Molecular layer deposition method and system

Abstract

An exemplary processing method may include flowing 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 an aldehyde-reactive group. The method may include removing a first deposition effluent containing the first deposition precursor from the substrate processing region. The method may include flowing a second deposition precursor into the substrate processing region. The second deposition precursor may include an amine-reactive group, which may react with the aldehyde-reactive group to form a second portion of the initial compound layer. The method may include removing a second deposition effluent containing 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.

Description

Technical Field

[0001] Cross - Reference to Related Applications

[0001] This application claims the benefit and priority of U.S. Provisional Application No. 16 / 935,385, entitled "MOLECULAR LAYER DEPOSITION METHOD AND SYSTEM", filed on July 22, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] Field of the Invention

[0002] This technology relates to semiconductor processing. Specifically, this technology relates to a method and system for depositing a carbon - containing material on a semiconductor substrate and performing an annealing conversion.

Background Art

[0003]

[0003] Integrated circuits are enabled by a process that creates complex, patterned material layers on a substrate surface. To create a patterned material on a substrate, a controlled method of forming and removing exposed materials is required. As device sizes continue to shrink, material formation can affect subsequent operations. For example, in a gap - filling operation, a material can be formed or deposited to fill a trench or other feature formed on a semiconductor substrate. These filling operations can be difficult because features can be characterized by a higher aspect ratio and reduced critical dimensions. For example, since deposition can occur at the top of the feature and along the sidewalls, continued deposition can pinch off the feature, including between the sidewalls within the feature, and create voids within the feature. This can affect the performance of the device and subsequent processing operations.

[0004]

[0004] Therefore, improved systems and methods that can be used to produce high - quality devices and structures are needed. These and other needs are addressed by this technology.

Summary of the Invention

[0005]

[0005] Embodiments of the present technology include a processing method for forming a carbon-containing material on a substrate using molecular layer deposition (MLD). This method may include introducing a first deposition precursor into a substrate processing area to form a first portion of an initial compound layer. The first deposition precursor may include aldehyde-reactive groups. This method may include removing a first deposition effluent containing the first deposition precursor from the substrate processing area. This method may include introducing a second deposition precursor into the substrate processing area. The second deposition precursor may include amine-reactive groups, which can react with aldehyde-reactive groups to form a second portion of the initial compound layer. This method may include removing a second deposition effluent containing the second deposition precursor from the substrate processing area. This method may include annealing the initial compound layer to form an annealed carbon-containing material on the surface of the substrate.

[0006]

[0006] 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 carbon-containing material on the surface of the substrate. The first deposition precursor may be delivered at a temperature of about 100°C or higher. The second deposition precursor may be delivered at a temperature of about 100°C or lower. The first and second deposition times may be about 5 seconds or less. The first deposition time may be longer than the second deposition time. By flowing the first deposition precursor, the pressure in the substrate processing area can be increased to a pressure range of about 1 millitorre to about 500 torre. Removal of the first deposition outflow from the substrate processing area may include a removal time of about 60 seconds or less. An exemplary thermal annealing temperature for annealing the compound layer may be about 100°C or higher (e.g., about 100°C to about 600°C). In some embodiments, the deposited and annealed initial compound layer shrinks by less than 10 volume% due to the annealing of the initial compound layer. In some embodiments, the substrate may include one or more substrate features characterized by an aspect ratio of about 5:1 or greater and a width of about 10 nm or less. In some embodiments, the method may further include depositing at least one additional compound layer on the initial compound layer, the initial compound layer and at least one additional compound layer forming an annealed carbon-containing material on the surface of the substrate.

[0007]

[0007] Embodiments of this technology also include a processing method that includes introducing a first deposition precursor into a substrate processing area. The first deposition precursor may be characterized by a first formula including: Y1-R1-Y2 [In the formula, R1 includes one or more alkyl groups, aromatic groups, or cycloalkyl groups, Y1 and Y2 independently contain a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, or an acyl chloride group. The first deposition precursor can react with reactive groups on the substrate surface within the substrate processing area to form a first portion of the initial compound layer on the substrate surface. This method may further include removing the first deposition effluent containing the first deposition precursor from the substrate processing area and introducing a second deposition precursor into the substrate processing area. The second deposition precursor may be characterized by a second formula comprising: Z1-R2-Z2 [In the formula, R2 includes one or more alkyl groups, aromatic groups, or cycloalkyl groups, Z1 and Z2 independently contain a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, or an acyl chloride group. The second deposition precursor may react with the first portion of the initial compound layer to form the second portion of the initial compound layer. The method may further include removing the second deposition effluent containing the second deposition precursor from the substrate processing area. The method may also include annealing the initial compound layer to form an annealed carbon-containing material on the surface of the substrate.

[0008]

[0008] In additional embodiments, exemplary R1 may be an aromatic group, exemplary Y1 and Y2 may independently be an aldehyde group or an isocyanate group, exemplary R2 may be an alkyl group, and exemplary Z1 and Z2 may be amino groups. The exemplary first deposition precursor may include terephthalaldehyde or 1,4-phenylenediisocyanate, and the exemplary second deposition precursor may include ethylenediamine. In further embodiments, removal of the first deposition precursor may include introducing a purge gas into the substrate processing area and removing a mixture of the first deposition effluent and the purge gas from the substrate processing area. The exemplary purge gas may include helium.

