TW201619428A - Low-k oxide deposition by hydrolysis and condensation - Google Patents

Abstract

Methods for depositing flowable dielectric films using halogen-free precursors and catalysts on a substrate are provided herein. Halogen-free precursors and catalysts include self-catalyzing aminosilane compounds and halogen-free organic acids. Flowable films may be used to fill pores in existing dielectric films on substrates having exposed metallization layers. The methods involve hydrolysis and condensation reactions.

Description

Low dielectric constant oxide deposition by hydrolysis and condensation

The present disclosure relates to semiconductor substrate processing and, more particularly, to low dielectric constant oxide deposition by hydrolysis and condensation.

As the feature size of integrated circuits (ICs) shrinks, the problem of increased resistance and resistance-capacitance coupling offsets any speed advantage derived from smaller device sizes, while limiting Improvement in device performance. Methods to improve device performance and reliability include the use of highly conductive metals such as copper and the use of low dielectric constant (low k/low-k, lower dielectric constant) materials.

The low-k material is a semiconductor-grade insulating material having a dielectric constant ("k") which is lower than the dielectric constant (i.e., 3.9) of cerium oxide (SiO ₂ ). With the increasing demand for advanced technology, ultra-low dielectric constant (ULK) dielectric materials having a k of less than 2.5 are used. The ULK dielectric can be obtained by incorporating the holes into the low-k dielectric to produce a porous dielectric material. Applications for ULK dielectrics include interlayer dielectrics (ILDs) of the back end of line (BEOL).

A method of depositing a film on a semiconductor substrate as provided in the present specification. In one aspect, a process gas comprising a ruthenium-containing precursor, an oxidant, and a halogen-free acid catalyst compound is introduced into the reaction chamber; and the substrate is exposed under conditions in which the condensed flowable film is formed on the substrate In the process gas, the chemical reaction forming the flowable membrane comprises S _N 1 hydrolysis mechanism and condensation

In certain embodiments, the halogen-free catalyst compound is selected from the group consisting of acetic acid, and a photosensitive organic acid catalyst, optionally selected from the group consisting of sulfonic acid, picric acid, tartaric acid, A group consisting of citric acid, ethylenediaminetetraacetic acid, pyrophosphoric acid, substituted derivatives of such acids, and combinations thereof. In certain embodiments, the substrate is exposed to the process gas when the substrate is exposed to UV radiation.

The oxidizing agent is selected from the group consisting of water, ozone, and peroxide. In various embodiments, the ruthenium containing precursor and the oxidant are introduced into the reaction chamber via separate inlets. In certain embodiments, the halogen-free catalyst compound is introduced into the reaction chamber independently of the ruthenium containing precursor and the oxidant.

In various embodiments, the method further comprises treating the flowable film, which can include exposing the flowable film to the oxidant and exposing the film to a thermal or plasma environment. In certain embodiments, the flowable membrane encloses pores having an average critical dimension between about 1 Å and about 1 nm.

Another aspect includes a method of depositing a film on a semiconductor substrate by the following steps: introducing a process gas comprising a ruthenium-containing precursor, an oxidant, and a halogen-free catalyst compound into the reaction chamber; and The substrate is exposed to the process gas under conditions in which the flow film is formed on the substrate, and the catalyst compound is selected from the group consisting of sulfonic acid, picric acid, tartaric acid, citric acid, ethylenediaminetetraacetic acid, pyrophosphoric acid, and combinations thereof The group that makes up.

In certain embodiments, the flowable film comprises a carbon doped cerium oxide film.

Another aspect includes a method of depositing a film on a semiconductor substrate by introducing a process gas including a ruthenium-containing precursor and an oxidant into a reaction chamber; and forming a condensable flowable film on the substrate The substrate is exposed to the process gas, and the ruthenium-containing precursor is a halogen-free autocatalytic amino decane compound, and the chemical reaction forming the flowable film comprises an amine group on the amino decane compound. The hydrolysis mechanism and condensation between the oxidant.

In certain embodiments, the ruthenium containing precursor is halogen free. In various embodiments, the method further comprises treating the flowable membrane by exposing the flowable membrane to the oxidant. In certain embodiments, the ruthenium containing precursor chemical structure comprises at least one N-alkylamine group.

The chemical structure of the ruthenium-containing precursor may comprise at least one ligand selected from the group consisting of N-alkylamines; N,N dialkylamines; alkoxy groups; alkyl groups; alkenyl groups; alkynyl groups; a group consisting of hydrogen; In certain embodiments, the flowable membrane encloses pores having an average critical dimension between about 1 Å and about 1 nm.

Another aspect includes a method of depositing a film on a semiconductor substrate by introducing a process gas containing a halogen-free germanium-containing precursor and an oxidant into a reaction chamber; and forming a condensable flowable film The substrate is exposed to the process gas under conditions on the substrate, and the halogen-free ruthenium-containing precursor is selected from the group consisting of dimethylaminotrimethyl decane, dimethylaminotriethyl decane, and double Dimethylaminodiethyl decane, trimethylaminomethyl decane, trimethylaminomethyl decane, trimethylamino decane, bisdimethylamino dimethyl decane, dimethyl Aminomethyl ethoxymethyl decane, methylaminodiethoxymethyl decane, trimethylamino vinyl decane, dimethylamino divinyl decane, bisdimethylamino ethoxy A group consisting of divinyl decane, ethoxy decane, and combinations thereof. In certain embodiments, the method further comprises treating the flowable membrane by exposing the flowable membrane to the oxidant.

These and other aspects are further described below with reference to the drawings.

In the following description, numerous specific details are set forth to provide a complete understanding of the embodiments presented. Embodiments of the present disclosure may still be practiced without some or all of these specific details. In other instances, well-known program operations have not been described in detail in order to avoid unnecessarily obscuring the disclosed embodiments. While the present invention has been described in connection with the specific embodiments, it is understood that

As the feature size of integrated circuits (ICs) shrinks, the problem of increased resistance and resistance-capacitance coupling offsets any speed advantage derived from smaller device sizes, while limiting Improvement in device performance. Methods to improve device performance and reliability include the use of highly conductive metals such as copper and the use of low dielectric constant (low k/low-k, lower dielectric constant) materials.

The low-k material is a semiconductor-grade insulating material having a dielectric constant ("k") which is lower than the dielectric constant (i.e., 3.9) of cerium oxide (SiO ₂ ). With the increasing demand for advanced technology, ultra-low dielectric constant (ULK) dielectric materials having a k of less than 2.5 are used. The ULK dielectric can be obtained by incorporating the holes into the low-k dielectric to produce a porous dielectric material. Applications for ULK dielectrics include interlayer dielectrics (ILDs) of the back end of line (BEOL).

Provided in the present specification is a method of depositing a dielectric film (including a low-k film) by a mechanism that causes formation of a flowable dielectric film. As used in this specification, the term "flowable dielectric film" is a flowable doped or undoped dielectric film having flow characteristics that provides consistent gap or pore filling. The term "flowable oxide film" is used to refer to a flowable doped or undoped tantalum oxide film. The term "flowable dielectric film" can include any dielectric film formed from a vapor phase reactant and flowable upon initial deposition, which comprises a film that is treated to be no longer flowable. The term "flowable dielectric film at the time of initial deposition" refers to a flowable dielectric film prior to any post-deposition treatment, densification, or curing. The flowable dielectric film at the initial deposition can be characterized as a soft gelatinous film, a gel having liquid flow characteristics, a liquid film, or a flowable film.

The methods disclosed in this specification can be particularly advantageous for depositing flowable oxides on structures comprising exposed metals. In such an example of a BEOL application, a low-k dielectric film (eg, ultra low-k carbon-doped oxide) can be deposited to form an ILD, which is subsequently etched to form The recess is exposed and the metal wire is exposed. The recess will eventually be filled with a metal such as copper. The ILD can be porous, however due to the metal precursor film or metal passing through the pores of the ILDs, the ILD suffers from potential degradation of the membrane. A low-k film as disclosed in this specification can be used to close the pores of the ILD.

Since the halogen-containing catalyst can react with the metallized layer exposed in certain regions of the substrate, the use of such catalysts can be problematic, especially chlorides and bromides may react more readily with the metallization layer. In one example, the fluoride can etch copper in an oxidized state or environment, and thus the fluorine-containing ruthenium precursor used to fill the pores or gaps on the substrate may degrade the region of the substrate. Degradation of this isoelectric characteristic on the substrate ultimately causes failure in the microelectronic device. Furthermore, the halide anion can be retained in the deposited film and then leached from the low-k dielectric layer and then into other portions of the overall structure, resulting in corrosion during integration, longer processing time, and Further processing steps. The halide anion also causes a shift in charge on the dielectric which degrades the dielectric properties of the dielectric.

The methods described in this specification include dielectric deposition in which a gap (eg, a gap between gates) or pores is filled with a dielectric material by using a halogen-free catalyst in the deposition of a flowable oxide ( Such as: pores in the ILD layer). In certain embodiments, forming a flowable film involves reacting a ruthenium containing precursor with an oxidant to form a condensed flowable film on the substrate. The formation of the film may be aided by a halogen-free catalyst, or the formation of the film may be catalyzed by a ligand containing a ruthenium precursor. The substrate is exposed to the process gas for a period of time sufficient to deposit a flowable film to fill at least a portion of the gap. The deposition process forms a soft gel-like film with good flow characteristics and provides consistent filling. In certain embodiments, the flowable film is an organic tantalum film, such as an amorphous organic tantalum film. In certain embodiments, the methods involve selectively condensing a liquid in a small space. The liquid can be a dielectric material or a precursor to which a dielectric material is to be deposited. Under certain physical conditions, the liquid is also selectively deposited only in the capillary (eg, pores in the layer or narrow etch gap), or the bulk liquid can be removed by evaporation, while the liquid in the capillary is Keep condensing. The process facilitates filling from bottom to top or from inside to outside by selectively depositing material into a narrow confined space of the integrated circuit.

The method described in this specification can be used for the pore closure of a porous dielectric layer, such as U.S. Patent Application Serial No. 14/464,071, entitled "FLOWABLE DIELECTRIC FOR SELECTIVE ULTRA LOW-K PORE SEALING" (Attorney Case No.: This application is filed concurrently with the present application and is hereby incorporated by reference in its entirety in its entirety in its entirety.

In addition to BEOL applications, these methods can also be used in front end of the line (FEOL) applications. These methods are particularly beneficial for BEOL applications because the catalysts and precursors used are halogen-free, and thereby can be used to fill pores with a flowable membrane without degrading or causing degradation of the underlying metal layer. The metal layer is exposed in the case of a reaction.

