Method of filling gap on surface of substrate

Abstract

A method of filling a gap on a surface of a substrate is provided. The method may include the steps of: (a) placing a substrate on a susceptor within a reaction chamber, the substrate including a gap; (b) a deposition step comprising: flowing a carbon precursor into the reaction chamber; wherein the chemical formula of the carbon precursor includes: a cyclic compound having a cyclic structure including C, H, and N; a carbonyl group; and at least one of methyl, ethyl, propyl, butyl, amido and / or hydroxyl; and exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a first deposited material; and (c) a treatment step including exposing the first deposition material to a deposition post-treatment to flow the first deposition material within the gap to form a carbon film.

Description

TECHNICAL FIELD

[0001] The present disclosure relates generally to methods of forming structures suitable for use in manufacturing electronic devices. More specifically, examples of the present disclosure relate to methods of forming structures including depositing a layer of material that can fill gaps on a surface of the structure. BACKGROUND

[0002] During the manufacture of devices such as semiconductor devices, it is often desirable to fill gaps on a 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 for some applications, deposition techniques for flowable carbon can exhibit low elastic modulus and low etch resistance. Additionally, the deposited carbon material can shrink significantly after an anneal process. Accordingly, improved methods of filling gaps on a substrate are desired.

[0004] Any discussion of documents, acts, materials, devices, articles or the like that has been included in this section for purposes of providing a context for the present disclosure is included in this section solely for purposes of providing a context for the present disclosure and is not to be taken as an admission that any or all of the discussion, setting forth, or suggestion in the background section was known or is part of the prior art. SUMMARY

[0005] The summary is provided to introduce a selection of concepts in a simplified form. These concepts are further described in detail in the detailed description of example embodiments of the disclosure below. The 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 example embodiments of the present disclosure, a method of filling a gap on a substrate is provided. The method can include the steps of: (a) placing a substrate on a susceptor within a reaction chamber, the substrate including a gap; (b) a deposition step including: flowing a carbon precursor into the reaction chamber; wherein a chemical formula of the carbon precursor includes: a cyclic compound having a cyclic 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 hydroxyl group; and exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a first deposited material; and (c) a processing step including: exposing the first deposited material to a post-deposition treatment to flow the first deposited material within the gap to form a carbon film.

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

[0008] According to further example embodiments of the present disclosure, the method can further include providing an inert gas and / or an atomic oxygen-containing gas during the processing step.

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

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

[0011] According to further example embodiments of the present disclosure, the inert gas can include N2and the atomic oxygen containing gas includes O2.

[0012] According to further example embodiments of the present disclosure, the ratio of O2may be greater than 25% in the total gas.

[0013] According to further example embodiments of the present disclosure, the post-deposition treatment can include annealing the substrate to a temperature of 200°C to 800°C.

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

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

[0016] According to further example embodiments of the present disclosure, the post-deposition treatment can include a UV cure.

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

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

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

[0020] According to further example embodiments of the present disclosure, the ring structure can include one of a pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, isobenzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzoisoxazole, indazole, benzoisothiazole, benzotriazole, purine, pyridine, phosphine, 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, phtalazine, acridine, 4aH-xanthene, 4aH-thioxanthene, 4aH-phenoxazine, 4a,10a-dihydro-10H-phenothiazine, carbazole, or combinations thereof.

[0021] According to further example embodiments of the disclosure, the carbonyl group can include one of an aldehyde, a ketone, a carboxylic acid, an ester, an amide, an enone, an acid chloride, an anhydride, or combinations thereof.

[0022] According to further example embodiments of the disclosure, one of the electrodes can be part of the susceptor.

[0023] According to further example embodiments of the disclosure, the carbon layer can have an elastic modulus greater than 7 GPa. BRIEF DESCRIPTION OF DRAWINGS

[0024] A more complete understanding of example embodiments of the present disclosure can be obtained by reference to the following detailed description when considered in connection with the following

[0025] Figure 1 A method according to example embodiments of the present disclosure is illustrated.

[0026] Figure 2 A structure according to example embodiments of the present disclosure is illustrated.

[0027] Figure 3 A plasma system according to example embodiments of the present disclosure is illustrated.

[0028] It is to be understood that the elements in the figures are shown for the purpose of simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some of the elements in the figures can be exaggerated relative to other elements to help improve the DETAILED DESCRIPTION

[0029] While certain embodiments and examples are disclosed herein, one of ordinary skill in the art will understand that modifications can be made of the disclosed embodiments and / or the uses of the present application and its general principles from the teachings herein. Thus, the disclosed application is not to be limited to the particular disclosed embodiments and / or working examples. Rather, the scope of the application is to be determined only by the following claims.

