Deposition of flowable silicon-containing films

Abstract

Methods for seamless gap filling are described, including forming a flowable film by exposing a surface of a substrate to a silicon-containing precursor and a co-reactant. The silicon-containing precursor has at least one alkenyl or alkynyl group. The flowable film may be cured by any suitable curing process to form a seamless gap fill.

Description

[0001] This application is a divisional application of a Chinese patent application with an application date of July 19, 2017, application number 201780044398.0, and name “Deposition of Flowable Silicon-Containing Films” (PCT application number PCT / US2017 / 042811). Technical Field

[0002] The present disclosure relates generally to methods of depositing thin films. Specifically, the present disclosure relates to a process for filling narrow trenches with flowable silicon-containing films. Background Art

[0003] In microelectronic device manufacturing, for many applications, it is necessary to fill narrow trenches with aspect ratios (AR) greater than 10:1 without voids. One application is for shallow trench isolation (STI). For this application, the film needs to be high quality (with a wet etch rate ratio of, for example, less than 2) across the trench with little leakage. As feature sizes decrease and aspect ratios increase, post-curing methods for deposited flowable films become difficult. This results in films with different compositions across the filled trench.

[0004] Conventional plasma enhanced chemical vapor deposition (PECVD) of dielectric films forms a "mushroom-shaped" film at the top of narrow trenches. This is because the plasma cannot penetrate into deep trenches. This results in the narrow trenches being clamped from the top; voids are formed at the bottom of the trenches.

[0005] In addition, silicon-containing films such as SiCO, SiCON, SiCN are widely used in the manufacture of semiconductor devices. For example, these carbon-containing gap-fill films can be used for patterning applications. Due to the presence of high carbon levels, these films generally show high etch selectivity compared to oxide films and nitride films. Etch selectivity is important for gap-fill films to be used in patterning applications. Therefore, there is a need for precursors and methods for depositing silicon-containing films. Summary of the invention

[0006] One or more embodiments of the present disclosure are directed to a processing method that includes exposing a substrate surface to a silicon-containing precursor and a co-reactant to deposit a flowable film. The silicon-containing precursor has at least one alkenyl or alkynyl group.

[0007] Additional embodiments of the present disclosure are directed to a processing method, the processing method comprising providing a substrate surface having at least one feature on the substrate surface. The at least one feature extends a depth from the substrate surface to a bottom surface and has a width defined by a first sidewall and a second sidewall. The substrate surface is exposed to a silicon-containing precursor and a co-reactant to form a flowable film on the substrate surface and the first sidewall, the second sidewall, and the bottom surface of the at least one feature. The flowable film fills the feature without substantially forming a seam. The silicon-containing precursor comprises a compound having any of structures IV:

[0008]

[0009] wherein each of R1-R6 is independently selected from the group consisting of: CR'CR" 2 、CCR'、H、Methyl、Ethyl、Propyl、Isopropyl、N-Butyl、Sec-Butyl、Isobutyl、T-Butyl、NR' 2 and OR', wherein R' and R" are independently selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, and at least one of R1-R6 is selected from the group consisting of: CR'CR" 2 or CCR'. The co-reactant includes an ammonia plasma. The flowable film is cured to solidify the film and form a substantially seamless gap fill.

[0010] Further embodiments of the present disclosure are directed to a processing method, the processing method comprising providing a substrate surface having at least one feature on the substrate surface. The at least one feature extends a certain depth from the substrate surface to the bottom surface and has a width defined by a first sidewall and a second sidewall. The substrate surface is exposed to a silicon-containing precursor and a co-reactant to form a flowable film on the substrate surface and the first sidewall, the second sidewall and the bottom surface of the at least one feature. The flowable film fills the feature without substantially forming a seam. The silicon-containing precursor comprises tetravinylsilane (Si(CHCH 2 ) 4 ) or tetraacetalide (Si(CCH) 4 ) and the co-reactant comprises ammonia plasma. The flowable film is cured to solidify the film and form a substantially seamless gap fill. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] In order to be able to understand the above-mentioned features of the present invention in detail, the present invention briefly summarized above can be described in more detail with reference to embodiments, some of which are shown in the accompanying drawings. However, it should be noted that the accompanying drawings only illustrate typical embodiments of the present invention and therefore should not be considered as limiting the scope of the present invention, as the present invention may allow other equivalent embodiments.

