Method of filling gaps on a substrate surface

Abstract

To provide a method for filling a gap on a surface of a substrate.SOLUTION: (a) placing a substrate on a susceptor in a reaction chamber, wherein the substrate comprises a gap; and (b) a deposition step comprising flowing a carbon precursor into the reaction chamber, wherein: The method of claim 1, wherein the chemical formula of the carbon precursor includes a cyclic compound having a ring structure including C, H, and N, a carbonyl group, and at least one of a methyl group, an ethyl group, a propyl group, a butyl group, an amine group, and / or a hydroxy group, and exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form the first deposition material. A deposition step comprising exposing; and (c) a treatment step, wherein the first deposition material is exposed to a post-deposition treatment and the first deposition material is flowed into the gap to form a carbon film.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 that include depositing a layer of material that can fill gaps on a surface of the structure. [Background technology]

[0002] During the manufacture of devices such as semiconductor devices, it is often desirable to fill gaps on the surface of a substrate. Some techniques for filling gaps include depositing a layer of flowable material, such as a flowable carbon material.

[0003] While the use of flowable carbon materials to fill gaps can work well in some applications, flowable carbon deposition techniques can exhibit low elastic modulus and poor etch resistance. Furthermore, the deposited carbon material can shrink significantly after an annealing process. Therefore, improved methods for filling gaps on substrates are desirable.

[0004] Any discussion, including the discussion of problems and solutions set forth in this section, is included in this disclosure solely for the purpose of providing a context for the disclosure, and should not be construed as an admission that any or all of the discussion was known at the time the invention was made or that it constitutes prior art. Summary of the Invention [Means for solving the problem]

[0005] This summary is provided to introduce some concepts in a simplified form that are described in more detail below in the detailed description of exemplary embodiments of this disclosure. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0006] According to an exemplary embodiment of the present disclosure, a method for filling a gap on a substrate may include: (a) placing the substrate on a susceptor in a reaction chamber, where the substrate includes the gap; (b) a deposition step including flowing a carbon precursor into the reaction chamber, where the carbon precursor has a chemical formula including a cyclic compound having a ring structure including C, H, and N, and at least one of a carbonyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an amine group, and / or a hydroxyl group; and exposing the carbon precursor to a plasma, where the carbon precursor reacts to form a first deposition material; and (c) a treatment step including exposing the first deposition material to a post-deposition treatment and flowing the first deposition material into the gap to form a carbon film.

[0007] According to further exemplary embodiments of the present disclosure, the temperature during the deposition step may be between 30°C and 700°C.

[0008] According to a further exemplary embodiment of the present disclosure, the method may further comprise providing an inert gas and / or an atomic oxygen-containing gas during the treatment step.

[0009] According to further exemplary embodiments of the present disclosure, the atomic oxygen-containing gas may include one of O2, O3, N2O, NO, NO2, CO2, CO, H2O, CH3OH, C2H5OH, or combinations thereof.

[0010] According to further exemplary embodiments of the present disclosure, the inert gas may include at least one of He, H2, N2, He, Ar, or combinations thereof.

[0011] According to a further exemplary embodiment of the present disclosure, the inert gas may include N2 and the atomic oxygen-containing gas includes O2.

[0012] According to further exemplary embodiments of the present disclosure, the proportion of O2 may be greater than 25% in the total gas.

[0013] According to further exemplary embodiments of the present disclosure, the duration of the post-deposition treatment may be from 1 second to 1800 seconds.

[0014] According to further exemplary embodiments of the present disclosure, the post-deposition treatment may include annealing the substrate to a temperature of 200°C to 800°C.

[0015] According to further exemplary embodiments of the present disclosure, the post-deposition treatment may include a plasma treatment.

[0016] According to further exemplary embodiments of the present disclosure, the post-deposition treatment may include UV (ultraviolet) curing.

[0017] According to further exemplary embodiments of the present disclosure, post-deposition treatment may be performed in a second reaction chamber.

