Method of filling trenches on substrate surface

Abstract

A method of filling a trench on a surface of a substrate is provided. The method may include the steps of: providing a substrate within a reaction chamber, the substrate including a plurality of narrow trenches and wide trenches formed on a surface of the substrate; a first deposition step including: (a) flowing a carbon precursor into the reaction chamber; (b) exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a first deposited material; (c) exposing the first deposition material to a post-deposition process to flow the first deposition material within the trench; (d) etching the first deposited material, wherein the first deposited material is substantially flat in the narrow trench and recessed in the wide trench; and a second deposition step including: (e) flowing a carbon precursor into the reaction chamber; (f) exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a second deposited material on the first deposited material.

Description

Technical Field

[0001] The present disclosure generally relates 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 that include depositing a layer of material that can fill trenches on a surface of the structure. Background Art

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

[0003] Although filling trenches with flowable carbon materials may work well for some applications, conventional deposition techniques for filling narrow and wide trenches using flowable carbon may result in large differences in thickness (overburden gain) between the narrow and wide trenches. Therefore, there is a need for improved methods for forming structures, particularly methods for filling narrow and wide trenches on a substrate surface with materials that reduce overburden gain.

[0004] Any discussion set forth in this section, including discussion of problems and solutions, has been included in the present disclosure merely to provide a context for the present disclosure and should not be considered as an admission that any or all of the discussions were known or constituted prior art at the time the present invention was made. Summary of the invention

[0005] This summary is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the detailed description of the example embodiments disclosed below. This summary is not intended to identify the 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 grooves on a substrate surface is provided. The method includes the following steps: providing a substrate in a reaction chamber, the substrate including a plurality of narrow grooves and wide grooves formed on the substrate surface; a first deposition step including: (a) flowing a carbon precursor into the reaction chamber; (b) exposing the carbon precursor to plasma, wherein the carbon precursor reacts to form a first deposition material; (c) exposing the first deposition material to a post-deposition treatment to flow the first deposition material in the grooves; (d) etching the first deposition material, wherein the first deposition material is substantially flat in the narrow grooves and recessed in the wide grooves; and a second deposition step including: (e) flowing a carbon precursor into the reaction chamber; (f) exposing the carbon precursor to plasma, wherein the carbon precursor reacts to form a second deposition material on the first deposition material.

[0007] According to further exemplary embodiments of the present disclosure, steps (d) to (f) may be repeated.

[0008] According to further exemplary embodiments of the present disclosure, the method may further include the step (g) of exposing the second deposition material to a post-deposition treatment.

[0009] According to further exemplary embodiments of the present disclosure, steps (d) to (g) may be repeated.

[0010] According to further exemplary embodiments of the present disclosure, the temperature during the first deposition step may be from about 50°C to about 600°C.

[0011] According to further exemplary embodiments of the present disclosure, the post-deposition treatment may include heating the substrate to a temperature of about 100°C to about 800°C.

[0012] According to further exemplary embodiments of the present disclosure, the temperature during the second deposition step may be from about 50°C to about 800°C.

[0013] According to a further exemplary embodiment of the present disclosure, the power of the plasma may be less than 2000W.

[0014] According to further exemplary embodiments of the present disclosure, in the case of a single RF power source, the frequency of the plasma may be 3 to 30 MHz.

[0015] According to a further exemplary embodiment of the present disclosure, the power of the plasma of the first deposition step may be 200 W or less.

[0016] According to further exemplary embodiments of the present disclosure, the pressure within the reaction chamber may be between about 100 Pa and about 1300 Pa.

[0017] According to further exemplary embodiments of the present disclosure, the post-deposition treatment may include a plasma treatment.

[0018] According to further exemplary embodiments of the present disclosure, plasma treatment may include exposing the inert gas and / or the nitrogen-containing gas to plasma.