[0009]

[0009] Embodiments of the present technology further include a processing method for performing two or more cycles to form a carbon-containing composite layer on a substrate. Each of the two or more cycles for forming the carbon-containing composite layer may include forming a first portion of a compound layer on the surface of the substrate, the first portion of the compound layer being formed by introducing a first deposition precursor into a substrate processing area, the first deposition precursor reacting with reactive groups on the surface of the substrate within the substrate processing area to form the first portion of the compound layer. Each of the two or more cycles may also include forming a second portion of a compound layer on at least a portion of the first compound layer, the second portion of the compound layer being formed by introducing a second deposition precursor into a substrate processing area, the second deposition precursor reacting 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 can be annealed to form an annealed carbon-containing material on the surface of the substrate.

[0010]

[0010] In additional embodiments, the first deposition precursor may include terephthalaldehyde or 1,4-phenylenediisocyanate, and the second deposition precursor may include ethylenediamine. In further embodiments, two or more carbon-containing compound layers shrink by less than 10% by volume upon annealing of the compound layers.

[0011]

[0011] Such technologies can offer many advantages over conventional systems and methods. For example, embodiments of the technology produce carbon-containing layers with significantly fewer voids, cracks, and other physical defects than carbon-containing materials formed by conventional methods. The technology can also form carbon-containing materials that are denser and less porous than materials formed by conventional methods. Further details of embodiments of the technology, along with many of their advantages and features, are described below in conjunction with the accompanying drawings. [Brief explanation of the drawing]

[0012]

[0012] The nature and advantages of the disclosed technology can be further understood by referring to the remainder of this specification and the drawings.

[0013] [Figure 1]

[0013] The steps in the formation of a portion of the compound layer deposited by the molecular layer deposition process according to some embodiments of this technology are shown. [Figure 2]

[0014] This is a schematic cross-sectional view of an exemplary processing chamber according to several embodiments of this technology. [Figure 3]

[0015] This section illustrates an exemplary operation in a processing method according to several embodiments of this technology.

[0014]

[0016] Some of the drawings are included as schematic diagrams. It should be understood that drawings are for illustrative purposes only and should not be considered to scale unless explicitly stated otherwise. In addition, as schematic diagrams, they are provided to aid understanding and may not include all aspects or information compared to realistic depictions, and may include materials that are exaggerated for illustrative purposes.

[0015]

[0017] In the attached drawings, similar components and / or features may have the same reference numeral. Furthermore, various components of the same kind may be distinguished by following the reference numeral with letters that distinguish similar components. Where only the first reference numeral is used herein, the description is applicable to any one of the similar components having the same first reference numeral, regardless of the letters. [Modes for carrying out the invention]

[0016]

[0018] Carbon-containing materials can be used in the fabrication of semiconductor devices for many structures and processes, including their use as mask materials, etching-resistant materials, and trench-filling materials, among other applications. Specific examples of applications for carbon-containing materials include the formation of hot-implant hard masks, metal gate (MG) cut hard masks, metal gate fabrication, and reverse stone patterning. Current techniques include the formation of these carbon-containing materials on semiconductor substrates using molecular layer deposition (MLD).

[0017]

[0019] 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 the surface of a semiconductor substrate, the precursor forming 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 contain unbound molecules of the first deposition precursor, is removed from the processing area where the semiconductor substrate is exposed. A second deposition precursor can then be introduced onto the semiconductor substrate, where 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 contain unbound molecules of the second deposition precursor, is removed from the processing area. Here, the semiconductor substrate 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 of the first and second layers may be constructed on the deposited layers until the number of constructed compound layers reaches the desired thickness of the carbon-containing material on the semiconductor substrate. The compound layers can then be annealed to form the carbon-containing material on the semiconductor substrate.

[0018]

[0020] This technology provides solutions to problems associated with conventional methods for forming carbon-containing materials on semiconductor substrates. For example, this technology forms carbon-containing materials with significantly fewer voids, cracks, and other physical defects than carbon-containing materials formed using spin-on-carbon (SOC) and fluid chemical vapor deposition (FCVD) methods. Furthermore, this technology can form carbon-containing materials that are denser and less porous than materials formed by SOC and FCVD.

[0019]

[0021] The high levels of hydrogen found in many SOC and FCVD precursors result in significant shrinkage when the as-deposited material is processed to form the final material. Shrinkage as high as 50 volume percent is not uncommon in as-deposited SOC and FCVD materials after processing, leading to the creation of gaps, cracks, and voids in the processed material, as well as stress on substrate features in contact with the material. This technology produces processed carbon-containing materials with shrinkage of less than 10 volume percent (e.g., 5–10 volume percent, approximately less than 5 volume percent) compared to the as-deposited material.

