Method for forming a structure comprising a carbon material, a structure formed using the method, and a system for forming a structure

Abstract

To provide a method and a system for forming a structure containing a carbon material; and to provide a structure formed by using the method or the system.SOLUTION: An illustrative method is to provide inert gas into a reaction chamber for plasma ignition, to provide a carbon precursor to the reaction chamber, and to form an initial viscous carbon material on the surface of a substrate by forming plasma in the reaction chamber, and further includes changing or forming a carbon material from the initial viscous carbon material, and forming a processed carbon material by processing the carbon material with active species.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates generally to methods of forming structures suitable for use in the manufacture of electronic devices. More specifically, examples of the present disclosure relate to methods of forming structures including carbon material layers, structures including such layers, and systems for carrying out the methods and / or for forming the structures. [Background technology]

[0002] During the manufacture of devices, such as semiconductor devices, it is often desirable to fill features (e.g., trenches or gaps) on a surface of a substrate with an insulating or dielectric material. Some techniques for filling features include depositing a layer of a flowable carbon material.

[0003] While the use of carbon materials to fill features can work well for some applications, filling features using conventional deposition techniques has several drawbacks, especially as the size of the features being filled decreases. For example, during deposition of carbon materials, such as techniques involving plasma processes, voids can form within the deposited material, especially within gaps. Such voids can remain even after reflowing the deposited material.

[0004] In addition to being flowable, it may be desirable for the carbon material to exhibit other properties, such as a desired harness or modulus and / or etch selectivity relative to other material layers. As device and feature sizes continue to decrease, it becomes increasingly difficult to apply traditional carbon material deposition techniques to manufacturing processes while obtaining the desired packing capabilities and material properties. Additionally, various attempts to deposit carbon materials onto the surface of a substrate have resulted in undesirable amounts of particles on the substrate surface.

[0005] Therefore, improved methods for forming structures, particularly methods for filling gaps in a substrate surface with carbon materials, reducing void formation in the carbon materials and / or providing desired carbon material properties and / or producing fewer particles, are desirable.

[0006] All descriptions, including descriptions of problems and solutions described in this section, are included in this disclosure solely for the purpose of providing a background for the disclosure and should not be construed as an admission that any or all of the descriptions were known at the time the invention was made or that they constitute prior art. Summary of the Invention [Means for solving the problem]

[0007] Various embodiments of the present disclosure relate to methods of forming structures (sometimes referred to herein as film structures) suitable for use in forming electronic devices. The manner in which various embodiments of the present disclosure address shortcomings of conventional methods and structures is described in more detail below, but generally, exemplary embodiments of the present disclosure provide improved methods of forming structures comprising carbon materials, structures comprising carbon materials, systems for carrying out the methods, and / or for forming structures. The methods described herein can be used to fill features on a surface of a substrate.

[0008] According to various embodiments of the present disclosure, a method of forming a structure is provided. An exemplary method includes providing a substrate in a reaction chamber, providing an inert gas to the reaction chamber, providing a carbon precursor to the reaction chamber, forming a plasma in the reaction chamber to form an initial viscous carbon material on a surface of the substrate, the initial viscous carbon material becoming a carbon material, and treating the carbon material with an active species to form a treated carbon material. An exemplary method may further include shutting off the flow of the carbon precursor to the reaction chamber, and optionally shutting off the plasma. A carbon material deposition cycle may include providing a carbon precursor to the reaction chamber, forming a plasma in the reaction chamber to form an initial viscous carbon material on a surface of the substrate, the initial viscous carbon material becoming a carbon material, shutting off the flow of the carbon precursor to the reaction chamber, and shutting off the plasma. The carbon material deposition cycle may be performed n times before the step of treating the carbon material with an active species, where n may range from 0 to 50, for example. The deposition and treatment cycle may include one or more carbon material deposition cycles, and the step of treating the carbon material with an active species. The deposition and treatment cycles can be performed N times, where N can range, for example, from 1 to about 50. The inert gas can be continuously flowed into the reaction chamber during the N deposition and treatment cycles. The treating step can be performed, for example, using an inert gas. The inert gas can include argon, helium, nitrogen, or any mixture thereof. The inert gas can be used to ignite a plasma during each carbon material deposition cycle and / or each deposition and treatment cycle. According to an example of the present disclosure, during a carbon material deposition cycle, the step of providing a carbon precursor to the reaction chamber occurs prior to and continues during the step of forming a plasma in the reaction chamber. According to a further example, during a carbon material deposition cycle, the steps of shutting off the flow of the carbon precursor and shutting off the plasma occur substantially simultaneously, or, alternatively, during a carbon material deposition cycle, the step of shutting off the flow of the carbon precursor occurs prior to the step of shutting off the plasma.According to some examples, the plasma is continuously formed in the reaction chamber during the steps of providing the carbon precursor to the reaction chamber, shutting off the flow of the carbon precursor, and treating the carbon material with the activated species. According to additional examples, the plasma is continuously formed in the reaction chamber during one or more repeated carbon material deposition cycles. According to still further examples, the plasma is continuously formed in the reaction chamber during at least one carbon material deposition cycle and at least one treatment step. According to further examples, during the carbon material deposition cycle, the plasma is continuously formed in the reaction chamber during the steps of providing the carbon precursor to the reaction chamber and shutting off the flow of the carbon precursor. According to further examples, after shutting off the flow of the carbon precursor, the power (e.g., RF power) provided to form the plasma is reduced (e.g., within only about 1.0 seconds). According to further examples, the power (e.g., RF power) to form the plasma is increased to perform the step of treating the carbon material with the activated species. According to various aspects of these embodiments, both the inert gas and the carbon precursor flow into the reaction chamber during the step of forming the plasma in the reaction chamber. The inert gas may be continuously flowed into the reaction chamber during the steps of providing the carbon precursor to the reaction chamber and forming the plasma in the reaction chamber. According to various examples of the present disclosure, the carbon precursor has the chemical formula: C. x H y N z In the formula, x is a natural number of 2 or more, y is a natural number, and z is 0 or a natural number. The carbon precursor may include a compound having a cyclic structure and / or at least one double bond (e.g., a cyclic compound). According to a further example, one or more steps are carried out at a temperature of 100° C. or less.