[0019] According to further exemplary embodiments of the present disclosure, the nitrogen-containing gas may be selected from nitrogen, NH 3 or N 2 O.

[0020] According to further exemplary embodiments of the present disclosure, etching may include exposing the inert gas and / or the oxygen-containing gas to a plasma.

[0021] According to further exemplary embodiments of the present disclosure, the carbon precursor may include a ring structure.

[0022] According to further exemplary embodiments of the present disclosure, the carbon precursor may include a carbonyl functional group.

[0023] According to further exemplary embodiments of the present disclosure, the cyclic structure may be selected from the group consisting of benzene; indene; cyclopentadiene; cyclohexane; pyrrole; furan; thiophene; oxazole; pyrazole; imidazole; oxazole; isoxazole; thiazole; indole; benzofuran; benzothiophene; isoindole; isobenzofuran; benzooxazole; benzimidazole; benzoxazole; benzothiazole; benzisoxazole; indazole; benzisothiazole; 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; phthalazine; acridine; 4aH-xanthene; 4aH-thioxanthene; 4aH-phenoxazine; 4a,10a-dihydro-10H-phenothiazine; or carbazole.

[0024] According to further exemplary embodiments of the present disclosure, the precursor may include one or more carbonyl groups and one or more of methyl, ethyl, propyl, butyl, amine, or hydroxyl groups.

[0025] According to further exemplary embodiments of the present disclosure, post-deposition processing may be performed in the second reaction chamber.

[0026] According to a further exemplary embodiment of the present disclosure, the etching step may be performed in the third reaction chamber. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] A more complete understanding of exemplary embodiments of the present disclosure may be obtained by referring to the detailed description and claims when considered in conjunction with the following illustrative drawings.

[0028] Figure 1 A method according to an exemplary embodiment of the present disclosure is shown.

[0029] Figure 2 A structure formed according to an exemplary embodiment of the present disclosure is shown.

[0030] Figure 3 A schematic diagram showing the structure in the prior art reference is shown.

[0031] Figure 4 A schematic diagram showing a structure according to an exemplary embodiment of the present disclosure.

[0032] Figure 5 A plasma system according to an exemplary embodiment of the present disclosure is shown.

[0033] It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the size of some elements in the drawings may be exaggerated relative to other elements to help understand the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0034] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited by the specifically disclosed embodiments described below.

[0035] As used herein, the term "substrate" may refer to any one or more underlying materials, including any one or more underlying materials that may be modified or on which a device, circuit, or film may be formed. A "substrate" may be continuous or non-continuous; rigid or flexible; solid or porous; and combinations thereof. A substrate may be in any form, such as a powder, a plate, or a workpiece. A plate-like substrate may include wafers of various shapes and sizes. A substrate may be made of semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide.

[0036] For example, a substrate in powder form can be used in drug manufacturing. The porous substrate can include a polymer. Examples of workpieces can include medical devices (such as stents and syringes), jewelry, tool equipment, components for battery manufacturing (such as anodes, cathodes, or separators), or components of photovoltaic cells, etc.

[0037] The continuous substrate may extend beyond the boundaries of the processing chamber in which the deposition process occurs. In some processes, the continuous substrate may be moved through the processing chamber so that the process continues until the end of the substrate is reached. The continuous substrate may be provided from a continuous substrate feed system to allow the continuous substrate to be manufactured and output in any suitable form.

[0038] Non-limiting examples of continuous substrates may include sheets, nonwoven films, rolls, foils, meshes, flexible materials, bundles of continuous filaments or fibers (eg, ceramic fibers or polymer fibers).The continuous substrate may also include a carrier or sheet on which a discontinuous substrate is mounted.

[0039] The illustrations presented herein are not meant to be actual views of any particular material, structure, or device but are merely idealized representations used to describe embodiments of the present disclosure.

