Cyclic amino compounds for low-k silylation

0001background Insulating films with low permittivity (low-k) are very much needed for semiconductor manufacturing (see, for example, International Technology Roadmap for Semiconductors, Interconnect chapter, 2007 edition). Low-k films are typically created by introducing pores containing air or other gases with a dielectric constant close to 1 into a matrix material with a dielectric constant in the range 2.0-3.0. The effective permittivity of the resulting porous membrane is typically less than 2.2.

0002The low-k matrix material is typically a hydrogenated carbon-doped silicon oxide (SiCOH), where the free surface is a silicon-bonded methyl group (CH).₃) Terminates. The treatment process, such as etching or chemical mechanical polishing, efficiently removes methyl terminations, leaving either dangling bonds or hydroxyl groups (Si-OH). As a result, the membrane becomes more hydrophilic and can easily absorb moisture. This in turn results in an increase in permittivity, to this extent depending on the intensity of the damaging process.

0003Another effect of carbon deprivation is its effect on critical size. For example, the etching process used to form trenches in low-k films will tend to leave carbon-poor trench walls. Subsequent wet stripping or cleaning processes can further widen this trench and reduce future size, further exacerbating the problem.

0004One solution to this problem is to repair the membrane by restoring carbon atoms with a silylating agent. Several groups of compounds, especially alkoxysilanes, chlorosilanes, and aminosilanes, have been used as silylating agents for low-k repair. Of these, alkoxysilanes have the lowest reactivity, but have the advantage that their chemical properties are perfectly compatible with SiCOH membranes.

0005Chlorosilanes are difficult to handle due to their high reactivity with atmospheric moisture and their tendency to form hydrochloric acid (HCl) as a silylation reaction by-product. HCl can be problematic for metal membranes that reside elsewhere in the circulation.

0006The use of aminosilanes for low-k repair has been shown in several sources. In U.S. Pat. No. 6,395,651, Smith et al. Claimed a nanoporous silica dielectric film treated with a surface modifier, such as hexamethyldisilazane (HMDS), and how to treat it with said surface modifier. It is described in the range of. The authors show that various methods of exposing the exemplary membrane to HMDS resulted in a hydrophobic membrane surface, but based on water droplet contact angle experiments, the untreated membrane remained hydrophilic. .. In a further example, in US Pat. No. 7,029,826, Hacker et al. Contacted a damaged silica dielectric film with a surface modifier, such as methyltriacetoxysilane (MTAS), to make the damaged film hydrophobic. The method of imparting sex is described in the claims. US Pat. No. 7,345,000 describes in the claims a method of treating a dielectric film by exposing it to a treated compound and an alkylsilane, wherein the treated compound is preferably HMDS. Chlorotrimethylsilane (TMCS), trichloromethylsilane (TCMS), and combinations thereof are listed.

0007U.S. Pat. No. 7,179,758, assigned to IBM (International Business Machines Corporation), considers compounds with two functional groups to be preferred over their monofunctional analogs. This is because, in theory, a bifunctional molecule can react with two adjacent Si-OH groups, and a monofunctional compound can react with only one Si-OH group. However, it has also been suggested that a post-silylation annealing step be used to "condensate" the remaining Si-OH groups to form new Si-O-Si bonds. IBM's exemplary processing process suggests that the bifunctional molecule bis (dimethylamino) dimethylsilane (BDMADMS) provides better hydrophobicity than the monofunctional molecule HMDS. ..

0008Examination of the above references separately or in combination reveals that reactive compounds with at least one Si-N bond in the active site are arguably the most effective for surface modification of silica-based membranes. This concept compared several trimethylsilyl- (TMS) donors with silanol groups on the surface of silica gel particles for their reactivity, K in the Journal of Liquid Chromotography, 11 (16), 3375-3384 (1988). It was concluded in a study by McMurtrey. The results of this study show that trimethylsilyl-imidazole (TMSI), which has a cyclic functional group containing nitrogen, is associated with all of the above compounds, as well as others known in the art, such as trimethylsilyldimethylamine (TMSDMA). In comparison, it suggests that it was more effective for this surface reaction. The licensed patents referenced above actually list TMSI as a treatment compound for either surface modification or dielectric repair, but so far nitrogen. The field of cyclic molecules contained remains unexplored in the art.

