deposition precursor and a diisocyanate-containing deposition precursor, the dialdehyde-containing precursor can be introduced via the second valve, and the diisocyanate-containing precursor can be introduced via the third valve.

[0039] Valve 242 can be any valve capable of precisely and repeatedly delivering short pulses of deposition precursor, carrier gas, and / or purge gas to chamber body 202. In some cases, the on / off cycle or pulse of valve 242 can be as fast as approximately 100 milliseconds or less. Valve 242 can be directly controlled, for example, by a system computer (such as a host computer) or by a chamber / dedicated controller (such as a programmable logic computer (PLC)). For example, valve 242 can be an electrically controlled (EC) valve.

[0040] Return to Figure 2 Control unit 280 (such as a programmed personal computer, workstation computer, etc.) can be coupled to chamber 200 to control processing conditions. For example, control unit 280 can be configured to control the flow of deposition precursors and purge gases from gas sources 238, 239, 240 through valves 242A, 242B during different stages of the substrate process sequence. Control unit 280 can be one of any form of general-purpose computer processor that can be used in an industrial environment to control various chambers and subprocessors.

[0041] Illustratively, control unit 280 includes a central processing unit (CPU), supporting circuitry, and memory containing associated control software. The CPU may use any suitable memory, such as random access memory, read-only memory, floppy disk drive, hard disk, or any other form of local or remote digital storage. Various supporting circuitry may be coupled to the CPU to support chamber 200. Control unit 280 may be coupled to another controller, such as a programmable logic controller (PLC) of valves 242A and 242B, positioned adjacent to the various chamber components. Bidirectional communication between control unit 280 and various other components of chamber 200 is handled via a plurality of signal cables collectively referred to as a signal bus. In addition to controlling the process gases and purge gases from gas sources 238, 239, and 240 and from the PLC of valves 242A and 242B, control unit 280 may also be configured to be responsible for the automated control of other activities used in wafer processing, such as wafer transport, temperature control, chamber evacuation, and other activities, some of which are described elsewhere herein.

[0042] Processing chamber 200 can be used in some embodiments of the present technology for processing methods that may include the formation, etching, or transformation of materials comprising semiconductor structures. It should be understood that the described chamber should not be considered limiting, and any chamber that can be configured to perform the described operations can be used similarly. Figure 3 Exemplary operations in a processing method 200 according to some embodiments of the present technology are illustrated. The method can be performed in various processing chambers and on one or more hosts or tools, including the aforementioned processing chamber 200. Method 300 may include a number of optional operations, which may or may not be specifically associated with some embodiments of the method according to the present technology. For example, many operations in the operation are described to provide a wider range of structure formations, but are not technically important, or can be performed by easily understood alternative methods. Method 300 may describe Figure 3 The operation illustrated in the diagram is as follows. Figure 3 The illustrations will be described in conjunction with the operation of method 300. It should be understood that the figures only illustrate partial schematic diagrams, and the substrate may contain any number of additional materials and features having the various features and aspects shown in the figures.

[0043] Method 300 may include additional operations prior to initiating the listed operations. For example, additional processing operations may include forming a structure on a semiconductor substrate, which may include both forming and removing material. For example, a transistor structure, a memory structure, or any other structure may be formed. Preprocessing operations may be performed in a chamber where method 300 can be performed, or processing may be performed in one or more other processing chambers prior to conveying the substrate to one or more semiconductor processing chambers where method 300 can be performed. In any case, method 300 may optionally include conveying the semiconductor substrate to a processing region of a semiconductor processing chamber, such as processing chamber 200 described above, or other chambers that may include components as described above. The substrate may be deposited on a substrate support, which may be a base such as substrate support 212, and may reside in a processing region (such as a processing volume) of the chamber.

[0044] An embodiment of the present technology shown in method 300 includes introducing a first deposition precursor into a substrate processing region 302. The first precursor may be a carbon-containing precursor having at least two reactive groups that can form bonds with groups on the surface of a substrate attached to the substrate processing region. Molecules of the first precursor react with the surface groups to form bonds connecting the first precursor molecules to the substrate surface. The reaction between the first precursor molecules and the groups on the substrate surface continues until most or all of the surface groups are bonded to the reactive groups on the first precursor molecules. A first portion of a compound layer of the deposition precursor is formed, which blocks further reaction between the first precursor molecules in the first precursor effluent and the substrate.