[0040] The specific embodiments shown and described are illustrations of the present invention and its best mode and are not intended to limit the scope of these aspects and embodiments in any way. In fact, for the sake of brevity, the traditional manufacturing, connection, preparation and other functional aspects of the system may not be described in detail. In addition, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in actual systems, and / or may not exist in some embodiments.

[0041] It should be understood that the configuration and / or method described herein are exemplary in nature, and these specific embodiments or examples should not be considered restrictive, because many variations are possible. The specific routines or methods described herein can represent one or more of any number of processing strategies. Therefore, the various actions shown can be performed in the order shown, in other orders, or omitted in some cases.

[0042] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts and / or properties disclosed herein, and any and all equivalents thereof.

[0043] In the present disclosure, "gas" may include materials that are gaseous at normal temperature and pressure, evaporated solids, and / or evaporated liquids, and may consist of a single gas or a gas mixture, depending on the context. Gases introduced without passing through a gas supply unit (e.g., a shower plate, etc.) may be used, for example, to seal a reaction space, and may include sealing gases, such as rare gases or other inert gases. The terms inert gas, carrier gas, and diluent gas refer to gases that do not participate in chemical reactions to an appreciable degree and / or gases that may excite precursors when plasma power is applied.

[0044] 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. For example, "film" and "thin film" may include 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. "Film" and "thin film" may include materials or layers with pinholes, but still at least partially continuous.

[0045] Figure 1A method 100 for filling a groove on a substrate surface according to an exemplary embodiment of the present disclosure is shown. The method 100 may include a step of providing a substrate in a reaction chamber (step 101), the substrate including a plurality of narrow grooves and wide grooves formed on the substrate surface. The method may also include a first deposition step 102, the step including: flowing a carbon precursor into the reaction chamber with a carrier gas (step 103); and exposing the carbon precursor to a plasma (step 106), wherein the carbon precursor reacts to form a first deposition material (step 104). After the first deposition step 102, the method includes: exposing the first deposition material to a post-deposition treatment to flow the first deposition material within the grooves (step 108); etching the first deposition material to etch the first deposition material, wherein the first deposition material is substantially flat in the narrow grooves and recessed in the wide grooves (step 109). Thereafter, the method further includes a second deposition step 112, which includes: flowing a carbon precursor into the reaction chamber together with a carrier gas (step 113); and exposing the carbon precursor to plasma (step 116), wherein the carbon precursor reacts to form a second deposition material on the first deposition material (step 114). Steps 109 to 112 may be repeated. After step 112, a step of exposing the second deposition material to a post-deposition treatment may be added.

[0046] During step 101 of providing a substrate within a reaction chamber, a substrate is provided into a reaction chamber of a gas phase reactor. According to an example of the present disclosure, the reaction chamber may form part of a deposition reactor, such as a plasma enhanced chemical vapor deposition (PECVD) reactor. The 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 combination tool.

[0047] 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 suitable for subsequent steps. For example, the temperature within the reaction chamber (e.g., the temperature of the substrate or substrate support) may be between about 50° C. and about 600° C. The pressure within the reaction chamber may be between about 100 Pa and about 1300 Pa. According to a specific example of the present disclosure, the substrate includes one or more features, such as narrow grooves and wide grooves.

[0048] During step 102, material may be deposited onto the substrate surface. According to an example of the present disclosure, material filling the trenches may be deposited during step 102. The deposited material may solidify and may include one or more voids within the trenches in one or more trenches.

[0049] As shown, step 102 may include the sub-steps of flowing a precursor 103 with a carrier gas and exposing the precursor to a plasma 106 .

[0050] During sub-step 103, a precursor suitable for forming the deposited material is provided to the reaction chamber. Low flow can be achieved to adjust the ratio of the precursor to other gases.