0009Overview Equation R₃The silylated compound of SiL is disclosed. Here, each R is independently selected from the group consisting of H, methyl, and ethyl; L is selected from the group consisting of 1,2,3-triazole, piperidine, 1-methylpiperazine, pyrrolidine, and pyrazole. Is a nitrogen-containing ring; one nitrogen in the nitrogen-containing ring is directly attached to the Si atom. This silylated compound has a total concentration of metal contaminants of less than 10 ppmw. The disclosed compounds may include one or more of the following aspects: The compound may be selected from the group consisting of trimethylsilylpyrrolidine, trimethylsilylpyrazole, trimethylsilyl-1,2,3-triazole, trimethylsilylpiperidine, and trimethylsilyl-4-methylpiperazine; Total concentration of metal contaminants less than 1ppmw; Boiling point below about 200 ° C; and / or -Boiling point of about 100 ° C to about 200 ° C.

0010Cyrilized drug delivery devices are also disclosed. This device has an inlet and outlet conduits of formula R₃It comprises a canister containing a silylating agent with SiL, where each R is independently selected from the group consisting of H, methyl, and ethyl; L is 1,2,3-triazole, piperidine, A nitrogen-containing ring selected from the group consisting of 1-methylpiperazine, pyrrolidine, and pyrazole; one nitrogen in the nitrogen-containing ring is directly attached to the Si atom. The device to be disclosed may include one or more of the following aspects: -The total concentration of metal contaminants of the silylating agent is less than 10ppmw. The silylating agent is selected from the group consisting of trimethylsilylpyrrolidine, trimethylsilylpyrazole, trimethylsilyl-1,2,3-triazole, trimethylsilylpiperidine, and trimethylsilyl-4-methylpiperazine; The end of the inlet conduit is located above the surface of the silylating agent and the end of the exit conduit is located below the surface of the silylating agent; and The end of the inlet conduit is located below the surface of the silylating agent and the end of the exit conduit is located above the surface of the silylating agent.

0011A method for repairing the dielectric film is also disclosed, in which the dielectric film is introduced into the chamber. Equation R₃A repair agent with SiL was introduced into the chamber, where each R was independently selected from the group consisting of H, methyl, and ethyl; L was 1,2,3-triazole, piperidine, 1-methyl. A nitrogen-containing ring selected from the group consisting of piperazine, pyrrolidine, and pyrazole; one nitrogen in the nitrogen-containing ring is directly attached to the Si atom. The repair agent is brought into contact with the dielectric film. The method of disclosure may include one or more of the following aspects: -Heating the dielectric film after introduction into the chamber and before introduction of the repair agent; -React the repair agent with the dielectric film for a suitable period following the contact step; Anneal the dielectric film following the repair agent reaction step; The repair agent is selected from the group consisting of trimethylsilylpyrrolidine, trimethylsilylpyrazole, trimethylsilyl-1,2,3-triazole, trimethylsilylpiperidine, and trimethylsilyl-4-methylpiperazine; and -The total concentration of metal contaminants in the repair agent is less than 10ppmw.

