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: (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; 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 annealing the substrate in an atomic oxygen-containing gas 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 trenches can work well for some applications, delamination of a film can occur after the film is formed on the deposited carbon material.

[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 the background art, is prior art to the present disclosure. 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 or essential features of the claimed subject matter, nor is it meant to be used in limiting 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: (a) placing a substrate on a pedestal within a reaction chamber, the substrate including a gap; (b) a deposition step including: flowing a carbon precursor into the reaction chamber; 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: annealing the substrate in an atomic oxygen containing gas to flow the first deposited material within the gap to form a carbon film.

[0007] According to further example embodiments of the present disclosure, the temperature during the deposition step can be between 30 °C and 350 °C.

[0008] According to further example embodiments of the present disclosure, the temperature during the treatment step can be between 200 °C and 800 °C.

[0009] According to further example embodiments of the present disclosure, the duration of the treatment step can be between 10 seconds and 2000 seconds.

[0010] According to further example embodiments of the present disclosure, the pressure of the treatment step can be between 100 Pa and 2000 Pa.

[0011] 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.

[0012] According to further example embodiments of the present disclosure, the method can further include providing an inert gas during the processing step.

[0013] 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.

[0014] According to further example embodiments of the present disclosure, a ratio of the atomic oxygen containing gas can be greater than 10% in the total gas.

[0015] According to further example embodiments of the present disclosure, the processing step can be performed in a second reaction chamber.

[0016] According to further example embodiments of the present disclosure, a power of the plasma can be between 30 W and 500 W.

[0017] According to further example embodiments of the present disclosure, a frequency of the plasma can be between 2.0 MHz and 2.45 GHz.

[0018] According to further example embodiments of the present disclosure, the carbon precursor can include a cyclic structure.

[0019] According to further example embodiments of the present disclosure, the carbon precursor can include a carbonyl functional group.

[0020] According to further example embodiments of the present disclosure, the cyclic structure can be selected from the group consisting of: benzene; indene; cyclopentadiene; cyclohexane; pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, iso-benzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzoisoxazole, indazol, 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 present disclosure, the carbon precursor can include one or more carbonyl groups and one or more of a methyl group, an ethyl group, a propyl group, a butyl group, an amine group, or a hydroxyl group.

[0022] According to further exemplary embodiments of the present disclosure, the carbonyl functional group can be selected from the group consisting of aldehyde, ketone, carboxylic acid, ester, amide, enone, acyl chloride, and anhydride.

[0023] According to further exemplary embodiments of the present disclosure, the method can further comprise a second deposition step to form a SiCON film, a SiCO film, a SiON, or a SiCN film on the carbon film.

[0024] According to further exemplary embodiments of the present disclosure, one of the electrodes can be part of the susceptor.

[0025] According to further exemplary embodiments of the present disclosure, a system for depositing a carbon material to fill a recess on a surface of a substrate is provided. The system can include a reaction chamber; and a controller to perform a deposition step and a treatment step. BRIEF DESCRIPTION OF DRAWINGS

[0026] A more complete understanding of exemplary embodiments of the present disclosure can be obtained by reference to the following detailed description when considered in connection with the following

[0027] Figure 1 A method according to exemplary embodiments of the present disclosure is illustrated.

[0028] Figure 2 A structure according to exemplary embodiments of the present disclosure is illustrated.

[0029] Figure 3a A structure according to exemplary embodiments of the present disclosure is illustrated.

[0030] Figure 3b A structure after a strip test according to exemplary embodiments of the present disclosure is illustrated.

[0031] Figure 4 A plasma system according to exemplary embodiments of the present disclosure is illustrated.

[0032] 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

[0033] 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 generally equivalent arrangements as will be appreciated by those skilled in the art. Accordingly, it is intended that the scope of the present application be governed only by the following claims and their equivalents.

[0034] 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.

[0035] By way of example, a substrate in the form of a powder can have applications for pharmaceutical manufacturing. A porous substrate can include 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.

[0036] A continuous substrate can extend beyond the boundaries of a processing chamber in which a deposition process occurs. In some processes, a continuous substrate can be moved through a processing chamber such that the process continues until the end of the substrate is reached. A 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.