[0018] According to further exemplary embodiments of the present disclosure, the power of the plasma may be between 10W and 3000W.

[0019] According to further exemplary embodiments of the present disclosure, the frequency of the plasma may be between 400 kHz and 100 MHz.

[0020] According to further exemplary embodiments of the present disclosure, the cyclic structure may be selected from the group consisting of pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, isobenzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzisoxazole, indazole, benzisothiazole, benzotriazole, purine, pyridine, phosphine The compound may include one of 4aH-xanthene, 4aH-thioxanthene, 4aH-phenoxazine, 4a,10a-dihydro-10H-phenothiazine, carbazole, or a combination thereof.

[0021] According to further exemplary embodiments of the present disclosure, the carbonyl group may comprise one of an aldehyde, a ketone, a carboxylic acid, an ester, an amide, an enone, an acyl chloride, an acid anhydride, or a combination thereof.

[0022] According to a further exemplary embodiment of the present disclosure, one of the electrodes may be part of the susceptor.

[0023] According to further exemplary embodiments of the present disclosure, the carbon layer may have an elastic modulus greater than 7 GPa.

[0024] A more complete understanding of the exemplary embodiments of the present disclosure can be obtained by reference to the detailed description and claims in light of the following illustrative figures. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 illustrates a method according to an exemplary embodiment of the present disclosure. [Figure 2] FIG. 1 illustrates a structure according to an exemplary embodiment of the present disclosure. [Figure 3] FIG. 1 illustrates a plasma system according to an exemplary embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0026] It should 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 understand the illustrated embodiments of the present disclosure.

[0027] While certain specific embodiments and examples are disclosed below, it will be understood by those skilled in the art that the scope of the invention extends beyond the specifically disclosed embodiments and / or uses of the invention, and obvious variations and equivalents thereof. It is therefore not intended that the scope of the disclosed invention should be limited by the specific disclosed embodiments described below.

[0028] As used herein, the term "substrate" can refer to any single or multiple underlying materials, including any single or multiple underlying materials that may be modified or upon which a device, circuit, or film may be formed. A "substrate" can be continuous or discontinuous, rigid or flexible, solid or porous, and combinations thereof. A substrate can be in any form, such as a powder, a plate, or a workpiece. A substrate in the form of a plate can include wafers of various shapes and sizes. A substrate can be made from semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide.

[0029] For example, the substrate in powder form may have applications in pharmaceutical manufacturing. The porous substrate may comprise a polymer. Examples of workpieces may include medical devices (e.g., stents and syringes), jewelry, tooling devices, components for battery manufacturing (e.g., anodes, cathodes, or separators), or components for photovoltaic cells, etc.

[0030] The continuous substrate may extend beyond the boundaries of the process chamber in which the deposition process occurs. In some processes, the continuous substrate may move through the process chamber, allowing the process to continue until the end of the substrate is reached. The continuous substrate may be supplied from a continuous substrate supply system to enable the production and output of the continuous substrate in any suitable form.

[0031] Non-limiting examples of continuous substrates can include sheets, nonwoven films, rolls, foils, webs, flexible materials, bundles of continuous filaments or fibers (e.g., ceramic or polymeric fibers). Continuous substrates may also include carriers or sheets onto which discontinuous substrates are attached.

[0032] The examples presented herein are not meant to be actual representations of any particular materials, structures, or devices, but are merely idealized representations used to describe embodiments of the present disclosure.

[0033] The specific embodiments shown and described are illustrative of the invention and its best mode and are in no way intended to otherwise limit the scope of aspects and implementations. Also, for purposes of brevity, conventional manufacturing, association, preparation, and other functional aspects of the systems may not be described in detail. Furthermore, connecting lines shown in the various figures are intended to represent example functional relationships and / or physical couplings between the various elements. Many alternative or additional functional relationships or physical connections may be present in an actual system and / or may not be present in some embodiments.