0012Notation and nomenclature Throughout the description and claims below, we use several abbreviations, symbols and terms, including: The abbreviation "HMDS" refers to hexamethyldisilazane; the abbreviation "MTAS" Refers to methyltriacetoxysilane; the abbreviation "TMCS" refers to chlorotrimethylsilane; the abbreviation "TCMS" refers to trichloromethyl; the abbreviation "BDMADMS" refers to bis (dimethylamino) dimethylsilane; the abbreviation "TMS" refers to trimethylsilyl. ((CH₃)₃-Si-); Abbreviation "TMSI" refers to trimethylsilylimidazole; Abbreviation "TMSDMA" refers to trimethylsilyldimethylamine; Abbreviation "ppmw" refers to percentage by weight; Abbreviation "ppb" refers to billions by weight The abbreviation "MIM" refers to metal-insulator-metal (the structure used in capacitors); the abbreviation "DRAM" refers to dynamic random access memory; the abbreviation "FeRAM" refers to strong dielectric random access memory Abbreviation; abbreviation "CMOS" refers to complementary metal oxide semiconductor; abbreviation "UV" refers to ultraviolet; abbreviation "RF" refers to high frequency; abbreviation "BOE" refers to buffer oxide etching; abbreviation "ER" Refers to the etching rate; the terms "monofunctional silylated compound", "repairing agent", "repairing agent", "silylating agent", "silylated compound", and "silylated compound" are of the formula R.₃Used interchangeably to refer to compounds with SiL, where each R is independently selected from the group consisting of H, methyl, and ethyl; L is 1,2,3-triazole, A nitrogen-containing ring selected from the group consisting of piperidine, 1-methylpiperazine, pyrrolidine, and pyrazole; one nitrogen in the nitrogen-containing ring is directly attached to the Si atom.

0013To further understand the nature and subject matter of the invention, the following detailed description presented in combination with the accompanying drawings should be referred to. In the accompanying drawings, similar elements are given similar or similar reference numbers.

0014<figref num="1">FIG. 1 is a side view of one embodiment of the silylated drug delivery device disclosed herein.</figref><figref num="2">FIG. 2 is a side view of a second embodiment of the silylated drug delivery device disclosed herein.</figref>

0015Description of preferred embodiments Non-limiting embodiments of methods, devices and compounds that can be used in the manufacture of semiconductors, photovoltaic cells, LCD-TFTs, or flat panel type devices are disclosed herein.

0016In the silylation process, the use of bifunctional compounds may not be advantageous and, in fact, may leave reactive ends on the membrane, which either improves the dielectric constant or leaves a pathway for significant moisture absorption. Will.

0017Our preliminary studies suggest that monofunctional silylated compounds are similar to or better than their polyfunctional analogs for the restoration of permittivity. The first test was performed using the following compounds with one, two, and three reactive groups, respectively. Tritrimethylethoxysilane Didimethyldiethoxysilane Methyltriethoxysilane They were repaired by exposing the damaged membrane to each of these three compounds in the vapor phase within a vacuum tube furnace system. For at least these three species, the results suggest that having one reactive group provides a dielectric constant recovery similar to that of two or three reactive species.

0018Our results are in contrast to those of US Pat. Nos. 7,179,758 (Chakrapani) and 7,029,826 (Hacker), which show that polyfunctional silylating agents provide better results than monofunctional agents. Although not wishing to be bound by theory, Applicants have found that the substrates examined in previous studies were very severely damaged by large amounts of silanol in close proximity to each other on the surface, but the more realistic surface is relatively We speculate that isolated silanols may not be significantly damaged and therefore may be repaired more efficiently by monofunctional repair agents.

0019Other monofunctional silylated compounds that may exhibit enhanced silylation capacity are of formula R₃Has SiL, where each R is independently selected from the group consisting of H, methyl, and ethyl; L is 1,2,3-triazole, piperidine, 1-methylpiperazine, pyrrolidine, and pyrazole. It is a nitrogen-containing ring selected from the group consisting of; one nitrogen in the nitrogen-containing ring is directly bonded to the Si atom. Preferably, at least two of R are methyl.

0020Without being bound by theory, the applicant believes that the cyclic structure of these monofunctional silylated compounds reduces steric hindrance. This ring prevents the hydrocarbon groups attached to the nitrogen atom from rotating to a position where they can block the interaction of nitrogen with silanol groups on the surface, thereby silyling these molecules. Make it very effective as a hydrocarbon. Preferably, the nitrogen-containing ring is saturated.

0021However, regardless of the above theory, not all nitrogen-containing ring structures have been found to be effective as L components. Neither pyrrole nor 1,2,4-triazole provides suitable repair of damaged membranes, as shown in Table 2 below. Applicants have not yet found a suitable theory to explain the lack of effect of these molecules.