[0030] As used herein, the term "substrate" can refer to any one or more underlying materials, including any one or more underlying materials that can be modified or on which a device, circuit, or film can 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 sheet, or a workpiece. A substrate in the form of a sheet can include wafers of various shapes and sizes. A substrate can be made of a semiconductor material, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide.

[0031] As an example, the substrate in powder form can have applications for pharmaceutical manufacturing. The porous substrate can comprise a polymer. Examples of workpieces can include medical devices such as stents and syringes, jewelry, tooling devices, components for battery manufacturing such as anodes, cathodes, or separators, or components of photovoltaic cells, among others.

[0032] The continuous substrate can extend beyond the boundaries of the processing chamber in which the deposition process occurs. In some processes, the continuous substrate can be moved through the processing chamber such that the process continues until the end of the substrate is reached. The continuous substrate can be supplied from a continuous substrate feed system to allow for the manufacture and output of the continuous substrate in any suitable form.

[0033] Non-limiting examples of continuous substrates can include a sheet, a nonwoven membrane, a roll, a foil, a web, a flexible material, a bundle of continuous filaments or fibers such as ceramic fibers or polymeric fibers. The continuous substrate can also include a carrier or sheet on which a non-continuous substrate is mounted.

[0034] The illustrations presented herein are not meant to be actual views of any particular material, structure or device, but are merely idealized representations that are employed to describe the embodiments of the present disclosure.

[0035] The particular implementations shown and described are illustrative examples of the application and its best mode and are not intended to limit the scope of aspects and implementations in any way. Rather, the subsequent portions of this disclosure will show and describe various alternatives, modifications, and enhancements. Indeed, for the sake of brevity, conventional manufacturing, connecting, preparing, and other functional aspects of the systems can not be described in detail. Furthermore, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical couplings between the various elements. Many alternative or additional functional relationships or physical connections can be present in a practical system, and / or absent in some embodiments.

[0036] It should be understood that the configurations and / or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein can represent one or more of any number of processing strategies. As such, various acts illustrated can be performed in the sequence illustrated, in other sequences, or omitted in some embodiments.

[0037] The subject matter of the present disclosure includes all novel and non-obvious combinations and sub-combinations of the various processes, systems and configurations described herein, and other features, functions, acts and / or properties disclosed herein, as well as any and all equivalents thereof.

[0038] In the present disclosure, "gas" can include materials that are gaseous at normal temperature and pressure, vaporized solids, and / or vaporized liquids, and can be composed 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 or the like, can be used, for example, to seal a reaction space, and can include a seal gas, such as a noble gas or other inert gas. The terms inert gas, carrier gas, and dilution gas refer to gases that do not participate in chemical reactions to a perceptible extent when plasma power is applied and / or can excite precursors.

[0039] As used herein, the terms "film" and "thin film" can refer to any continuous or non-continuous structure and material deposited by the methods disclosed herein. For example, "film" and "thin film" can include a 2D material, nanorod, nanotube, or nanoparticle or even a partial or full molecular layer or a partial or full atomic layer or atomic and / or molecular clusters. "Film" and "thin film" can include a material or layer with pinholes but still be at least partially continuous.

[0040] Figure 1 A method 100 of filling trenches on a surface of a substrate according to example embodiments of the present disclosure is shown. The method 100 can include the following steps: (a) placing a substrate on a pedestal within a reaction chamber, the substrate including a gap (step 101); (b) a deposition step including: flowing a carbon precursor into the reaction chamber (step 103); and exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a first deposition material (step 104); and (c) a treatment step including: exposing the first deposition material to a post-deposition treatment to flow the first deposition material within the gap (step 107).

[0041] During the step 101 of providing the substrate on a pedestal within a reaction chamber, the substrate can be provided into a reaction chamber of a gas phase reactor. According to examples of the present disclosure, the reaction chamber can form part of a deposition reactor, such as a plasma enhanced chemical vapor deposition (PECVD) reactor. The various steps of the methods described herein can be performed within a single reaction chamber (e.g., continuously), or can be performed in multiple reaction chambers, such as reaction chambers on a cluster tool.

[0042] During the step 101, the substrate can be brought to a desired temperature and / or the reaction chamber can be brought to a desired pressure, such as a temperature and / or pressure suitable for the subsequent steps. By way of example, the temperature within the reaction chamber (e.g., the temperature of the substrate or substrate support) can be in a range between about 30 °C to about 700 °C. The pressure within the reaction chamber can be maintained between 1 Pa and 20,000 Pa. According to particular examples of the present disclosure, the substrate includes one or more features, such as a gap.