[0034] It should be understood that the configurations and / or approaches described in this disclosure are exemplary in nature, and that these specific embodiments or examples are not to be considered limiting, as numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. As such, the various illustrated operations may be performed in the order illustrated, in other orders, or omitted in some cases.

[0035] The subject matter of the present disclosure includes all novel and non-obvious combinations and subcombinations of the various processes, systems, and configurations, and other features, functions, operations and / or properties disclosed herein, as well as all equivalents thereof.

[0036] In this disclosure, "gas" may include materials that are gases, vaporized solids, and / or vaporized liquids at ambient temperature and pressure, and may consist of a single gas or a mixture of gases, depending on the circumstances. Gases introduced without passing through a gas supply unit, such as a shower plate, may be used, for example, to seal the reaction space and may include sealing gases such as noble gases or other inert gases. The terms inert gas, carrier gas, and diluent gas refer to gases that do not participate appreciably in chemical reactions and / or that can excite precursors when plasma power is applied.

[0037] As used herein, the terms "film" and "thin film" may refer to any continuous or discontinuous structure and material deposited by the methods disclosed herein. "Films" and "thin films" can include, for example, two-dimensional (2D) materials, nanorods, nanotubes, or nanoparticles, or even partial or complete molecular layers, or partial or complete atomic layers, or clusters of atoms and / or molecules. "Films" and "thin films" include materials or layers that have pinholes, but may still be at least partially continuous.

[0038] 1 illustrates a method 100 for filling trenches on a surface of a substrate according to an exemplary embodiment of the present disclosure. The method 100 may include: (a) placing the substrate on a susceptor in a reaction chamber (step 101), where the substrate includes a gap; (b) a deposition step (step 102), where the deposition step includes flowing a carbon precursor into the reaction chamber (step 103) and exposing the carbon precursor to a plasma (step 104), where the carbon precursor reacts to form a first deposition material; and (c) a treatment step (step 107), where the treatment step includes exposing the first deposition material to a post-deposition treatment to cause the first deposition material to flow into the gap.

[0039] During step 101 of providing a substrate on a susceptor in a reaction chamber, the substrate may be provided in a reaction chamber of a gas-phase reactor. According to examples of the present disclosure, the reaction chamber may form part of a deposition reactor, such as a Plasma Enhanced Chemical Vapor Deposition (PECVD) reactor. Various steps of the methods described herein may be performed in a single reaction chamber (e.g., serially) or may be performed in multiple reaction chambers, such as reaction chambers on a cluster tool.

[0040] During step 101, 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 appropriate for a subsequent step. By way of example, the temperature (e.g., of the substrate or substrate support) within the reaction chamber may range from about 30°C to about 700°C. The pressure within the reaction chamber may be maintained between 1 Pa and 20,000 Pa. According to certain examples of the present disclosure, the substrate includes one or more features, such as a gap.

[0041] A carbon precursor may be flowed onto the surface of the substrate during step 103. A carbon precursor for filling gaps may be flowed during step 103.

[0042] The chemical formula of the carbon precursor includes a cyclic compound having a ring structure containing C, H, and N, a carbonyl group, and at least one of a methyl group, an ethyl group, a propyl group, a butyl group, an amine group, and / or a hydroxy group. The cyclic structure may comprise one of pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, isobenzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzisoxazole, indazole, benzisothiazole, benzotriazole, purine, pyridine, phosphinine, pyrimidine, pyrazine, pyridazine, triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, hexazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, pteridine, phthalazine, acridine, 4aH-xanthene, 4aH-thioxanthene, 4aH-phenoxazine, 4a,10a-dihydro-10H-phenothiazine, carbazole, or a combination thereof.

[0043] The carbonyl group may comprise one of an aldehyde, ketone, carboxylic acid, ester, amide, enone, acyl chloride, acid anhydride, or combinations thereof.

[0044] During step 103, one or more inert gases, carrier gases, and diluent gases, such as argon, helium, nitrogen, or any mixture thereof, may be provided to the reaction chamber.