[0020]

[0022] This technology also provides a solution to problems associated with 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 chemical vapor deposition (HDPCVD), often result in ion sputtering that damages substrate features on the semiconductor substrate. Furthermore, re-sputtered ions and other nuclides that can cause defects in the deposited carbon-containing material can be generated. In addition, these deposition methods often result in non-uniform material deposition within and around substrate features, voids within and around substrate trenches and steps, and non-uniform surfaces in flat substrate areas. This technology can form carbon-containing materials with high levels of conformability at narrow substrate features (e.g., dimensions less than approximately 25 nm wide) and high aspect ratios (e.g., AR greater than 10:1) without requiring plasma that can damage substrate features during deposition.

[0021]

[0023] Figure 1 shows a simplified cross-section of a substrate surface during six phases of an exemplary MLD process for forming a compound layer on the substrate surface. The first cross-section 102 shows a portion of the substrate having a reactive surface nuclide “-X” that can be utilized for bonding with a first deposition precursor having the formula: TIFF0007842078000001.tif26170[where “-Y” represents a reactive group capable of forming a covalent bond with the “-X” group on the substrate surface under the corresponding reaction conditions]. The next cross-section 104 shows the introduction of the first deposition precursor onto the substrate surface and the formation of covalent bonds between some molecules of the precursor and the -X groups on the surface. The subsequent cross-section 106 shows the molecules of the first deposition precursor that saturate the available -X groups to form a first portion (e.g., the first monolayer) of the compound layer and leave additional precursor molecules floating in the gas phase as part of the first deposition precursor effluent. The next cross-section 108 shows the removal of unreacted molecules in the first deposition precursor from the vicinity of the substrate surface to prepare for the introduction of the second deposition precursor.

[0022]

[0024] In some embodiments, the -X groups can have a greater number density (e.g., -X groups per unit area) in some portions of the substrate than in other portions. For example, the number of -X groups present per unit area at the bottom of a gap, trench, or other substrate feature of the substrate can be greater than the number of -X groups on the sidewalls (e.g., vertical walls) of the substrate feature. For example, in some embodiments, the base of the feature can more readily form the reactive ligand of the first deposition precursor, and thus, the base unit area of the substrate can generate at least 1.1 times the number of reactive ligands, at least 1.2 times the number of reactive ligands, at least 1.4 times the number of reactive ligands, at least 1.6 times the number of reactive ligands, at least 1.8 times the number of reactive ligands, at least 2.0 times the number of reactive ligands, at least 2.5 times the number of reactive ligands, at least 3.0 times the number of reactive ligands, at least 5.0 times the number of reactive ligands, at least 10.0 times the number of reactive ligands, or a greater number of reactive ligands than the sidewalls. In these embodiments, the MLD process forms a compound layer on the bottom surface of the substrate feature where the -X groups have a greater number density and forms little or no compound layer on the sidewall surface of the substrate feature where the number density of the -X groups is lower or zero. These embodiments facilitate bottom-up gap filling of the compound layer within the substrate feature and significantly reduce the likelihood of voids or seams forming from the MLD deposition material accumulating on the sidewalls of the substrate feature.

[0023]

[0025] The second deposition precursor shown in this example has the formula: The formula is represented by TIFF0007842078000002.tif14170 [wherein "-Z" represents a reactive group capable of forming covalent bonds with unreacted "-Y" groups on a layer formed by the reaction of the first deposition precursor with available "-X" groups on the substrate surface]. Section 110 shows that the second deposition precursor is introduced to the substrate surface, and some molecules of the second precursor form covalent bonds with available "-Y" groups in the layer formed by the first precursor. Section 112 shows molecules of the second deposition precursor that saturate the available "-Y" groups to form a second portion of the compound layer (e.g., a second monolayer), leaving further 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 in preparation for the formation of an additional compound layer for forming a carbon-containing material on the substrate or for processing the compound layer.

[0024]

[0026] In the embodiment shown in Figure 1, the first deposition precursor may include two reactive groups "-Y" positioned para around a central aromatic ring. Exemplary -Y groups may include hydroxide groups, aldehyde groups, ketone groups, acid groups, amino groups, isocyanate groups, thiocyanate groups, or acyl chloride groups, among other reactive groups. In additional embodiments, there may be two or more -Y groups, three or more -Y groups, four or more -Y groups, or five or more -Y groups positioned around the aromatic ring. Additional embodiments also include other combinations of -Y groups in the first deposition precursor, where each -Y group is the same reactive group, where at least two -Y groups are different reactive groups, or where all -Y groups are different reactive groups. Specific examples of the first deposition precursor include, among others, hydroquinone, terephthalaldehyde, terephthaloyl chloride, and p-phenylenediamine.

[0025]

[0027] The second deposition precursor of the embodiment shown in Figure 1 contains two reactive groups "-Z" positioned on the carbons on either side of the ethyl group. The reactive "-Z" groups are selected to be reactive with the "-Y" group under processing conditions close to the substrate surface on which the first portion of the compound layer is formed. Exemplary "-Z" groups may include hydroxide groups, aldehyde groups, ketone groups, acid groups, amino groups, isocyanate groups, thiocyanate groups, or acyl chloride groups, among other reactive groups. Specific examples of the second deposition precursor include, among others, ethylene glycol and ethylenediamine.