[0012] Figure 1 A cross-sectional view showing substrate features according to one or more embodiments of the present disclosure;

[0013] Figure 2 Shows Figure 1 a cross-sectional view of a substrate feature having a flowable film thereon; and

[0014] Figure 3 SEM images of films deposited according to one or more embodiments of the present disclosure are shown. DETAILED DESCRIPTION

[0015] Before describing several exemplary embodiments of the present invention, it should be understood that the present invention is not limited to the details of construction or process steps set forth in the following description. The present invention is also capable of other embodiments and can be practiced or carried out in various ways.

[0016] As used herein, "substrate" refers to any substrate or a material surface formed on a substrate on which film processing is performed during a manufacturing process. For example, substrate surfaces on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials (such as metals, metal nitrides, metal alloys, and other conductive materials), depending on the application. Substrates include, but are not limited to, semiconductor wafers. The substrate can be exposed to a pretreatment process to polish, etch, reduce, oxidize, hydroxylate, anneal, UV cure, E-beam cure, and / or bake the substrate surface. In addition to performing film processing directly on the surface of the substrate itself, in the present invention, any of the disclosed film processing steps can also be performed on a lower layer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such lower layers as indicated by the context. Thus, for example, in the case where a film / layer or a portion of a film / layer has been deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0017] Embodiments of the present disclosure provide methods for depositing gap fill films (e.g., SiC, SiCO, SiCN, SiCON) in high aspect ratio (AR) structures with small dimensions. Some embodiments advantageously provide methods involving cyclic deposition-treatment processes that can be performed in a cluster tool environment. Some embodiments advantageously provide seamless high quality silicon-containing films to fill high AR trenches with small dimensions. Some embodiments advantageously provide films containing high carbon content. In one or more embodiments, the high carbon content films can be advantageously used in hard mask and low-k flowable applications.

[0018] One or more embodiments of the present disclosure are directed to a process for depositing a flowable silicon-containing film capable of filling high aspect ratio structures (e.g., AR>8:1). Embodiments of the present disclosure provide new precursors to produce SiC, SiOC, SiCN, SiOCN, SiO, and SiN flowable films for gap filling applications using F-CVD (flowable chemical vapor deposition). Precursors of various embodiments include alkenyl (vinyl) and / or alkynyl groups. In one or more embodiments, the precursor is exposed to reactive radicals to initiate radical-induced polymerization in a deposition chamber.

[0019] The deposited flowable films are generally unstable and age when exposed to atmospheric conditions. The flowable films of some embodiments are deposited by, for example, 3 / O 2 The silicon-containing precursor and free radical form are deposited as co-reactants. Then ozone / UV / steam annealing / NH 3 These films are cured by annealing or the like to obtain cured films.

[0020] For descriptive purposes, the deposition of a flowable CVD film for a gap fill application is described. However, one skilled in the art will appreciate that the described precursors and methods are not limited to gap fill applications and can be used for any silicon-containing film. Figure 1 A partial cross-sectional view of a substrate 100 having a feature 110 is shown. For illustrative purposes, the figures show a substrate having a single feature; however, one skilled in the art will appreciate that there may be more than one feature. The shape of feature 110 may be any suitable shape, including, but not limited to, a groove and a cylindrical via. As used herein, the term "feature" refers to any intentional surface irregularity. Suitable examples of features include, but are not limited to: a groove having a top, two sidewalls, and a bottom; a peak having a top and two sidewalls. The feature may have any suitable aspect ratio (the ratio of the depth of the feature to the width of the feature). In some embodiments, the aspect ratio is greater than or equal to approximately 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, or 40:1.

[0021] The substrate 100 has a substrate surface 120. The at least one feature 110 forms an opening in the substrate surface 120. The feature 110 extends a depth D from the substrate surface 120 to a bottom surface 112. The feature 110 has a first sidewall 114 and a second sidewall 116, which define a width W of the feature 110. The open area formed by the sidewalls and the bottom is also referred to as a gap.

[0022] One or more embodiments of the present disclosure are directed to a processing method in which a substrate surface is provided having at least one feature on the substrate surface. As used herein, the term "providing" means placing a substrate into a location or environment for further processing.