[0009] According to yet further exemplary embodiments of the present disclosure, a film structure is formed, at least in part, according to the methods described herein. The film structure may include a treated carbon layer containing 45 atomic % or more of carbon. Additionally or alternatively, the film structure may include less than 50 particles of size greater than 50 nm detectable on a 300 mm wafer on a surface of the treated carbon layer having a layer thickness of 100 nm or more.

[0010] According to yet further exemplary embodiments of the present disclosure, a system is provided for carrying out the methods described herein and / or for forming the membrane structures described herein.

[0011] These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of specific embodiments which refer to the accompanying drawings, and the invention is not limited to any particular embodiment disclosed.

[0012] A more complete understanding of the exemplary embodiments of the present disclosure can be obtained by reference to the detailed description and claims when considered in conjunction with the following illustrative drawings. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 illustrates a method in an exemplary embodiment of the present disclosure. [Diagram 2] FIG. 2 illustrates a scanning transmission electron microscope image of a membrane structure including a carbon layer. [Diagram 3] FIG. 3 illustrates another method in an exemplary embodiment of the present disclosure. [Figure 4] FIG. 4 illustrates another method in an exemplary embodiment of the present disclosure. [Diagram 5] FIG. 5 illustrates another method in an exemplary embodiment of the present disclosure. [Figure 6] FIG. 6 illustrates another method in an exemplary embodiment of the present disclosure. [Figure 7]FIG. 7 illustrates another method in an exemplary embodiment of the present disclosure. [Figure 8] FIG. 8 illustrates a system according to an exemplary embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale, for example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure.

[0015] Although certain specific embodiments and examples are disclosed below, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention, as well as obvious modifications and equivalents thereof, and therefore it is not intended that the scope of the disclosed invention should be limited by the specific disclosed embodiments described below.

[0016] The present disclosure generally relates to methods of depositing materials, methods of forming (e.g., film) structures, film structures formed using the methods, and systems for performing the methods and / or for forming film structures. By way of example, the methods described herein may be used to fill features such as gaps (e.g., trenches or vias) on a surface of a substrate with a material such as a carbon (e.g., dielectric) material. The terms gap and recess may be used interchangeably.

[0017] To mitigate void and / or seam formation during the gap-filling process, the deposited carbon material may be initially flowable and flow into and fill the gap. The exemplary structures described herein may be used for a variety of applications including, but not limited to, cell isolation in 3D cross-point memory devices, self-aligned vias, dummy gates, reverse tone patterns, PC RAM isolation, cut hard masks, DRAM storage node contact (SNC) isolation, and the like.

[0018] In this disclosure, "gas" can refer to a material that is a gas, vaporized solid, and / or vaporized liquid at ambient temperature and pressure, and may be comprised of a single gas or a mixture of gases depending on the situation. Gases other than process gases, i.e., gases introduced without passing through a gas distribution assembly such as a showerhead or other gas distribution device, can be used to seal the reaction space with a sealing gas such as a noble gas. In some cases, such as in the context of material deposition, the term "precursor" can refer to a compound that participates in a chemical reaction that produces another compound, particularly a compound that constitutes the membrane matrix or the backbone of the membrane, and the term "reactant" can refer to a compound that activates the precursor, modifies the precursor, or catalyzes the reaction of the precursor, in some cases other than the precursor, for example, when power (e.g., radio frequency (RF) power) is applied, the reactant can provide elements (e.g., O, H, N, C) to the membrane matrix and become part of the membrane matrix. In some cases, the terms "precursor" and "reactant" can be used interchangeably. The term "inert gas" refers to a gas that does not participate in chemical reactions to any appreciable extent and / or that excites precursors (e.g., to promote polymerization of the precursors), for example, when power (e.g., RF power) is applied, but, unlike the reactants, may not become part of the film matrix to any appreciable extent.

[0019] The term "substrate" as used herein may refer to any underlying material or material that may be used to form a device, circuit, or film, or any underlying material or material on which a device, circuit, or film may be formed. The substrate may include one or more layers overlying or underlying a bulk material, which may include bulk materials such as silicon (e.g., single crystal silicon), other Group IV materials such as germanium, compound semiconductor materials such as III-V or II-VI semiconductors. Additionally, the substrate may include various features, such as gaps (e.g., recesses or vias), lines or protrusions, such as lines with gaps formed therebetween, and the like, formed on or in or on at least a portion of the layer or bulk material of the substrate. By way of example, the one or more features may have a width of about 10 nm to about 100 nm, a depth or height of about 30 nm to about 1,000 nm, and / or an aspect ratio of about 3.0 to about 100.0.