[0026]

[0028] The -Y and -Z groups can be selected to form a covalent reaction bond when these groups come into contact near the substrate surface. Exemplary combinations of -Y and -Z groups in the first and second deposition precursors may include acyl-Y chloride and hydroxyl-Z group, and aldehyde-Y and amino-Z group, among 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, and p-phenylenediamine and succinaldehyde, among other combinations.

[0027]

[0029] In yet another embodiment, the first deposition precursor may contain a central bonding group other than a phenyl group, and the second deposition precursor may contain a central bonding group other than an ethylene group. For example, the first and second deposition precursors are Y-R1-Y and ZR2-Z [In the formula, the -Y group is as described above, and the -R1- and -R2- groups can independently represent alkyl groups, aromatic groups, or cycloalkyl groups among other types of hydrocarbon groups].

[0028]

[0030] Figure 2 is a cross-sectional view of an exemplary processing chamber 100 according to several embodiments of the present technology. The figure may show an overview of a system that incorporates one or more aspects of the present technology and / or can carry out one or more deposition or other processing operations according to embodiments of the present technology. Additional details of the chamber 200 or the methods carried out may be described further below. While the chamber 200 may be used to form a composite layer according to several embodiments of the present technology, it should be understood that the method may be carried out similarly in any chamber in which composite film formation may take place.

[0029]

[0031] Referring to Figure 2, the chamber 200 includes a chamber body 202 having a slit valve 208 formed in its side wall 204, and a substrate support 212 disposed within it. The substrate support 212 is attached to a lift motor 214 for raising and lowering the substrate support 212 and the substrate 210 placed on it. The substrate support 212 may also include a vacuum chuck, electrostatic chuck, or clamp ring for securing the substrate 210 to the substrate support 212 during processing. Furthermore, the substrate support 212 can be heated using an embedded heating element such as a resistance heater, or using radiant heat such as a heating lamp placed above the substrate support 212. A purge ring 222 may be placed on the substrate support 212 and define a purge channel 224 that provides a purge gas to prevent deposition on the peripheral portion of the substrate 210.

[0030]

[0032] The precursor delivery device 230 is located on top of the chamber body 202 and delivers precursors such as deposition precursor, carrier gas, and / or purge gas to the chamber 200. The vacuum system 278 communicates with the pumping channel 279 to help discharge deposition effluent and / or other gases from the chamber 200 and maintain a desired pressure or a desired pressure range inside the pumping zone 266 of the chamber 200.

[0031]

[0033] The precursor delivery device 230 includes a chamber lid 232 having an expansion channel 234 formed in its central portion. The chamber lid 232 also includes a bottom surface 260 extending from the expansion channel 234 to the peripheral portion of the chamber lid 232. The bottom surface 260 is sized and shaped to substantially cover the substrate 210 placed on the substrate support 212. The expansion channel 234 has an inner diameter that gradually increases from the upper part 237 to the lower part 235 adjacent to the bottom surface 260 of the chamber lid 232. The velocity of the precursor flowing through the expansion channel is reduced due to the expansion of the precursor as it flows through the expansion channel 234. The reduced precursor velocity reduces the likelihood of blowing off reactants adsorbed on the surface of the substrate 210.

[0032]

[0034] The precursor delivery device 230 also includes at least two high-speed operating 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 diamino-containing precursor. When a third deposition precursor is desired, a third valve can be dedicated to the third deposition precursor. For example, if the MLD process involves exposing the substrate to both a dialdehyde-containing precursor and a diisocyanate-containing deposition precursor, the dialdehyde-containing precursor can be introduced through the second valve and the diisocyanate-containing precursor can be introduced through the third valve.

[0033]

[0035] Valve 242 may be any valve capable of accurately and repeatedly delivering short pulses of deposition precursor, carrier gas, and / or purge gas into the chamber body 202. In some cases, the on / off cycle or pulse of valve 242 may be as fast as approximately 100 milliseconds or less. Valve 242 may be controlled directly by a system computer, such as a mainframe, or by a chamber / application-specific controller, such as a programmable logic computer (PLC). For example, valve 242 may be an electronically controlled (EC) valve.

[0034]

[0036] Returning to Figure 2, a control unit 280, such as a programmed personal computer or workstation computer, can be connected to the chamber 200 to control processing conditions. For example, the control unit 280 may be configured to control the flow of deposition precursor and purge gas from gas sources 238, 239, and 240 through valves 242A and 242B during different stages of the substrate process sequence. The control unit 280 can be any form of general-purpose computer processor that can be used in an industrial environment to control various chambers and subprocessors.