0022Illustrative preferred molecules include:<chemistry num="1"><img id="000002" he="183" wi="159" file="JP5705751B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0023Preferably, the monofunctional silylated compound has high volatility to facilitate its delivery to the processing chamber in the vapor phase for vapor phase treatment. If liquid phase treatment is used, the volatility should be low enough to be easily delivered as a liquid, but sufficient to facilitate the removal of any unreacted silylating agent by evaporative drying after treatment. Should be high. For vapor phase delivery, the boiling point of the silylating agent is preferably less than about 200 ° C. For liquid phase delivery, the boiling point is preferably about 100 ° C to about 200 ° C. For example, trimethylsilylpiperidin has a boiling point of about 166 ° C, trimethylsilylpyrrolidine has a boiling point of about 144 ° C, and trimethylsilyl1,2,3-triazole has a boiling point of about 163 ° C (all at atmospheric pressure). ), All of these are within the preferred range.

0024Synthesis method The molecules to be disclosed can be synthesized by conventional methods, such as the scheme below:<chemistry num="2"><img id="000003" he="107" wi="159" file="JP5705751B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0025The reaction can be carried out under an inert atmosphere, for example, with running dry nitrogen. Starting material¹RNH and²R₃Si-N¹R is commercially available.

0026Preferred purity In order to avoid contamination of the dielectric film to be repaired, it is important that the monofunctional silylated compound is free of contaminants, especially metal contaminants known to be particularly undesirable in the dielectric film. .. Metal contaminants include elements of the Group IA-IIIA or I-VIIIB of the Periodic Table. Preferably, the total concentration of metal contaminants in the compound should be less than 10 ppmw (per million by weight), more preferably less than 1 ppmw. For example, the standard value of the target metal content is shown in Table 1 at 130 ppbw (weight billion percent).<tables num="1"><img id="000004" he="178" wi="142" file="JP5705751B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0027In general, the metal content of interest can be reached by distillation using known methods. Metallic components in the structure of the distillation system should be minimized and should not be carefully allowed to leak at all. New distillation systems will generally require operational adjustments at 100% reflux before starting the collection of distilled products.

0028Cyrilized chemical delivery device The monofunctional silylated compound can be delivered to the semiconductor processing tool by the disclosed silylated drug delivery device. 1 and 2 show two embodiments of the disclosed silylated drug device 1.

0029FIG. 1 is a side view of one embodiment of the silylated drug delivery device 1. In FIG. 1, the disclosed monofunctional silylated compound 10 is housed in a container 20 having two conduits, an inlet conduit 30 and an outlet conduit 40. Those skilled in the art of precursors will recognize that the container 20, inlet conduit 30, and outlet conduit 40 are manufactured to prevent leakage of gaseous monofunctional silylated compound 10 even at high temperatures and pressures. Will.

0030The container is fluidly connected to other components of the semiconductor processing tool via valves 35 and 45. Preferably, the container 20, inlet conduit 30, valve 35, outlet conduit 40, and valve 45 are made of 316L EP or 304 stainless steel. However, those skilled in the art will appreciate that other non-reactive materials can also be used in the teachings herein and that the corrosive monofunctional silylated compound 10 requires the use of more corrosion resistant materials such as Hastelloy or Inconel. Will admit that there is.

0031In FIG. 1, the end 31 of the inlet conduit 30 is located above the surface 11 of the monofunctional silylated compound 10, while the end 41 of the exit conduit 40 is located above the surface 11 of the monofunctional silylated compound 10. It is located below. In this embodiment, the monofunctional silylated compound 10 is preferably in liquid form. An inert gas, such as, but not limited to, nitrogen, argon, helium, and mixtures thereof may be introduced into the inlet conduit. The inert gas pressurizes the container 20 so as to push the liquid monofunctional silylated compound 10 into the outlet conduit 40 and into a member of the semiconductor processing tool (not shown). Vaporizers can be mentioned as semiconductor processing tools, which are carriers such as helium, argon, nitrogen or mixtures thereof to deliver steam to the chamber where the wafer to be repaired is installed and the processing takes place in the vapor phase. Converts a liquid monofunctional silylated compound 10 into vapor with or without a gas or carrier gas. Alternatively, the liquid monofunctional silylated compound 10 may be delivered directly to the wafer surface as a jet or aerosol.