[0051] The precursor may include one or more carbon atoms. According to various examples of the present disclosure, the precursor includes a cyclic structure and / or a carbonyl functional group. Exemplary cyclic structures include cyclic structures selected from the following: benzene; indene; cyclopentadiene; cyclohexane; pyrrole; furan; thiophene; oxazole; pyrazole; imidazole; oxazole; isoxazole; thiazole; indole; benzofuran; benzothiophene; isoindole; isobenzofuran; benzooxazole; benzimidazole; benzoxazole; benzothiazole; benzisoxazole; indazole; benzisothiazole; benzotriazole; purine; pyridine; In some embodiments, the precursor comprises one or more carbonyl groups, such as 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5 ... The carbonyl group may include one or more functional groups, such as selected from C1-C6 (eg, C1-C3) alkane, alkene, or alcohol functional groups. The carbonyl functional group may facilitate reflow of the deposited material during step 106. The precursor may be 2-hydroxy-2-methylpropiophenone.

[0052] During step 106, the precursor is exposed to (e.g., directed) plasma to polymerize the precursor, thereby becoming a viscous fluid and initially solidifying on the substrate surface. The plasma power used for deposition can range from about 10 W to about 2000 W. The RF frequency of the plasma power can range from 400 kHz to 100 MHz.

[0053] According to an example of the present disclosure, steps 103 and 106 may overlap. According to a further example, the duration of step 106 may be shorter than that of step 103. For example, step 106 may start after step 103 and / or end before step 103 ends.

[0054] During step 108, a treatment may be used to flow the material deposited during step 101. The treatment may include a thermal treatment (eg, increasing the temperature of the substrate) and / or a plasma treatment.

[0055] In the case of thermal treatment, step 108 may include heating the substrate to a temperature of about 50° C. to about 800° C. In some cases, the substrate temperature during step 108 may be higher than the substrate temperature during step 101. During step 108, the pressure within the reaction chamber may be between about 100 Pa and about 1300 Pa. According to further examples of the present disclosure, during step 108, an inert gas and / or a nitrogen-containing gas may be provided to the reaction chamber. Exemplary nitrogen-containing gases may include nitrogen, NH3, or N2O. The duration of step 108 may be from about 5 seconds to about 3000 seconds.

[0056] In the case of plasma treatment, step 108 includes forming the reactive species from a gas. The gas may include a nitrogen-containing gas, such as a gas selected from nitrogen, NH3, or N2O. The reactive species may be formed using, for example, a direct plasma.

[0057] The power used to form the plasma may be in the range of about 10 W to about 2000 W. The frequency of the power may be in the range of about 400 kHz to about 100 MHz. The duration of the plasma treatment step may be from about 5 seconds to about 3000 seconds. During the plasma treatment step, the temperature in the reaction chamber may be about 50° C. to about 800° C. or about 100° C. to about 800° C. During the plasma treatment, the pressure in the reaction chamber may be between about 100 Pa to about 1300 Pa.

[0058] During steps 102 and / or 108, one or more inert gases, such as argon, helium, nitrogen, or any mixture thereof, may be provided to the reaction chamber (e.g., continuously during steps 104 and 106). During this step, the flow rate of the inert gas to the reaction chamber may be from about 500 sccm to about 8000 sccm. The inert gas may be used to facilitate ignition and / or maintenance of a plasma within the reaction chamber, purge reactants and / or byproducts from the reaction chamber, and / or act as a carrier gas to help deliver precursors to the reaction chamber.

[0059] Figure 2 A structure 202 formed according to a further example of the present disclosure is shown. The structure 202 may include a substrate 206 and protrusions 210, 221 formed thereon. The structure 202 includes a deposited material 218 overlying the substrate 206. As shown, the deposited material 218 from the deposition step 101 includes a void 215 formed within a trench 222 between the protrusions 210 and 221. After the material 218 is deposited (e.g., enough material to fill the trench 222), the deposited material 218 may be exposed to a post-deposition treatment (step 108) to cause the deposited material 218 to flow within the trench 222 to form a structure 204 including a treated material 224.

