JP2021527331A - Compositions, and Methods of Using Compositions for Depositing Silicon-Containing Membranes - Google Patents

Abstract

Described herein are silicon-containing films, such as, but not limited to, silicon carbide, silicon nitride, silicon oxide, silicon oxynitride, carbon-doped silicon nitride, carbon-doped silicon oxide or carbon-doped. A composition and a method of using a composition for forming a silicon nitride film on the surface of a substrate having at least surface characteristics. In one embodiment, the silicon-containing film is deposited using a compound that contains a carbon-carbon double bond or a carbon-carbon triple bond. The plasma sources used include both remote plasma sources and in situ plasma sources that work in combination.

Description

Described herein are processes for the manufacture of electronic devices. More specifically, what is described herein is a composition for forming a silicon-containing film in a deposition process, eg, but not limited to, fluid chemical vapor phase deposition. Exemplary silicon-containing films that can be deposited using the compositions and methods described herein are, but are not limited to, silicon oxide, silicon nitride, silicon carbide, silicon nitride, carbon dope. Includes a film of nitrogen oxide or carbon-doped silicon nitride.

In the manufacture of microelectronics, narrow trenches with an aspect ratio (AR) greater than 10: 1 need to be filled without forming voids for many applications. One application is shallow trench isolation (STI). For this application, the membrane needs to be of very low leakage and of high quality (eg, wet etching rate ratio less than 2) through the trench. As the size of the structure decreases and the aspect ratio increases, the post-curing method of the deposited fluid film becomes more difficult. The result is a membrane with a compositional change through the filled trench.

Conventional plasma-enhanced chemical vapor deposition (PECVD) of dielectric films forms a "mushroom-shaped" film at the top of a narrow trench. This is due to the inability of the plasma to penetrate deep trenches. This results in pinching off the narrow trench from the top and forming voids at the bottom of the trench.

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-filled membranes can be used for patterning applications. Due to their high carbon levels, these films typically exhibit high etching selectivity compared to oxide and nitride films. Etching selectivity may be important for gap-filled membranes used in patterning applications. Therefore, there is a need for precursors and methods for depositing silicon-containing films.

U.S. Patent Application Publication No. 2008/0025907 discloses the process of forming a silicon-containing film on a substrate by a method known as fluid CVD or FCVD. The FCVD process is useful for many applications, including depositing gap-filled membranes in high aspect ratio structures with small dimensions. According to the disclosed process, the precursor is exposed to reactive radicals that initiate radical-induced polymerization in the deposition chamber. Reactive radicals are created using plasma energy. The plasma can be generated or ignited in the processing chamber (eg, direct or in situ plasma) or generated outside the processing chamber and flowed into the processing chamber (eg, remote plasma).

The compositions or formulations described herein, and methods using the compositions or formulations, deposit a silicon-containing film on at least a portion of the substrate surface that provides the desired film properties for post-deposition treatment. By doing so, it overcomes the problems of the prior art. The compositions and methods of the present invention have the following properties: i) Measured using Toho's stress tool, in the range of about 10 to about 20 MPa after thermosetting, about 150 to about 190 MPa after ultraviolet (UV) curing. It is possible to provide a silicon-containing film having a film tensile stress in the range of 1) ^{and a density in the range of about 1.35 to about 2.10 g / cm 3 as measured by ii) X-ray reflectance.}

The silicon-containing film is selected from the group consisting of silicon nitride, silicon carbide, silicon oxide, carbon-doped silicon nitride, silicon oxynitride, and carbon-doped silicon nitride. In certain embodiments, the substrate comprises surface features. As used herein, the term "surface feature" refers to a substrate having one or more of holes, trenches, shallow trench isolation (STI), vias, refillable shapes or the like. Means a partially manufactured substrate. The composition may be a premixed composition, a premixed mixture (mixed before being used in the deposition process) or an in situ mixture (mixed during the deposition process). Accordingly, in the present disclosure, the terms "mixture", "combination" and "composition" are interchangeable.

In one embodiment, a method for depositing a silicon-containing film in a fluid chemical vapor deposition process is provided. Substrates with surface features are placed in one or more temperature reactors in the range of −20 ° C. to about 100 ° C. The composition is introduced into the reactor and the composition _{comprises at least one compound having the formula R n} SiR ¹⁴ _-n , where R is a linear or branched C _{2 to} C ₆ alkenyl group, direct. Selected from chain or branched C _{2 to} C ₆ alkynyl groups; R ¹ selected from hydrogen, methyl and straight or branched C _{2 to} C ₁₀ alkyl groups; n from 1, 2, 3 and 4 The number to be selected. A plasma source is provided to react at least one compound at least partially to form a fluid liquid oligomer. The fluid liquid oligomer fills at least some of the surface features at least partially. Plasma sources include both remote and in situ plasma sources that work in combination.