[0035]

[0037] Exemplary, the control unit 280 comprises a central processing unit (CPU), support circuits, and memory including associated control software. The CPU can use any suitable memory, such as random access memory, read-only memory, a floppy disk drive, a hard disk, or any other form of local or remote digital storage. Various support circuits may be connected to the CPU to support the chamber 200. The control unit 280 may be connected to other controllers located adjacent to individual chamber components, such as the programmable logic controllers for valves 242A and 242B. Bidirectional communication between the control unit 280 and various other components of the chamber 200 is handled through a number of signal cables collectively called a signal bus. In addition to controlling process gases and purge gases from gas sources 238, 239, and 240, and from the programmable logic controllers for valves 242A and 242B, the control unit 280 can be configured to handle other operations used in wafer processing, such as automatic control of wafer transport, temperature control, and chamber exhaust, some of which are described separately herein.

[0036]

[0038] The processing chamber 200 may be used in some embodiments of the Art for processing methods that may include forming, etching, or transforming materials for semiconductor structures. It should be understood that the chambers described are not limiting, and any chamber that can be configured to perform the operations described may be used similarly. Figure 3 shows an exemplary operation in processing method 200 according to some embodiments of the Art. This method may be performed in various processing chambers, including the processing chamber 200 described above, and on one or more mainframes or tools. Method 300 may include a number of optional operations that may or may not be specifically associated with some embodiments of the methods according to the Art. For example, many operations are described to provide a broader range of structure formation and may not be important to the Art, or may be performed by alternative methodologies for ease of understanding. Method 300 describes the operations schematically shown in Figure 3, and its description is provided in conjunction with the operations of Method 300. It should be understood that the figure is only a partial schematic and the substrate may include any number of additional materials and features having various properties and embodiments as shown.

[0037]

[0039] Method 300 may include additional operations before commencing the enumerated operations. For example, additional processing operations may include forming a structure on the 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. The prior processing operations may be performed in the chamber in which Method 300 may be carried out, or the processing may be carried out in one or more other processing chambers before the substrate is delivered into one or more semiconductor processing chambers in which Method 300 may be carried out. In any case, Method 300 may optionally include delivering the semiconductor substrate to a processing area of ​​a semiconductor processing chamber, such as the processing chamber 200 described above, or other chambers that may include the components described above. The substrate may be deposited on a substrate support, which may be a pedestal such as the substrate support 212, or may be located in a processing area of ​​a chamber such as a processing volume.

[0038]

[0040] Embodiments of the technique shown in Method 300 include introducing a first deposition precursor into a substrate processing area 302. The first precursor may be a carbon-containing precursor having at least two reactive groups capable of forming bonds with groups attached to the substrate surface in the substrate processing area. The molecules of the first precursor react with the surface groups to form bonds that link the first precursor molecules to the substrate surface. The reaction between the first precursor molecules and the groups on the substrate surface continues until almost all 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, blocking further reactions between the first precursor molecules and the substrate in the first precursor effluent.

[0039]

[0041] The formation rate of the first portion of the compound layer may depend not only on the temperature of the deposition precursor flowing into the substrate processing area, but also on the temperature of the substrate. Exemplary substrate temperatures during the formation operation may be about 50°C or higher, about 60°C or higher, about 70°C or higher, about 80°C or higher, about 90°C or higher, about 100°C or higher, about 110°C or higher, about 120°C or higher, about 130°C or higher, about 140°C or higher, about 150°C or higher, or higher. In some embodiments, by maintaining the substrate temperature at an elevated temperature, for example, 100°C or higher, the number of available nucleation sites along the substrate can be increased, improving the formation by improving the formation range at each location and reducing void formation.

[0040]

[0042] The deposition precursor can be delivered at any number of temperatures to increase ligand formation across the entire substrate and improve initial formation and the overall formation range of the substrate. The first deposition precursor can be delivered at a temperature of about 80°C or higher, and may be delivered at about 90°C or higher, about 100°C or higher, about 110°C or higher, or higher. By increasing the deposition of the first precursor, an increased number of deposition sites can be formed, allowing the material to grow more seamlessly on the substrate. Additionally, this may allow the second deposition precursor to be delivered at a lower temperature than the first. 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, so delivering the first deposition precursor at a higher temperature can ensure sufficient formation across the entire substrate. The second deposition precursor can then react with the reactive groups of the first deposition precursor at a lower temperature. For example, the second deposition precursor can be delivered at a temperature of about 100°C or lower, and may be delivered at a temperature of about 90°C or lower, about 80°C or lower, about 70°C or lower, about 60°C or lower, about 50°C or lower, about 40°C or lower, or even lower.

[0041]

[0043] The formation rate of the first portion of the compound layer may also depend on the pressure of the first deposition precursor effluent within the substrate processing area. Exemplary effluent pressures within the substrate processing area can range from about 1 millitorre to about 500 tors. Additional exemplary ranges include, among others, 1 torre to about 20 tors, 5 torre to 15 tors, and 9 torre to 12 tors.