[0023] like Figure 2 As shown, a flowable film 150 is formed on the substrate surface 120 and the first sidewall 114, the second sidewall 116 and the bottom surface 112 of the at least one feature 110. The flowable film 150 fills the at least one feature 110 so that substantially no seams are formed. A seam is a gap formed in a feature, between the sidewalls of the feature 110, but not necessarily in the middle of the sidewalls of the feature 110. As used herein, the term "substantially no seams" means that any gap formed in the film between the sidewalls is less than about 1% of the cross-sectional area of ​​the sidewalls.

[0024] The flowable film 150 may be formed by any suitable process. In some embodiments, the formation of the flowable film is accomplished by plasma enhanced chemical vapor deposition (PECVD). In other words, the flowable film may be deposited by a plasma enhanced chemical vapor deposition process.

[0025] Embodiments of the present disclosure advantageously provide a class of silicon-containing precursors for depositing flowable CVD films. Some embodiments advantageously provide methods for gap filling without forming seams. Some embodiments advantageously provide methods for curing flowable CVD films, wherein trenches or surface features are filled in a seamless manner.

[0026] Embodiments of the present disclosure are directed to a process comprising exposing a substrate surface to a silicon-containing precursor and a co-reactant to deposit a flowable film. The silicon-containing precursor has at least one alkenyl or alkynyl group to allow participation in a free radical polymerization reaction. Structure IV provides an example of a silicon-containing precursor used with various embodiments of the present disclosure.

[0027]

[0028] The R groups (R1-R6) of formula (I) are each independently selected from the group consisting of: CR'CR" 2、CCR'、H、Methyl、Ethyl、Propyl、Isopropyl、N-Butyl、Sec-Butyl、Isobutyl、T-Butyl、NR' 2 and OR'. The R' and R" groups are independently selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. At least one of R1-R6 (R1-R4 for Formula I) is selected from CR'CR" 2 or CCR". It will be understood by those skilled in the art that the use of the term "R group" refers to any one of R1 to R6 (R1-R4 for Formula I). ​​In some embodiments, at least one of the R groups is not hydrogen. In some embodiments, at least one of the R groups is methyl. In some embodiments, at least one of the R groups is ethyl. In some embodiments, at least one R group is vinyl. In some embodiments, each of the R groups is the same group.

[0029] In one or more embodiments, the silicon precursor includes a vinyl group such that one or more of the R groups of the silicon-containing precursor includes CR'CR" 2 In some embodiments, the R groups of the silicon-containing precursor all include CR'CR" 2 In one or more embodiments, the R groups of the silicon precursor substantially all include CR'CR" 2 As used herein, "substantially all" means that greater than or equal to about 95% of the R groups are the specified group. In some embodiments, each R' is the same substituent and each R" is the same substituent. In one or more embodiments, the silicon-containing precursor includes tetravinylsilane (Si(CHCH 2 ) 4 ).

[0030] In one or more embodiments, the silicon-containing precursor includes an alkynyl group such that one or more of the R groups of the silicon-containing precursor include CCR'. In some embodiments, the R groups of the silicon-containing precursor all include CCR'. In one or more embodiments, the R groups of the silicon precursor substantially all include CCR'. As used herein, "substantially all" means that greater than or equal to about 95% of the R groups are the specified group. In some embodiments, each R' is the same substituent and each R" is the same substituent. In one or more embodiments, the silicon-containing precursor includes tetraethynylsilane (Si(CCH) 4 ).

[0031] A Si-containing precursor having any structure IV can be vaporized into a CVD chamber, and a suitable co-reactant (e.g., NH 3 / O 2 / CO 2 / CO / Ar / He / H 2 or a combination thereof) is delivered to the CVD chamber by, for example, an RPS (remote plasma source), which generates plasma-active species as co-reactants. The plasma-activated co-reactant molecules (free radicals) have high energy and can react with Si-containing precursor molecules in the gas phase to form corresponding flowable polymers. In some embodiments, the plasma is generated using a plasma gas, which includes NH 3 , O 2 , CO 2 , CO, Ar, He or H 2 In some embodiments, the plasma gas comprises ammonia, or consists essentially of ammonia. As used herein, the term "consisting essentially of" means that greater than or equal to about 90 molecular percent of the reactants in the plasma are ammonia.