[0043] During step 103, a carbon precursor can be flowed onto the surface of the substrate. During step 103, the carbon precursor can be flowed to fill the gap.

[0044] The chemical formula of the carbon precursor includes a cyclic compound having a cyclic 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 hydroxyl group. The cyclic structure can include one of a pyrrole, a furan, a thiophene, a phosphazole, a pyrazole, an imidazole, an oxazole, an isoxazole, a thiazole, an indole, a benzofuran, a benzothiophene, an isoindole, an isobenzofuran, a benzophosphazole, a benzimidazole, a benzoxazole, a benzothiazole, a benzoisoxazole, an indazol, a benzoisothiazole, a benzotriazole, a purine, a pyridine, a phosphine, a pyrimidine, a pyrazine, a pyridazine, a triazine, a 1,2,4,5-tetrazine, a 1,2,3,4,-tetrazine, a 1,2,3,5-tetrazine, a hexazine, a quinoline, an isoquinoline, a quinoxaline, a quinazoline, a cinnoline, a pteridine, a phthalazine, an acridine, a 4aH-xanthene, a 4aH-thioxanthene, a 4aH-phenoxazine, a 4a,10a-dihydro-10H-phenothiazine, a carbazole, or a combination thereof.

[0045] The carbonyl group can include one of an aldehyde, a ketone, a carboxylic acid, an ester, an amide, an enone, an acid chloride, an anhydride, or a combination thereof.

[0046] During step 103, one or more inert gases, carrier gases, and dilution gases, such as argon, helium, nitrogen, or any mixture thereof, can be provided to the reaction chamber.

[0047] During step 104, a plasma can be generated in the reaction chamber by applying a first radio frequency (RF) power to one of the one or more electrodes of the reaction chamber. The plasma power for deposition can range from about 10 W to about 3000 W. The RF frequency of the plasma power can range from 400 kHz to 100 MHz. In some embodiments, a second RF power can be applied to one of the one or more electrodes of the reaction chamber.

[0048] During step 107, the first deposition material can be exposed to a post-deposition treatment to flow the first deposition material within the gap to form a carbon film. The post-deposition treatment can include heating the substrate to a temperature of 200 °C to 800 °C. The duration of the post-deposition treatment can be between 1 second and 1800 seconds.

[0049] The post-deposition treatment can include annealing the substrate at a temperature from 200 °C to 800 °C. A process gas (including an inert gas and / or an atomic oxygen containing gas) can be provided to the reaction chamber during the post-deposition treatment. The atomic oxygen containing gas can include one of O2, O3, N2O, NO, NO2, CO2, CO, H2O, CH3OH, C2H5OH, or combinations thereof. The inert gas can include at least one of He, H2, N2, He, Ar, or combinations thereof. The inert gas can include N2and the atomic oxygen containing gas includes O2. The percentage of O2may be greater than 25% of the process gas.

[0050] The post-deposition treatment can include a plasma treatment. Further, the post-deposition treatment can include a UV cure to reduce the treatment time. The post-deposition treatment can be performed in a second reaction chamber.

[0051] Figure 2 A structure formed according to example embodiments of the disclosure is shown. The structure 202 can include a substrate 206 and protrusions 210, 221 formed thereon. The structure 202 includes a deposited material 218 covering the substrate 206. As shown, the deposited material 218 from the deposition step 101 includes voids 215 formed within a trench 222 between the protrusions 210 and 221. After the deposition of the material 218 (e.g., enough material to fill the trench 222), the deposited material 218 can be exposed to a curing (post-deposition treatment) step to flow the deposited material 218 within the trench 222 to form a structure 204 including an annealed material 224.

[0052] The annealed material (carbon film) 224 can exhibit desired properties by using a carbon precursor including a cyclic compound having a cyclic 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 hydroxyl group. These properties can include high modulus, low shrinkage, and high etch resistance. The elastic modulus of the annealed material can be greater than 7 GPa. The shrinkage can be less than 50%. The etch resistance can be improved by more than 70% compared to a carbon film formed by an oxygen containing carbon precursor.

[0053] Figure 3 A plasma reactor system 500 according to example embodiments of the disclosure is shown. The plasma reactor system 500 can be used to perform one or more steps or sub-steps as described herein and / or form one or more structures or portions thereof as described herein.