[0042]

[0044] The first deposition precursor effluent may remain in the substrate processing area for a period of time to form a first portion of the compound layer almost or completely. The precursor may be delivered in alternating pulses to grow the material. In some embodiments, the pulse duration of one or both of the first and second deposition precursors may be about 0.5 seconds or longer, about 1 second or longer, about 2 seconds or longer, about 3 seconds or longer, about 4 seconds or longer, about 5 seconds or longer, about 10 seconds or longer, about 20 seconds or longer, about 40 seconds or longer, about 60 seconds or longer, about 80 seconds or longer, about 100 seconds or longer, or longer. In some embodiments, the first deposition precursor may be pulsed for a longer period than the second deposition precursor. Similar to the temperature described above, increasing the residence time of the first deposition precursor can produce improved adhesion across the substrate. The second deposition precursor can then react more readily with the ligand of the first deposition precursor, and therefore the second deposition precursor can be pulsed for a shorter period of time, which can improve throughput. For example, in some embodiments, the second precursor may be pulsed for about 90% or less of the time the first precursor is pulsed. The second precursor may also be pulsed for about 80% or less of the time the first precursor is pulsed, or for about 70% or less of the time the first precursor is pulsed, about 60% or less of the time the first precursor is pulsed, about 50% or less of the time the first precursor is pulsed, about 40% or less of the time the first precursor is pulsed, about 30% or less of the time the first precursor is pulsed, or for a shorter time.

[0043]

[0045] Method 300 also includes an operation to purge or remove first deposition precursor effluent from the substrate processing area 304 following the formation of the first portion of the compound layer. The effluent can be removed by discharge from the substrate deposition area over a period ranging from about 10 seconds to about 100 seconds. Additional exemplary time ranges may include, among other exemplary time ranges, about 20 seconds to about 50 seconds and 25 seconds to about 45 seconds. However, in some embodiments, extending the purging time may cause reaction sites to begin to be removed, potentially reducing uniform formation. Therefore, in some embodiments, purging may be carried out over a period of about 60 seconds or less, and may be carried out over a period of about 50 seconds or less, about 40 seconds or less, or about 30 seconds or less, or shorter. In some embodiments, a purge gas may be introduced into the substrate processing area to assist in the removal of effluent. Exemplary purge gases include, among other purge gases, helium and nitrogen.

[0044]

[0046] After the removal of the first deposition precursor effluent, the second deposition precursor can be introduced into the substrate processing area 306. The second precursor may be a carbon-containing precursor having at least two reactive groups capable of forming bonds with unreacted reactive groups of the first deposition precursor that formed the first portion of the compound layer. The molecules of the second precursor react with the unreacted reactive groups of the first deposition precursor to form bonds that link 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 completed their reaction with the second precursor molecules. A second portion of the compound layer of the deposition precursor is formed that blocks further reactions between the second precursor molecules in the second precursor effluent and the first portion of the compound layer.

[0045]

[0047] The formation rate of the second portion of the compound layer may also depend on the pressure of the second deposition precursor effluent within the substrate processing area. Exemplary effluent pressures within the substrate processing area can range from about 1 Torre to about 20 Torre. Additional exemplary ranges include, among others, 5 Torre to 15 Torre and 9 Torre to 12 Torre.

[0046]

[0048] Method 300 also includes an operation to purge or remove a second deposition precursor effluent from the substrate processing area 308 following the formation of the second portion of the compound layer. The effluent can be removed by discharge from the substrate deposition area over a period ranging from about 10 seconds to about 100 seconds. Additional exemplary time ranges may include, among other exemplary time ranges, about 20 seconds to about 50 seconds and 25 seconds to about 45 seconds. In some embodiments, a purge gas may be introduced into the substrate processing area to assist in the removal of the effluent. Exemplary purge gases include, among other purge gases, helium and nitrogen.

[0047]

[0049] Embodiments of Method 300 include a determination 310 of whether a target thickness of the as-deposited carbon-containing material has been achieved following one or more cycles of forming the compound layer (e.g., following the formation of the first and second portions of the compound layer). If the target thickness of the as-deposited carbon-containing material has not been achieved, a new cycle of forming the first and second portions of the compound layer is performed. If the target thickness of the as-deposited carbon-containing material has been achieved, no further cycles for forming another compound layer are initiated. The exemplary number of cycles for forming the compound layer may include 1 to 2000 cycles. Further exemplary ranges of cycle numbers may include 50 to 1000 cycles and 100 to 750 cycles, among other exemplary ranges. The exemplary range of target thickness for discontinuing further cycles of forming the compound layer may 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 other exemplary thickness ranges.

[0048]

[0050] In embodiments of Method 300, a carbon-containing material can be annealed as it is deposited on a substrate.312 Exemplary annealing may include thermal annealing of a carbon-containing material made from one or more consecutive 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 other exemplary temperature ranges. Exemplary times for thermal annealing may include about 1 minute to about 120 minutes, about 10 minutes to about 60 minutes and about 20 minutes to about 40 minutes, among other exemplary time ranges.

[0049]

[0051] In some embodiments, Method 300 may include optional processing operations, such as pretreatment, which may be performed to prepare the substrate surface for deposition. For example, the substrate surface may be exposed to one or more of the following: a chemical etchant, heat treatment, plasma, or passivation gas, before introducing the pretreated substrate into the first deposition precursor.