[0020] In some embodiments, a "film" refers to a layer extending in a direction perpendicular to the thickness direction. In some embodiments, a "layer" refers to a material having a particular thickness formed on a surface, and may be a synonym of a film, or a non-film structure. A film or layer may be composed of a separate single film or layer, or multiple films or layers, having particular properties, and the boundaries between adjacent films or layers may or may not be distinct, and may or may not be defined based on any physical, chemical, and / or other characteristics, formation process or sequence, and / or function or purpose of the adjacent films or layers. A layer or film may or may not be continuous. Furthermore, a single film or layer may be formed using multiple deposition cycles and / or multiple deposition and processing cycles.

[0021] As used herein, the term "carbon layer" or "carbon material" may refer to a layer whose chemical formula can be expressed as including carbon. A layer that includes a carbon material may include other elements, such as one or more of nitrogen and hydrogen.

[0022] As used herein, the term "structure" may refer to a partially or fully fabricated device structure. By way of example, a structure may be a substrate or may include a substrate upon which one or more layers and / or features are formed.

[0023] As used herein, the term "atomic layer deposition" may refer to a deposition process in which deposition cycles, typically multiple successive deposition cycles, are performed in a process chamber. Cyclic deposition processes may include cyclic chemical vapor deposition processes (CVD) and atomic layer deposition processes. Cyclic deposition processes may include one or more cycles involving plasma activation of precursors, reactants, and / or inert gases.

[0024] In this disclosure, "continuously" can refer to without breaking vacuum, without interruption in the time sequence, without any intervening material steps, without changing processing conditions immediately following a subsequent step, or, in some embodiments or circumstances, without any intervening distinct physical or chemical structures between the two structures other than the two structures themselves.

[0025] The liquidity (e.g., initial liquidity) may be determined as follows:

[0026] [Table 1]

[0027] B / T refers to the ratio of the thickness of the film deposited at the bottom of the recess to the thickness of the film deposited on the top surface where the recess is formed before the recess is filled. Generally, the higher the aspect ratio of the recess, the higher the B / T ratio, so wide recesses with aspect ratios of about 1 or less are typically used to evaluate flowability. The B / T ratio can generally be higher when the aspect ratio of the recess is higher. As used herein, a "flowable" film or material exhibits good or better flowability.

[0028] As described in more detail below, film fluidity is obtained temporarily, for example, when a volatile hydrocarbon precursor is polymerized by plasma and deposited on the surface of a substrate, the gaseous precursor being activated or fragmented by energy provided by a plasma gas discharge to initiate polymerization. The resulting polymeric material may exhibit a temporarily fluid behavior. When the deposition process is completed and / or after a short period of time (e.g., about 3.0 seconds), the film may no longer be fluid, but rather solidified, and thus may not require the use of a separate solidification process.

[0029] In this disclosure, any two variables may constitute a workable range for that variable, and any range stated may include or exclude the endpoints. In some embodiments, further, any value of a stated variable (whether they are stated as "about" or not) may refer to an exact or approximate value, may include equivalents, may refer to an average, a median, a representative value, or a majority, etc. Furthermore, in this disclosure, the terms "comprise", "comprise", "have", and "have" may, in some embodiments, independently refer to "typically or broadly include", "comprise", "consist essentially of", or "consist of". In this disclosure, any defined meaning, in some embodiments, does not necessarily exclude the ordinary and customary meaning.

[0030] A method according to an exemplary method of the present disclosure includes providing a substrate in a reaction chamber, providing an inert gas to the reaction chamber, supplying a carbon precursor to the reaction chamber, forming a plasma in the reaction chamber to form an initial viscous carbon material on a surface of the substrate, where the initial viscous carbon material becomes a carbon material, and treating the carbon material with an active species to form a treated carbon material. The method may also include shutting off the flow of the carbon precursor to the reaction chamber and shutting off the plasma.

[0031] During the step of providing the substrate in the reaction chamber, the substrate is provided in the reaction chamber of a gas-phase reactor. According to examples of the present disclosure, the reaction chamber may form part of a cyclic deposition reactor, such as an atomic layer deposition (ALD) (e.g., PEALD) reactor or a chemical vapor deposition (CVD) (e.g., PECVD) reactor. The various steps of the methods described herein may be performed in a single reaction chamber or may be performed in multiple reaction chambers, such as reaction chambers of a cluster tool.

[0032] During the step of providing the substrate in the reaction chamber, the substrate may be brought to a desired temperature and / or the reaction chamber may be brought to a desired pressure, such as a temperature and / or pressure suitable for a subsequent step. By way of example, the temperature in the reaction chamber (e.g., of the substrate or substrate support) may be 100° C. or less. The pressure in the reaction chamber may be from about 200 Pa to about 1,250 Pa. According to certain examples of the present disclosure, the substrate includes one or more features, such as a recess.

[0033] During the step of providing an inert gas to the reaction chamber, one or more inert gases, such as argon, helium, nitrogen, or any mixture thereof, are provided to the reaction chamber. As a specific example, the inert gas is or includes helium. The flow rate of the inert gas into the reaction chamber during this step may be from about 500 sccm to about 8,000 sccm. As described in more detail below, the inert gas may be used to purge reactants and / or by-products from the reaction chamber, to ignite a plasma in the reaction chamber, and / or may be used as a carrier gas to assist in the delivery of precursors to the reaction chamber. The power used to ignite and maintain the plasma may range from about 50 W to about 800 W. The frequency of the power may range from about 2.0 MHz to about 27.12 MHz.