[0054] The plasma reactor system 500 can include a pair of electrically conductive flat top electrode 4 and bottom electrode 2 parallel to and facing each other in the interior 11 (reaction zone) of the reaction chamber 3. Plasma can be excited within the reaction chamber 3 by applying, for example, RF power (e.g., 13.56 MHz, 27 MHz, or 60 MHz) and / or low frequency power from the power source 25 to one electrode (e.g., the top electrode 4) and electrically grounding the other electrode (e.g., the bottom electrode 2). A temperature regulator can be provided in the bottom electrode 2 (serving as the substrate support 2), and the temperature of the substrate 1 placed thereon can be maintained at a desired temperature. The top electrode 4 can serve as a gas distribution device, such as a showerhead. One or more of the gas lines 20, 21, and 22 can be used to introduce reactant gas, carrier gas, inert gas, dilution gas (if any), precursor gas, etc. into the reaction chamber 3, respectively, through the showerhead 4. Although shown as having three gas lines, the reactor system 500 can include any suitable number of gas lines.

[0055] In the reaction chamber 3, a circular duct 13 with an exhaust line 7 can be provided through which gas in the interior space 11 of the reaction chamber 3 can be exhausted. Additionally, the transfer chamber 5 provided below the reaction chamber 3 can be provided with a seal gas line 24 to introduce seal gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer zone) of the transfer chamber 5, wherein a separation plate 14 (a gate valve through which a wafer is transferred into or out of the transfer chamber 5 is omitted in this figure) for separating the reaction zone and the transfer zone can be provided. The transfer chamber can also be provided with an exhaust line 6.

[0056] Those skilled in the art will appreciate that the apparatus includes one or more controllers programmed or otherwise configured to cause performance of one or more method steps as described herein. As those skilled in the art will appreciate, the controllers are in communication with various power supplies, heating systems, pumps, robots, and gas flow controllers or valves of the reactor.

[0057] In some embodiments, a dual chamber reactor can be used (two sections or compartments for processing wafers are provided in close proximity to each other), wherein the reactant gas and inert gas can be supplied through a common line, while the precursor gas is supplied through a non-common line.

[0058] The example embodiments of the present disclosure described above do not limit the scope of the present invention, as the embodiments are merely examples of embodiments of the present invention. Any equivalent embodiments are intended to fall within the scope of the present invention. Indeed, various modifications such as, for example, alterations to the use combinations of the elements described herein, can become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method comprising the steps of: (a) placing a substrate on a susceptor within a reaction chamber, the substrate comprising a gap; (b) a deposition step comprising: flowing a carbon precursor into the reaction chamber; wherein the chemical formula of the carbon precursor comprises: a cyclic compound having a cyclic structure comprising 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; and exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a first deposition material; and (c) a treatment step comprising: exposing the first deposition material to a post-deposition treatment to flow the first deposition material within the gap to form a carbon film.

2. The method of claim 1, wherein, a temperature during the deposition step is between 30 °C and 700 °C.

3. The method of claim 1, further comprising providing an inert gas and / or an atomic oxygen containing gas during the treatment step.

4. The method of claim 3, wherein, the atomic oxygen containing gas comprises one of O2, O3, N2O, NO, NO2, CO2, CO, H2O, CH3OH, C2H5OH, or a combination thereof.

5. The method of claim 3, wherein, the inert gas comprises at least one of He, H2, N2, He, Ar, or a combination thereof.

6. The method of claim 5, wherein, the inert gas comprises N2 and the atomic oxygen containing gas comprises O2.

7. The method of claim 6, wherein, a ratio of O2 is greater than 25% in the total gas.

8. The method of claim 1, wherein, a duration of the post-deposition treatment is between 1 second and 1800 seconds.

9. The method of claim 1, wherein, the post-deposition treatment comprises annealing the substrate to a temperature of 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 a UV cure.

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

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

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

15. The method of claim 1, the cyclic structure comprises one of a pyrrole, a furan, a thiophene, a phosphazole, a pyrazole, an imidazole, an oxazole, an isoxazole, a thiazole, an indole, a benzofuran, a benzothiophene, an isoindole, an isobenzofuran, a benzophosphazole, a benzimidazole, a benzoxazole, a benzothiazole, a benzoisoxazole, an indazol, a benzoisothiazole, a benzotriazole, a purine, a pyridine, a phosphine, a pyrimidine, a pyrazine, a pyridazine, a triazine, a 1,2,4,5-tetrazine, a 1,2,3,4,-tetrazine, a 1,2,3,5-tetrazine, a hexazine, a quinoline, an isoquinoline, a quinoxaline, a quinazoline, a cinnoline, a pteridine, a phtalazine, an acridine, a 4aH-xanthene, a 4aH-thioxanthene, a 4aH-phenoxazine, a 4a,10a-dihydro-10H-phenothiazine, a carbazole, or a combination thereof.

16. 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 acid chloride, an 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, an elastic modulus of the carbon film is greater than 7 GPa.

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