[0060] Figure 3A schematic diagram of a structure in a prior art reference is shown. During step 301, which includes the substeps of flowing a precursor and exposing the precursor to a plasma, a material is deposited onto the surface of the substrate. The deposited material can solidify and can include one or more voids within a groove in one or more grooves. If step 301 uses high flow conditions (using, for example, a high flow rate), the voids may be small, but this may result in large overburden increments (e.g., 50 nm) between narrow grooves and wide grooves. During step 308, the material deposited during step 301 can flow using processing. After step 308, the overburden increment is still large (e.g., 60 nm).

[0061] Figure 4 A schematic diagram of a structure according to an exemplary embodiment of the present disclosure is shown. During step 101, which includes the substeps of flowing a precursor and exposing the precursor to a plasma, a material is deposited onto the surface of a substrate. The deposited material may solidify and may include one or more voids within a trench in one or more trenches. If step 101 uses low flow conditions (e.g., low flow), the voids may be large, but the incremental coverage between the narrow trench and the wide trench is almost zero.

[0062] During step 108, the material deposited during step 101 can be made to flow using a process. The coverage increments are modest, for example 25 nm.

[0063] During step 109, the first deposited material can be etched to be substantially flush in narrow trenches and recessed in wide trenches, maintaining the same overburden increment. Step 109 can include exposing an inert gas and / or an oxygen-containing gas to a plasma. Additionally, step 109 can be performed in another reaction chamber.

[0064] During the second deposition step 112 including the sub-steps of flowing the carbon precursor and exposing the carbon precursor to plasma, a second deposition material may be formed on the first deposition material. Since the volume of the deposition material in the recessed portion of the wide trench is small, the coverage increment between the narrow trench and the wide trench may be close to zero (e.g., less than 10 nm).

[0065] Figure 5 A plasma reactor system 500 is shown according to an exemplary embodiment of the present disclosure. The plasma reactor system 500 can be used to perform one or more steps or sub-steps described herein, and / or form one or more structures described herein, or portions thereof.

[0066] The plasma reactor system 500 may include a pair of conductive plate electrodes 4, 2 that are parallel and face each other in the interior 11 (reaction zone) of the reaction chamber 3. Plasma can be ignited in the reaction chamber 3 by applying, for example, HRF power (e.g., 13.56 MHz, 27 MHz, or 60 MHz) and / or low frequency power from a power supply 25 to one electrode (e.g., electrode 4) and electrically grounding the other electrode (e.g., electrode 2). A temperature regulator may be provided in the lower platform 2 (lower electrode), and the temperature of the substrate 1 placed thereon may be maintained at a desired temperature. The electrode 4 may be used as a gas distribution device, such as a shower plate. Reactant gas, dilution gas (if any), precursor gas, etc. may be introduced into the reaction chamber 3 through the shower plate 4 using one or more of the gas pipelines 20, gas pipelines 21, and gas pipelines 22, respectively. Although three gas pipelines are shown, the reactor system 500 may include any suitable number of gas pipelines.

[0067] In the reaction chamber 3, a circular duct 13 with an exhaust line 7 may be provided, through which the 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 may be provided with a sealed gas line 24 to introduce the sealed gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer zone) of the transfer chamber 5, wherein a partition plate 14 for separating the reaction zone and the transfer zone may be provided (a gate valve for transferring the wafer into or out of the transfer chamber 5 is omitted in this figure). The transfer chamber may also be provided with an exhaust line 6. In some embodiments, the deposition and treatment steps may be performed in the same reaction space, so that two or more (e.g., all) steps may be performed continuously without exposing the substrate to air or other oxygen-containing atmospheres.

[0068] Those skilled in the art will appreciate that the apparatus includes one or more controllers that are programmed or otherwise configured to perform one or more of the method steps described herein. The controller is in communication with various power supplies, heating systems, pumps, robots, and gas flow controllers or valves of the reactor, as will be appreciated by those skilled in the art.