[0045] The formation rate of the first portion of the compound layer can depend on the temperature of the substrate and the temperature of the deposition precursor flowing into the substrate processing area. Exemplary substrate temperatures during the formation operation can be greater than or about 50°C, greater than or about 60°C, greater than or about 70°C, greater than or about 80°C, greater than or about 90°C, greater than or about 100°C, greater than or about 110°C, greater than or about 120°C, greater than or about 130°C, greater than or about 140°C, greater than or about 150°C, or higher. By maintaining an elevated substrate temperature (such as to greater than or about 100°C in some embodiments), an increased number of nucleation sites can be obtained along the substrate, which can improve formation and reduce void formation by improving coverage at each location.

[0046] The deposition precursor can be delivered at any number of temperatures to achieve increased ligand formation across the entire substrate, thereby improving initial formation and coverage across the entire substrate. The first deposition precursor can be delivered at temperatures greater than or about 80°C, and can be delivered at temperatures greater than or about 90°C, greater than or about 100°C, greater than or about 110°C, or higher. By increasing the deposition of the first precursor, an increased number of deposition sites can be formed, which allows for more seamless material growth on the substrate. Furthermore, this allows for the delivery of a second deposition precursor at temperatures below the first temperature. In some embodiments, the reaction between the second deposition precursor and the first deposition precursor may occur more readily than the reaction between the first deposition precursor and the substrate, and therefore delivering the first deposition precursor at elevated temperatures ensures adequate formation across the entire substrate. Subsequently, the second deposition precursor can react with the reactive groups of the first deposition precursor at lower temperatures. For example, the second deposition precursor can be transported at a temperature below or about 100°C, and can be transported at a temperature below or about 90°C, below or about 80°C, below or about 70°C, below or about 60°C, below or about 50°C, below or about 40°C or lower.

[0047] The formation rate of the first portion of the compound layer may also depend on the pressure of the first deposition precursor effluent in the substrate processing region. Exemplary effluent pressures in the substrate processing region may range from about 1 mTorr to about 500 Torr. Other exemplary ranges include 1 Torr to about 20 Torr, 5 Torr to 15 Torr, and 9 Torr to 12 Torr, among other exemplary ranges.

[0048] The first deposition precursor effluent can be retained in the substrate processing area for a period of time to almost completely or completely form a first portion of the compound layer. The precursor can be delivered in alternating pulses to allow material growth. In some embodiments, the pulse duration of one or both of the first and second deposition precursors can be greater than or about 0.5 seconds, greater than or about 1 second, greater than or about 2 seconds, greater than or about 3 seconds, greater than or about 4 seconds, greater than or about 5 seconds, greater than or about 10 seconds, greater than or about 20 seconds, greater than or about 40 seconds, greater than or about 60 seconds, greater than or about 80 seconds, greater than or about 100 seconds, or longer. In some embodiments, the first deposition precursor can be pulsed for a longer time than the second deposition precursor. Similar to the temperature described above, by increasing the residence time of the first deposition precursor, improved adhesion can be generated across the entire substrate. Subsequently, the second deposition precursor can react more readily with the ligands of the first deposition precursor, and therefore the second deposition precursor can be pulsed for a shorter time, which improves yield. For example, in some embodiments, the second precursor may be pulsed for less than or about 90% of the time the pulse reaches the first precursor. The second precursor may also be pulsed for less than or about 80% of the time the pulse reaches the first precursor, less than or about 70% of the time the pulse reaches the first precursor, less than or about 60% of the time the pulse reaches the first precursor, less than or about 50% of the time the pulse reaches the first precursor, less than or about 40% of the time the pulse reaches the first precursor, less than or about 30% of the time the pulse reaches the first precursor, or even shorter.

[0049] Method 300 further includes an operation 304 of purging or removing the first deposition precursor effluent from the substrate processing region after the formation of the first portion of the compound layer. The effluent can be removed by pumping it out of the substrate deposition region for a period ranging from about 10 seconds to about 100 seconds. Additional exemplary time ranges may include about 20 seconds to about 50 seconds, and 25 seconds to about 45 seconds, among others. However, in some embodiments, the increased purging time may begin to remove reactive sites, which could reduce uniform formation. Therefore, in some embodiments, purging may be performed for less than or about 60 seconds, and may be performed for less than or about 50 seconds, less than or about 40 seconds, less than or about 30 seconds, or even less. In some embodiments, a purging gas may be introduced into the substrate processing region to aid in the removal of the effluent. Exemplary purging gases include helium and nitrogen, among others.