0032FIG. 2 is a side view of the second embodiment of the silylated chemical delivery device 1. In FIG. 2, the end 31 of the inlet conduit 30 is located below the surface 11 of the monofunctional silylated compound 10, while the end 41 of the exit conduit 40 is located on the surface 11 of the monofunctional silylated compound 10. It is located above. FIG. 2 further comprises any heating element 25 capable of increasing the temperature of the monofunctional silylated compound 10. In this embodiment, the monofunctional silylated compound 10 may be in solid or liquid form. Inert gases such as, but not limited to, nitrogen, argon, helium, and mixtures thereof are introduced into the inlet conduit. The inert gas forms bubbles and passes through the monofunctional silylated compound 10, and carries a mixture of the inert gas and the vaporized monofunctional silylated compound 10 to the outlet conduit and the member of the semiconductor processing tool.

0033Both Figures 1 and 2 include valves 35 and 45. Those skilled in the art will recognize that valves 35 and 45 may be in open or closed positions to allow flow through conduits 30 and 40, respectively.

0034If the monofunctional silylated compound 10 is in the form of vapor, or if sufficient vapor pressure is present above the solid / liquid phase, then device 1 of either FIG. 1 or 2 is present. Simpler devices with one conduit terminating above the surface of any solid or liquid can also be used. In this case, the monofunctional silylated compound 10 is delivered in the form of vapor through the conduit 30 or 40, respectively, by simply opening valve 35 in FIG. 1 or valve 45 in FIG. The device 1 may be maintained at a temperature suitable for providing sufficient vapor pressure to deliver the monofunctional silylated compound 10 in the form of vapor, for example by the use of any heating element 25.

0035Although FIGS. 1 and 2 disclose two embodiments of the silylated drug delivery device 1, those skilled in the art will monofunctionalize both the inlet and outlet conduits 40 without departing from the disclosure herein. It will be appreciated that the sex silylated compound 10 can be placed above or below the surface 11. Further, the inlet conduit 30 may be a filling port. Finally, one of ordinary skill in the art will use the monofunctional silylated compounds disclosed to other delivery devices, such as the ampoules disclosed in WO 2006/059187 to Jurcik et al., Without departing from the teachings herein. Will allow delivery to semiconductor processing tools.

0036How to repair In the disclosed repair method, the disclosed molecule is brought into contact with a dielectric film to restore carbon atoms to the film. Those skilled in the art will recognize that the method of treating silica-based membranes described herein is not limited by conditions or specific groups of hardware specified in detail. Without departing from the spirit of the disclosed treatment methods, large differences in sample exposure conditions, such as temperature, time, pressure, and flow rate, will apply to the molecules to be disclosed. Similarly, the equipment used to expose a sample to the disclosed molecule can be diverse without departing from the disclosed method.

0037The disclosed dielectric film repair methods include the damaged dielectric film and Equation R.₃It involves introducing a repair agent with SiL into the chamber, where each R is independently selected from the group consisting of H, methyl, and ethyl; L is 1,2,3-triazole, piperidine. , 1-Methylpiperazin, pyrrolidine, and pyrazole, a nitrogen-containing ring selected from the group; one nitrogen in the nitrogen-containing ring is directly attached to the Si atom. The repair agent is brought into contact with the damaged dielectric film.

0038The chamber is used to control the exposure environment of the sample. The substrate and the dielectric film may optionally be heated to a certain temperature by an external energy source, such as a conductive or radioactive source. The repair agent can be introduced into the chamber in either the liquid or vapor phase. The repair agent is allowed to react with the dielectric film for a period suitable for fully or partially restoring the properties of the film. Optionally, following the repair agent reaction step, the substrate and dielectric film may be annealed with an external energy source, such as a conductive or radioactive source.