In one particular embodiment, at least one of the remote plasma source and the in-situ plasma source is a nitrogen plasma, a plasma containing nitrogen and helium, a plasma containing nitrogen and argon, an ammonia plasma, a plasma containing ammonia and helium, ammonia. And argon-containing plasma, helium plasma, argon plasma, hydrogen plasma, hydrogen and helium-containing plasma, hydrogen and argon-containing plasma, ammonia and hydrogen-containing plasma, organic amine plasma, oxygen-containing plasma, oxygen and hydrogen-containing. Includes plasma sources selected from the group consisting of plasmas and combinations thereof.

In another embodiment, the plasma source for the remote plasma source and / or the in-situ plasma source is a hydrocarbon plasma, a plasma containing hydrocarbons and helium, a plasma containing hydrocarbons and argon, a carbon dioxide plasma, a carbon monoxide plasma. , Plasma containing hydrocarbons and hydrogens, plasmas containing hydrocarbons and nitrogen sources, plasmas containing hydrocarbons and oxygen sources, and carbon source plasmas containing combinations thereof.

In any of the above embodiments, or in alternative embodiments, the fluid liquid or oligomer is treated at one or more temperatures in the range of about 100 ° C to about 1000 ° C to remove at least a portion of the material. Increase the density.

In some embodiments, the post-heat treated material is exposed to plasma, infrared light, chemical treatment, electron beam or ultraviolet light to form a dense film.

The above steps define one cycle for the methods described herein; the cycle can be repeated until the desired thickness of the silicon-containing membrane is obtained. In this embodiment or another embodiment, the steps of the methods described herein can be performed in a reordered manner and can be performed continuously or simultaneously (eg, during at least a portion of another step). It is understood that it can be any combination of them.

Various embodiments of the present invention can be used alone or in combination with each other.

It is a scanning electron microscope (SEM) photograph which shows the result of Example 1. FIG. It is an SEM photograph which shows the result of Example 2. 3 is an SEM photograph showing the result of Example 3. It is an SEM photograph which shows the result of Example 5.

Described herein is an FCVD method for depositing silicon-containing membranes in a fluid chemical vapor phase deposition process.
The step of placing a substrate with surface features in a reactor at one or more temperatures in the range of −20 ° C. to about 100 ° C.;
It has the formula R _n SiR ¹⁴ _-n , in which R is selected from the linear or branched C _{2 to} C ₆ alkenyl groups and the linear or branched C _{2 to} C ₆ alkynyl groups, and R ¹ Introduces into the reactor a composition comprising hydrogen and _{at least one compound selected from the C 1 to} C ₁₀ alkyl groups of the branched chain and n being a number selected from 1, 2, 3 and 4; In addition, a plasma source is provided in the reactor and at least one compound is reacted at least partially to form a fluid liquid oligomer, wherein the fluid liquid oligomer at least partially reacts at least some of the surface features. The plasma source comprises a step of including both a remote plasma source and an in-situ plasma source that work in combination.

Typically, membranes deposited, for example by fluid chemical vapor deposition treatment, undergo membrane shrinkage during post-treatment due to low process temperatures. Voids and seams may form in the membrane due to significant membrane contraction and increased membrane stress. Therefore, it has been difficult to densify the film without increasing the film stress or creating voids. The compositions and methods described herein improve the filling of at least some of the surface features on the substrate by using the disclosed precursors and the compositions containing the disclosed precursors. Overcome these problems.

An embodiment of the disclosure provides a method of depositing a gap-filled membrane (eg, SiC, SiCO, SiCN, SiCON) on a high aspect ratio (AR) structure with small dimensions. Advantageously, some embodiments provide methods that include a cycle deposition process that can be performed in a cluster tool environment. Advantageously, some embodiments provide high quality silicon-containing membranes without seams that fill high AR trenches with small dimensions. Advantageously, some embodiments provide a membrane with a high carbon content. Advantageously, in one or more embodiments, high carbon content membranes can be used in hardmask and low-k fluid applications.

One or more embodiments of the disclosure are intended for a process in which a fluid silicon-containing membrane can be deposited, which can be packed with structures with high aspect ratios (eg AR> 8.1). An embodiment of the disclosure is a novel precursor that uses F-CVD (Fluid Chemical Vapor Deposition) to produce SiC, SiOC, SiCN, SiOCN, SiO and SiN fluidized films for gap filling applications. I will provide a. Precursors of various embodiments include alkenyl (vinyl) and / or alkynyl groups. In one or more embodiments, the precursor is exposed to reactive radicals that initiate radical-induced polymerization in the deposition chamber.