[0050] After removing the first deposition precursor effluent, a second deposition precursor can be introduced into the substrate processing region 306. The second precursor may be a carbon-containing precursor having at least two reactive groups, which can form bonds with unreacted reactive groups of the first deposition precursor forming a first portion of the compound layer. Molecules of the second precursor react with the unreacted reactive groups of the first deposition precursor to form bonds linking the second precursor molecules to the first precursor molecules. The reaction between the second precursor molecules and the first precursor molecules continues until most or all of the unreacted reactive groups on the first precursor molecules have reacted with the second precursor molecules. A second portion of the compound layer of the deposition precursor is formed, which blocks further reaction between the second precursor molecules in the second precursor effluent and the first portion of the compound layer.

[0051] The formation rate of the second portion of the compound layer may also depend on the pressure of the effluent from the second deposition precursor in the substrate processing region. Exemplary effluent pressures in the substrate processing region may range from about 1 to about 20 Torr. Other exemplary ranges include 5 to 15 Torr, and 9 to 12 Torr, among others.

[0052] Method 300 further includes an operation 308 of purging or removing a second deposition precursor effluent from the substrate processing area after the second portion of the compound layer has been formed. The effluent can be removed by pumping it out of the substrate deposition area for a period ranging from about 10 seconds to about 100 seconds. Additional exemplary time ranges may include about 20 seconds to about 50 seconds, and 25 seconds to about 45 seconds, among others. In some embodiments, a purge gas may be introduced into the substrate processing area to aid in the removal of the effluent. Exemplary purge gases include helium and nitrogen, among others.

[0053] In the embodiment shown in method 300, after one or more cycles of forming a compound layer (e.g., after forming a first portion and a second portion of the compound layer), it is determined whether a target thickness 310 of the deposited carbon-containing material on the substrate has been reached. If the target thickness of the deposited carbon-containing material has not been reached, another cycle of forming the first portion and the second portion of the compound layer is performed. If the target thickness of the deposited carbon-containing material has been reached, another cycle for forming another compound layer is not started. The exemplary number of cycles for forming the compound layer may include 1 to 2000 cycles. Additional exemplary ranges of the number of cycles may include 50 to 1000 cycles, and 100 to 750 cycles, among others. Exemplary target thickness ranges for interrupting further cycles of forming the compound layer include about 10 nm to about 500 nm. Additional exemplary thickness ranges may include about 50 nm to about 300 nm, and 100 nm to about 200 nm, among others.

[0054] In the embodiment shown in method 300, the deposited carbonaceous material on the substrate may be annealed 312. Exemplary annealing may involve the thermal annealing of the deposited carbonaceous material comprising one or more continuous compound layers. Exemplary temperature ranges for thermal annealing may include about 100°C to about 600°C. Additional exemplary temperature ranges may include about 200°C to about 500°C, and about 300°C to about 450°C, among others. Exemplary times for thermal annealing may include a range of about 1 minute to about 120 minutes, about 10 minutes to about 60 minutes, and about 20 minutes to about 40 minutes, among others.

[0055] In some embodiments, method 300 may include optional processing operations, such as pretreatment, which may be performed to prepare a substrate surface for deposition. For example, before introducing the pretreated substrate into the first deposition precursor, the substrate surface may be exposed to one or more of a chemical etchant, thermal treatment, plasma, or passivating gas.

[0056] This technique includes forming an annealed carbonaceous material that exhibits almost no shrinkage compared to a deposited material. Exemplary shrinkage ranges compared to the deposited material include shrinkage rates of less than about 20%, less than about 15%, less than about 10%, and less than about 5% for the annealed material. Exemplary shrinkage ranges compared to the deposited carbonaceous material include shrinkage rates of about 15% to about 5% and about 10% to about 5% for the annealed material.

[0057] As described above, many molecular layer deposition precursors can be used with this technology to form carbon-containing materials on a substrate. Exemplary deposition precursors include a first deposition precursor and a second deposition precursor. The first deposition precursor may contain two or more first deposition reactive groups, said two or more first deposition reactive groups being operable to form bonds with reactive groups on the substrate surface and reactive groups on the second deposition precursor. In some embodiments, said two or more deposition reactive groups are identical, and in other embodiments, two of said two or more deposition reactive groups may be different. Examples of first deposition precursors include precursors having the following formula: Y-R1-Y, R1 may include one or more of alkyl, aryl or cycloalkyl, and other groups, and Y can independently include hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, or acyl chloride groups, as well as other reactive groups.

[0058] Specific examples of first deposition precursors include hydroquinone, terephthalaldehyde, terephthaloyl chloride, and p-phenylenediamine.

[0059] The second deposition precursor may comprise two or more second deposition reactive groups, said two or more second deposition reactive groups being operable to form bonds with an unreacted reactive group "Y" on the first deposition precursor. In some embodiments, said two or more second deposition reactive groups are identical, and in other embodiments, two or more of said two or more second deposition reactive groups are different. Examples of second deposition precursors include precursors having the following formula: Z-R2-Z, R2 may include one or more of alkyl, aryl or cycloalkyl, and other groups, and Z can independently include hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, or acyl chloride groups, as well as other reactive groups.