Advantages of using halogen-free catalytic deposition include (1) eliminating corrosion of the overall structure, (2) preventing trace levels of halides from incorporating into the dielectric, and (3) reducing the use of unmodified or undoped The cost of the catalyst. The halogen-free organic acid can also be independently transported to control the shrinkage and porosity of the deposited film by controlling the relative proportions of precursor, catalyst, water, and solvent in the final mixture. Furthermore, due to the formation of a hydrophilic surface on the upper surface of the deposited film, the deposition process can be repeated on the same film after the end of a deposition cycle to grow a thicker film. The halogen-free precursors and/or catalysts in the process of the present specification belong to the following two classes: organic acids, and autocatalytic decanes. Organic acid

The deposition of the cerium oxide dielectric film into the pores or spaces can be catalyzed by a halogen-free organic acid and using hydrolysis and condensation reactions. Figure 1 is a depiction of an example of a chemical mechanism for the hydrolysis of an organic ruthenium precursor using an acid catalyst. Hydronium ions are produced in solution, and hydrolysis can occur in aqueous (aqueous) or non-aqueous/non-hydrolyzed solutions using alcohols, solvents, or other chemicals as hydrogen-oxygen (-OH) The source of the bit base.

Figure 1 shows an exemplary S _N 1 mechanism for acid catalyzed hydrolysis of a decane oxide reaction. As shown, in the first step, protonation of the -OR ligand occurs, whereby the hydronium ion is generated by attacking oxygen in one of the ligands on the decane oxide compound by the halogen-free organic acid. Forming an intermediate state of a hydrogen atom having an oxygen atom bonded to the ligand, and generating a micro-positive organic alcohol ROH group on the decane oxide compound. In the next step, during the desorption of the ROH alcohol leaving group and during the formation of the Si-OH bond, the synergistic nucleophilic S _N 1 caused by the H ₂ O water molecules attacks the center of the precursor of the precursor. The resulting compound is a Si(OR) ₃ OH compound, ROH, and the hydronium ion is regenerated. In certain embodiments, not all of the ligands on the Si(OR) ₄ compound react with the hydronium ion. In various embodiments, one or more of the ligands bonded to the center of the crucible are organic groups rather than alkoxides. For example, a ruthenium compound that can be used in place of the decane oxide depicted in Figure 1 can have the formula SiR(OR') ₃ , where R and R' are organic functional groups or other organic chains. The mechanism of Figure 1 can be repeated for other ROH ligands on the decane oxide compound, which can thereby form the sterol or alkyl sterol compound to be used in the subsequent condensation mechanism.

The excited Si—OH groups in the sterol or alkyl sterol compound begin to polycondense and form a —Si—O—Si—mesh structure in which the H ₂ O molecules are co-products with each condensation reaction. Released. In various embodiments, a carbon-doped cerium oxide film is formed after the condensation. For example, various carbon atoms can be embedded in the film due to any unreacted -OR groups or remaining -R groups at the center of the crucible. Condensation results in less branched oligomers and, depending on the situation, may occur via three competing mechanisms: alcoxolation, oxolation, and olation.

The dealcoholization condensation is a reaction, and the bridged oxo group is formed by removing the alcohol molecules by the reaction. This mechanism is essentially the same as hydrolysis, in which a deuterium atom replaces the hydrogen atom entering the group. The following chemical reaction represents an example of a dealcoholization reaction in which M is a metal such as ruthenium:

The dehydration condensation is a reaction in which the bridged side oxy group is formed by removing water molecules by the reaction. Two exemplary mechanisms are provided in Figures 2A and 2B. In FIG. 2A, SiR ₁ (OH) ₃ and SiR ₂ (OH) _{3 are provided} as exemplary alkyl sterols, which are produced by the hydrolysis mechanism described above with respect to FIG. The two compounds react to remove water molecules while forming a –Si–O–Si–mesh structure. The various forms of forming the -Si-O-Si-mesh structure after various cycles between the sterol compounds having various organic groups or -OR ligands are shown, for example. It should be noted that this is a carbon-doped cerium oxide film, and thus R1, R2, and R3 are various organic compounds. Similarly, as shown in Figure 2B, the two-Si(OH) ₃ compound reacts to remove water molecules as the -Si-O-Si- bond is formed. Figure 2B also shows the formation of the -Si-O-Si-network when this reaction is repeated between other -Si(OH) ₃ groups. It should be noted that Figures 2A and 2B depict certain unreacted -OH groups. In the condensation reaction, not all -OH groups may react; however, most of the -OH groups will react to form the -Si-O-Si-network. A general chemical equilibrium model depicting an example of a hydroxylation reaction is shown in Reaction 2:

The hydroxyl group is a reaction, and the bridged side oxy group is formed by removing the solvent molecules by the reaction, and can occur when the sufficient coordination of hydrazine is not achieved. In this case, bridged coordinating hydroxo groups can be formed by removing solvent molecules. Then, depending on the concentration of water in the medium, it can be H ₂ O or ROH.

In certain embodiments, acetic acid is used as the halogen-free organic acid. The acetic acid catalyzed dielectric deposition mechanism can be as follows. First, the ruthenium-containing precursor and acetic acid can be reacted in a hydrolysis or solvolysis reaction for removing alcohol molecules. This mechanism generally maps the above-described S _N 1 hydrolysis mechanism with respect to Figure 1, and can be summarized in Reaction 3 below.

In certain embodiments, the resulting M-OAc compound can undergo subsequent hydrolysis reactions with the alcohol, such that MOH can be formed and the carboxy organic compound removed, as shown in Reaction 4 below.

Whether the reaction causes an M-OAc compound in Reaction 3 or an MOH compound in Reaction 4, the compound can be subjected to condensation by a dealcoholization condensation, dehydration condensation, or a hydroxylation mechanism as described above. For example, the M-OAc compound can undergo the following reactions with the M-OR compound:

As shown in reaction 5a, the condensation reaction removes the carboxylic acid compound having an R ligand, and the M-O-M network structure is formed. In various embodiments, the metal M is tantalum such that a -Si-O-Si-mesh structure is formed.

In certain embodiments, the condensation reaction can occur between two M-OR compounds, resulting in the removal of the ether R-O-R and the formation of the M-O-M network, as shown in Reaction 5b below.

4A is a flow diagram of a method for depositing a dielectric film in accordance with an embodiment of the present disclosure. The dielectric film is deposited on the substrate in the reaction chamber. In some implementations, the dielectric film will be deposited in a confined space, such as a void or gap in a porous dielectric.

The substrate is placed into the reaction chamber. Positioning the substrate to the chamber can involve securing the substrate to the base or other support in the chamber. For this purpose, an electrostatic chuck, a vacuum chuck, or a mechanical chuck can be utilized. In various embodiments, the substrate comprises a plurality of pores and/or gaps, which may be channels, cavities, vias, and the like.

In applications where pores are filled, the porous membrane may comprise mesoporosity and/or microporosity. Mesoporosity generally refers to pore sizes of 2 nm–50 nm, while microporosity refers to pore sizes of less than 2 nm. In a dielectric having interconnected porosity, at least some of the interconnected pores may be sized to continuously have micropores of about angstroms to nanometers, connected to have a diameter of from about nanometers to tens of nanometers. Medium pore size. Although this method can also be used to seal non-connected pores and provide a smooth deposition surface, a particular use in closing the connected pores can be found, leaving the unclosed person to provide a diffusion pathway through the membrane. In various embodiments, the critical dimension of the pores is from about 1 Å to about 1 nm.

In applications where the gap on the substrate is to be filled (e.g., shallow trench isolation), the gap may have a critical dimension of 1 to 50 nm, such as 10 to 30 nm. The critical dimension refers to the width of the opening where the pore or gap is at its narrowest point. In some embodiments, the gap has an aspect ratio between 3:1 and 60:1. The substrate may be a semiconductor substrate such as germanium, silicon-on-insulator (SOI), gallium arsenide, etc., and may include a metallization layer exposed on the surface of the substrate, or may be one or more materials. . Examples of materials include nitrides, oxides, carbides, oxynitrides, carbon oxides, tellurides, and bare bismuth, or other semiconductor materials. Additional examples of materials used in BEOL processing include copper, tantalum, tantalum nitride, titanium, titanium nitride, tantalum, and cobalt.

For applications in which pores are filled, the substrate may comprise a ULK film having a dielectric constant of 2.4 or less. Examples of ULK films include carbon doped oxide (CDO) films, zeolite films, and polymer films. The ULK film can comprise pores to be filled with a flowable dielectric. The substrate can comprise an exposed metal such as an exposed copper wire.

In some implementations, one or more surfaces of the substrate are processed prior to the methods of Figures 4A and 4B. Since the flowable dielectric material has a shorter nucleation delay on the dielectric surface relative to the metal surface, a pretreatment process can be used in some implementations to increase selectivity. One or more pre-treatments can be used to control the surface termination on the substrate to enhance or hinder subsequent flowable dielectric deposition. In some implementations, a pre-treatment is used that interacts differently with the porous dielectric material to be blocked, and with the exposed metal surface, if present. In this way, the selectivity of the flowable dielectric deposit into the pores is increased.

The pretreatment may depend on the particular surface on which the flowable dielectric material will deposit or be prevented from depositing. For deposition on tantalum nitride and tantalum oxide materials, the production of sterol (Si-OH) terminations provides good wetting for the deposition of flowable oxides. In some implementations, the porous dielectric film that has undergone a dielectric constant recovery (k-recovery) process to recover the Si–C bond removed during etching can be pretreated to Several changed to Si-OH terminals.

Used to create a hydrophilic surface to promote wetting (especially for hydrophobic dielectric precursors (eg, carbon-containing dielectric precursors)). The prior treatment is disclosed in U.S. Provisional Patent Application Serial No. 61/895,676, which is incorporated herein by reference. The present invention is incorporated herein by reference. In some implementations, the methods involve exposing the porous dielectric to an oxidizing gas, and in some embodiments, exposing to a hydrogen-containing oxidizing gas. However, for many pore sealing applications, there may be exposed metal surfaces that should not be oxidized. Thus, although oxidation treatment may be used in some implementations to increase the wettability of certain porous materials, in such processes, the oxidation treatment can be avoided.

An example of a useful pre-treatment in a pore-closure application is disclosed in U.S. Patent Application Serial No. 14/464,071, entitled "FLOWABLE DIELECTRIC FOR SELECTIVE ULTRA LOW-K PORE SEALING" (Attorney Docket No.: LAMRP 102/3358) -1US), the application is filed concurrently with the present application, and is incorporated herein by reference.