In one embodiment, the method of the present development comprises placing a substrate having surface features in a reactor at one or more temperatures in the range of −20 ° C. to about 100 ° C.

As used herein, "base material" refers to any base material, or a material surface formed on a base material that is membrane treated during a manufacturing process. For example, the surface of the substrate that can be treated is a material 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 material, such as metals, nitrides, metal alloys, and other conductive materials, depending on the application. The base material includes, but is not limited to, a semiconductor wafer. The substrate can be subjected to a pretreatment process for polishing, etching, reducing, oxidizing, hydroxylating, annealing, UV curing, electron beam curing and / or baking the surface of the substrate. In addition to direct film treatment on the surface of the substrate itself, some of the membrane treatment steps disclosed in the present invention are also on the underlying layer formed on the substrate, as disclosed in more detail below. It can be done and the term "base material surface" is intended to include such underlayers when the context intends. Thus, for example, when a film / layer or a partial film / layer is deposited on the surface of the substrate, the exposed surface of the newly deposited film / layer becomes the surface of the substrate.

As described above, the method deposits a film on at least a portion of the surface of a substrate with surface features. The substrate is placed in the reactor and the substrate is held at at least one temperature in the range of about -20 ° C to about 100 ° C. In one particular embodiment, the temperature of the substrate is lower than the temperature of the walls of the chamber. The substrate temperature is kept below 100 ° C., preferably below 25 ° C., most preferably below 10 ° C. and above −20 ° C.

As described above, the substrate comprises one or more surface features. In one particular embodiment, one or more surface features have a width of 1 μm or less, a width of 500 nm or less, a width of 50 nm or less, or a width of 10 nm. In this embodiment or another embodiment, the aspect ratio (depth: width ratio) of the surface features, if present, is 0.1: 1 or greater, 1: 1 or greater, 10: 1 or greater, 20: 1. Or more, or 40: 1 or more. The substrate can be a single crystal silicon wafer, a silicon carbide wafer, an aluminum oxide (sapphire) wafer, a glass sheet, a metal foil, an organic polymer film, or a three-dimensional polymer, glass, silicon or metal. It may be an article. Substrates are a variety of materials well known in the art, including films of silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, gallium arsenide, gallium nitride and the like. Can be coated. These coatings may be a complete coating of the substrate, may be a multi-layer of various materials, or may be partially etched to expose the underlying layer of the material. The surface may also have a photoresist material exposed and developed in a pattern such that the surface is partially coated with a substrate.

In one aspect of the invention, the substrate comprises at least one element selected from the group consisting of _{Si, SiO x, SiN, SiGe, SiOC and SiON.} In another aspect of the invention, the silicon-containing film of the invention can be used as a hardmask and can provide etching selectivity to the photoresist. In a further aspect of the invention, the silicon-containing film of the invention functions as a dielectric film between conductive materials, as a barrier between a conductor and other dielectrics, or as a film in a sandwich dielectric. ..

The method used to form a film or coating as described herein is a fluid chemical deposition process. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, cycle fluid chemical vapor phase deposition (CFCVD) or plasma enhanced fluid chemical gas phase deposition (PEFCVD). As used herein, the term "fluid chemical vapor deposition process" means that the substrate is exposed to one or more volatile precursors, which react and / or react on the surface of the substrate. Any process that decomposes to provide a silicon-containing species of fluid oligomers, which in turn yields a solid film or material for further treatment, and in some cases at least some of the oligomeric species contain polymer species. say. The precursors, reagents and sources used herein are sometimes described as "gaseous", but the precursors are directly in the reactor with or without an inert gas. It is understood that it may be either a liquid or a solid carried by vaporization, bubbling or sublimation. In some cases, the vaporized precursor can pass through the plasma generator. In one embodiment, the membrane is deposited using a plasma-based (eg, remotely generated or in situ) CVD process. As used herein, the term "reactor" includes, but is not limited to, reaction chambers or deposition chambers.

を含むがそれらに限定されない。 The method of the present development also has the formula R _n SiR ¹⁴ _-n , in which R is a linear or branched C _{2 to} C ₆ alkenyl group, linear or branched C _{2 to} C ₆ alkynyl. Selected from groups; R ¹ is selected from hydrogen and C _{1 to} C ₁₀ alkyl groups on branched chains; n is a number selected from 1, 2, 3 and 4 Reacting compositions containing at least one compound Includes the process of introducing into the vessel. Exemplary compounds for the above formula are:

Including, but not limited to them.