[0037] Non-limiting examples of a continuous substrate can include a sheet, a nonwoven film, a roll, a foil, a web, a flexible material, a bundle of continuous filaments or fibers (such as ceramic fibers or polymeric fibers). A continuous substrate can also include a carrier or sheet on which a non-continuous substrate is mounted.

[0038] 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.

[0039] 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 claims are intended to cover all such alternatives, modifications, and equivalents. For example, the particular elements shown are not intended to be limiting, such that alternate elements can be used in place of those shown. Further, while the particular implementations shown include a particular series of steps or functions, alternate implementations can perform the steps out of order, or concurrently, or can include additional or alternative steps.

[0040] It will be appreciated that, of the configurations and / or methods described herein, that the configurations and / or methods are exemplary, and that these specific embodiments or examples are not meant to be limiting by any means. The particular routines or methods described herein can represent one or more of any number of processing strategies. As such, acts shown can be performed in the sequence shown, in other sequences, or in parallel, in some cases. Additionally, the use of "adapted to" or "configured to" herein can mean that an element is so adapted or configured, either alone or in combination with other elements, such that an element need not perform functions literally recited by that element.

[0041] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations disclosed herein, and any and all equivalents thereof.

[0042] 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 (e.g., 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.

[0043] 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, nanorods, nanotubes, or nanoparticles or even partial or full molecular layers or partial or full atomic layers or atomic and / or molecular clusters. "Film" and "thin film" can include materials or layers with pinholes but are still at least partially continuous.

[0044] 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 (step 102) 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: annealing the substrate in an atomic oxygen containing gas to flow the first deposition material within the gap to form a carbon film (step 107).

[0045] 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.

[0046] During 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 subsequent steps. For example, the temperature within the reaction chamber, such as the temperature of the substrate or substrate support, can be in a range between about 30 °C to about 350 °C. The pressure within the reaction chamber can be maintained between 100 Pa and 2000 Pa. According to particular examples of the present disclosure, the substrate includes one or more features, such as a gap.

[0047] 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.

[0048] The carbon precursor can include a cyclic structure. The cyclic structure can be selected from the group consisting of benzene; indene; cyclopentadiene; cyclohexane; pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, isobenzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzoisoxazole, indazol, 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.

[0049] The carbon precursor can include a carbonyl functional group. The carbonyl functional group can be selected from the group consisting of aldehyde, ketone, carboxylic acid, ester, amide, enone, acid chloride, anhydride, or combinations thereof.

[0050] The carbon precursor can include one or more carbonyl groups and one or more of a methyl group, an ethyl group, a propyl group, a butyl group, an amine group, or a hydroxyl group.

[0051] During step 103, one or more inert gases, carrier gases, and dilution gases can be provided to the reaction chamber, such as argon, helium, nitrogen, or any mixture thereof.

[0052] 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 30 W to about 500 W. The RF frequency of the plasma power can range from 2.0 MHz to 2.45 GHz. In some embodiments, a second RF power can be applied to one of the one or more electrodes of the reaction chamber.

[0053] During step 107, the first deposited material can be exposed to a treatment to cause the first deposited material to flow within the gap. The treatment can include annealing the substrate to a temperature of 200°C to 800°C. The duration of the treatment step can be between 10 seconds and 1000 seconds. The pressure of the treatment can be between 100 Pa and 2000 Pa. The treatment step can be performed in a second reaction chamber.

[0054] The treatment can include annealing the substrate in an atomic oxygen containing gas. The atomic oxygen containing gas can include one of O2, O3, N2O, NO, NO2, CO2, CO, H2O, CH3OH, C2H5OH, or combinations thereof. Additionally, an inert gas can be provided to the reaction chamber during the treatment step. The inert gas can include at least one of He, H2, N2, He, Ar, or combinations thereof. The ratio of the atomic oxygen containing gas can be greater than 10% in the total gas.

[0055] Figure 2 A structure formed according to an example embodiment 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 deposited material 218 (e.g., enough material to fill the trench 222), the deposited material 218 can be exposed to a solidification (treatment) step to cause the deposited material 218 to flow within the trench 222 to form a structure 204 including an annealed film 224.