[0032] The plasma may be generated or ignited within the processing chamber (eg, direct plasma), or may be generated outside the processing chamber and flow into the processing chamber (eg, remote plasma).

[0033] The flowable film 150 may be formed at any suitable temperature. In some embodiments, the flowable film 150 is formed at a temperature in the range of about -20°C to about 100°C. The temperature may be kept low to preserve the thermal budget of the formed device. In some embodiments, forming the flowable film occurs at a temperature below about 300°C, 250°C, 200°C, 150°C, 100°C, 75°C, 50°C, 25°C, or 0°C.

[0034] Films with high carbon content can have many applications, for example, in hard mask patterning and for flowable low-K films. In some embodiments, a flowable film using any structure IV precursor can deposit a film with a high carbon content. In some embodiments, the film has a carbon content of up to about 85 atomic percent. In one or more embodiments, the flowable film has a carbon content greater than about 40 atomic percent, 45 atomic percent, 50 atomic percent, 55 atomic percent, 60 atomic percent, 65 atomic percent, 70 atomic percent, 75 atomic percent, or 80 atomic percent and less than about 95 atomic percent, 90 atomic percent, or 85 atomic percent. In some embodiments, the flowable film has a carbon content of about 40 atomic percent to about 85 atomic percent, or about 50 atomic percent to about 85 atomic percent, or about 60 atomic percent to about 80 atomic percent.

[0035] The composition of the flowable film can be adjusted by changing the composition of the reactant gas. In some embodiments, the flowable film includes one or more of SiC, SiCO, SiCN, SiCON, SiO, and SiN. To form an oxygen-containing film, the co-reactant can include, for example, one or more of oxygen, ozone, or water. To form a nitrogen-containing film, the co-reactant can include, for example, ammonia, hydrazine, NO 2 or N 2 To form a carbon-containing film, the reaction gas may include, for example, one or more of propylene and acetylene. Those skilled in the art will appreciate that other substances or combinations of substances may be included in the mixture of the reaction gas to change the composition of the flowable film.

[0036] Flowable films can be deposited on the wafer (the temperature of the wafer can be from -10°C to 200°C), and because of their fluidity, the polymer will flow through the trenches and fill the gaps. These films are then subjected to a curing step such as ozone / UV / steam annealing / NH 3 Annealing to obtain a stable film. In some embodiments, the method provides one or more of SiC, SiCO, SiCN, SiCON, SiO and / or SiN flowable films. Therefore, after forming the flowable film 150, the film can be cured to solidify the flowable film and form a substantially seamless gap filling. In one or more embodiments, curing the flowable film includes exposing the flowable film to one or more of ozone, UV light, steam annealing, ammonia annealing and oxygen plasma. In some embodiments, the flowable film is cured by exposing the film to a UV curing process. The UV curing process can be carried out at a temperature in the range of about 10°C to about 550°C. The UV curing process can occur within any suitable time range sufficient to solidify the flowable film. UV curing can be performed with different parameters (e.g., power, temperature, environment). In some embodiments, UV curing occurs in an acetylene / ethylene environment.

[0037] In some embodiments, curing the flowable film comprises thermal annealing. The thermal annealing can be performed at any suitable temperature and in any suitable environment. In some embodiments, the flowable film is cured by thermal annealing in an acetylene / ethylene environment.

[0038] In some embodiments, curing the flowable film includes exposure to a plasma or an electron beam. The plasma exposure for curing the film includes a plasma separate from the PECVD plasma. The plasma material and the processing chamber can be the same, and the plasma curing is a different step from the PECVD process.

[0039] In some embodiments, curing the flowable film includes exposing the flowable film to a steam anneal and / or an oxygen plasma. The use of a steam anneal and / or an oxygen plasma can reduce the carbon content of the flowable film so that the cured film has a lower carbon content than the as-deposited flowable film. The use of a steam anneal and / or an oxygen plasma can convert the deposited flowable SiC, SiCN or SiCO film into SiO. The carbon content of such a film has been substantially removed; this means that less than about 5% carbon is present in the film pre-curing.