0039The dielectric film is arranged on the substrate. The dielectric film will be composed of at least Si, C, O, and H and may have other elemental components mixed in. The substrate may include other layers in addition to the dielectric film. Disclosed in U.S. Pat. Nos. 6,312,793, 6,479,110, 6,756,323, 6,953,984, 7,030,468, 7,049,427, 7,282,458, 7,288,292, and 7,312,524 and U.S. Patent Application 2007/0057235. An exemplary, but non-limiting reference to the deposition process is incorporated herein by reference. For example, US Patent Application Publication No. 2007/0057235 discloses a method for forming a layer of carbon-doped silicon oxide on a substrate. Similarly, U.S. Pat. Nos. 6,312,793, 6,479,110, 6,756,323, 7,030,468, 7,049,427, 7,282,458, 7,288,292, and 7,312,524 are also referred to as precursors (hydrocarbon molecules or organic molecules). ) Combination of plasma-enhanced chemical vapor deposition is disclosed. The most important common points of these processes are further described here.

0040The substrate will be installed in the reaction chamber of the deposition tool. The precursor used to form the dielectric film may be delivered directly to the reactor as a gas, delivered as a liquid and vaporized directly in the reactor, or an inert carrier gas, eg, It may be carried by helium or argon, but not limited to. For example, the precursor may be vaporized at a temperature of about 70 ° C to about 110 ° C in the presence of a carrier gas prior to introduction into the reaction chamber. Alternatively, the precursor may be deposited on the substrate in liquid form, for example by a spin-on process.

0041The type of substrate on which the dielectric is deposited will vary depending on the intended end use. In some embodiments, the substrate is an oxide used as a dielectric in MIM, DRAM, ReRam technology or a gate insulating film in CMOS technology (eg, SiO).₂, SiON, or HfO₂System material, TiO₂System material, ZrO₂Materials such as series materials, rare earth oxide materials, ternary oxide materials, etc.), and metals used as conductive materials in such applications, such as tungsten, titanium, tantalum, ruthenium, or copper, plus silicon. It may include doped or non-doped silicon optionally coated with a layer of oxide. In other embodiments, the substrate is a copper interconnect and insulation region, eg, SiO.₂Alternatively, it may contain another low-k material, optionally coated with a sealing layer such as SiN. Other examples of substrates that may be coated with an insulating film are, but are not limited to, solid substrates such as metal substrates (eg Ru, Al, Ni, Ti, Co, Pt, and metal silicides such as TiSi).₂, CoSi₂, And NiSi₂); Metal Nitride-Containing Substrates (eg TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); Semiconductor Materials (eg Si, SiGe, GaAs, InP, Diamond, GaN, and SiC); Insulators ( For example, SiO₂, Si₃N₄, HfO₂, Ta₂O₅, ZrO₂, TiO₂, Al₂O₃, And barium strontium titanate); or other substrates containing any number of combinations of these materials. The actual substrate used will also depend on the dielectric film used.

0042The precursor used to form the membrane is introduced into the membrane deposition chamber and contacted with the substrate to form an insulating film on at least one surface of the substrate. The membrane deposition chamber may be any enclosure or chamber of the device in which the deposition method is performed, eg, but not limited to parallel plate reactors, cold wall reactors, hot wall reactors, single-wafer reactors, multi-wafer reactors, etc. Or it could be another type of deposition system.

0043As discussed in detail in the incorporated prior art, the film may then be made porous by an additional process to reduce the dielectric constant of the insulating film. Such processes include, but are not limited to, annealing, UV light, or electron beams.

0044Based on the disclosure here and in the references incorporated by reference, those skilled in the art will appreciate process variables controlled during membrane deposition, such as RF power, precursor mixtures and flow rates, pressures in reactors, and substrates. Appropriate values such as temperature could be easily selected.

0045Substrate and membrane structures may be placed in the deposition chamber described above during the rest of the steps of the disclosed method. Alternatively, the substrate and membrane structures may be introduced into another device used to control the exposure environment of the sample, such as the evaporative drying system described below.