[0060] Specific examples of second deposition precursors include ethylene glycol and ethylenediamine.

[0061] A substrate on which a carbon-containing material is formed may include a material in which one or more features may be formed. The substrate may include any number of materials used in semiconductor processing. The substrate material may be or include silicon, germanium, dielectric materials comprising silicon oxide or silicon nitride, metallic materials, or any combination of these materials. The substrate may also include one or more substrate features formed within the substrate. According to the present technology, substrate features may be characterized by any shape or configuration. In some embodiments, features may be or include trench structures or pores formed within the substrate.

[0062] Although substrate features can be characterized by any shape or size, in some embodiments, substrate features can be characterized by a high aspect ratio or by the ratio of the feature's depth to the width across the feature. For example, in some embodiments, substrate features can be characterized by an aspect ratio greater than or about 5:1, and can be characterized by an aspect ratio greater than or about 10:1, greater than or about 15:1, greater than or about 20:1, greater than or about 25:1, greater than or about 30:1, greater than or about 40:1, greater than or about 50:1, or greater. Furthermore, the feature can be characterized by a narrow width or diameter across the feature (including between two sidewalls) of a size less than or about 20 nm, and can be characterized by a width across the feature less than or about 15 nm, less than or about 12 nm, less than or about 10 nm, less than or about 9 nm, less than or about 8 nm, less than or about 7 nm, less than or about 6 nm, less than or about 5 nm, or smaller.

[0063] In the foregoing description, numerous details have been set forth for purposes of explanation in order to provide an understanding of various embodiments of the present technology. However, it will be apparent to those skilled in the art that certain embodiments may be practiced without some of these details or with additional details.

[0064] Several embodiments have been disclosed, and those skilled in the art will recognize that various modifications, alternative constructions, and equivalents can be used without departing from the spirit of the embodiments. Furthermore, to avoid unnecessarily obscuring the present technology, many well-known processes and elements have not been described. Therefore, the above description should not be considered as limiting the scope of the present technology. Additionally, methods or processes may be described as sequential or step-by-step, but it should be understood that operations may be performed simultaneously or in a different order than listed.

[0065] In the case of a range of values ​​provided, it should be understood that, unless the context explicitly indicates otherwise, every intermediate value between the upper and lower limits of this range, up to the smallest fraction of the lower limit unit, is also specifically disclosed. Any narrower range between any clarified or unclarified intermediate value within the clarified range and any other clarified or intermediate value within this clarified range is covered. The upper and lower limits of those smaller ranges may be independently included in or excluded from the range, and each range, whether or not it includes either the upper or lower limit, or both, is also covered within this technique, subject to any specifically excluded limit values ​​within the clarified range. When the clarified range includes one or both of the limit values, it also includes ranges that exclude one or both of the included limit values.

[0066] As used herein and in the appended claims, unless the context clearly indicates otherwise, the singular forms “a”, “an”, and “the” include plural references. Thus, for example, the reference to “a precursor” includes multiple such precursors, and the reference to “the layer” includes one or more layers and their equivalents known to those skilled in the art, and so on.

[0067] Furthermore, when used in this specification and the appended claims, the terms “comprises(s)”, “comprising”, “contain(s)”, “containing”, “include(s)” and “including” are intended to specify the presence of the stated features, integers, components, or operations, but they do not exclude the presence or addition of one or more other features, integers, components, operations, actions, or groups.

Claims

1. A processing method, comprising the following steps: A first deposition precursor is introduced into a substrate processing region to form a first portion of an initial compound layer, wherein the first deposition precursor includes aldehyde reactive groups; Remove the first deposit effluent, which includes the first deposit precursor, from the substrate processing area; A second deposition precursor is introduced into the substrate processing region, wherein the second deposition precursor includes amine reactive groups, and wherein the amine reactive groups react with the aldehyde reactive groups to form a second portion of the initial compound layer; Remove the second deposition effluent, which includes the second deposition precursor, from the substrate processing area; as well as The initial compound layer is annealed at a temperature of 300°C to 600°C to form an annealed carbon-containing material on the surface of the substrate.

2. The processing method as described in claim 1, wherein the processing method further comprises the following steps: At least one additional compound layer is deposited on the initial compound layer, wherein the initial compound layer and the at least one additional compound layer form the annealed carbon-containing material on the surface of the substrate.