In the above formula and throughout the specification, the term "linear or branched chain alkyl" represents a linear functional group having 1-10, 3-10 or 1-6 carbon atoms. In the above formula and throughout the specification, the term "branched chain alkyl" represents a linear functional group having 3-10 or 1-6 carbon atoms. Alkyl groups exemplary linear or branched include methyl (Me), ethyl (Et), isopropyl (Pr ^i), isobutyl (Bu ^i), sec-butyl (Bu ^s), tert-butyl (Bu ^t) , Isopentyl, tert-pentyl (am), isohexyl and neohexyl, but not limited to them. In certain embodiments, the alkyl group has one or more functional groups attached thereto, such as, but not limited to, an alkoxy group, a dialkylamino group or a combination thereof. It's okay. In other embodiments, the alkyl group does not have one or more functional groups attached to it. The alkyl group may be saturated or instead unsaturated.

In the above formula and throughout the specification, the term "cyclic alkyl" represents a cyclic group having 3-10 or 5-10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups. In certain embodiments, the cyclic alkyl group may have one or more C _{1 to} C ₁₀ linear, branched substituents, or substituents containing an oxygen or nitrogen atom. In this embodiment or another embodiment, the cyclic alkyl group may have one or more linear or branched alkyl or alkoxy groups, such as a methylcyclohexyl group or a methoxycyclohexyl group, as substituents.

In the above formula and throughout the specification, the term "aryl" represents an aromatic cyclic functional group having 3 to 10 carbon atoms, 5 to 10 carbon atoms or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, trill and o-xylyl.

In the above formula and throughout the specification, the term "alkenyl group" has one or more carbon-carbon double bonds and contains 2-12, 2-10 or 2-6 carbon atoms. Represents a group having. Exemplary alkenyl groups include, but are not limited to, vinyl or allyl groups.

The term "alkynyl group" refers to a group having one or more carbon-carbon triple bonds and having 2-12 or 2-6 carbon atoms.

The term "alkylene group" refers to a group derived from an alkyl by the removal of two hydrogen atoms. Exemplary alkylene groups include, but are not limited to _{, methylene (−CH 2} −) or ethylene (−CH ₂ CH _{2 −) groups.}

As used herein in the above formula and throughout the specification, the term "unsaturated" means that a functional group, substituent, ring or bridge is one or more carbon double or triple bonds. Means to have. Examples of unsaturated rings are not limited to the following, but may be aromatic rings, such as phenyl rings. The term "saturated" means that a functional group, substituent, ring or bridge does not have one or more double or triple bonds.

In certain embodiments, one or more of the alkyl, alkenyl, alkynyl, aryl and / or cyclic alkyl groups in the formula above are "substituted" or, for example, in place of a hydrogen atom. It may have one or more atoms or groups of atoms substituted with. Exemplary substituents include, but are not limited to, oxygen, sulfur, halogen atoms (eg F, Cl, I or Br), nitrogen, alkyl groups and phosphorus. In other embodiments, one or more of the alkyl, alkenyl, alkynyl, aromatic and / or aryl groups in the above formula may not be substituted.

The silicon precursor compound preferably has substantially no halogen-based ions such as chlorine or metal ions such as Al. As used herein, the term "substantially absent" refers to halogen-based ions (or halides) such as chlorides, fluorides, bromides and iodides, Al ³⁺ ions, Fe ^2+,. When it comes to Fe ³⁺ , Ni ²⁺ and Cr ³⁺ , it means less than 5 ppm (by mass), preferably less than 3 ppm, more preferably less than 1 ppm, most preferably 0 ppm. Chloride or metal ions are known to act as decomposition catalysts for silicon precursors. Significant levels of chloride in the final product can degrade the silicon precursor. The gradual decomposition of silicon precursors can directly affect the membrane deposition process, which makes it difficult to meet membrane specifications for semiconductor manufacturing. In addition, shelf life or stability is negatively affected by the higher degradation rates of silicon precursors, thereby making it difficult to guarantee a shelf life of 1-2 years. In addition, silicon precursors are known to form flammable and / or pyrophoric gases such as hydrogen and silane upon decomposition. Therefore, the accelerated decomposition of silicon precursors raises safety and performance concerns associated with the formation of these flammable and / or pyrophoric gaseous by-products.

The compounds disclosed herein can be transported to a fluid chemical vapor deposition reactor in a variety of ways, including but not limited to gas phase extraction, bubbling or direct liquid injection (DLI). .. In one embodiment, a liquid transport system is utilized. In another embodiment, the reactor is equipped with a dual plenum shower head to keep the remotely generated plasma species separate from the gas phase of the precursor, which means that they are in the reactor. It is until the fluid liquid is deposited by combining with. In an alternative embodiment, a combined liquid transport and flash vaporization process apparatus, such as a turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, can be used to transport the low volatility material by volume. And results in reproducible transport and deposition without thermal decomposition of the precursor. In liquid transport formulations, the precursors described herein can be transported in pure liquid form or can instead be used in solvent formulations or compositions containing precursors. Thus, in certain embodiments, the precursor formulation may contain solvent components with suitable properties that may be desirable and advantageous in a given end-use application to form a film on the substrate.