[0050]

[0052] This technology involves forming annealed carbon-containing materials with minimal shrinkage compared to the as-deposited material. Exemplary shrinkage ranges include approximately less than 20%, less than 15%, less than 10%, and less than 5% shrinkage of the annealed material compared to the as-deposited material. Exemplary shrinkage ranges also include approximately 15% to 5% and approximately 10% to 5% shrinkage of the annealed material compared to the as-deposited carbon-containing material.

[0051]

[0053] As described above, a number of molecular layer deposition precursors can be used in the current technique 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 capable of forming bonds with reactive groups on the substrate surface and reactive groups on the second deposition precursor. In some embodiments, the two or more deposition reactive groups are the same, and in additional embodiments, two of the two or more deposition reactive groups may be different. An example of the first deposition precursor is given by formula: YR1-Y [In the formula, R1 may include one or more of the following groups: alkyl groups, aromatic groups, or cycloalkyl groups.] Y independently includes precursors having other reactive groups, which may include hydroxide groups, aldehyde groups, ketone groups, acid groups, amino groups, isocyanate groups, thiocyanate groups, or acyl chloride groups. Specific examples of the first deposition precursor include, in particular, hydroquinone, terephthalaldehyde, terephthaloyl chloride, and p-phenylenediamine.

[0052]

[0054] The second deposition precursor may contain two or more second deposition reactive groups capable of forming a bond with the unreacted reactive group "Y" on the first deposition precursor. In some embodiments, the two or more second deposition reactive groups are the same, and in additional embodiments, two of the two or more second deposition reactive groups are different. An example of the second deposition precursor is given by formula: ZR2-Z [In the formula, R2 may include one or more of the following groups: alkyl groups, aromatic groups, or cycloalkyl groups.] Z independently includes precursors having other reactive groups, which may include hydroxide groups, aldehyde groups, ketone groups, acid groups, amino groups, isocyanate groups, thiocyanate groups, or acyl chloride groups. Specific examples of the second deposition precursor include, in particular, ethylene glycol and ethylenediamine.

[0053]

[0055] A substrate on which a carbon-containing material is formed may include a material on which one or more features may be formed. The substrate may include any number of materials used in semiconductor processing. The substrate material may include, or may include, a dielectric material containing silicon, germanium, silicon oxide or silicon nitride, a metallic material, or any number of combinations of these materials. The substrate may also include one or more substrate features formed within the substrate. The substrate features may be characterized by any shape or configuration according to the art. In some embodiments, the features may include, or may include, a trench structure or opening formed within the substrate.

[0054]

[0056] While substrate features can be of any shape or size, in some embodiments, substrate features can be characterized by a higher aspect ratio or a ratio of the depth of the feature to the width across the feature. For example, in some embodiments, substrate features can be characterized by an aspect ratio of about 5:1 or greater, and may be about 10:1 or greater, about 15:1 or greater, about 20:1 or greater, about 25:1 or greater, about 30:1 or greater, about 40:1 or greater, about 50:1 or greater, or larger. In addition, features can be characterized by a narrow width or diameter across the feature, including between two sidewalls, for example, a dimension of about 20 nm or less, and a width across the feature of about 15 nm or less, about 12 nm or less, about 10 nm or less, about 9 nm or less, about 8 nm or less, about 7 nm or less, about 6 nm or less, about 5 nm or less, or smaller.

[0055]

[0057] In the above description, numerous details have been presented for illustrative purposes 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 can be carried out without some of these details, or with additional details.

[0056]

[0058] While several embodiments have been disclosed, those skilled in the art will recognize that various modifications, alternative structures, and equivalents can be used without departing from the spirit of the embodiments. In addition, some well-known processes and elements have not been described in order to avoid unnecessarily obscuring the Art. Therefore, the above description should not be construed as limiting the scope of the Art. Furthermore, while methods or processes may be described sequentially or stepwise, it should be understood that operations may be performed simultaneously or in an order different from that described.

[0057]

[0059] Where a range of values ​​is provided, unless explicitly stated otherwise in the context, each intermediary value between the upper and lower limits of that range is specifically disclosed down to the smallest unit of the lower limit. This includes any narrower range between any listed or unlisted intermediary values ​​within the stated range, and any other listed or intermediary values ​​within that stated range. The upper and lower limits of such narrower ranges may be independently included in or excluded from that range, and each range in which one or both limit values ​​are included, or neither is included, is also included in this art and applies to any limit values ​​that are specifically excluded from the stated range. Where a stated range includes one or both limit values, it also includes ranges that exclude one or both of these included limit values.

[0058]

[0060] As used herein and in the claims, the singular forms “a,” “an,” and “the” include multiple references unless the context clearly indicates otherwise. Thus, for example, “a precursor” includes multiple such precursors, “the layer” includes one or more layers and equivalents known to those skilled in the art, and so on.

[0059]

[0061] Furthermore, when used herein and in the claims, the terms “comprise(s),” “comprising,” “contain(s),” “containing,” “include(s),” and “including” are intended to identify the presence of the described feature, integer, component, or operation, and not to exclude the presence or addition of one or more other features, integers, components, operations, actions, or groups.