[0045] During step 104, a plasma may be generated in the reaction chamber by applying a first radio frequency (RF) power to one of one or more electrodes of the reaction chamber. The plasma power range for deposition may be in the range of about 10 W to about 3000 W. The RF frequency of the plasma power may be in the range of 400 kHz to 100 MHz. In some embodiments, a second RF power may be applied to one of the one or more electrodes of the reaction chamber.

[0046] During step 107, the first deposition material may be exposed to a post-deposition treatment to flow the first deposition material into the gap to form a carbon film. The post-deposition treatment may include heating the substrate to a temperature between 200°C and 800°C. The duration of the post-deposition treatment may be between 1 second and 1800 seconds.

[0047] The post-deposition treatment may include annealing the substrate at a temperature between 200°C and 800°C. A treatment gas (including an inert gas and / or an atomic oxygen-containing gas) may be provided to the reaction chamber during the post-deposition treatment. The atomic oxygen-containing gas may include one of O2, O3, NO2O, NO, NO2, CO2, CO, H2O, CH3OH, C2H5OH, or a combination thereof. The inert gas may include at least one of He, H2, N2, He, Ar, or a combination thereof. The inert gas may include N2, and the atomic oxygen-containing gas includes O2. The proportion of O2 may be greater than 25% of the treatment gas.

[0048] The post-deposition treatment may include a plasma treatment. Additionally, the post-deposition treatment may include a UV (ultraviolet) cure to reduce processing time. The post-deposition treatment may be performed in a second reaction chamber.

[0049] 2 illustrates a structure formed according to an exemplary embodiment of the present disclosure. Structure 202 may include a substrate 206 and protrusions 210, 221 formed thereon. Structure 202 includes a deposition material 218 overlying substrate 206. As shown, deposition material 218 from deposition step 101 includes a void 215 formed in trench 222 between protrusions 210 and 221. After material 218 (e.g., sufficient material to fill trench 222) is deposited, deposition material 218 may be exposed to a curing (post-deposition processing) step to cause deposition material 218 to flow into trench 222 and form structure 204 including annealed material 224.

[0050] By using a carbon precursor containing a cyclic compound having a ring structure containing C, H, and N, a carbonyl group, and at least one of a methyl group, an ethyl group, a propyl group, a butyl group, an amine group, and / or a hydroxyl group, the annealed material (carbon film) 224 can exhibit desirable properties. These properties can include a high elastic modulus, low shrinkage, and high etching resistance. The elastic modulus of the annealed material can be greater than 7 GPa. The shrinkage can be less than 50%. The etching resistance can be improved by more than 70% compared to carbon films formed with oxygen-containing carbon precursors.

[0051] 3 illustrates a plasma reactor system 500 according to an exemplary embodiment of the present disclosure. The plasma reactor system 500 may be used to perform one or more steps or substeps described herein and / or to form one or more structures or portions thereof described herein.

[0052] The plasma reactor system 500 may include a pair of conductive flat-plate upper and lower electrodes 4 and 2, parallel and facing each other, in the interior 11 (reaction zone) of the reaction chamber 3. Plasma can be excited in the reaction chamber 3, for example, by applying RF power (e.g., 13.56 MHz, 27 MHz, or 60 MHz) and / or low-frequency power from a power source 25 to one electrode (e.g., the upper electrode 4) and electrically grounding the other electrode (e.g., the lower electrode 2). The lower electrode 2 (which functions as the substrate support 2) may be provided with a temperature regulator, so that the temperature of the substrate 1 disposed thereon can be maintained at a desired temperature. The upper electrode 4 may function as a gas distribution device, such as a shower plate. Reactant gases, carrier gases, inert gases, diluent gases (if present), precursor gases, and / or the like may 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 shown with three gas lines, reactor system 500 may include any suitable number of gas lines.