[0034] During the step of providing a carbon precursor to the reaction chamber, a precursor for forming a layer of carbon material is introduced into the reaction chamber. An exemplary precursor is represented by the formula C x H y N zwhere x is a natural number equal to or greater than 2, y is a natural number, and z is zero or a natural number. For example, x can range from about 2 to about 15, y can range from about 4 to about 30, and z can range from about 0 to about 10. The precursor can include a chain or cyclic molecule having two or more carbon atoms and one or more hydrogen atoms, such as a molecule represented by the formula above. In certain examples, the precursor can be or can include one or more cyclic (e.g., aromatic) structures and / or at least one double bond.

[0035] Referring momentarily to Figure 2, Figure 2(a) illustrates a structure 202 including a substrate 204 having gaps 206, 208, and 210 formed therein, and a carbon layer 212 covering a surface 214 of the substrate 204. Figure 2(b) illustrates a structure 216 including a substrate 218 having gaps 220, 222, and 224 formed therein, and a carbon layer 226 covering a surface 228 of the substrate 218. The deposition conditions for structures 202 and 216 were the same except that the precursor used to form structure 202 was 1,3,5,trimethylcyclohexane and the precursor used to form structure 216 was 1,3,5,trimethylbenzene, suggesting that the use of a precursor having at least one carbon (e.g., carbon-carbon) double bond may be beneficial for filling the recesses while reducing void formation.

[0036] The flow rate of the carbon precursor from the carbon precursor source to the reaction chamber may vary depending on other process conditions. By way of example, the flow rate may be from about 100 sccm to about 3,000 sccm. Similarly, the duration of each step of providing the carbon precursor to the reaction chamber may vary depending on various considerations. By way of example, the duration may range from about 1.0 seconds to about 35.0 seconds.

[0037] During the step of forming a plasma in the reaction chamber to form an initially viscous carbon material on the surface of the substrate, the precursor is converted to the initially viscous material using the excited species. The initially viscous carbon material can become a carbon material, for example, through further reaction with the excited species. The carbon material can be solid or substantially solid.

[0038] During the step of shutting off the flow of the carbon precursor to the reaction chamber, the flow of the carbon precursor to the reaction chamber is stopped. In some cases, the flow of the precursor is reduced and may not be shut off completely for various steps.

[0039] During the step of breaking the plasma, the plasma may be extinguished. The step of breaking may include reducing the power used to generate the plasma.

[0040] Treating the carbon material with an active species to form a treated carbon material includes exposing the carbon material to the active species, e.g., active species formed using a plasma. The treating step can include forming the species from an inert gas, such as an inert gas provided during the providing of the inert gas to the reaction chamber. The power used to form the plasma can range from about 50 W to about 800 W. The frequency of the power can range from about 2.0 MHz to about 27.12 MHz.

[0041] According to exemplary aspects of the present disclosure, the activated species are formed by using a plasma (e.g., radio frequency and / or microwave plasma). Direct plasma and / or remote plasma may be used to form the activated species. In some cases, an inert gas may be continuously flowed into the reaction chamber, and the activated species may be periodically formed by cycling the power used to form the plasma. The temperature in the reaction chamber during the process of treating the carbon material may be 100° C. or less. The pressure in the reaction chamber during the seed formation for the treatment may be about 200 Pa to about 1,250 Pa. The seed formation for the treatment process may be formed in the same reaction chamber used for one or more steps or other steps, or may be a separate reaction chamber, such as another reaction chamber of the same cluster tool.

[0042] The steps of the various methods described herein may overlap and need not be performed in the order described above. Furthermore, in some cases, various steps, or portions thereof, may be repeated one or more times before the method proceeds to the next step.

[0043] 1 and 3-7 illustrate examples of pulse timing sequences of methods according to exemplary embodiments of the present disclosure. The figures illustrate inert gas, carbon precursor, and plasma power pulses, with gas and / or plasma power being supplied to the reactor system for a pulse period. The width of the pulses may not necessarily indicate the time associated with each pulse, and the illustrated pulses may indicate the relative start times of the various pulses. Similarly, the heights may not necessarily indicate a particular amplitude or value, but may indicate relative high and low values. These examples are merely illustrative and are not intended to limit the scope of the present disclosure or claims.

[0044] 1 illustrates a method 100. Method 100 includes a plurality of carbon material deposition cycles i, ii...n, and a plurality of deposition and treatment cycles 1, 2...N. According to these example embodiments, n and N can range from about 1 to about 50.

[0045] The method 100 may include continuously supplying an inert gas to the reaction chamber during one or more carbon material deposition cycles i, ii...n, and / or one or more deposition and treatment cycles 12...N. In the illustrated example, the inert gas is provided to the reaction chamber for a pulse period 102, which begins before the first (i) deposition cycle and ends after the last (N) deposition and treatment cycle. A pulse period may simply be referred to as a pulse.

[0046] After the start of pulse period 102, a carbon precursor is provided to the reaction chamber for pulse period 104. Pulse period 104 can range, for example, from about 1.0 seconds to about 35.0 seconds. Each pulse period 104 can be the same or can vary in time.

[0047] After initiation of the flow of carbon precursor into the reaction chamber, power is provided to form a plasma for a pulse period 106. Thus, in the illustrated example, both the inert gas and the carbon precursor are provided to the reaction chamber as the plasma is ignited / formed. The pulse period 106 can range, for example, from about 1.0 seconds to about 30.0 seconds. Each pulse period 106 can be the same or can vary in time.