[0040] In some embodiments, any of the structure IV precursors can be used in a flowable process with another precursor (co-flowed with another Si-containing precursor) to deposit films of various compositions. For example, a structure IV precursor can be used with trisilylamine (TSA) / NH 3 The process is used to add carbon to the membrane. 3 The flowable film obtained by the process is a SiO or SiN film. By adding a silicon-containing precursor of structure IV, a SiCO, SiCON or SiCN film can be deposited. In another example, the silicon-containing precursor can be mixed with octamethylcyclotetrasiloxane (OMCTS) / O 2 OMCTS / O 2 The process results in a SiOC film, and the structure IV precursor can be used to further increase the C% in the film. SiC, SiOC, SiCN, SiOCN, SiO and SiN flowable films can be obtained by the method. In a further example, TSA / silane (Si x H y ) / OMCTS can be mixed or co-flowed with structure IV precursors to deposit SiCO, SiCON or SiN films.

[0041] In some embodiments, a silicon precursor of structure IV is added to another process to dope carbon into a silicon film. For example, a silicon deposition process may have some of the precursors from formula IV added to the process to add carbon atoms to the film. Some embodiments of the present disclosure are directed to methods of doping carbon into a film by co-flowing a carbon-containing silane with a silane amine to form a flowable film. In one or more embodiments, tetravinylsilane is co-flowed with trisilylamine and ammonia plasma to form a film having a carbon content greater than or equal to about 50%, 60%, 70%, 75%, or 80% by atom.

[0042] In some embodiments, the flowable film is doped with another element. For example, some flowable films may be doped with one or more of B, As, or P. The flowable film may be doped with elements such as boron (B) and phosphorus (P) to improve the properties of the film. Precursors containing boron and phosphorus may co-flow with the Si-containing precursor during the deposition process, or may be infiltrated after the deposition is complete. The boron-containing precursor may be an aminoborane / borane compound, and the phosphorus-containing precursor may be a phosphate / phosphite compound. In some embodiments, doping the flowable film includes co-flowing a dopant precursor with a silicon-containing precursor. In some embodiments, doping the flowable film includes injecting the dopant element in a separate process.

[0043] Some embodiments of the present disclosure are directed to methods of obtaining SiC, SiCO, SiCON, SiCN, SiN, SiO flowable films from silanes and hydrocarbons. Suitable hydrocarbons include, but are not limited to, those shown in structures VI-XV.

[0044]

[0045] In some embodiments, the silane precursor includes a compound without carbon atoms. Those skilled in the art will appreciate that the compounds listed as structures VI-XV represent only some possible silane precursors. The structures shown may be modified to include silane substituents or other atoms.

[0046] At least one precursor of structure IV and any hydrocarbon (C x H y ) can be used in any combination. Structure IV and hydrocarbon (C x H y ) is vaporized into a CVD chamber, and a co-reactant (e.g., NH 3 / O 2 / CO 2 / CO / Ar / He / H 2 or a combination thereof) is delivered to the chamber by an RPS (remote plasma source) which will generate plasma active species as co-reactants. The plasma activated co-reactant molecules (radicals) have high energy and react with Si-containing precursor molecules in the gas phase to form corresponding flowable polymers. These polymers will be deposited on the wafer (the temperature of the wafer can be from -10°C to 200°C), and because of their fluidity, the polymers will flow through the trenches and perform gap filling. These films are then subjected to a curing step such as ozone / UV / steam annealing / NH 3 Annealing to obtain stable SiC, SiCO, SiCON, SiCN, SiN, SiO films.

[0047] Example 1 - From tetravinylsilane ((Si(CHCH 2 ) 4 , called TVS) and NH 3 Plasma Deposition of Flowable SiCON Films

[0048] Tetravinylsilane (TVS) and remote NH are deposited by CVD at a temperature range of about 80°C, 100°C, and 130°C at a pressure of less than about 1 Torr. 3 The as-deposited film had a refractive index of 1.58 and a wet etch rate of 1.8 A / min in 100:1 diluted HF. Figure 3 A SEM image of the flowable membrane is shown in .

[0049] Example 2 - From tetraethynylsilane (Si(CCH) 4 and NH 3 Plasma Deposition of Flowable SiCON Films

[0050] from tetraethynylsilane and remote NH 3 The as-deposited film has a refractive index of about 1.58.

[0051] Example 3 - Increasing TSA / NH by co-flowing TVS with TSA 3 C% in process

[0052] By heating TVS / TVA and NH 3 Plasma co-flow to obtain a flowable film. 3 The flowable membranes obtained had almost no carbon in the membrane, whereas the flowable membranes obtained by co-flowing TVS and TSA had carbon content as high as 80%.