0046The substrate and membrane may optionally be heated to a certain high temperature by an external energy source, such as a conductive or radioactive source. Depending on the monofunctional silylated compound used, heat can aid in the silylation reaction. For example, temperatures in the range of about 100 ° C to about 400 ° C, preferably about 200 ° C to about 300 ° C can be found to be beneficial in certain situations. However, under other circumstances, monofunctional silylated compounds can decompose at elevated temperatures and therefore work at room temperature, eg, at about 20 ° C to about 30 ° C, requires additional heating. It may be optimal without any.

0047The silylated compound may be introduced into the chamber and carried to the substrate and membrane structure in either the liquid or vapor phase, whereby the silylated compound contacts the membrane and completes the properties of the membrane. Alternatively, the compound is contacted with the membrane for a period suitable for partial recovery. The silylated compound may be delivered directly to the device as a gas, delivered as a liquid and vaporized directly in the device, or an inert carrier gas such as, but not limited to, nitrogen, helium, argon, or these. You may carry it by the combination of. Preferably, the silylated compound is vaporized in the presence of a carrier gas at a temperature of about 20 ° C to about 150 ° C, more preferably about 70 ° C to about 110 ° C, prior to introduction into the apparatus.

0048Alternatively, the silylated compound may be brought into contact with the membrane in a liquid phase. This can be achieved by placing the substrate and membrane in a liquid bath for a period of time suitable to fully or partially restore the properties of the membrane. Another option may be to introduce the liquid silylated compound into the processing chamber and deliver it to the membrane, optionally by spin-on process, by jet, flow, or spray.

0049The silylated compound reacts with the membrane for a suitable period of about 5 seconds to about 3 hours, more preferably about 1 minute to about 1 hour, even more preferably about 1 minute to about 5 minutes. After the silylated compound reacts with the film, the properties of the film are completely or partially restored, as shown by the increased depth and etching rate parameters described in more detail below.

0050Following the silylated compound reaction step, the substrate and membrane structures may optionally be annealed by an external energy source, such as a conductive or radioactive source. Annealing may help remove residual unreacted silanol. However, if the compound used can remove most of the unreacted silanol, the annealing step may not be necessary. The annealing process may be performed on the same device.

0051Description of the evaluation system The device used to evaluate the effectiveness of the disclosed silylated compounds comprises a stainless steel vacuum tubular furnace, in which a heat susceptor is mounted, in which the substrate to be processed is placed. To. Upstream of the tube furnace is a chemical delivery system, which is equipped with a bubbler that is sealed and contains restoration chemicals and a purified nitrogen gas delivery system.

0052Prior to delivery of the repair agent, the vacuum system is pumped to base pressure, followed by a continuous purge stream of nitrogen for 5 minutes. Once the system reaches a stable temperature, repair chemicals are added either by flowing nitrogen carrier gas under controlled flow and pressure conditions, or by filling the vacuum tube with pure chemical vapors to steady pressure without nitrogen dilution. Deliver to the board in the gas phase.

0053Following exposure of the substrate to repair chemicals, the system is purged with a steady stream of nitrogen for 5 minutes and filled with nitrogen to atmospheric pressure to remove the substrate.

0054Evaluation of restoration Following treatment with the given silylated compounds, some repair parameters were measured. This is expected to change significantly as a result of the repair process when compared to the damaged membrane. In particular, two parameters for film resistance to wet etching with a 600: 1 buffered oxide etching (BOE) solution are specified here. In this test, the wet etching process is performed after the film has been repaired and is not the damage-causing process described herein. The "depth" parameter indicates the percentage of damaged membrane repaired by a given compound. By definition, an undamaged membrane has a depth of 100%, while a damaged membrane has a depth of 0%. For example, if the damaged film is wet-etched to a depth of 50 nm after 1 hour of exposure to the etching solution and the repaired film is wet-etched to a depth of 25 nm after the same exposure, then for the repaired film Depth = 50%.