Claims

1. A first deposition precursor containing an aldehyde-reactive group is introduced into the substrate processing region to form a first portion of the initial compound layer. To remove the first deposit outflow containing the first deposit precursor from the substrate processing area, A second deposition precursor containing an amine-reactive group that reacts with the aldehyde-reactive group is introduced into the substrate processing region to form a second portion of the initial compound layer. To remove the second deposit outflow containing the second deposit precursor from the substrate processing area, and The initial compound layer is annealed to form an annealed carbon-containing material on the surface of the substrate. Includes, A processing method in which the first deposition time is longer than the second deposition time.

2. The processing method according to claim 1, further comprising depositing at least one additional compound layer 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 according to claim 1, wherein the first deposition precursor is delivered at a temperature of approximately 100°C or higher.

4. The processing method according to claim 1, wherein the second deposition precursor is delivered at a temperature of approximately 100°C or lower.

5. The processing method according to claim 1, wherein the first deposition time and the second deposition time are approximately 5 seconds or less.

6. The processing method according to claim 1, wherein the first deposition precursor is delivered at a temperature higher than the temperature at which the second deposition precursor is delivered.

7. The processing method according to claim 1, wherein the flow of the first deposition precursor increases the pressure in the substrate processing area from about 1 millitorre to about 500 torre.

8. The processing method according to claim 1, wherein the removal of the first deposited and flowing material from the substrate processing area has a removal time of approximately 60 seconds or less.

9. The processing method according to claim 1, wherein the annealing of the initial compound layer includes thermal annealing at a temperature in the range of about 100°C to about 600°C.

10. The processing method according to claim 1, wherein the initial compound layer shrinks by less than 10 volume percent by annealing of the initial compound layer.

11. The processing method according to claim 1, wherein the features in the substrate include a substrate feature having an aspect ratio of about 5:1 or more, the substrate feature has a width across the substrate feature of about 10 nm or less, and the number of reactive surface nuclides per unit area is greater at the bottom of the substrate feature than at the side walls of the substrate feature.

12. The first deposition precursor is introduced into the substrate processing region, wherein the first deposition precursor is: Y １ -R １ -Y ２ [In the formula, R １ This includes one or more alkyl groups, aromatic groups, or cycloalkyl groups. Y １ and Y ２ [The first formula includes independently a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, or an acyl chloride group] The first deposition precursor reacts with reactive groups on the surface of the substrate within the substrate processing region to form a first portion of the initial compound layer on the surface of the substrate, thereby introducing the first deposition precursor into the substrate processing region. To remove the first deposit outflow containing the first deposit precursor from the substrate processing area, The second deposition precursor is introduced into the substrate processing region, wherein the second deposition precursor is: Z １ -R ２ -Z ２ [In the formula, R ２ This includes one or more alkyl groups, aromatic groups, or cycloalkyl groups. Z １ and Z ２ [The second formula includes independently a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, or an acyl chloride group] The second deposition precursor reacts with the first portion of the initial compound layer to form the second portion of the initial compound layer, thereby introducing the second deposition precursor into the substrate processing region. To remove the second deposit outflow containing the second deposit precursor from the substrate processing area, and Annealing the initial compound layer to form an annealed carbon-containing material on the surface of the substrate. Including the first deposition time being longer than the second deposition time, A processing method wherein the first and second deposition precursors comprise terephthaloyl chloride and ethylene glycol, terephthalaldehyde and ethylenediamine, or p-phenylenediamine and succinaldehyde.

13. R １ It contains an aromatic group, Y １ and Y ２ Each independently contains an aldehyde group, R ２ contains an alkyl group, Z １ and Z ２ The processing method according to claim 12, wherein the amino group is included.

14. The treatment method according to claim 12, wherein the first deposition precursor comprises terephthalaldehyde.

15. The treatment method according to claim 12, wherein the second deposition precursor contains ethylenediamine.

16. The removal of the first deposition precursor is Introducing purge gas into the substrate processing area, and The mixture of the first deposit and the purge gas is removed from the substrate processing area. The processing method according to claim 12, including the method described in claim 12.

17. The treatment method according to claim 16, wherein the purge gas contains helium.

18. This involves performing two or more cycles to form a carbon-containing composite layer on a substrate, Each of the two or more cycles forming the carbon-containing composite layer is 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 the substrate processing region, and the first deposition precursor reacts with reactive groups on the surface of the substrate within the substrate processing region to form the first portion of the compound layer, and The method involves forming a second portion of a 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. This includes carrying out two or more cycles to form a carbon-containing composite layer on a substrate, and Annealing two or more carbon-containing composite layers on the substrate to form an annealed carbon-containing material on the surface of the substrate. Including the first deposition time being longer than the second deposition time, A processing method wherein the first and second deposition precursors comprise terephthaloyl chloride and ethylene glycol, terephthalaldehyde and ethylenediamine, or p-phenylenediamine and succinaldehyde.

19. The processing method according to claim 18, wherein two or more carbon-containing compound layers shrink by less than 10 volume percent by annealing of the compound layers.

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