[0056] Figure 3a A structure according to an example embodiment of the disclosure is shown. A second film 240 can be formed on the annealed film 224. A second deposition step can be performed to form the second film 240. The second film 240 can include at least one of a SiCON film, a SiCO film, SiON, SiN, SiCOH, or a SiCN film. The thickness of the structure 224 can be less than 70 nm.

[0057] Figure 3b A structure after a tape test according to an example embodiment of the disclosure is shown. To check the adhesion between the annealed film 224 and the second film 240, a tape test can be performed. The annealed film 224 can be torn when N2 is used during the treatment step. By annealing the substrate under an atomic oxygen containing gas atmosphere, the annealed film 224 can not be torn. The annealed film 224 using an atomic oxygen containing gas can have a higher density compared to using N2 gas for the treatment step.

[0058] Figure 4A plasma reactor system 500 according to an exemplary embodiment of the present 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.

[0059] The plasma reactor system 500 can include a pair of 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, 60 MHz, or 2.45 GHz) 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 shower plate. 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 through the shower plate 4, respectively. Although shown as having three gas lines, the reactor system 500 can include any suitable number of gas lines.

[0060] 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, a 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.

[0061] 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.

[0062] In some embodiments, a multi-chamber reactor (in which multiple portions or compartments for processing a wafer are disposed in proximity to each other) can be used, in which reactant gas and inert gas can be supplied through a common line, while precursor gas is supplied through a non-common line.

[0063] The example embodiments of the present disclosure described above do not limit the scope of the application, because these embodiments are merely examples of embodiments of the application. Any equivalent embodiments are intended to fall within the scope of the application. Indeed, various modifications such as, for example, variations in sizes, dimensions, structures, shapes and proportions of the various elements showing and describing the preferred embodiment, can be made to the application from the description and illustrations without departing from the scope of the application. 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; 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: annealing the substrate in an atomic oxygen containing gas 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 350 °C.

3. The method of claim 1, wherein, a temperature during the treatment step is between 200 °C and 800 °C.

4. The method of claim 1, wherein, a duration of the treatment step is between 10 seconds and 2000 seconds.

5. The method of claim 1, wherein, a pressure of the treatment step is between 100 Pa and 2000 Pa.

6. The method of claim 1, wherein, the atomic oxygen containing gas comprises one of O2, O3, N2O, NO, NO2, CO2, CO, H2O, CH3OH, C2H5OH, or combinations thereof.

7. The method of claim 1, further comprising providing an inert gas during the treatment step.

8. The method of claim 7, wherein, the inert gas comprises at least one of He, H2, N2, He, Ar, or combinations thereof.

9. The method of claim 7, wherein, a ratio of the atomic oxygen containing gas is greater than 10% in the total gas.

10. The method of claim 1, wherein, the treatment step is performed in a second reaction chamber.

11. The method of claim 1, wherein, a power of the plasma is between 30 W and 500 W.

12. The method of claim 1, wherein, a frequency of the plasma is between 2.0 MHz and 2.45 GHz.

13. The method of claim 1, wherein, the carbon precursor comprises a cyclic structure.

14. The method of claim 1, wherein, the carbon precursor comprises a carbonyl functional group.

15. The method of claim 13, wherein, the cyclic structure is selected from the group consisting of: benzene; indene; cyclopentadiene; cyclohexane; pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, iso-benzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzoisoxazole, indazol, 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.

16. The method of claim 1, wherein, the carbon precursor comprises one or more carbonyl groups and one or more of methyl, ethyl, propyl, butyl, amine, or hydroxyl groups.

17. The method of claim 14, wherein, the carbonyl functional group is selected from the group consisting of aldehyde, ketone, carboxylic acid, ester, amide, enone, acid chloride, and anhydride.

18. The method of claim 1, further comprising a second deposition step to form a SiCON film, SiCO film, SiON, SiN, SiCOH, or SiCN film on the carbon film.

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

20. A system for depositing a carbon material to fill a recess on a surface of a substrate, the system comprising: a reaction chamber; and a controller to perform the deposition step and the treatment step of claim 1.

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