In certain embodiments, the substrate may include one or more pre-deposition treatments, such as, but not limited to, plasma treatments, heat treatments, chemical treatments, ultraviolet light exposures, electron beam exposures and combinations thereof. In response, it can affect the properties of one or more of the membranes. These pre-deposition treatments can occur under an atmosphere selected from Inactivity, Oxidation and / or Reduction.

The method of the present development comprises providing a plasma source in a reactor and at least partially reacting at least one compound having _{the formula R n} SiR ¹⁴ _{-n to form a fluid liquid oligomer.} The sexual liquid oligomer fills at least a portion of the surface features at least partially, and the plasma source includes both a remote plasma source and an in-situ plasma source that work in combination.

The process of this development uses two plasma sources-a remote plasma source and an in-situ RF plasma source (eg, capacitive coupling) -when viewed by a scanning electron microscope (SEM), which has the best gap filling properties. Produces a post-deposited and cured membrane with virtually no visible voids. Remote and in situ plasma sources that work in combination mean that both plasma sources are activated at least in part of the time between depositions. In other embodiments, both plasma sources are activated for at least a quarter of the time between depositions. In other embodiments, both plasma sources are activated for at least half of the time between depositions. In other embodiments, both plasma sources are activated for at least 3/4 of the time between depositions. In yet another embodiment, both plasma sources are activated during the entire time during deposition.

The plasma power applied to the remote plasma source (RPS) is 1000-3000 W, preferably 2000-3000 W. The plasma power to the in situ plasma source is 100-1000 W, preferably 200-300 W.

The energy is _{applied to at least one compound having the formula R n} SiR ¹⁴ _-n and a plasma source to induce a reaction to form a fluid silicon-containing film or coating on the substrate. Such energies are, but are not limited to, heat, plasma, pulsed plasma, helicon wave plasma, high density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and their methods. It can be provided by a combination. In certain embodiments, a second RF frequency source can be used to alter the plasma properties on the substrate surface. In embodiments where deposition involves plasma, the plasma generation process is a direct plasma generation process in which the plasma is generated directly in the reactor, or a remote plasma in which the plasma is instead generated outside the reactor and supplied into the reactor. It may include a developmental process.

At least one of the remote plasma source and the in situ plasma source may contain nitrogen. Nitrogen-containing plasmas include nitrogen plasma, nitrogen / hydrogen plasma, nitrogen / helium plasma, nitrogen / argon plasma, ammonia plasma, ammonia / helium plasma, ammonia / argon plasma, ammonia / nitrogen plasma, NF ₃ , NF ₃ plasma, and organic. It can be selected from the group consisting of amine plasma and combinations thereof. At least one compound reacts with a nitrogen source to form a silicon nitride or silicon nitride film (indefinite ratio) on surface features and at least a portion of the substrate. As used herein, the term "organic amine" refers to an organic compound having at least one nitrogen atom. Examples of organic amines are, but are not limited to, methylamine, ethylamine, propylamine, isopropylamine, tert-butylamine, sec-butylamine, tert-amylamine, ethylenediamine, dimethylamine, trimethylamine, diethylamine, pyrrole, 2 , 6-Dimethylpiperidin, di-n-propylamine, di-isopropylamine, ethylmethylamine, N-methylaniline, pyridine and triethylamine.

At least one of the remote plasma source and the in situ plasma source may contain carbon. In such an embodiment, the plasma source is a hydrocarbon plasma, a plasma containing hydrocarbons and helium, a plasma containing hydrocarbons and argon, a carbon dioxide plasma, a carbon monoxide plasma, a plasma containing hydrocarbons and hydrogen, a hydrocarbon. It is selected from, but is not limited to, a plasma containing a nitrogen source, a plasma containing a hydrocarbon and an oxygen source, and a carbon source plasma containing a combination thereof. At least one compound reacts with a carbon source to form a silicon carbide film (indefinite ratio), a silicon nitride film, a silicon nitride film, a silicon oxycarbide film, or a silicon oxycarbonitride film. Form at least in part of.

In different embodiments, the plasma source is selected from, but not limited to, hydrogen plasma, helium plasma, argon plasma, xenon plasma and combinations thereof. At least one compound reacts with the plasma to form a silicon nitride film, a silicon carbide film or a silicon nitride film on at least a surface feature and a substrate.

At least one of the remote plasma source and the in situ plasma source may contain oxygen. In such embodiments, the oxygen-containing sources are water (H ₂ O), oxygen (O ₂ ), oxygen plasma, ozone (O ₃ ), NO, NO ₂ , carbon monoxide (CO), carbon dioxide (CO). ₂ ), N ₂ O plasma, carbon monoxide (CO) plasma, carbon dioxide (CO ₂ ) plasma and combinations thereof can be selected from the group.