[0053] The reaction chamber 3 may be provided with a circular duct 13 having an exhaust line 7 through which gas within the interior 11 of the reaction chamber 3 may be exhausted. Furthermore, the transfer chamber 5 disposed below the reaction chamber 3 may be provided with a seal gas line 24 for introducing a seal gas into the interior 11 of the reaction chamber 3 through the interior 16 (transfer zone) of the transfer chamber 5, and may be provided with a separation plate 14 for separating the reaction zone from the transfer zone (a gate valve through which the wafer passes when being transferred in and out of the transfer chamber 5 is omitted from this drawing). The transfer chamber may also be provided with an exhaust line 6.

[0054] Those skilled in the art will appreciate that the apparatus includes one or more controllers programmed or otherwise configured to perform 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 various power sources, heating systems, pumps, robotics, and gas flow controllers or valves of the reactor.

[0055] In some embodiments, a dual chamber reactor (two zones or compartments for processing wafers located close to each other) may be used, and the reactant and noble gases may be supplied through shared lines, while the precursor gases are supplied through non-shared lines.

[0056] 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 invention. All 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 within the scope of the appended claims.

Claims

1. (a) placing a substrate on a susceptor in a reaction chamber, the substrate including a gap; (b) a depositing step, flowing a carbon precursor into the reaction chamber, the carbon precursor having a chemical formula: a cyclic compound having a ring structure containing C, H, and N; a carbonyl group, at least one of a methyl group, an ethyl group, a propyl group, a butyl group, an amine group, and / or a hydroxy group; and a depositing step including exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a first deposition material; (c) a processing step comprising: a processing step including exposing the first deposition material to a post-deposition treatment and flowing the first deposition material into the gap to form a carbon film.

2. The method of claim 1 , wherein the temperature during the depositing step is from 30° C. to 700° C.

3. The method of claim 1 further comprising providing an inert gas and / or an atomic oxygen-containing gas during said processing step.

4. The atomic oxygen-containing gas is O ２ , O ３ , N ２ O, NO, NO ２ , CO ２ , CO, H ２ O, CH ３ OH, C ２ H ５ 4. The method of claim 3, wherein the hydroxyl group is selected from the group consisting of hydroxyl, hydroxypropyl ...

5. The inert gas is He, H ２ , N ２ 4. The method of claim 3, wherein the gas comprises at least one of: He, Ar, or a combination thereof.

6. The inert gas is N ２ and the atomic oxygen-containing gas is O ２ The method of claim 5 , comprising:

7. The above O ２ The method of claim 6, wherein the proportion of the total gas is greater than 25%.

8. The method of claim 1 , wherein the post-deposition treatment has a duration of 1 to 1800 seconds.

9. The method of claim 1 , wherein the post-deposition treatment comprises annealing the substrate to a temperature of from 200° C. to 800° C.

10. The method of claim 1 , wherein the post-deposition treatment comprises a plasma treatment.

11. The method of claim 1 , wherein the post-deposition treatment comprises an ultraviolet cure.

12. The method of claim 1 , wherein the post-deposition treatment occurs in a second reaction chamber.

13. The method of claim 1 , wherein the power of the plasma is between 10 W and 3000 W.

14. The method of claim 1 , wherein the plasma has a frequency between 400 kHz and 100 MHz.

15. The cyclic structure may be selected from the group consisting of pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, isobenzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzisoxazole, indazole, benzisothiazole, benzotriazole, purine, pyridine, phosphinine, pyrimidine, and pyrazine. , pyridazine, triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, hexazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, pteridine, phthalazine, acridine, 4aH-xanthene, 4aH-thioxanthene, 4aH-phenoxazine, 4a,10a-dihydro-10H-phenothiazine, carbazole, or a combination thereof.

16. 10. The method of claim 1, wherein the carbonyl group comprises one of an aldehyde, a ketone, a carboxylic acid, an ester, an amide, an enone, an acyl chloride, an acid anhydride, or a combination thereof.

17. The method of claim 1 , wherein one of the electrodes is part of the susceptor.

18. The method of claim 1 , wherein the carbon film has an elastic modulus greater than 7 GPa.

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