[0053] According to one or more embodiments, the substrate is processed before and / or after the layer is formed. The processing can be performed in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is moved from the first chamber to a separate second chamber for further processing. The substrate can be moved directly from the first chamber to the separate processing chamber, or the substrate can be moved from the first chamber to one or more transfer chambers and then moved to the separate processing chamber. Therefore, the processing equipment may include multiple chambers connected to the transfer station. Such equipment may be referred to as a "cluster tool" or a "cluster system" or the like.

[0054] In general, a cluster tool is a modular system that includes multiple chambers that perform various functions, including substrate centering and orientation, degassing, annealing, deposition, and / or etching. According to one or more embodiments, the cluster tool includes at least one first chamber, and a central transfer chamber. The central transfer chamber can house a robot that is capable of shuttling substrates between processing chambers and between processing chambers and a load lock chamber. The transfer chamber is typically maintained under vacuum conditions and provides an intermediate platform for shuttling substrates from one chamber to another and / or to a load lock chamber positioned at the front end of the cluster tool. Two well-known cluster tools that may be suitable for the present invention are and Both are available from Applied Materials, Inc., of Santa Clara, Calif. However, the exact arrangement and combination of chambers may be modified for the purpose of performing specific steps of the processes as described herein. Other available processing chambers include, but are not limited to, cyclic layer deposition (CLD; Cyclical Layer Deposition), atomic layer deposition (ALD; Atomic Layer Deposition), chemical vapor deposition (CVD; Chemical Vapor Deposition), physical vapor deposition (PVD; Physical Vapor Deposition), etching, pre-cleaning, chemical cleaning, thermal treatment (such as RTP), plasma nitridation, degassing, orientation, hydroxylation, and other substrate processes. By performing the processes in chambers on a cluster tool, the substrate can be avoided from surface contamination due to atmospheric impurities and not oxidized prior to deposition of subsequent films.

[0055] According to one or more embodiments, the substrate is continuously under vacuum or "load lock" conditions and is not exposed to ambient air when moving from one chamber to the next. The transfer chamber is therefore "pumped" under vacuum and at vacuum pressure. An inert gas may be present in the processing chamber or the transfer chamber. In some embodiments, an inert gas is used as a purge gas to remove some or all of the reactants. According to one or more embodiments, a purge gas is injected at the outlet of the deposition chamber to prevent reactants from moving from the deposition chamber to the transfer chamber and / or additional processing chamber. Thus, the inert gas flow forms an air curtain at the outlet of the chamber.

[0056] Substrates can be processed in a single substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Substrates can also be processed in a continuous manner similar to a conveyor system, where multiple substrates are individually loaded into a first portion of the chamber, moved through the chamber, and unloaded from a second portion of the chamber. The shape of the chamber and associated conveyor system can form a straight path or a curved path. In addition, the processing chamber can be a carousel, where multiple substrates move around a central axis and are exposed to deposition, etching, annealing, cleaning, etc. processes throughout the carousel path.

[0057] During processing, the substrate may be heated or cooled. Such heating or cooling may be accomplished by any suitable means, including but not limited to changing the temperature of the substrate support and flowing heated or cooled gases to the substrate surface. In some embodiments, the substrate support includes a heater / cooler that can be controlled to conductively change the substrate temperature. In one or more embodiments, the gas (reactive gas or inert gas) employed is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is positioned within the chamber adjacent to the substrate surface to convectively change the substrate temperature.

[0058] The substrate may also be stationary or rotated during processing. A rotating substrate may be rotated continuously or in discrete steps. For example, the substrate may be rotated throughout the process, or the substrate may be rotated slightly between exposures to different reactive or purge gases. Rotating the substrate (continuously or in steps) during processing may help produce a more uniform deposition or etching by minimizing the effects of local variations in, for example, gas flow geometry.

[0059] References throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in conjunction with the embodiment is included in at least one embodiment of the invention. Thus, phrases such as "in one or more embodiments," "certain embodiments," "in one embodiment," or "in an embodiment" appearing throughout this specification do not necessarily refer to the same embodiment of the invention. Furthermore, particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0060] Although the present invention has been described herein with reference to specific embodiments, it will be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and variations may be made to the methods and apparatus of the present invention without departing from the spirit and scope of the present invention. Therefore, the present invention is intended to include modifications and variations within the scope of the appended claims and their equivalents.