In addition, after the silicon-containing film has been deposited, the substrate is described above under specific process conditions sufficient for the silicon nitride film to form a film of silicon oxide, silicon nitride or carbon-doped silicon oxide. It can be treated with an oxygen-containing source (ie, optionally treated).

In certain embodiments, the reactor is either a subatmospheric pressure or a pressure below 750 torr (10 ⁵ Pascals (Pa)), or 100torr (13332Pa) or less pressure. In other embodiments, the reactor pressure is maintained in the range of about 0.1 torr (13 Pa) to about 10 torr (1333 Pa).

Fluid membranes are generally not stable when deposited and stabilize when exposed to atmospheric conditions. The fluid membranes of some embodiments are deposited by a silicon-containing precursor and, for example _{, the radical form of NH 3} / O _{2 as a copolymer.} These films are then cured by ozone / UV / vapor annealing / NH ₃ annealing and the like to give a cured film.

In certain embodiments, the fluid liquid or oligomer is treated at one or more temperatures in the range of about 100 ° C to about 1000 ° C to densify at least a portion of the material. In other embodiments, the fluid liquid or oligomer is an oxygen-containing source of the following under specific process conditions sufficient for the silicon nitride film to form a film of silicon oxide, silicon nitride or carbon-doped silicon oxide. It is processed by exposing it to at least one of them. Oxygen-containing sources are water (H ₂ O), oxygen (O ₂ ), oxygen plasma, ozone (O ₃ ), NO, N ₂ O, carbon monoxide (CO), carbon dioxide (CO ₂ ), N ₂ O. You can choose from the group consisting of plasma, carbon monoxide (CO) plasma, carbon dioxide (CO _{2) plasma and combinations thereof.}

In some embodiments, the post-heat treated material receives plasma, infrared light, chemical treatment, electron beam or ultraviolet light to form a dense film. In one embodiment of the invention, the post-treatment, including ultraviolet light exposure, is performed under conditions that produce gaseous by-products.

The above steps define one cycle for the methods described herein; the cycle can be repeated until the desired thickness of the silicon-containing membrane is obtained.

The present development demonstrates the use of precursor selection to provide a film with the desired silicon: carbon ratio (Si: C). Membrane deposition using tetravinylsilane (TVS) provides a Si: C ratio of about 1: 4. The precursor has a 1: 8 Si: C. Selection of precursors with many Si atoms contained in the ring structure will result in higher Si: C, as seen, for example, in 1,1,3,3-tetravinyl-1,3-disilacyclobutane. A film having can be produced. The chemical structure is expected to provide 1: 3 Si: C. The use of precursors such as allyl-substituted disilacyclobutane is potentially low Si: C, sometimes 1: 1 based on the improved potential of the allyl group as a leaving group during deposition or membrane hardening. Si: C reaching 1 can be provided.

The fluid film 150 can be formed at any suitable temperature. In some embodiments, the fluid film 150 is formed at a temperature in the range of about −20 ° C. to about 100 ° C. The temperature can be kept low so as to maintain the temperature budget of the device being formed. In some embodiments, the formation of the fluid film occurs at temperatures below about 300 ° C, 250 ° C, 200 ° C, 150 ° C, 100 ° C, 75 ° C, 50 ° C, 25 ° C or 0 ° C.

Membranes with high carbon content can have many uses, such as in hardmask patterning and for fluid low K films. In some embodiments, fluidized membranes using the precursors disclosed herein are capable of depositing membranes with high carbon content. In some embodiments, the membrane has a maximum carbon content of about 85 at%. In one or more embodiments, the fluidized membrane has a carbon content higher than about 40, 45, 50, 55, 60, 65, 70, 75 or 80 at% and lower than about 95, 90 or 85 at%. Have. In some embodiments, the fluidized membrane has a carbon content in the range of about 40 to about 85 at%, in the range of about 50 to about 85 at% or in the range of about 60 to about 80 at%.

The composition of the fluid membrane can be adjusted by changing the composition of the reactive gas. In some embodiments, the fluidizing membrane comprises one or more of SiC, SiCO, SiCN, SiCON, SiO and SiN. To form an oxygen-containing membrane, the copolymer may contain, for example, one or more of oxygen, ozone or water. To form a nitrogen-containing membrane, the copolymer may contain, for example, one or more of _{ammonia, hydrazine, NO 2} or N _2. To form the carbon-containing membrane, the reactive gas may contain, for example, one or more of propylene and acetylene. Those skilled in the art will appreciate that combinations of other species can be included in the reactive gas mixture to alter the composition of the fluid membrane.