According to various embodiments, the pre-treatment operation may involve exposure to a plasma, such as a plasma containing hydrogen, oxygen, nitrogen, helium, argon species, or some combination thereof. The plasma can be generated downstream or in situ by a remote plasma generator, an inductively coupled plasma generator, or a capacitively coupled plasma generator, such as an Astron® remote plasma source. In some implementations, the pretreatment can avoid in situ plasma to avoid damaging the porous dielectric layer. In an alternate embodiment, the pre-treatment operation involves exposing the substrate to a pre-treatment chemical in a non-plasma environment. Specific process conditions can vary depending on the implementation. In some of these embodiments, the substrate can be exposed to a pretreatment chemical in the presence of energy from another source of energy, including a source of thermal energy, a source of ultraviolet light, a source of microwaves, and the like. In certain embodiments, the substrate is pretreated with exposure to a catalyst, surfactant, or adhesion promoting chemical in addition to or in place of the pre-treatment operations described above. If so, the previous processing operation can occur in the deposition chamber or can occur in another chamber before the substrate is transferred to the deposition chamber.

Returning to Figure 4A, in operation 402a, the substrate is exposed to a hafnium-containing precursor and a halogen-free organic acid catalyst. In various embodiments, the substrate is also exposed to an oxidant. Sometimes, although not necessarily, there may be an inert carrier gas. In certain embodiments, a liquid injection system is used to introduce the gases. In certain embodiments, the ruthenium containing precursor and oxidant may be introduced via separate inlets or in the mixing tank and/or showerhead just prior to introduction into the chamber. As discussed further below, the catalyst and/or optional dopant can be incorporated into one of the reactants, premixed with one of the reactants, or introduced separately. Solvents or other surfactants can also be added to the process gas. In certain embodiments, the substrate is exposed to the precursor and catalyst when the substrate is exposed to ultraviolet radiation.

In certain embodiments, the ruthenium containing precursor is an alkoxy decane. Alkoxyoxanes which may be used include, but are not limited to, the following: H _x -Si-(OR) _y wherein x = 0-3, x + y = 4, and R is a substituted or unsubstituted alkyl group; ' _x -Si-(OR) _y , wherein x = 0-3, x+y = 4, R is a substituted or unsubstituted alkyl group, and R' is a substituted or unsubstituted alkyl or alkane An oxy or alkoxyalkane group; and H _x (RO) _y -Si-Si-(OR) _y H _x , wherein x = 0-2, x+y = 3, and R is substituted Or unsubstituted alkyl.

Examples of ruthenium-containing precursors include CH ₃ Si(OCH ₂ ) ₃ ; 1-(triethoxydecyl)-2-(diethoxymethyl decyl)ethane (1-(triethoxysilyl)-2- (diethoxymethylsilyl)ethane), 1,2,3,4,5,6-hexamethoxy-1,2,3,4,5,6-hexamethylcyclohexane (1,2,3,4,5 ,6-hexamethoxy 1,2,3,4,5,6-hexamethylcyclohexasilane); 1,2-dimethoxy-1,1,2,2-tetramethyldioxane (1,2-dimethoxy-1, 1,2,2-tetramethyldisilane); 1,4-dioxa-2,3,5,6-tetraoxacyclohexane; 1,4-dioxa-2,3,5,6-tetrasilacyclohexane; BTEOSE, bis-triethoxysilylethane; BTEOSM, bis-triethoxysilylmethane; butasilanes; cyclobutasilane; cycloheptane Cycloheptasilane; cyclohexasilane; cyclooctasilane; cyclopentasilane; decabutaoxycyclopentasilane; diethoxymethylsilane; DES, diethoxysilane; dimethoxymethylsilane; dimethoxy hydrazine (DMOS, dimethoxysilane); dimethyldiethoxysilane; dimethyldimethoxysilane; disilane; dodecamethoxycyclohexasilane ); ethylsilane; heptasilane; HEODS, hexaethoxydisilane; hexaethoxydiazide alkane (HEDS-H, hexaethoxydisilazoxane); hexamethoxydioxane ( HMODS, hexamethoxydisilane); hexamethoxydisilazoxane; hexamethoxydisiloxane; hexasilane; hydrogen silsesquioxane; methyl - hexamethylene dioxetane (HMDS-CH ₃ , methyl hexamethoxydisilazoxane); methyl-diethoxysilane; methyl-dimethoxysilane ; methylsilane; methyl triethoxy orthosilicate (MTEOS, methyltriethoxyorthosilicate); methyl-triethoxysilane (MTES, methyl-triethoxysilane); methyltrimethoxysilane MTMOS, methyltrimethoxysilane; methyl-trimethoxysilane; NMTS, nonamethoxytrisilazoxane; octaethoxycyclobutasilane; Octahydroo POSSTM, Polyhedral Oligomeric Silsesquioxane; octamethoxycyclic sulfoxane (OMCS, octamethoxycyclic silazoxane); octamethoxydodecasiloxane (OMODDS, octamethoxydodecasiloxane); octamethoxy Oxytomane (OMOTS, octamethoxytrisiloxane); octamethyl-1,4 dioxa-2,3,5,6-tetradecylcyclohexane (octamethyl-1,4,dioxa-2,3,5,6 -tetrasilacyclohexane); octamethylcyclotetrasiloxane; Octasilanes; Pentasilanes; SiH ₄ , silane; T8-Hydridospherosiloxane ; tert-butoxydisilane; Si(OAc) ₄ , tetraacetoxysilane; TEOS, tetraethoxysilane; tetraisocyanatesilane Four Tetramethoxysilane; TMOS, tetramethoxysiloxane; tetramethylcyclotetrasiloxane; tetramethylorthosilicate; tetramethylorthosilicate 4MS, tetramethylsilane; tetraoxymethylcyclotetrasiloxane; tetravinyltetramethylcyclotetrasiloxane; tetraethyltetramethylcyclotetrasiloxane; triethoxy decane (SiH(OAc) ₃ , triacetoxysilane); triethoxysilane (TES, triethoxysilane); triethoxysiloxane (TRIES, triethoxysiloxane); trimethoxymethyl decane (TMOMS, trimethoxymethylsilane); trimethoxy decane (TMS or TriMOS, Trimethoxysilane); trimethylmethoxysilane; trimethylmethoxysilane; trimethylethoxysilane; triphenylethoxysilane; trisilane; and tri-tert-butoxy Tri-t-butoxylsilanol. A further example of a ruthenium-containing precursor includes, but is not limited to, the following: silane (SiH ₄ , silane); disilane; trisilane; hexasilane; cyclohexasilane; Alkane, such as methylsilane, and ethylsilane.

In some embodiments, in addition to another precursor (eg, as a dopant), a carbon doped ruthenium precursor is used, or a carbon doped ruthenium precursor is used alone. The carbon doped yttrium precursor may comprise at least one Si—C bond. Carbon-doped cerium precursors that may be used include, but are not limited to, R' _x -Si-R _y , where x = 0-3, x + y = 4, and R is a substituted or unsubstituted alkyl group, And R' is a substituted or unsubstituted alkyl, alkoxy or alkoxyalkyl group; and SiH _x R' _y -R _z wherein x = 1-3, y = 0-2, x+y +z = 4, R is a substituted or unsubstituted alkyl group, and R' is a substituted or unsubstituted alkyl, alkoxy or alkoxyalkyl group.

Examples of carbon doped precursors have been proposed in the foregoing, and further examples include, but are not limited to, 3MS, trimethylsilane, tetramethylsilane, diethoxymethyl decane (DEMS, diethoxymethylsilane), dimethyl dimethoxysilane (DMDMOS, dimethyldimethoxysilane), methyl-triethoxysilane (MTES, methyl-trimethoxysilane), methyl-trimethoxysilane, methyl Methyl-diethoxysilane, methyl-dimethoxysilane, trimethoxymethylsilane, dimethoxymethylsilane, dimethoxymethylsilane, And bis(trimethylsilyl)carbodiimide.

In certain embodiments, an amino decane precursor is used. The aminodecane precursor includes, but is not limited to, H _x -Si-(NR) _y wherein x = 0-3, x + y = 4, and R is an organic hydride group.

Examples of amine decane precursors have been proposed in the foregoing, and further examples include, but are not limited to, BTBAS, bis-tert-butylamino silane or tris(dimethylamino) decane (tris) Dimethylamino)silane).

The halogen-free organic acid catalyst can be a proton donor having a pH between about 1 and about 7, and having a pKa between about 1 and about 6. A good proton donor can be a compound that readily gives its proton/H ⁺ , which results in a higher reaction rate. The pKa is related to the rate of the reaction due to the catalytic nature of the organic acid.

The halogen-free organic acid catalyst comprises 1) an acid comprising nitric acid, phosphoric acid, sulfuric acid; and 2) a carboxylic acid derivative comprising R-COOH, wherein R is a substituted or unsubstituted alkyl group, an aromatic group, an acetamidine group A phenolic group and a R-COOC-R carboxylic anhydride. The carboxylic acid derivatives may have the structure of a general organic structure as follows:

Examples of the halogen-free organic acid catalyst comprising ethylenediaminetetraacetic acid _{(C 10 H 16 N 2 O} 8, ethylenediaminetetraacetic acid), picric acid _{(C 6 H 3 N 3 O} 7), and acetic acid (CH ₃ COOH):

Further examples of organic acids that can be used as catalysts include, but are not limited to, tartaric acid (C ₄ H ₆ O ₆ ), citric acid (C ₆ H ₈ O ₇ ), formic acid (HCOOH), oxalic acid (HO ₂ CCO ₂ H), Sulfonic acid (RS(=O) ₂ -OH), benzoic acid (C ₆ H ₅ CO ₂ H), methanesulfonic acid (CH ₃ SO ₃ H), any other substituted derivative of such acids, or combination. In certain embodiments, certain other non-organic acids may be used, including pyrophosphoric acid (H ₄ P ₂ O ₇ ), phosphoric acid (H ₃ PO ₄ ), and sulfuric acid (H ₂ SO ₄ ). In certain embodiments, a fluorine-containing organic acid may be suitable, such as trifluoromethanesulfonic acid (CF ₃ SO ₃ H), or trifluoroacetic acid (CF ₃ CO ₂ H), but it should be noted that the fluoride anion may cause a substrate Pollution and degradation in the process, and thus may be avoided in other implementations. In various embodiments, the halogen-free organic acid is photosensitive. Photosensitive catalysts can be defined by comparisons in the dark with respect to shrinkage (or other hardening characteristics) of the film under illumination. For example, a reticle pattern applied to an uncured flowable oxide film can be transferred to the thickness profile of the oxide. Preliminary data from the deposition using acetic acid showed sensitivity, compared to the control wafers left under the fluorescent lamp in the clean room, for the wafers held in the dark, observed after thermal hardening Degrees have less 38% - 45% shrinkage. No such phenomenon was observed by the same test conducted on the film deposited by the chlorine catalyst. In the embodiment in which operation 402a is performed, the reaction rate can be increased when the substrate is exposed to UV radiation and a photosensitive halogen-free organic acid is used.