Claims

1. A processing method comprising: The substrate surface is exposed to a silicon-containing precursor and a co-reactant at a temperature in the range of -20°C to 100°C to deposit a flowable film, the silicon-containing precursor comprising a compound having structure IV or V: wherein each of R1-R6 is independently selected from the group consisting of: CR'CR"2, CCR', H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, NR'2 and OR', wherein R' and R" are independently selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, and the flowable film has a carbon content greater than 55 atomic percent and less than 95 atomic percent; as well as The flowable film is cured to form a cured film.

2. The processing method according to claim 1, characterized in that The co-reactant includes a plasma comprising a plasma gas.

3. The processing method of claim 1, wherein at least one of R1-R6 is selected from the group consisting of: CR'CR"2 or CCR'.

4. The processing method according to claim 3, characterized in that: One or more of R1-R6 of the silicon-containing precursor is CR'CR"2.

5. The processing method according to claim 4, characterized in that: R1-R6 of the silicon-containing precursor all include CR'CR"2.

6. The processing method according to claim 5, characterized in that: Each R' is the same, and each R" is the same substituent.

7. The processing method according to claim 3, characterized in that: One or more of R1-R6 of the silicon-containing precursor is CCR'.

8. The processing method according to claim 7, characterized in that: R1-R6 of the silicon-containing precursor all include CCR'.

9. The processing method according to claim 8, characterized in that: Each R' is the same, and each R" is the same substituent.

10. The processing method according to claim 2, characterized in that: The plasma gas includes one or more of NH3, O2, CO2, CO, Ar, He or H2.

11. The processing method according to claim 10, characterized in that: The plasma gas includes ammonia.

12. The processing method according to claim 1, characterized in that: Curing the flowable film includes exposing the flowable film to one or more of ozone, UV light, steam annealing, ammonia annealing, and oxygen plasma.

13. The processing method according to claim 12, characterized in that: The cured film includes one or more of SiC, SiOC, SiCN, SiOCN, SiO or SiN.

14. The processing method according to claim 2, characterized in that: Further comprising doping the flowable film with one or more of B, As or P.

15. The processing method according to claim 1, characterized in that: The silicon-containing precursor co-flows with the silane precursor.

16. A processing method comprising: A substrate surface having at least one feature thereon is exposed to a silicon-containing precursor and a co-reactant to form a flowable film on the substrate surface and on a first sidewall, a second sidewall, and a bottom surface of the at least one feature, the at least one feature extending a depth from the substrate surface to the bottom surface, the at least one feature having a width defined by the first sidewall and the second sidewall, the flowable film filling the feature without substantially forming a seam, the silicon-containing precursor comprising a compound having any of structures IV-V: wherein each of R1-R6 is independently selected from the group consisting of: CR'CR"2, CCR', H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, NR'2 and OR', wherein R' and R" are independently selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, at least one of R1-R6 is selected from the group consisting of: CR'CR"2 or CCR', and the co-reactant comprises ammonia plasma; and The flowable film is cured to solidify the film and form a substantially seamless gap fill, the flowable film having a carbon content greater than 55 atomic percent and less than 95 atomic percent.

17. A processing method comprising: A substrate surface having at least one feature thereon is exposed to a silicon-containing precursor and a co-reactant at a temperature in the range of -20°C to 100°C to form a flowable film, the at least one feature extending a depth from the substrate surface to a bottom surface, the at least one feature having a width defined by a first sidewall and a second sidewall, the flowable film being formed on the substrate surface and on the first sidewall, the second sidewall, and the bottom surface of the at least one feature, the flowable film filling the feature without substantially forming a seam, the silicon-containing precursor comprising a compound having any of structures IV-V: wherein each of R1-R6 is independently selected from the group consisting of: CR'CR"2, CCR', H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, NR'2 and OR', wherein R' and R" are independently selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, at least one of R1-R6 is selected from the group consisting of: CR'CR"2 or CCR', and the co-reactant comprises ammonia plasma; and The flowable film is cured to solidify the film and form a substantially seamless gap fill, the flowable film having a carbon content greater than 55 atomic percent and less than 95 atomic percent.

Images