[0048] As shown in this example, pulse period 104 and pulse period 106 may end at approximately or substantially the same time (e.g., within 10, 5, 2, 1, or 0.5 percent of each other). Once the flow of carbon precursor and plasma power to the reaction chamber is stopped, the reaction chamber may be purged for a purge period or pulse period 108. Pulse period 108 may range, for example, from about 5.0 seconds to about 30.0 seconds. Each pulse period 108 may be the same or may vary in time.

[0049] The power (eg, applied to the electrodes) during step 106 can range from about 100 W to about 800 W. The frequency of the power can range from about 2.0 MHz to about 27.12 MHz.

[0050] After pulse period 108, the plasma power may be increased to a desired level to treat the carbon material with the activated species during pulse period 110. The power level and pressure in the reaction chamber may be as described above. Pulse period 110 may range, for example, from about 1.0 seconds to about 30.0 seconds. Each pulse period 110 may be the same or may vary in time.

[0051] After treating the carbon material with the activated species during pulse period 110, the reaction chamber may be purged for pulse period 112. Pulse period 112 may range, for example, from about 10.0 seconds to about 70.0 seconds. Each pulse period 112 may be the same or may vary in time.

[0052] 3 illustrates another method 300. Similar to method 100, method 300 includes a plurality of carbon material deposition cycles i, ii...n, and one or more deposition and processing steps or cycles 1...N. According to these example embodiments, n can range from about 1 to about 50, and N can range from about 1 to about 50.

[0053] The method 300 may include continuously supplying an inert gas to the reaction chamber during one or more carbon material deposition cycles i, ii...n and / or one or more deposition steps and a treatment step 1, 2, 3, 4...N. In the illustrated example, the inert gas is provided to the reaction chamber for a pulse period 302, which may begin before the first (i) deposition cycle and end after the last (N) deposition and treatment cycle.

[0054] After initiation of pulse period 302, a carbon precursor is provided to the reaction chamber for pulse period 304. Pulse period 304 can be, for example, in the range of about 1.0 seconds to about 5.0 seconds.

[0055] After initiation of the flow of carbon precursor into the reaction chamber, power is provided to form a plasma for a pulse period 306. In the illustrated example, the flow of carbon precursor is stopped before the plasma is ignited / formed. While this method may be suitable for some applications, the method 300 may result in undesirably high particles on the surface of the treated carbon layer, e.g., having a layer thickness of 100 nm or more, much more than 50 particles with a detectable size of 50 nm or more on a 300 mm wafer.

[0056] In contrast, Figures 1 and 4-7 illustrate methods of depositing carbon materials with less than 50, 40, 30, 10, or 5 particles detectable in size greater than 50 nm on a 300 mm wafer on a surface of a treated carbon layer having a relatively low, layer thickness of 100 nm or greater. One technique for reducing the number of particles on a surface during a method of forming a structure described herein includes maintaining power for plasma formation while the flow of the carbon precursor is stopped.

[0057] 4 illustrates a method 400 according to examples of the present disclosure. Method 400 includes a plurality of carbon material deposition cycles i, ii...n and one or more deposition steps and a single processing step 1...N. According to these example embodiments, n can range from about 1 to about 50, and N can range from about 1 to about 50.

[0058] The method 400 may include continuously supplying an inert gas to the reaction chamber during one or more carbon material deposition cycles i, ii...n, and / or one or more deposition cycles and a processing cycle 1...N. In the illustrated example, the inert gas is provided to the reaction chamber during a pulse period 402, which begins before the first (i) deposition cycle and ends after the last (N) deposition and processing cycle.

[0059] After the pulse period 402 is initiated, power is provided to form a plasma for the pulse period 406. An inert gas may be used to ignite the plasma. The plasma may be continuous for the duration of the pulse period 406. The pulse period 406 may be, for example, in a range from about 3.0 seconds to about 3,600.0 seconds. The power (e.g., applied to the electrodes) during the pulse period 406 may be in a range from about 100 W to about 800 W. The frequency of the power may be in a range from about 2.0 MHz to about 27.12 MHz.

[0060] Once the plasma is formed, a carbon precursor pulse period 404 may begin. In the illustrated example, both an inert gas and a carbon precursor are provided to the reaction chamber during the pulse period 404. At the end of the pulse period 404, the inert gas pulse and the plasma power pulse continue. This is believed to facilitate the reduction of particles on the surface of the substrate or layers thereon that would otherwise form on the surface during the carbon material deposition cycle, such as particles that may form during the method 300. The duration of the pulse period 404 may range, for example, from about 1.0 seconds to about 30.0 seconds. The pulse period 404 may be performed n times prior to the treatment pulse 410.

[0061] The reaction chamber may be purged for a pulse period 408. During this time, power for plasma formation may be continuously supplied to the reactor system. Similarly, after n carbon material deposition cycles, the reaction chamber may be purged for a pulse period 412. Also, after the treatment step 410, i.e., after deposition and treatment cycle N, the reaction chamber may be purged for a pulse period 414. If desired, the next deposition and treatment cycle may begin. As mentioned above, the duration of one or more pulses may be the same or may vary.

[0062] 5 illustrates another method 500 according to an example of the present disclosure. Method 500 is similar to method 400, except that the plasma power is pulsed for each carbon material deposition cycle i, ii...n.

[0063] The method 500 may include continuously supplying an inert gas to the reaction chamber during one or more carbon material deposition cycles i, ii...n, and / or one or more deposition cycles and a processing cycle 1, 2, 3, 4...N. In the illustrated example, the inert gas is provided to the reaction chamber during a pulse period 502, which begins before the first deposition cycle and ends after the last (N) deposition and processing cycle.