Examples of oxidizing agents include, but are not limited to, ozone (O ₃ ), peroxides containing hydrogen peroxide (H ₂ O ₂ ), oxygen (O ₂ ), water (H ₂ O), alcohols (such as methanol, ethanol, and Isopropanol), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrous oxide (N ₂ O), carbon monoxide (CO), and carbon dioxide (CO ₂ ).

According to various embodiments, the catalyst and other reactants can be introduced simultaneously or in a particular order. For example, in certain embodiments, an acidic compound can be introduced into the reactor at the beginning of the deposition process to catalyze the hydrolysis reaction, followed by introduction of a basic compound near the end of the hydrolysis step to inhibit the hydrolysis reaction, followed by catalytic condensation. reaction. The acid or base is introduced by general transport or rapid transport or "puffing" to rapidly catalyze or inhibit the hydrolysis or condensation reaction during the deposition process. The pH adjustment or change by blowing can occur at any time during the deposition process, and different processing timings and sequences can result in different films having the properties required for different applications. Several examples of catalysts have been proposed above.

The solvent can be non-polar or polar and protonic or aprotic. The solvent can be combined with the choice of dielectric precursor to improve miscibility in the oxidant. The non-polar solvent comprises an alkane and an alkene; the polar aprotic solvent comprises acetone and an acetate; and the polar protic solvent comprises an alcohol and a carboxyl compound.

Examples of solvents that may be employed include alcohols such as isopropanol, ethanol, and methanol; or other compounds that are miscible with the reactants, such as ethers, carbonyls, nitriles. Solvents are optional and, in certain embodiments, may be introduced individually or with an oxidant or another process gas. Examples of solvents include, but are not limited to, methanol, ethanol, isopropanol, acetone, acetonitrile, dimethylformamide, and dimethyl hydrazine, tetrahydrofuran (THF), dichloromethane, hexane, benzene, toluene, iso-heptane Alkane, and diethyl ether. In certain embodiments, the solvent can be introduced by blowing or by conventional means prior to the other reactants. In certain embodiments, particularly where the precursor and oxidant have low miscibility, the solvent can be introduced by blowing the solvent into the reactor to promote hydrolysis.

Sometimes, although not necessarily, there may be an inert carrier gas. For example, nitrogen, helium, and/or argon can be introduced into the chamber along with one of the above compounds.

Other possible reactions involving bis-, tri-, and tetra-acid catalysts include ligand exchange which results in the formation of a chelating intermediate compound or transition state, and the chelating intermediate compound or transition state The hydrolysis and condensation are ultimately carried out to produce the desired oxide network. However, such compounds may condense more slowly than monodentate intermediates.

During operation 402a, conditions in the chamber cause the ruthenium containing compound to react with the oxidant to form a flowable film on the substrate. The formation of the film can be assisted by the presence of a catalyst. The method is not limited to a particular reaction mechanism, for example, the reaction mechanism may comprise a condensation reaction, a vapor phase reaction to produce a vapor phase product that condenses, a condensation of one or more reactants prior to the reaction, or a combination thereof.

The conditions of the reaction allow the ruthenium-containing compound and the co-reactant to undergo a condensation reaction to condense on the surface of the substrate to form a flowable film. In certain embodiments, the reaction occurs in a dark or non-plasma environment, meaning that the substrate is not exposed to the plasma during the deposition phase of the process (operations 402a and 404). In other embodiments, the reaction occurs in the presence of a plasma that is generated distally or in a deposition chamber. A method of depositing a flowable film for gap filling via a plasma-enhanced chemical vapor deposition (PECVD) process is described in U.S. Patent Application Serial No. 12/334,726, the disclosure of which is incorporated herein This specification is incorporated by reference.

The chamber pressure can be between about 1 and 200 Torr, and in some embodiments, between 10 and 75 Torr. In a particular embodiment, the chamber pressure is about 10 Torr.

The partial pressure of the process gas component can be characterized by the vapor pressure and range of the constituents, where Pp is the partial pressure of the reactant and Pvp is the vapor pressure of the reactant at the reaction temperature. Precursor partial pressure ratio (Pp/Pvp) = 0.01-1, for example: 0.01-0.5 Oxidant partial pressure ratio (Pp/Pvp) = 0.25-2, for example: 0.5-1 Solvent partial pressure ratio (Pp/Pvp) = 0 -1, for example: 0.1-1

In certain embodiments, the process gas is characterized by a precursor partial pressure ratio between 0.01 and 0.5, an oxidant partial pressure ratio between 0.5 and 1, and a solvent between 0.1 and 1. (if any) partial pressure ratio. In the same or other embodiments, the process gas is characterized by the following: Oxidant: Precursor partial pressure ratio (Pp oxidant / Pp precursor) = 0.2-30, for example: 5-15 Solvent: oxidant partial pressure ratio (Pp solvent / Pp oxidant) = 0-30, for example: 0.1-5

In certain embodiments, the process gas is characterized by an oxidant between about 5 and 15: a precursor partial pressure ratio, and a solvent between about 0.1 and 5: an oxidant partial pressure ratio.

In certain embodiments, the substrate temperature is between about -20 ° C and 100 ° C. In certain embodiments, the temperature is between about -20 ° C and 30 ° C, such as between -10 ° C and 10 ° C. Pressure and temperature can be varied to adjust deposition time; high pressure and low temperature are generally beneficial for rapid deposition. High temperatures and low pressures will result in slower deposition times. Therefore, increasing the temperature may involve increasing the pressure. In one embodiment, the temperature is about 5 ° C and the pressure is about 10 Torr. The exposure time depends on the reaction conditions and the pore size. According to various embodiments, the deposition rate is from about 100 angstroms/minute to 1 micrometer/minute. Under these conditions, the substrate is exposed to the reactants for a period of time sufficient to deposit a flowable film in the pores. In certain embodiments, the deposition time is from 0.1 to 5 seconds.

The amount of coagulation is controlled by its partial pressure relative to the saturated vapor pressure of the reactants, which is fixed for a given deposition temperature. The dependency of the fill rate on the critical dimension can be adjusted by varying the partial pressure. In this way, the selectivity can be adjusted to improve the ability to be deposited only in the pores or as otherwise required. For example, at a partial pressure of a sufficiently low dielectric precursor, no condensation or deposition occurs in any size feature. As the partial pressure increases, the dielectric precursor condenses in the small features, and as the partial pressure increases, deposition occurs in the increased feature size. In this way, it is possible, for example, to block the deposition of the ULK film in the etched trench of 20 nm while allowing the ULK film to deposit in the pores.

In certain implementations, a continuous film can be allowed to deposit on the surface of the porous dielectric film. In this regard, the partial pressure is controlled to allow the film to be formed in trenches of critical dimensions. Depending on the implementation, the partial pressure may be fixed to an appropriate extent or may be raised after deposition in the pores. In certain embodiments, a terminating agent such as a decylating agent can be introduced to cap the surface and stop the reaction. An example includes "(dimethylamino)trimethylnonane" which methylates the surface methyl group and stops the reaction. Further details of the process for the closure of the pores are set forth in U.S. Patent Application Serial No. 14/464,071, the entire disclosure of which is hereby incorporated by reference. The application is filed concurrently with the present application and is incorporated herein by reference.

As shown in operation 404, the flowable film is thereby deposited on the surface of the substrate. In void and gap fill applications, the substrate is exposed to process gases for a period of time sufficient to deposit a flowable film to fill at least some of the pores and gaps. This deposition process typically forms a soft gel-like film with good flow characteristics and provides consistent filling. These methods are not limited to gap or pore filling, however, and can also be used to deposit blanket films. For example, as mentioned above, a continuous film may be allowed to form on the surface of the porous dielectric.

After the flowable film has been deposited on the substrate, in operation 406, the flowable film at the initial deposition is optionally hardened to form the desired dielectric layer. In certain implementations, when the film is still in a flowable, reactive state, it is first exposed to the plasma species. Produced, for example, from a process gas having a main component of hydrogen (H ₂ ), helium (He), nitrogen (N ₂ ), or argon (Ar) as discussed in U.S. Provisional Patent Application Serial No. 61/895,883. Plasma. In such cases, plasma exposure will generally occur at substantially the same temperature as when deposited, such that the film does not undergo heat activated curing. Such plasma exposure can be effective to densify the film if the flowable film in the pores is still flowable. In certain embodiments, the plasma exposure is effective to drive the overall deposition reaction to near completion to form the flowable film.

When the film is in a thermally reactive state, block 406 of Figure 4 can be performed in addition to or instead of exposing the film. In some embodiments, block 406 can involve post-deposition hardening that can occur at temperatures that are much higher than the deposition temperature. Such hardening can be further crosslinked and the terminal groups in the film, such as -OH and -H groups, are removed, and the density and hardness of the film are further enhanced. Depending on the composition of the film, the hardening can also cause the film to shrink.

The film can be cured by simple thermal annealing, exposure to downstream or direct plasma, exposure to ultraviolet or microwave radiation, or exposure to another source of energy. The thermal annealing temperature can be above 300 ° C (depending on the allowable thermal budget). This treatment can be carried out in an inert environment (Ar, He, etc.) or in an environment that may be reactive. An oxidizing environment (using O ₂ , N ₂ O, O ₃ , H ₂ O, H ₂ O ₂ , NO, NO ₂ , CO, CO _{2 ,} etc.) may be used, however, in some cases, nitrogen-containing compounds are to be avoided. Nitrogen is prevented from being incorporated into the film. In other embodiments, the environment may be used nitride (using _{N 2, N 2 O, NH} 3, NO, NO 2 , etc.), and allows a considerable amount of nitrogen incorporated into the film. In some embodiments, a mixture of oxidizing and nitriding environments is used. Carbonaceous chemicals can be used to incorporate a certain amount of carbon into the deposited film. According to various embodiments, the composition of the densified film depends on the initial deposited film composition and the processing chemistry. For example, in certain embodiments, the Si(OH) _x pre-deposited gel is converted to a SiO network structure using oxidative plasma hardening. In other embodiments, the Si(OH) _x pre-deposited gel is converted to a SiON network. In other embodiments, the Si(NH) _x pre-deposited gel is converted to a SiON network.

In some embodiments, the film is treated by exposure to a remote or direct (inductive or capacitive) plasma. This can cause the flowable film to be converted from top to bottom into a densified solid film. The plasma can be inert or reactive. Helium and argon plasma are examples of inert plasmas; oxygen and water vapor plasmas are examples of oxidizing plasmas (for example, such as removing carbon as desired). Hydrogen-containing plasma can also be used. An example of a hydrogen-containing plasma is a plasma produced from a mixture of hydrogen (H ₂ ) and a diluent (e.g., an inert gas). The temperature during plasma exposure is generally above about 25 °C. In certain embodiments, oxygen or an oxygen-containing plasma is used to remove carbon. In certain embodiments, the temperature during plasma exposure can be lower, such as -15 °C to 25 °C.