3. The processing method of claim 1, wherein the first deposition precursor is transported at a temperature greater than or equal to 100°C.

4. The processing method of claim 1, wherein the second deposition precursor is transported at a temperature less than or equal to 100°C.

5. The processing method as described in claim 1, wherein the first deposition time and the second deposition time are less than or equal to 5 seconds.

6. The processing method of claim 1, wherein the first deposition time is longer than the second deposition time.

7. The processing method of claim 1, wherein the flow step of the first deposition precursor increases the pressure in the substrate processing region to a pressure range of 1 mTorr to 500 Torr.

8. The processing method of claim 1, wherein the step of removing the first deposited effluent from the substrate processing area has a removal time of less than or equal to 60 seconds.

9. The processing method of claim 1, wherein the annealing step of the initial compound layer comprises thermal annealing at a temperature in the range of 300°C to 450°C.

10. The processing method of claim 1, wherein the initial compound layer shrinks by less than 10% of its volume due to the annealing step of the initial compound layer.

11. The processing method of claim 1, wherein the substrate comprises a substrate feature characterized by an aspect ratio greater than or equal to 5:1, and wherein the substrate feature is characterized by a width across the substrate feature of less than or equal to 10 nm.

12. A processing method, comprising the following steps: A first deposition precursor is introduced into the substrate processing area, wherein the first deposition precursor has a first formula, the first formula comprising: Y1-R1-Y2, Wherein R1 includes one or more of alkyl, aryl, or cycloalkyl groups, and Y1 and Y2 independently include hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, or acyl chloride groups, and The first deposition precursor reacts with reactive groups on the surface of the substrate in the substrate processing area to form a first portion of an initial compound layer on the surface of the substrate. Remove the first deposit effluent, which includes the first deposit precursor, from the substrate processing area; A second deposition precursor is introduced into the substrate processing region, wherein the second deposition precursor has a second formula, the second formula comprising: Z1-R2-Z2, Wherein R2 includes one or more of alkyl, aryl, or cycloalkyl groups, and Z1 and Z2 independently include hydroxyl, aldehyde, ketone, acid, amino, isocyanate, thiocyanate, or acyl chloride groups. The second deposition precursor reacts with the first portion of the initial compound layer to form the second portion of the initial compound layer; Remove the second deposition effluent, comprising the second deposition precursor, from the substrate processing area; and The initial compound layer is annealed at a temperature of 300°C to 600°C to form an annealed carbon-containing material on the surface of the substrate.

13. The processing method of claim 12, wherein R1 comprises an aryl group, Y1 and Y2 independently comprise an aldehyde or isocyanate group, R2 comprises an alkyl group, and Z1 and Z2 comprise an amino group.

14. The processing method of claim 12, wherein the first deposition precursor comprises terephthalaldehyde or 1,4-phenyl diisocyanate.

15. The processing method of claim 12, wherein the second deposition precursor comprises ethylenediamine.

16. The processing method of claim 12, wherein the removal step of the first deposition precursor includes the following steps: The purified gas flows into the substrate processing area, and Remove the mixture of the first deposited effluent and the purified gas from the substrate processing area.

17. The processing method of claim 16, wherein the purified gas comprises helium.

18. A processing method, comprising the following steps: Perform two or more cycles to form a carbon-containing composite layer on a substrate to form two or more carbon-containing composite layers; Each of the two or more cycles that form the carbon-containing composite layer includes the following steps: A first portion of an initial compound layer is formed on the surface of the substrate, wherein the first portion of the initial compound layer is formed by introducing a first deposition precursor into a substrate processing region, wherein the first deposition precursor reacts with reactive groups on the surface of the substrate in the substrate processing region to form the first portion of the initial compound layer, wherein the first deposition precursor is delivered to the substrate processing region at a first temperature; and A second portion of the initial compound layer is formed on at least a portion of the first portion of the initial compound layer, wherein the second portion of the initial compound layer is formed by introducing a second deposition precursor into the substrate processing region, wherein the second deposition precursor reacts with the first portion of the initial compound layer to form the second portion of the initial compound layer, and wherein the second deposition precursor is delivered to the substrate processing region at a second temperature lower than the first temperature; and The two or more carbon-containing composite layers on the substrate are annealed to form an annealed carbon-containing material on the surface of the substrate.

19. The processing method of claim 18, wherein the first deposition precursor comprises terephthalaldehyde or 1,4-phenyl diisocyanate, and the second deposition precursor comprises ethylenediamine.

20. The processing method of claim 18, wherein the two or more carbon-containing composite layers shrink by less than 10% of their volume due to the annealing step of the two or more carbon-containing composite layers.

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