[0064] After pulse period 502 is initiated, power is provided to form a plasma during pulse period 506. An inert gas may be used to ignite the plasma. In an illustrative example, pulse period 506 continues after the flow of carbon precursor is stopped (pulse period 504). Pulse period 506 may range, for example, from about 1.0 seconds to about 20.0 seconds. Power (e.g., applied to the electrodes) during pulse period 506 may range from about 100 W to about 800 W. The frequency of the power may range from about 2.0 MHz to about 27.12 MHz.

[0065] Once the plasma is formed, a carbon precursor pulse period 504 may begin. In the illustrated example, both an inert gas and a carbon precursor are provided to the reaction chamber during the pulse period 504. At the end of the pulse period 504, the inert gas pulse and the plasma power pulse continue. Again, this is believed to facilitate the reduction of particles that would otherwise form on the surface of the substrate during the carbon material deposition cycle. The duration of the pulse period 504 may range, for example, from about 1.0 seconds to about 30.0 seconds. The pulse period 504 and the pulse period 506 may be performed n times before the treatment pulse period 510.

[0066] During the process, the inert gas pulse period 502 continues and the power to form the plasma is again increased to a desired level during pulse period 510. The power (e.g., applied to the electrodes) during pulse period 510 can range from about 100 W to about 800 W. The frequency of the power can range from about 2.0 MHz to about 27.12 MHz. The duration of pulse period 510 can range, for example, from about 1.0 seconds to about 30.0 seconds.

[0067] During pulse period 504, the reaction chamber may be purged for pulse period 508. During at least a portion of this time, power for plasma formation may be provided to the reactor system. Similarly, after n carbon material deposition cycles, the reaction chamber may be purged for pulse period 512. During at least a portion of pulse period 512, power for plasma formation may be provided to the reactor system. After process step 510, i.e., after deposition and processing cycle N, the reaction chamber may be purged for pulse period 514. If desired, the next deposition and processing cycle may begin. As described above, the pulses for one or more cycles may be the same or may vary.

[0068] FIG. 6 shows a method 600 having one carbon material deposition cycle 601 followed by a treatment step 603 for each deposition and treatment cycle 605 .

[0069] Similar to methods 400 and 500, method 600 may include continuously supplying an inert gas to the reaction chamber during a carbon material deposition cycle 601 and a deposition and treatment cycle 605. N one-time deposition steps and one-time treatments may be performed, where N may range from about 1 to about 50. In the illustrated example, the inert gas is provided to the reaction chamber for a pulse period 602, which begins before the deposition cycle 601 and ends after the deposition and treatment cycle 605.

[0070] After pulse period 602 is initiated, power is provided to form a plasma during pulse period 606. An inert gas may be used to ignite the plasma. In an illustrative example, pulse period 606 continues after the flow of carbon precursor is stopped (pulse period 604). Pulse period 606 may range, for example, from about 3.0 seconds to about 1,000.0 seconds. The power (e.g., applied to the electrodes) during pulse period 604 may range from about 100 W to about 800 W. The frequency of the power may range from about 2.0 MHz to about 27.12 MHz.

[0071] Once the plasma is formed, a carbon precursor pulse period 604 may begin. In the illustrated example, both an inert gas and a carbon precursor are provided to the reaction chamber during the pulse period 604. At the end of the pulse period 604, the inert gas pulse and the plasma power pulse continue. Again, this is believed to facilitate the reduction of particles that would otherwise form on the surface of the substrate during the carbon material deposition cycle. The duration of the pulse period 604 may range, for example, from about 1.0 seconds to about 30.0 seconds.

[0072] During process step 603, the inert gas pulse period 602 continues and the power to form the plasma is again increased to a desired level. The power (e.g., applied to the electrodes) during the pulse period 610 can range from about 100 W to about 800 W. The frequency of the power can range from about 2.0 MHz to about 27.12 MHz. The duration of the pulse period 610 can range, for example, from about 1.0 seconds to about 30.0 seconds.

[0073] After pulse period 604, the reaction chamber may be purged for pulse period 608. During at least a portion of this time, power for plasma formation may be supplied to the reactor system so that power is supplied while the flow of the carbon precursor is stopped. Similarly, after carbon material deposition and treatment cycle 605, the reaction chamber may be purged for pulse period 612. During at least a portion of pulse period 612, power for plasma formation may be supplied to the reactor system. As mentioned above, the times of the various pulses of the cycle may be the same or different.

[0074] 7 illustrates a method 700 according to yet a further example of the present disclosure. Method 700 may be similar to method 100, with method 700 showing additional ignition and transition steps. Any of the methods described herein may include an ignition and / or transition step.

[0075] Similar to method 100, method 700 may include continuously supplying an inert gas to the reaction chamber during a carbon material deposition cycle 701 and / or a single deposition and treatment cycle 709. N single deposition steps and one-time treatment steps are performed, where N may range from about 1 to about 50. In the illustrated example, the inert gas is provided to the reaction chamber for a pulse period 702, which begins before the deposition cycle 701 and ends after the deposition and treatment cycle 709.

[0076] After pulse period 702 is initiated, power is provided to form a plasma during pulse period 706. An inert gas may be used to ignite the plasma. In an illustrative example, pulse period 706 is stopped approximately simultaneously with or after the cessation of the flow of carbon precursor (pulse period 704). Pulse period 706 may range, for example, from about 3.0 seconds to about 40.0 seconds. Power (e.g., applied to the electrodes) during pulse period 706 may range from about 100 W to about 800 W. The frequency of the power may range from about 2.0 MHz to about 27.12 MHz.