The temperature during hardening can be distributed from 0 to 600 ° C, and at a particular processing stage, the upper end of the temperature range is determined by the thermal budget. In certain embodiments, the temperature is distributed from about 200 °C to 550 °C. The pressure can range from 0.1 to 10 Torr and the high oxidant pressure is used to remove carbon.

Other annealing processes including rapid thermal processing (RTP) may also be used to cure and shrink the film. Higher temperatures and other energy sources can be used if an ectopic process is used. The ectopic treatment includes high temperature annealing (700-1000 ° C) in an environment such as N ₂ , O ₂ , H ₂ O, Ar, and He. In certain embodiments, the ectopic treatment involves exposing the film to ultraviolet radiation, for example, in a UV thermal processing (UVTP) process. For example, a temperature of 100 ° C or higher (eg, 100 ° C - 400 ° C) combined with UV exposure can be used to harden the film. Other flash hardening processes including RTP or laser annealing can also be used.

In some embodiments, operation 406 is not performed. In certain embodiments, the deposited film undergoes a post-treatment with an excess of oxidant such that the oxidant (eg, water) continues to flow into the chamber to react with the deposited flowable film. This post treatment allows the reaction to continue to form a -Si-O-Si- bond by removing any residual ligand.

Due to the sensitivity of various organic acid catalysts, the photolysis effect can help catalyze the hydrolysis and condensation of such compounds to form a flowable film, while mitigating or eliminating subsequent processing in operation 406. In this way, a flowable film deposited using a photosensitive catalyst and light can be used to purify the –Si—O—Si–mesh structure without substantial post-treatment. For example, thermal hardening can be used instead of UV hardening. In the absence of oxygen, the reaction of an alkoxydecane with an organic acid produces a photoluminescent material by introducing carbon impurities into the ruthenium network. The thickness and shrinkage are adjusted by exposure to light, which indicates that the deposited film is photosensitive and can affect the mechanism of the hydrolysis reaction. In certain embodiments, a transient metastable transient phase may be formed in the reaction between the ruthenium containing precursor and the photosensitive catalyst, which may be a chelate complex. Autocatalytic decane

The deposition of the cerium oxide dielectric film into the pores and interstices can be catalyzed by autocatalytic decane undergoing hydrolysis and condensation reactions. The various autocatalytic decanes can be amine decanes. In certain embodiments, an amine decane having one or more secondary amines is used.

Figure 3 shows an example of the mechanism of the hydrolysis reaction of the self-catalyzed decylamine. In the first step, electrons from the nitrogen in one of the amine groups are bonded to hydrogen atoms on the water molecule, thereby causing protonation of the -NHR' ligand and formation of a negative -OH hydroxide group. This intermediate state has a hydrogen atom bonded to the nitrogen of the -NHR' ligand, thereby forming a -NH ₂ R' amine group with a micro-positive charge. In the next step, the synergistic nucleophilic S _N 1 caused by the -OH hydroxide group attacks the ruthenium center of the compound, accompanied by the cleavage of the NH ₂ R amine leaving group. The final step of displaying the liberated amine compound R'NH2 and SiR (NHR ') ₂ OH. Such steps may be repeated for each of -NHR 'alkoxy group on silicon to form Si (OH) ₃ R. In certain embodiments, one or more of the ligands on the autocatalytic decane may not react. The meaning of autocatalytic decane is that the compound has a catalyzed group attached to decane such that the amino decane can undergo hydrolysis with water or a proton donor to form the desired intermediate product prior to condensation.

Amines can be hydrolyzed in water to produce a sterol-rich product in an alkaline medium (e.g., pH > 7) resulting in a rapidly catalyzed condensation to produce the desired oxide network. The excited Si-OH groups begin to polycondense and form a -Si-O-Si-mesh structure in which H ₂ O molecules are released as a co-product with each condensation reaction. Since ammonia or alkylamine will be evolved during the deposition process and removed as a by-product, no nitrogen will remain in the resulting sol-gel film by selecting a suitable autocatalytic decane.

The resulting sterol-rich product can undergo a condensation mechanism to form a -Si-O-Si-mesh structure. The condensation mechanism can be the condensation mechanism described above with respect to Figure 2A, or the condensation mechanism described above with respect to Figure 2B. In certain embodiments, certain organic ligands on the sterol compound may remain bonded to the decane throughout the condensation process to produce a carbon-doped cerium oxide compound. The condensation mechanism can comprise dealcohol condensation, dehydration condensation, hydroxylation, or any combination thereof.

4B is a flow diagram of a method of depositing a dielectric film, in accordance with an embodiment of the disclosure. A substrate containing gaps or pores is placed into the reaction chamber or chamber. Any of the methods described above with respect to Figure 4A can be used to place the substrate to the chamber.

In operation 402b, the substrate is exposed to autocatalytic decane and an oxidant. Sometimes, although not necessarily, there may be an inert carrier gas. In certain embodiments, a liquid injection system is used to introduce the gases. In certain embodiments, the cerium-containing compound and the oxidizing agent can be introduced via separate inlets or in the mixing tank and/or showerhead just prior to introduction into the chamber. As discussed further below, the catalyst and/or optional dopant can be incorporated into one of the reactants, premixed with one of the reactants, or introduced separately. Alcohol can also be added to the process gas.

An example of an autocatalytic decane comprises an amino decane. The amino decane that can be used includes, but is not limited to, the following general chemical formula: H _x -Si-(NR) _y , where x = 0-3, x + y = 4, and R is an organic hydride group. For example, the structure of the autocatalytic decane can be as follows:

In the above structure, R1, R2, R3, and R4 may be the same or different N-alkylamines. Certain autocatalytic decanes may have at least one N-alkylamine attached to the oxime or directly coordinated to the oxime, wherein the other organofunctional group is attached to the oxime. A total of up to 4 different ligands (including alkylamines) can be selected. Some examples of such different ligands that may be selected are: N-alkylamines; N,N dialkylamines; alkoxy groups; alkyl groups; alkenyl groups; alkynyl groups; aryl groups;

Examples of autocatalytic decanes include amino decanes such as dimethylaminotrimethylsilane, dimethylaminotriethylsilane, and bisdimethylaminodiethylsilane. ):

Further examples of autocatalytic decanes include, but are not limited to, 1,1,1,3,3,3-hexamethyldioxane (HDMS, (CH ₃ ) ₃ SiN(H)Si(CH ₃ ) ₃ ) ; Bis(diethylamino)silane; bis(trimethylsilyl)carbodiimide; bis-third butyl decane (BTBAS, bis- Tert-butylamino silane); cyclic azasilanes; hexamethyldisilazane; methylsilatrane; silatrane Tetrakis(dimethylamino)silane; tris(dimethylamino)silane; trisylamine (TSA, trisilylamine); trimethylamine Trisdimethylamino methylsilane; trisdimethylamino silane; trismethylamino methylsilane; trismethylamino silane; bisdimethylamino Bisdimethylamino dimethylsilane; bisdimethylamino ethoxy methyl Silane); methylamino diethoxy methyl silane; trismethylamino vinyl silane; bismethylamino divinyl silane; Bisdimethylamino ethoxy vinyl silane; acetoxysilanes; and combinations thereof.

In certain embodiments, ethoxylated decane can be used as the ruthenium containing precursor. In certain embodiments, the reaction can begin with the deposition of a precursor based on an ethenoxy group, followed by an amine based catalyst or an amine decane, such as any of the above. Examples of precursors based on ethoxylated groups include, but are not limited to, tetraoxydecane, and decane:

Examples of oxidizing agents include any of the oxidizing agents described above with respect to Figure 4A. In certain embodiments, the distal plasma generator can supply an activated oxidant species. One or more dopant precursors, catalysts, inhibitors, buffers, surfactants, solvents, and other compounds can be introduced.

The autocatalytic decane and oxidant can be introduced simultaneously or in a specific order. In certain embodiments, a solvent can be used. The solvent may have any of the foregoing properties relating to the organic acid catalyzed flowable film, and may be any of the foregoing organic acid catalyzed flowable films. In certain embodiments, an inert carrier gas is present. Any of the reactants (self-catalyzing decane, decane-containing precursor, oxidizing agent, solvent, catalyst, etc.) used in operation 402a of Figure 4A or operation 402b of Figure 4B, alone or in combination with one or more other reactants. It can be introduced before the remaining reactants. Again, in certain embodiments, one or more of the reactants may continue to flow into the reaction chamber after the remaining reactants are shut off.

In certain implementations, the amine decane can also be used as a dielectric constant recovery agent to process ULK or other low k films prior to operation 404 or concurrently with operation 404. The dielectric constant repellent is discussed in U.S. Patent Application Serial No. 14/464,071, the entire disclosure of which is incorporated herein by reference in its entirety in The application is filed concurrently with the present disclosure and is incorporated herein by reference.

The autocatalytic decane can be introduced together with the process gas of the oxidant and the solvent as described above with respect to the partial pressure described in FIG. 4A. The exposure time and chamber pressure and temperature can also be any of those described above with respect to Figure 4A.

As shown in operation 404 of Figure 4B, a flowable film is thereby deposited on the surface of the substrate. The flowable film can be deposited to a thickness as described above with respect to Figures 4A and 4B at a deposition rate similar to that described above with respect to Figures 4A and 4B. In many embodiments, the flowable film may still contain some residual amine groups. In various embodiments, the flowable film can be a carbon doped yttrium oxide film.

In operation 406, any of the techniques or methods described above with respect to FIG. 4A can be used to harden the deposited film. In certain embodiments, the -OH peak may occur in the Fourier transform infrared spectrum due to the reaction of the amine groups remaining on the unhydrolyzed or unhardened precursor with oxygen in the air. However, since the -OH group in the film deposited before hardening is small, the UV hardening operation can be shortened or excluded. If UV hardening is carried out, this UV hardening will remove all residual amine groups. In certain embodiments, the deposited film is subjected to a post treatment with an excess of oxidant to continue to form a -Si-O-Si- bond by removing any residual ligand (eg, an amine group). In various embodiments, operation 406 may not be performed depending on the autocatalytic decane used to deposit the flowable film. In some embodiments, only thermal hardening is performed in operation 406.