[0069] In some embodiments, a multi-chamber module (for processing multiple portions or compartments of a wafer positioned close to each other) may be used, wherein reactant gases and inert gases may be supplied through shared lines, while precursor gases are supplied through non-shared lines.

[0070] The exemplary embodiments disclosed above do not limit the scope of the present invention, because these embodiments are merely examples of embodiments of the present invention. Any equivalent embodiments are within the scope of the present invention. In fact, various modifications of the present disclosure, such as alternative useful combinations of the described elements, will become apparent to those skilled in the art from the description, except those shown and described herein. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method comprising the following steps: Providing a substrate in a reaction chamber, the substrate comprising a plurality of narrow grooves and wide grooves formed on a surface of the substrate; The first deposition step comprises: (a) flowing a carbon precursor into a reaction chamber; (b) exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a first deposition material; (c) exposing the first deposition material to a post-deposition treatment to cause the first deposition material to flow within the trench; (d) etching the first deposited material, wherein the first deposited material is substantially planar in the narrow trenches and is recessed in the wide trenches; and The second deposition step comprises: (e) flowing a carbon precursor into a reaction chamber; (f) exposing the carbon precursor to a plasma, wherein the carbon precursor reacts to form a second deposition material on the first deposition material.

2. The method according to claim 1, wherein: Repeat steps (d) to (f).

3. The method of claim 1, further comprising the step (g) of exposing the second deposition material to a post-deposition treatment.

4. The method according to claim 3, wherein: Repeat steps (d) to (g).

5. The method according to claim 1, wherein: The temperature during the first deposition step is from about 50°C to about 600°C.

6. The method according to claim 1, wherein: The post-deposition treatment includes heating the substrate to a temperature of about 100°C to about 800°C.

7. The method according to claim 1, wherein: The temperature during the second deposition step is from about 50°C to about 800°C.

8. The method according to claim 1, wherein: The power of the plasma is less than 2000W.

9. The method according to claim 5, wherein: In the case of a single RF power source, the frequency of the plasma is 3 to 30 MHz.

10. The method according to claim 1, wherein: The power of the plasma in the first deposition step is 200W or less.

11. The method according to claim 1, wherein: The pressure within the reaction chamber is between about 100 Pa and about 1300 Pa.

12. The method according to claim 1, wherein: The post-deposition treatment includes a plasma treatment.

13. The method according to claim 12, wherein: The plasma treatment includes exposing an inert gas and / or a nitrogen-containing gas to a plasma.

14. The method according to claim 13, wherein: The nitrogen-containing gas is selected from nitrogen, NH3 or N2O.

15. The method of claim 1, wherein etching comprises exposing an inert gas and / or an oxygen-containing gas to a plasma.

16. The method according to claim 1, wherein: The carbon precursor includes a ring structure.

17. The method according to claim 1, wherein: The carbon precursor comprises a carbonyl functional group.

18. The method according to claim 16, wherein: The cyclic structure is selected from: benzene; indene; cyclopentadiene; cyclohexane; pyrrole; furan; thiophene; phosphazoline; pyrazole; imidazole; oxazole; isoxazole; thiazole; indole; benzofuran; benzothiophene; isoindole; isobenzofuran; benzophosphazoline; benzimidazole; benzoxazole; benzothiazole; benzisoxazole; indazole; benzisothiazole; 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; phthalazine; acridine; 4aH-xanthene; 4aH-thioxanthene; 4aH-phenoxazine; 4a,10a-dihydro-10H-phenothiazine; or carbazole.

19. The method according to claim 1, wherein: The precursor comprises one or more carbonyl groups and one or more of methyl, ethyl, propyl, butyl, amine or hydroxyl groups.

20. The method according to claim 1, wherein: The post-deposition treatment is performed in the second reaction chamber.

21. The method according to claim 20, wherein: The etching step is performed in the third reaction chamber.

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