[0077] Powering the plasma initiates an ignition period 705. The ignition period 705 may continue until the plasma is stabilized and / or until a carbon precursor pulse period 704 is initiated. The duration of the pulse period 705 may range from about 2.0 seconds to about 10.0 seconds.

[0078] Once the plasma is formed, a carbon precursor pulse period 704 may begin. In the illustrated example, both an inert gas and a carbon precursor are provided to the reaction chamber during pulse period 704. Upon completion of pulse period 704 and / or pulse period 706, the inert gas continues for a transition period 707. The duration of pulse period 704 may range, for example, from about 1.0 seconds to about 30.0 seconds. The duration of pulse period 705 may range, for example, from about 2.0 seconds to about 10.0 seconds.

[0079] At the end of the transition period 707, the power for the plasma is increased to again form the plasma. During the process step 703 (pulse period 710), the inert gas pulse period 702 continues and the power to form the plasma is maintained at a desired level. The power (e.g., applied to the electrodes) during the pulse period 710 can range from about 100 W to about 800 W. The frequency of the power can range from about 2.0 MHz to about 27.12 MHz. The duration of the pulse period 710 can range, for example, from about 1.0 seconds to about 30.0 seconds.

[0080] After the pulse period 704, the reaction chamber may be purged for a transition period 707. During at least a portion of this time, power for plasma formation may be supplied to the reactor system so that power is supplied while the flow of the carbon precursor is stopped. Similarly, after the carbon material deposition cycle and the treatment cycle 709, the reaction chamber may be purged for a pulse period 712. During at least a portion of the pulse period 712, the power for plasma formation may be turned off. The duration of each of the pulses for the different cycles may be the same or may vary.

[0081] 8 illustrates a reactor system 800 according to an exemplary embodiment of the present disclosure. The reactor system 800 may be used to perform one or more of the steps or substeps described herein and / or to form one or more structures or portions thereof described herein.

[0082] The reactor system 800 includes a pair of conductive flat plate electrodes 4, 2 parallel and facing each other in the interior 11 (reaction zone) of the reaction chamber 3. A plasma can be excited in the reaction chamber 3, for example, by applying HRF power (e.g., 13.56 MHz to 27 MHz) from a power source 25 to one electrode (e.g., electrode 4) and electrically grounding the other electrode (e.g., electrode 2). The lower stage 2 (lower electrode) can be provided with a temperature regulator, and the temperature of the substrate 1 disposed thereon can be kept constant at a desired temperature. The electrode 4 can function as a gas distribution device, such as a shower plate. Reactant gases, diluent gases (if present), precursor gases, and / or the like can be introduced into the reaction chamber 3 through the shower plate 4 using one or more of gas lines 20, 21, and 22, respectively. Although illustrated with three gas lines, the reactor system 800 can include any suitable number of gas lines.

[0083] The reaction chamber 3 is provided with a circular duct 13 having an exhaust line 7 through which gas in the interior 11 of the reaction chamber 3 can be exhausted. In addition, the transfer chamber 5 arranged below the reaction chamber 3 is provided with a sealing gas line 24 for introducing a sealing gas into the interior 11 of the reaction chamber 3 through the interior 16 (transfer zone) of the transfer chamber 5, and is provided with a separation plate 14 for separating the reaction zone from the transfer zone (a gate valve through which the wafer is transferred in and out of the transfer chamber 5 is omitted from this figure). The transfer chamber is also provided with an exhaust pipe 6. In some embodiments, the deposition and treatment steps are carried out in the same reaction space, so that two or more (e.g., all) steps can be performed without exposing the substrate to air or other oxygen-containing atmosphere.

[0084] In some embodiments, the continuous flow of inert or carrier gas into the reaction chamber 3 can be achieved using a flow path system (FPS), providing a bypass line with a precursor reservoir (bottle) in the carrier gas line and switching between the main line and the bypass line. When only carrier gas is intended to be delivered to the reaction chamber, the bypass line is closed, whereas when both carrier gas and precursor gas are intended to be delivered to the reaction chamber, the main line is closed and the carrier gas flows through the bypass line and exits the bottle together with the precursor gas. In this way, the carrier gas can flow continuously into the reaction chamber and pulse the precursor gas by switching between the main line and the bypass line without substantially fluctuating the reaction chamber.

[0085] Those skilled in the art will appreciate that the apparatus includes one or more controllers 26 programmed or otherwise configured to cause one or more of the method steps described herein. As will be appreciated by those skilled in the art, the controllers are in communication with the various power sources, heating systems, pumps, robotics, and gas flow controllers or valves of the reactor.

[0086] In some embodiments, a dual chamber reactor (two zones or compartments for processing wafers located close to each other) can be used, and reactant gases and noble gases can be supplied through shared lines, while precursor gases are supplied through non-shared lines.