In some embodiments, UV hardening is not used. In particular, when a secondary amine is used as the autocatalytic decane, the solvent reacts with the secondary amine to remove most of the -OH, and thus thermal annealing can be used to remove any residual -OH groups. The thermal annealing temperature can be above 300 ° C (depending on the allowable thermal budget). This treatment can be carried out in an inert environment (Ar, He, etc.) or in an environment that may be reactive. The reaction of the tertiary amine with the solvent described in this specification can form a film having a ligand which may not be removed using only thermal hardening or annealing. When the tertiary amine is reacted with the solvent, UV hardening can then be used to remove the -OH group. device

The method of the present invention can be performed on a wide variety of modules. Any device (including HDP-CVD reactor, PECVD reactor, sub-atmospheric CVD reactor) installed for dielectric film deposition, any chamber for CVD reactions, and for pulsed deposition ( These methods are carried out on the chambers of PDL, pulsed deposition layers.

Such devices can take many different forms. In general, the device will contain one or more modules, each of which contains a chamber or reactor (sometimes containing multiple stations) that covers one or more wafers and is suitable for wafer processing. . For processing, each chamber can cover one or more wafers. The one or more chambers maintain the wafer in a defined single or multiple position (with or without motion such as rotation, vibration, or other disturbances). When processing, each wafer is supported in place by a susceptor, wafer chuck, and/or other wafer support equipment. For certain operations in which the wafer will be heated, the device may include a heater, such as a heating plate.

In practice, the pretreatment can be performed in a module that is the same or different from the flowable dielectric deposit. FIG. 5 shows an illustrative tool assembly 560 that includes a wafer transfer system 595 and load lock chamber 590, a flowable deposition module 570, and a pre-deposition processing module 580. Additional modules may also be included, such as a post-deposition processing module, and/or one or more additional deposition modules 570 or hardening modules 580.

Modules for pre-treatment or hardening include SPEED or SPEED Max, INOVA Reactive Preclean Module (RPM), Altus Ultimate Fill (EFx, ExtremeFill) module, Vector Extreme pre-processing module (for Plasma, UV, or IR pretreatment or hardening), SOLA (for UV pretreatment or hardening), and Vector or Vector Extreme modules. These modules can be attached to the same architecture as the flowable deposition module. Also, any of these modules can be on different architectures. The system controller can be connected to any or all of the components of the tool; its configuration and connections can vary based on the particular implementation. An example of a system controller is described below with reference to FIG.

Figure 6 shows an example of a deposition chamber for flowable dielectric deposition. The deposition chamber 600 (also referred to as a reactor, or reactor chamber) includes a chamber housing 602, a top plate 604, a baffle 606, a showerhead 608, a pedestal post 624, and is provided for flowable dielectric deposition A closed volume seal 626. Wafer 610 is supported by chuck 612 and insulating ring 614. Chuck 612 includes RF electrode 616 and resistive heating element 618. The chuck 612 and the insulating ring 614 are supported by the base 620 and include a platform 622 and a base post 624. The base post 624 is interfaced with a base transmission (not shown) through a seal 626. The base post 624 includes a platform coolant line 628 and a pedestal purge line 630. The showerhead 608 includes a common reactant gas chamber 632 and a precursor gas chamber 634, which are individually supplied by a common reactant gas line 636 and a precursor gas line 638. The common reactant gas line 636 and the precursor gas line 638 can be heated prior to reaching the showerhead 608 in the region 640. Although a dual flow chamber is described in this specification, a single flow chamber may also be used to direct gas into the chamber. For example, the reactants can be supplied to the showerhead and can be mixed in a single gas chamber prior to introduction into the reactor. Both 620' and 620 refer to the pedestal, but refer to their position at the descending (620) and lifting (620'), respectively.

The chamber is provided with (or connected to) a gas delivery system for delivering reactants to the reactor chamber 600. The gas delivery system can supply one or more common reactants (eg, an oxidant, including water, oxygen, ozone, peroxides, alcohols, etc.) to the chamber 610, which can be supplied separately, or It is supplied by mixing with an inert carrier gas. The gas delivery system can also supply one or more dielectric precursors (e.g., triethoxysilane) to the chamber, the dielectric precursors can be supplied separately, or inert The carrier gas is mixed and supplied. The gas delivery system can also be configured to deliver one or more processing reagents for cleaning the plasma processing reactor as described in this specification. For example, for plasma processing, hydrogen, argon, nitrogen, oxygen, or other gases may be delivered.

The deposition chamber 600 acts as a closed environment in which deposition of flowable dielectric can occur. In many embodiments, the deposition chamber 600 features a radially symmetric interior. Reducing or eliminating the offset of the radially symmetric interior will help ensure that the flow of reactants occurs radially on the wafer 610 in a balanced manner. Interference with reactant flow caused by radial asymmetry can cause more or less deposition on certain areas of wafer 610 than in other areas, which can create undesirable changes in wafer uniformity. .

The deposition chamber 600 contains several major components. Structurally, deposition chamber 600 can include a chamber housing 602 and a top plate 604. The top plate 604 is configured to be attached to the chamber housing 602 and provides a closed interface between the chamber housing 602 and the gas distribution manifold/spray head, electrodes, or other modular device. Different top plates 604 can be used with the same chamber housing 602 depending on the particular equipment requirements of the process.

The chamber housing 602 and top plate 604 can be machined from aluminum (e.g., 6061-T6), although other materials can be used, including other grades of aluminum, aluminum oxide, and other non-aluminum materials. The use of aluminum allows for easy machining and handling, and the improved heat transfer characteristics of aluminum can be achieved.

The top plate 604 can be provided with a resistive heating cladding to maintain the top plate 604 at the desired temperature. For example, the top plate 604 can be provided with a resistive heating cladding to maintain the top plate 604 at a temperature between -20 ° C and 100 ° C. Instead of a resistive heating cladding or as an alternative to a resistive heating cladding, an alternative heating source can be used, such as circulating the heated liquid via top plate 604 or providing a resistive heater cartridge to top plate 604.

The chamber housing 602 can be provided with a resistive heater cartridge configured to maintain the chamber housing 602 at a desired temperature. Other temperature control systems can also be used, such as circulating heated fluid through holes in the walls of the chamber. During the flowable dielectric deposition, the temperature of the interior walls of the chamber can be controlled to a temperature between -20 ° C and 100 ° C. In some implementations, the top plate 604 may not include a heating element and may rely on thermal conduction of thermal energy from the resistance heater cartridge of the chamber as an alternative to maintaining the desired temperature. Various embodiments may be configured to control the temperature of the interior walls of the chamber and other surfaces on which deposition is not desired (eg, pedestals, baffles, and sprinklers) to a temperature that is about 10 ° C to 40 higher than the target deposition process temperature. °C. In some implementations, the elements can be maintained at temperatures above this range.

During processing, the inner wall of the reactor can be maintained at a temperature that is elevated relative to the temperature at which wafer 610 is maintained, by actively heating and maintaining the temperature of deposition chamber 600. During the deposition of the flowable film, the temperature of the inner wall of the reactor is raised relative to the temperature of the wafer, and the condensation of the reactants on the inner wall of the deposition chamber 600 can be minimized. If the coagulation of the reactants occurs on the inner wall of the deposition chamber 600, the condensate may form a deposited layer on the inner wall, which is undesirable.

In addition to or in lieu of heating chamber housing 602 and/or top plate 604, a hydrophobic coating can be applied to some or all of the wetted surface of deposition chamber 600, as well as other components having a wetted surface (eg, pedestal 620, Insulation ring 614, or platform 622) to prevent condensation. Such hydrophobic coatings may be resistant to process chemistry and processing temperature ranges (eg, processing temperatures ranging from -20 ° C to 100 ° C). Certain hydrazine-based and fluorocarbon based hydrophobic coatings (eg, polyethylene) may not be compatible with an oxidizing (eg, plasma) environment and may not be suitable. Nanotechnology-based coatings having superhydrophobic properties can be used; such coatings can be ultra-thin and, in addition to having hydrophobic properties, can also have oleophobic properties that allow such coatings It prevents the condensation and deposition of many reactants and can be used for flowable film deposition. An example of a suitable superhydrophobic coating is titanium dioxide (TiO ₂ ).

The deposition chamber 600 can also include a remote plasma source port that can be used to introduce the plasma process gas into the deposition chamber 600. For example, a remote plasma source can be provided as a means of introducing process gases into the reaction zone without the need to transport process gases via showerhead 608. In certain embodiments, the distal plasma species can be delivered via the showerhead 608.

In plasma processing, direct plasma or remote plasma can be used. In the previous example, the process gas could be delivered via a showerhead. The showerhead 608 can include a heating element or a thermal conduction path that maintains the temperature of the showerhead within acceptable process parameters during processing. If direct plasma is used, the showerhead 608 can also include an RF electrode for creating a plasma environment within the reaction zone. The pedestal 620 can also include an RF electrode for creating a plasma environment within the reaction zone. Such a plasma environment can be created by using capacitive coupling between the supply electrode and the ground electrode; the supply electrode (which can be coupled to the plasma generator) can correspond to the RF electrode in the showerhead 608. The ground electrode can correspond to the RF electrode of the pedestal. Alternative configurations are also allowed. The electrodes can be configured to produce a 13.56 MHz range, a 27 MHz range, or, more broadly, an RF energy between 50 KHz and 60 MHz. In some embodiments, a plurality of electrodes can be provided, each configured to generate RF energy in a particular frequency range. In embodiments where the showerhead 608 includes a powered RF electrode, the chuck 612 can include or be a grounded RF electrode. For example, chuck 612 can be a grounded aluminum electrode that can result in enhanced susceptor throughout the susceptor-chuck-to-wafer interface due to the high thermal conductivity of aluminum relative to other materials (eg, ceramic) Cooling effect.

FIG. 7 is a schematic illustration of another example of an apparatus 700 suitable for implementing the method of the claimed invention. In this example, device 700 can be used for flowable dielectric deposition, and for in situ or remote plasma pre-treatment or post-treatment. Apparatus 700 includes a processing chamber 718 and a remote plasma generator 706. Processing chamber 718 includes a base 720, a showerhead 714, a system controller 722, and other components described below. In the example of FIG. 7, device 700 also includes RF generator 716, although in some embodiments, the RF generator may not be present.

Processing reagents (e.g., H2, He, Ar, N2) can be supplied to the remote plasma generator 706 from various sources of processing reagents (e.g., source 702). The source of the treatment reagent can be a storage tank containing one reagent or a mixture of reagents. Furthermore, equipment level reagent sources can be used. The processing reagent mixture can then flow into processing chamber 718 via connection line 708 where it is dispensed via showerhead 714 to process wafers or other substrates on susceptor 720.

The chamber 718 can include a sensor 724 for sensing various materials and their individual concentrations, pressures, temperatures, and other process parameters, and providing information of the reactor conditions to the system controller 722 during the process. Examples of chamber sensors that can be monitored during processing include a mass flow controller, a pressure sensor (eg, a pressure gauge), and a thermocouple located in the susceptor. The sensor 724 can also include an infrared detector or optical detector to monitor the presence of gas in the chamber. The volatile by-products and other excess gas systems are removed from chamber 718 via an outlet 726 that includes a vacuum pump and valve.