The fluid film can be deposited on the wafer (wafer temperature can be −10 ° C to 200 ° C), and due to their fluidity, the polymer flows through the trench and fills the gap. .. These films are then subjected to a curing step, such as ozone / UV / vapor annealing / NH ₃ annealing, to obtain stable films. In some embodiments, the method provides one or more of SiC, SiCO, SiCN, SiCON, SiO and / or SiN fluidized membranes. Therefore, after the formation of the fluidized membrane 150, the membrane is cured and the fluidized membrane can be solidified to form a gap filling with virtually no seams. In one or more embodiments, curing the fluid film comprises exposing the fluid film to one or more of ozone, ultraviolet light, vapor annealing, ammonia annealing and oxygen plasma. In some embodiments, the fluidized membrane is cured by exposing the membrane to a UV curing process. The UV curing process can be carried out at temperatures in the range of about 10 ° C to about 550 ° C. The UV curing process can be carried out for any suitable time frame required to fully solidify the fluidized membrane. UV curing can be performed with various parameters such as power, temperature, environment and the like. In some embodiments, UV curing occurs in an acetylene / ethylene environment.

In one embodiment, a method for depositing a silicon-containing film in a fluid chemical vapor deposition process is provided, wherein the substrate with surface features is one in the range of −20 ° C. to about 100 ° C. The step of placing in a reactor at multiple temperatures; having the formula R _n SiR ¹ _4-n , where R is a linear or branched C _{2 to} C ₆ alkenyl group, linear or branched C. _{At least one compound selected from 2 to} C ₆ alkynyl groups, R ¹ selected from hydrogen and C _{1 to} C ₁₀ alkyl groups of the branched chain, and n being a number selected from 1, 2, 3 and 4. A step of introducing the composition containing the compound into a reactor; and a step of providing a plasma source into the reactor and reacting at least one compound at least partially to form a fluid liquid oligomer, which is a fluid liquid. The oligomer is at least partially filled with at least some of the surface features, and the plasma source comprises a step that includes both a remote plasma source and an in-situ plasma source that work in combination.

The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims.

A fluid chemical vapor deposition (FCVD) film was deposited on a single crystal silicon wafer substrate with medium resistance (8-12 Ωcm) and a Si patterned wafer. In certain embodiments, the resulting silicon-containing film or coating is a predeposition treatment, eg, but not limited to, plasma treatment, heat treatment, chemical treatment, ultraviolet light exposure, infrared exposure, electron beam exposure. And / or can be subjected to other treatments that affect the properties of one or more of the membranes.

Sedimentation in a modified FCVD chamber in an Applied Materials Precision 5000 system can be performed using either a silane or TEOS process kit. The chamber has a direct liquid injection (DLI) transport capability. A precursor is a liquid having a transport temperature that depends on the boiling point of the precursor. To deposit the initial fluid nitride film, a typical liquid precursor flow velocity is 100-5000 mg / min, the power density of the insitu plasma is 0.25-3.5 W / cm ² , and the pressure is 0. It was .75-12 Torr. To densify the as-deposited fluid membrane, the membrane is thermally annealed in vacuum using a modified PECVD chamber at 100-1000 ° C, preferably 300-400 ° C, and / Or UV cured. The thickness and refractive index (RI) at 632 nm were measured by an SCI reflector or a Woollam ellipsometer. Typical film thickness was in the range of 10-2000 nm. The binding properties and hydrogen content (Si—H, CH and N—H) of silicon-based films were measured and analyzed by a Nicolet transmission Fourier transform infrared spectroscopy (FTIR) tool. All density measurements were made using the X-ray Reflectivity (XRR) method. X-ray photoelectron spectroscopy (XPS) analysis and secondary ion mass spectrometry (SIMS) were performed to determine the elemental composition of the membrane. The fluidity and gap filling effect in the patterned wafer was observed by scanning electron microscopy (SEM) observation of the cross section using a Hitachi S-4700 system with a resolution of 2.0 nm.

Fluid CVD deposition was performed according to the following conditions.

Example 1: Sedimentation Conditions-3000W Remote Plasma Source (RPS); 200W In situ; 2torr; 1500sccm NH ₃ ; 1500mg / min Tetravinylsilane (TVS). With reference to FIG. 1, the membrane shows voids after curing.

Example 2: Sedimentation conditions-3000W RPS; 200W in situ; 2torr; 1000sccm NH ₃ ; 1500mg / min TVS. Referring to FIG. 2, less NH ₃ flow reduces membrane voids.

Example 3: Sedimentation conditions-3000W RPS; 0W in situ; 2torr; 1000sccm NH ₃ ; 1500mg / min TVS. With reference to FIG. 3, it can be seen that stopping the in situ plasma causes a pinch-off at the top of the feature.