[0087] The exemplary embodiments of the present disclosure described above do not limit the scope of the present invention, as these embodiments are merely examples of embodiments of the present invention. Any equivalent embodiments are intended to be within the scope of the present invention. Indeed, various modifications of the present disclosure, in addition to those shown and described herein, such as alternative useful combinations of the described elements, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to be included within the scope of the appended claims. [Explanation of symbols]

[0088] 100 ways 102, 104, 106, 108, 110, 112 Pulse period 202 Structure 204 Base material 206, 208, 210 Gap 212 Carbon Layer 214 Surface of the substrate 204 216 Structure 218 Base material 220, 222, 224 Gap 226 Carbon Layer 228 Surface of substrate 218 300 ways 302, 304, 306 Pulse period 400 ways 402, 404, 406, 408, 412, 414 Pulse period 410 Processing 500 ways 502, 504, 506, 508, 512, 514 Pulse period 510 Processing 600 ways 601 Carbon Material Deposition Cycle 602, 604, 606, 608, 610, 612 Pulse period 603 Processing 605 Deposition and Processing Cycle 700 methods 701 Carbon Material Deposition Cycle 702, 704, 706, 710, 712 Pulse period 703 Processing 705 Ignition cycle 707 Transition Cycle 709 Deposition and Processing Cycle 800 Processing Systems 1 Base material 2 Conductive flat plate electrodes (lower stage) 3. Reaction chamber 4. Conductive flat plate electrode (shower plate) 5. Transfer chamber 6 Exhaust pipe 7 Exhaust Line 11 Inside the reaction chamber 13 Circular Duct 14 Separation plate 20, 21, 22 Gas lines 24 Sealing gas line 25 Power supply

Claims

1. 1. A method of forming a structure, the method comprising the steps of: providing a substrate within a reaction chamber, the substrate comprising one or more recesses; providing an inert gas to the reaction chamber for plasma ignition; providing a carbon precursor to the reaction chamber; forming a plasma in the reaction chamber to form an initial viscous carbon material on a surface of the substrate, the initial viscous carbon material becoming a carbon material; stopping the flow of the carbon precursor into the reaction chamber; terminating the plasma; and a step of igniting a plasma without providing the carbon precursor after a predetermined period of time has elapsed since cessation of the plasma to treat the carbon material with an active species to form a treated carbon material, wherein the power for the plasma to treat the carbon material is the same as the power for the plasma in the step of forming the initially viscous carbon material.

2. The process further comprises: providing a carbon precursor to the reaction chamber; forming a plasma in the reaction chamber to form an initial viscous carbon material on a surface of the substrate; stopping the flow of the carbon precursor; terminating the plasma; and The method of claim 1 , comprising the step of treating the carbon material with an active species N times to fill the one or more recesses.

3. The method of claim 2, wherein N ranges from about 1 to about 50.

4. 4. The method of claim 1, wherein the step of providing a carbon precursor to the reaction chamber during a carbon material deposition cycle occurs prior to and continues during the step of forming a plasma in the reaction chamber.

5. The method of any of claims 1 to 4, wherein the steps of stopping the flow of the carbon precursor and stopping the plasma during a carbon material deposition cycle occur substantially simultaneously.

6. The method of any of claims 1 to 4, wherein during a carbon material deposition cycle, the step of stopping the flow of the carbon precursor occurs before the step of stopping the plasma.

7. The method of any of claims 1 to 4, wherein the RF power provided to form the plasma is reduced after the step of stopping the flow of the carbon precursor.

8. The method according to any one of claims 1 to 7, wherein the step of treating the carbon material with activated species is carried out by increasing the RF power to form a plasma.

9. The method of any of claims 1 to 8, wherein both the inert gas and the carbon precursor flow into the reaction chamber during the step of forming a plasma in the reaction chamber.

10. The method of any of claims 1 to 9, wherein an inert gas flows continuously into the reaction chamber during the steps of providing a carbon precursor to the reaction chamber and forming a plasma in the reaction chamber.

11. The deposition and treatment cycle comprises: performing one or more carbon material deposition cycles, and thereafter treating the carbon material with an active species; The deposition and treatment cycle is performed multiple times for N depositions and one treatment step; The method of claim 1 , wherein the inert gas flows continuously into the reaction chamber during the N deposition and single treatment steps.

12. 10. The method of claim 1, wherein the steps of forming a plasma in the reaction chamber to form an initial viscous carbon material on a surface of the substrate and terminating the plasma are repeated multiple times prior to the step of treating the carbon material with an active species.

13. 13. The method of any of claims 1 to 12, wherein during a carbon material deposition cycle, a plasma is continuously formed in the reaction chamber during the steps of providing a carbon precursor to the reaction chamber and stopping the flow of the carbon precursor.

14. The method of claim 1 , wherein a plasma is continuously formed in the reaction chamber during one or more carbon material deposition cycles.

15. 15. The method of any of claims 1 to 14, wherein the duration of the step of forming a plasma in the reaction chamber to form an initial viscous carbon material during a carbon material deposition cycle is from about 1.0 seconds to about 30.0 seconds.

16. The method of any of claims 1 to 15, wherein the duration of the step of treating the carbon material with activated species during a deposition and treatment cycle is from about 1.0 seconds to about 30.0 seconds.

17. The method of any of claims 1 to 16, wherein the inert gas comprises argon, helium, nitrogen, or any mixture thereof.

18. The chemical formula of the carbon precursor is: ｘ H ｙ N ｚ wherein x is a natural number of 2 or more, y is a natural number, and z is 0 or a natural number.

19. The method of any one of claims 1 to 18, wherein the carbon precursor comprises a cyclic structure having at least one double bond.

20. The following steps: providing the carbon precursor to the reaction chamber; forming the plasma in the reaction chamber to form the initial viscous carbon material on a surface of the substrate; stopping the flow of the carbon precursor; terminating the plasma; and The method according to any of the preceding claims, wherein the temperature in the reaction chamber during the step of treating the carbon material with active species is below 100°C.

21. A system for carrying out the process according to any one of claims 1 to 20.

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