In some embodiments, system controller 722 is used to control process conditions for deposition, and/or pre- or post-treatment. System controller 722 will typically include one or more memory devices and one or more processors. The processor can include a CPU or computer, an analog and/or digital input/output connection, a stepper motor controller board, and the like. In general, there may be a user interface coupled to system controller 722. The user interface can include a graphical software display that displays a screen, the device and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, and the like.

In some embodiments, system controller 722 can also control all activities during the process, including gas flow rate, chamber temperature, and generator processing parameters. System controller 722 executes system control software that includes sets of instructions for controlling the timing of a particular process, the mixture of gases, the chamber pressure, the temperature of the susceptor (and substrate), and other parameters. The system controller 722 can also control the concentration of various process gases in the chamber by adjusting valves, liquid delivery controllers, and MFCs in the delivery system, and flow restriction valves and discharge lines. System controller 722 executes system control software that includes a set of instructions to control the timing of a particular process, the flow rate of gases and liquids, chamber pressure, substrate temperature, and other parameters. In some embodiments, other computer programs stored on a memory device coupled to the controller can be used. In some embodiments, system controller 722 controls the transfer of substrates into and out of various components of the device.

Computer code for controlling the process in the order of the process can be written in any conventional computer readable stylized language: for example, a combination language, C, C++, Pascal, Fortran or other languages. The compiled object code or script is executed by the processor to execute the job identified in the program. The system software can be designed or configured in many different ways. For example, various chamber component subprograms or control items can be programmed to control the operation of the chamber components required to perform the process. Examples of programs or program sections for this purpose include process gas control codes and pressure control codes.

In some embodiments, system controller 722 is part of a system that can be part of the above examples. Such systems may include semiconductor processing equipment including one or more processing tools, one or multiple chambers, one or more stages for processing, and/or specific processing elements (wafer pedestals, gas flow systems, etc.). The systems can be integrated with the electronic device to control the operation of the semiconductor wafer or substrate before, during, and after processing. These electronic devices may be referred to as "controllers" which may control various components or sub-components of one or more systems. Depending on the needs of the process and/or the type of system, system controller 722 can be programmed to control any of the processes disclosed in this specification, including processing gas delivery, temperature settings (eg, heating and/or cooling). , pressure setting, vacuum setting, power setting, RF (radio frequency) generator setting, RF matching circuit setting, frequency setting, flow rate setting, fluid delivery setting, position and operation setting, access tool and connection to a specific system or Wafer transfer of other transfer tools and/or load lock chambers that interface with a particular system interface.

Broadly speaking, controller 722 can be defined as an electronic device having various integrated circuits, logic, memory, and/or software that receive commands, send commands, control operations, allow cleaning operations, allow end point measurements, and the like. The integrated circuit may include a firmware in the form of firmware for storing program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and/or execution. One or more microprocessors or microcontrollers of program instructions (eg, software). The program instructions can be instructions that are transmitted to controller 722 in various individual settings (or program files) that define operational parameters for performing a particular process on a semiconductor wafer, or for a semiconductor wafer, or for a system. In some implementations, the operational parameter can be part of a formulation defined by a process engineer for one or more layers, materials, metals, oxides, ruthenium, ruthenium dioxide, surfaces, circuits And/or one or more processing steps are completed during manufacture of the die of the wafer.

In some implementations, controller 722 can be part of a computer or connected to a computer that is integrated with the system, connected to the system, or connected to the system via a network, or a combination thereof. For example, controller 722 can be located in the "cloud" or all or part of a fab host computer system that can allow remote access to wafer processing. The computer can achieve remote access to the system to monitor the current manufacturing process, view past manufacturing operations history, view trends or performance metrics from multiple manufacturing operations, and change current processing parameters to set processing Steps to continue the current process or start a new process. In some instances, a remote computer (eg, a server) can provide process recipes to the system over a network, which can include a local area network or the Internet. The remote computer can include a user interface that can be parameterized and/or configured for input or programming, and the parameters or settings are then transmitted from the remote computer to the system. In some examples, controller 722 receives an instruction in the form of a material that specifies parameters for each of the processing steps to be performed during one or more operations. It should be appreciated that the parameters may be specific to the type of process to be performed, and the type of tool (the controller 722 is configured to interface with or control the tool interface). Thus, as noted above, the controller 722 can be dispersed, for example by including one or more separate controllers that are connected together through a network and operate toward a common target, such as the processes described in this specification and control. An example of a separate controller for such purposes may be one or more integrated circuits on the chamber that are located at one of the remote end (eg, at the platform level, or part of the remote computer) or A plurality of integrated circuit connections are combined to control the process on the chamber.

An exemplary system can include a plasma etch chamber or module, a deposition chamber or module, a rotary rinsing chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel etch chamber, or Module, physical vapor deposition (PVD) chamber or module, chemical vapor deposition (CVD) chamber or module, atomic layer deposition (ALD) chamber or Modules, ALE, atomic layer etch chambers or modules, ion implantation chambers or modules, track chambers or modules, and may be associated with the manufacture and/or production of semiconductor wafers or Any other semiconductor processing system used therein, but is not limited thereto.

As described above, depending on the process steps (or complex process steps) to be performed by the tool, the controller 722 can communicate with one or more of the following: one or more other tool circuits or modules, other tool components, cluster tools, Other tool interfaces, traction tools, proximity tools, tools throughout the factory, main computer, another controller, or the location of tools that carry or carry wafer containers away from the semiconductor manufacturing plant and/or Tool for material transfer.

The controller parameters are related to process conditions, such as the timing of each operation, the pressure inside the chamber, the substrate temperature, and the process gas flow rate. These parameters are provided to the user in the form of a recipe and can be entered using the user interface. Signals for monitoring the process may be provided by analog and/or digital input connections of system controller 722. The signal for controlling the process can be output on the analogy of the device and the digital output connection.

The disclosed methods and apparatus can also be implemented in systems including lithography and/or patterned hardware for semiconductor fabrication. Furthermore, the disclosed method can be practiced in a lithography and/or patterning process prior to or after the disclosed method. The apparatus/process described in this specification can be used in conjunction with, for example, a lithographic patterning tool or process for fabricating or manufacturing semiconductor devices, displays, LEDs, photovoltaic panels, etc., generally (although not necessarily), such Tools/processes will be used together or included in a common manufacturing facility. The lithographic patterning of the film typically involves some or all of the following operations (each operating with a number of suitable tools): (1) applying a photoresist to a workpiece (eg, a substrate) using a spin coating or spray coating tool. (2) using a heating plate, or a heating furnace, or a UV hardening tool to harden the photoresist; (3) exposing the photoresist to visible light, or UV light, or x-ray light using a tool such as a wafer stepper; (4) developing the photoresist using a tool such as a wet cleaning station to selectively remove the photoresist, thereby patterning it; (5) transferring the photoresist pattern to the lower layer by using a dry or plasma-assisted etching tool In the film or workpiece; and (6) the photoresist is removed using a tool such as an RF or microwave plasma photoresist stripper. Experimental experiment 1

An experiment was conducted to compare the shrinkage and evaluate the sensitivity of the organic acid catalyst. Acetate and a ruthenium containing precursor (AP LTO 400) were used to deposit the film on the wafer. The wafer was held in the dark and then the wafer was thermally cured at 375 °C. The second film is deposited on the wafer using acetic acid and a ruthenium containing precursor (AP LTO 400). The wafer was left in a clean room with a fluorescent lamp for a period of time that was the same length as the previous film was kept in the dark, after which the wafer was thermally hardened at 375 °C.

The results show that the film exhibits photosensitivity characteristics such that after thermal hardening, the film has less film for the wafer held in the dark than the wafer that is left under the fluorescent lamp of the clean room. 38%-45% shrinkage. The deposited film also exhibits a change in thickness over the portion of the wafer covered by the visible light cap of the wafer transfer cassette in which the wafer is stored. The wafer is held in the uppermost slot of the wafer transfer cassette.

The film deposited by the catalysis of chlorine does not exhibit a change in shrinkage rate with respect to the film left in the dark relative to the film remaining under the fluorescent lamp. The results show that acetic acid as a catalyst exhibits a catalytic effect of sensitization which promotes a reaction between a catalyst, an oxidant, and a ruthenium-containing precursor to deposit a flowable film having improved properties. Experiment 2

An experiment was conducted to compare the spectra of an uncured film deposited by a halogen-free organic acid catalyst and an uncured infrared spectroscopy (FTIR) deposited from a halide acid catalyst.

Using chlorotriethoxydecane as the halide acid catalyst, and methyltriethoxydecane as the ruthenium containing precursor (AP LTO 430® from Air Products and Chemicals, Inc.), and water as the oxidant, A flowable film is deposited on the wafer. The reactants are introduced into the reaction chamber for a duration of about 220 seconds. The film was deposited to a thickness of about 3500 angstroms at a temperature of -0.5 ° C and a chamber pressure of 45 Torr. The deposited film system was analyzed using its FTIR spectrum. The spectrum of the membrane catalyzed by the halide acid is shown in Figure 8, as shown by curve 801.

A flowable film is deposited on the wafer using acetic acid as the halogen-free organic acid catalyst, AP LTO 400 as the ruthenium-containing precursor, and water as the oxidant. The reactants are introduced into the reaction chamber for a duration of about 375 seconds. The film was deposited to a thickness of about 3500 angstroms at a temperature of -0.5 ° C and a chamber pressure of 45 Torr. The deposited film system was analyzed using its FTIR spectrum, which is shown in Figure 8, as curve 803.

As shown, the curve associated with the membrane catalyzed by the organic acid shows a peak of the -OH bond at about 3300 cm ^-1 , which can be attributed to the uncured nature of the deposited film. The curve of the membrane catalyzed by the halide acid has a lower peak of the -OH bond. It should be noted that at about 1127 cm ^-1 , the curve of the film catalyzed by the organic acid has a peak which is higher than the peak of the curve of the film catalyzed by the halide acid, which is related to -Si-O-Si – The cage key structure of the key is associated. At about 965 cm ^-1 , the curve of the film catalyzed by the organic acid also has a higher peak associated with the Si–O bond in the Si–OH bond. The peak integral is normalized to the thickness to match the trend of the peak height.