Example 4: Sedimentation Conditions-TVS Only; 3000W RPS; 200W In situ; 2torr; 1000sccm NH ₃ ; 1500mg / min TVS; TVS + Trisilylamine (TSA); 3000W RPS; 200W In situ; 2torr; 1000sccm NH ₃ ; 1500mg / min TVS + 900sccm TSA. With reference to Table 1, it can be seen that adding TSA to the chamber does not increase the uptake of N into the membrane. It activates the membrane for environmental oxidation.

Additional Notes in Example 4: The chemical composition was determined by X-ray photoelectron spectroscopy (XPS). Some surface oxidation was observed on the TVS membrane. The bulk of the membrane had slight oxidation. Surface and bulk oxidation was very high in the TVS + TSA membrane.

Example 5: Sedimentation Conditions-TVS Only; 0W RPS; 200W In situ; 8torr; 400sccm NH ₃ ; 2000mg / min TVS; 200sccmHe; Sedimentation for 5sec; The deposited membranes showed fluidity when used, but after curing they showed visible porosity in the filled features. Compared to FIG. 2, these membranes are considered to have a significantly lower density in the features.

Although certain principles of the invention have been described above in conjunction with embodiments or embodiments, it is clearly understood that this description is merely an example and does not limit the scope of the invention.

Claims (12)

A method for depositing silicon-containing films in a fluid chemical vapor deposition process.
The step of placing a substrate with surface features in a reactor at one or more temperatures in the range of −20 ° C. to about 100 ° C.;
It has the formula R _n SiR ¹⁴ _-n , in which R is selected from the straight or branched C _{2 to} C ₆ alkenyl groups and the straight or branched C _{2 to} C ₆ alkynyl groups, R ¹ A composition comprising hydrogen, methane and _{at least one compound selected from linear or branched C 2 to} C ₁₀ alkyl groups and n being a number selected from 1, 2, 3 and 4 in the reactor. Process to introduce to
A step in which a plasma source is provided in a reactor and at least one compound is at least partially reacted to form a fluid liquid oligomer, wherein the fluid liquid oligomer at least partially reacts at least some of the surface features. A method comprising a step of filling and including a remote plasma source and an in-situ plasma source in which the plasma source works in combination. At least one of the remote plasma source and the in-situ plasma source is nitrogen plasma, plasma containing nitrogen and hydrogen, plasma containing nitrogen and helium, plasma containing nitrogen and argon, ammonia plasma, plasma containing ammonia and helium, ammonia and argon. The method of claim 1, comprising a plasma source selected from the group consisting of plasmas comprising plasma, plasmas comprising ammonia and nitrogen, NF _{3 plasmas, organic amine plasmas and combinations thereof.} At least one of the remote plasma source and the in-situ plasma source is a hydrocarbon plasma, a plasma containing hydrocarbons and helium, a plasma containing hydrocarbons and argon, a carbon dioxide plasma, a carbon monoxide plasma, a plasma containing hydrocarbons and hydrogen, The method of claim 1, comprising a plasma containing a hydrocarbon and nitrogen source, a plasma containing a hydrocarbon and an oxygen source, and a carbon source plasma selected from the group consisting of combinations thereof. The method of claim 1, wherein at least one of the remote plasma source and the in-situ plasma source is selected from the group consisting of hydrogen plasma, helium plasma, argon plasma, xenon plasma and combinations thereof. At least one of the remote plasma source and the in-situ plasma source is water (H ₂ O) plasma, oxygen plasma, ozone (O ₃ ) plasma, NO plasma, N ₂ O plasma, carbon monoxide (CO) plasma, carbon dioxide ( CO ₂ ) The method of claim 1, comprising a plasma source containing oxygen selected from the group consisting of plasma and combinations thereof. The first aspect of the present invention further comprises a step of treating the fluid liquid oligomer at one or more temperatures in the range of about 100 ° C. to about 1000 ° C. to cure the fluid liquid oligomer to form a cured film. Method. The method of claim 1, wherein the reactor pressure is maintained below 100 torr. The method according to claim 1, wherein the silicon-containing film is selected from the group consisting of films of silicon carbide, silicon nitride, silicon oxide, carbon-doped silicon nitride, carbon-doped silicon oxide, silicon oxynitride and carbon-doped silicon nitride. .. At least one compound

The method according to claim 1, which is selected from the group consisting of. The method of claim 9, wherein at least one compound comprises tetravinylsilane. A film obtained by the method according to any one of claims 1 to 10. It has at least one of the following characteristics: i) film tensile stress in the range of about 150 to about 190 MPa after UV curing and ii) density in the range of ^{about 1.35 to about 2.10 g / cm 3.} The film according to claim 11.

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