Figure 9 provides an FTIR spectrum of a film (903) catalyzed by an organic acid and a film (901) catalyzed by a halide acid after UV hardening is performed on the two films. During UV curing, for example, the reaction to replace all -CH ₃ -OH group. As shown in Fig. 9, the curve of the film catalyzed by the organic acid showed that almost no -OH group appeared. Since the deposited film is similar to the film catalyzed by the halide acid, the film is deposited without using a catalyst which may generate any halide which will react with the underlying metallization layer in the wafer, so the result shows that The use of halogen-free organic acid catalysts is a viable and effective method. Furthermore, without being bound by a particular theory, the rate constant can be increased due to the sensitivity of the various acid catalysts such that when the wafer is exposed to light, any organic groups can leave the center of the crucible and assist in the formation of -Si– O–Si–mesh structure. Experiment 3EXPERIMENT 3

Figure 10 provides an FTIR spectrum of film 1001 catalyzed by uncured halide acid and film 1005 derived from uncured aminooxane. The film 1005 derived from the uncured amino decane exhibits an N-H composition at 3400 cm ^-1 and exhibits a strong frequency associated with CH ₂ at ~2900 cm ^-1 and -1400 cm ^-1 . The frequency does not appear in the film 1001 catalyzed by the uncured halide acid. In the region corresponding to the frequency of –Si–O–Si–, a higher peak intensity is observed at ~1050 cm ^-1 , indicating that the membrane catalyzed by the alkylamine can be compared to the membrane catalyzed by the halide It has an oxide network structure with a higher degree of condensation.

Figure 11 provides the FTIR spectrum of film 1101 and aminodecane-derived film 1103 catalyzed by a halide acid after hardening the films by UV. As shown, the films have nearly identical FTIR spectra, meaning that the films are identical after UV hardening. This shows that the use of an amino decane precursor is an effective alternative that excludes any possible reaction between the layer on the substrate and the halogen. Experiment 4

An experiment was conducted to evaluate the uncured film deposited using the amino decane precursor. The membrane derived from the unhardened amino decane containing unhydrolyzed precursor traces, under ambient conditions, eventually hydrolyzes the coordinating amine ligand to the -OH group. The FTIR spectrum in Figure 12 shows an uncured film having the frequency of Si–N and N–H bonds from the decylamine remaining in the precursor (individually 890 cm ^-1 and 3407 cm ^-1 ) when the film The Si–N and N–H bonds are eventually hydrolyzed to Si–OH (wideband at ~3500 cm ^-1 ) while remaining in the surrounding environment. Experiment 5

Table 1 below shows the refractive index, dielectric constant (k), carbon concentration, and deposition rate of a flowable film deposited using an organic acid catalyst, a halide-containing catalyst, and an amino decane precursor. Table 1 characteristics of the film in conclusion

Although the foregoing embodiments have been described in detail for the purposes of clarity of the invention, it is apparent that certain changes and modifications may be implemented within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and devices of the present embodiments. Therefore, the present embodiments are to be considered as illustrative and not restrictive

402a‧‧‧ operation
402b‧‧‧ operation
404‧‧‧ operation
406‧‧‧ operation
560‧‧‧Tool combination
570‧‧‧Flowable deposition module/deposition module
580‧‧‧Predeposition processing module/hardening module
590‧‧‧Load lock room
595‧‧‧ wafer transfer system
600‧‧‧Sedimentation chamber/reactor/reactor chamber
602‧‧‧Case shell
604‧‧‧ top board
606‧‧ ‧ baffle
608‧‧‧Sprinkler
610‧‧‧ wafer
612‧‧‧ chuck
614‧‧‧Insulation ring
616‧‧‧RF electrode
618‧‧‧Resistive heating element
620‧‧‧Base (down position)
620'‧‧‧Base (lifting position)
622‧‧‧ platform
624‧‧‧Base pillar
626‧‧‧Seal
628‧‧‧ platform coolant line
630‧‧‧Pedestrian flushing pipeline
632‧‧‧Common reactant gas chamber
634‧‧‧Precursor air chamber
636‧‧‧Common reactant gas pipeline
638‧‧‧Precursor gas pipeline
640‧‧‧Area
700‧‧‧ Equipment
702‧‧‧Reagent source/source
706‧‧‧Remote plasma generator
708‧‧‧Connected pipeline
714‧‧‧Sprinkler
716‧‧‧RF generator / in-situ plasma generator (figure)
718‧‧‧Processing chamber/chamber
720‧‧‧Base
722‧‧‧System Controller/Controller
724‧‧‧ sensor
726‧‧‧Export
801‧‧‧Spectral spectral curve of membrane catalyzed by unhardened halide acid
803‧‧‧Spectral curve of membrane catalyzed by unhardened organic acid
901‧‧‧Spectral curve of membrane catalyzed by UV-hardened halide acid
903‧‧‧Spectral curve of membrane catalyzed by UV-hardened organic acid
1001‧‧‧Spectrum curve of membrane catalyzed by unhardened halide acid
1005‧‧‧ Spectral curve of a film derived from unhardened amino decane
1101‧‧‧Spectral curve of membrane catalyzed by UV-hardened halide acid
1103‧‧‧Spectral curve of membranes derived from UV-hardened amino decane
1207‧‧‧ Spectral curves of membranes derived from uncured amino decane after 3 days in air
Spectral curve of a film derived from uncured amino decane at the initial deposition of 1209‧‧

1, 2A, 2B, and 3 are schematic illustrations of chemical mechanisms in accordance with various embodiments.

4A and 4B are flow diagrams of a method of depositing a film, in accordance with various embodiments.

Figure 5 is a schematic illustration of an apparatus for performing an operation, in accordance with various embodiments.

6 and 7 are schematic illustrations of chambers for performing various methods, in accordance with various embodiments.

8-12 are spectra of a Fourier transform infrared spectroscopy (FTIR) of a deposited film, which is compared with a film deposited according to various embodiments.

1001‧‧‧Spectrum curve of membrane catalyzed by unhardened halide acid

1005‧‧‧ Spectral curve of a film derived from unhardened amino decane

Claims (20)

A method of depositing a film on a semiconductor substrate, the method comprising: introducing a process gas comprising a ruthenium-containing precursor, an oxidant, and a halogen-free acid catalyst compound into a reaction chamber; and forming a condensable flowable film on the condensed The substrate is exposed to the process gas under conditions on the substrate, wherein the chemical reaction forming the flowable film comprises a S _N 1 hydrolysis mechanism and condensation. A method of depositing a film on a semiconductor substrate according to the first aspect of the invention, wherein the halogen-free catalyst compound is selected from the group consisting of acetic acid and a photosensitive organic acid catalyst. A method of depositing a film on a semiconductor substrate according to the first aspect of the patent application, wherein the oxidizing agent is selected from the group consisting of water, ozone, and peroxide. A method of depositing a film on a semiconductor substrate as in the first aspect of the patent application, wherein the ruthenium-containing precursor and the oxidant are introduced into the reaction chamber via separate inlets. A method of depositing a film on a semiconductor substrate according to the first aspect of the patent application, wherein the halogen-free catalyst compound is introduced into the reaction chamber independently of the ruthenium-containing precursor and the oxidant. A method of depositing a film on a semiconductor substrate according to the second aspect of the patent application, wherein the photosensitive organic acid catalyst is selected from the group consisting of sulfonic acid, picric acid, tartaric acid, citric acid, ethylenediaminetetraacetic acid, pyrophosphoric acid, and the like. a group of substituted derivatives, and combinations thereof. A method of depositing a film on a semiconductor substrate as in claim 2, wherein the substrate is exposed to the process gas when the substrate is exposed to UV radiation. The method of depositing a film on a semiconductor substrate according to any one of claims 1 to 7, further comprising treating the flowable film. A method of depositing a film on a semiconductor substrate as in claim 8 wherein treating the flowable film comprises exposing the flowable film to the oxidant and exposing the film to a thermal or plasma environment. A method of depositing a film on a semiconductor substrate according to any one of claims 1 to 7, wherein the flowable film encloses a pore having an average critical dimension of between about 1 Å and about 1 nm. A method of depositing a film on a semiconductor substrate, the method comprising: introducing a process gas comprising a ruthenium-containing precursor, an oxidant, and a halogen-free catalyst compound into a reaction chamber; and forming a condensable flowable film on the substrate The substrate is exposed to the process gas under conditions, wherein the catalyst compound is selected from the group consisting of sulfonic acid, picric acid, tartaric acid, citric acid, ethylenediaminetetraacetic acid, pyrophosphoric acid, and combinations thereof. A method of depositing a film on a semiconductor substrate, as in claim 11, wherein the flowable film comprises a carbon-doped cerium oxide film. A method of depositing a film on a semiconductor substrate, the method comprising: introducing a process gas comprising a ruthenium-containing precursor and an oxidant into a reaction chamber; and, under the condition that the condensed flowable film is formed on the substrate, The substrate is exposed to the process gas, wherein the ruthenium-containing precursor is a halogen-free autocatalytic amino decane compound, and a chemical reaction in which the flowable film is formed comprises an amine group on the amino decane compound and the oxidant The mechanism of hydrolysis, and condensation. A method of depositing a film on a semiconductor substrate as claimed in claim 13 wherein the germanium-containing precursor is halogen-free. The method of depositing a film on a semiconductor substrate as claimed in claim 13 or 14 further comprises treating the flowable film by exposing the flowable film to the oxidizing agent. A method of depositing a film on a semiconductor substrate as claimed in claim 13 or 14, wherein the chemical structure of the ruthenium-containing precursor comprises at least one N-alkylamine group. The method of depositing a film on a semiconductor substrate according to claim 16 , wherein the chemical structure of the germanium-containing precursor further comprises at least one ligand selected from the group consisting of N-alkylamines; N, N a group consisting of a dialkylamine; an alkoxy group; an alkyl group; an alkenyl group; an alkynyl group; an aryl group; A method of depositing a film on a semiconductor substrate as claimed in claim 13 or 14, wherein the flowable film encloses an aperture having an average critical dimension of between about 1 Å and about 1 nm. A method of depositing a film on a semiconductor substrate, the method comprising: introducing a process gas containing a halogen-free germanium-containing precursor and an oxidant into a reaction chamber; and forming a condensable flowable film on the substrate And exposing the substrate to the process gas, wherein the halogen-free ruthenium-containing precursor is selected from the group consisting of dimethylaminotrimethyl decane, dimethylaminotriethyl decane, and bisdimethylamino Diethyldecane, trimethylaminomethyl decane, trimethylaminomethyl decane, trimethylamino decane, bisdimethylamino dimethyl decane, bisdimethylamino ethoxy Methyl decane, methylaminodiethoxymethyl decane, trimethylamino vinyl decane, bismethylaminodivinyl decane, bisdimethylamino ethoxy divinyl decane a group consisting of decyloxydecane, and combinations thereof. The method of depositing a film on a semiconductor substrate according to claim 19, further comprising treating the flowable film by exposing the flowable film to the oxidant.