0055The wet etching rate parameter, or ER, is measured by wet etching in a 600: 1 BOE solution for 12 to 24 minutes and is reported in units of Å / sec. This part of the film is believed to represent the steady-state bulk film etching rate. Both of these parameters, ER and depth, are believed to indicate a recovery process towards the original membrane properties with respect to the effectiveness of the silylation process.

0056Table 1 outlines the parameters described above for the unpatterned blanket membrane. Treatment is applied for each silylated compound at a steady pressure of 10 Torr at 300 ° C. for a period of 1 hour. For the disclosed molecules 1-3, the repair depth is about 40% or more, while the best comparative molecule (1) repairs only 26%. Similarly, the disclosed molecules reduce bulk ER values by more than 40% compared to damaged membranes. The best comparative molecules reduce bulk ER values by about 25% against membranes compared to membranes. Sample treatment using comparative molecules 4 and 5 does not show effective repair after treatment.<tables num="2"><img id="000005" he="94" wi="159" file="JP5705751B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0057Many additional steps relating to the details, materials, processes, and arrangement of parts described and illustrated herein to illustrate the properties of the invention are described by those skilled in the art in the appended claims. And it will be understood that it may be done within the scope. Therefore, the present invention is not intended to be limited to the particular embodiments shown above and in the accompanying drawings.<u style="single">Hereinafter, the inventions described in the claims of the original application of the present application will be added.</u><u style="single">[1] Equation R</u>_{<u style="single">3</u>}<u style="single">SiL silylated compounds, each R being independently selected from the group consisting of H, methyl, and ethyl; L being 1,2,3-triazole, piperidine, 1-methylpiperazine, pyrrolidine, and A nitrogen-containing ring selected from the group consisting of pyrazoles; one nitrogen in the nitrogen-containing ring is directly attached to a Si atom; silylation in which the total concentration of metal contaminants in the compound is less than 10 ppmw. Compound.</u><u style="single">[2] The silylated compound according to [1], wherein the compound is selected from the group consisting of trimethylsilylpyrrolidine, trimethylsilylpyrazole, trimethylsilyl-1,2,3-triazole, trimethylsilylpiperidine, and trimethylsilyl-4-methylpiperazine.</u><u style="single">[3] The silylated compound according to [2], wherein the total concentration of the metal contaminant is less than 1 ppmw.</u><u style="single">[4] The silylated compound according to [1], which further comprises a boiling point of less than about 200 ° C.</u><u style="single">[5] The silylated compound according to [4], wherein the boiling point is about 100 ° C to about 200 ° C.</u><u style="single">[6] Cyrilized chemical delivery device: with inlet and outlet conduits, of formula R</u>_{<u style="single">3</u>}<u style="single">It comprises a canister containing a silylating agent with SiL, where each R is independently selected from the group consisting of H, methyl, and ethyl; L is 1,2,3-triazole, piperidine, A nitrogen-containing ring selected from the group consisting of 1-methylpiperazine, pyrrolidine, and pyrazole; a silylated drug delivery device in which one nitrogen in the nitrogen-containing ring is directly attached to a Si atom.</u><u style="single">[7] The silylated drug delivery device according to [6], wherein the silylating agent has a total concentration of metal contaminants of less than 10 ppmw.</u><u style="single">[8] The silylation according to [7], wherein the silylating agent is selected from the group consisting of trimethylsilylpyrrolidine, trimethylsilylpyrazole, trimethylsilyl-1,2,3-triazole, trimethylsilylpiperidine, and trimethylsilyl-4-methylpiperazine. Drug delivery device.</u><u style="single">[9] The end of the inlet conduit is located above the surface of the silylating agent and the end of the exit conduit is located below the surface of the silylating agent [6]. Cyrilized chemical delivery device.</u><u style="single">[10] The end of the inlet conduit is located below the surface of the silylating agent and the end of the exit conduit is located above the surface of the silylating agent [6]. Cyrilized chemical delivery device.</u><u style="single">[11] A method of repairing a dielectric film: the process of introducing the dielectric film into a chamber;</u>_{<u style="single">3</u>}<u style="single">The step of introducing a repair agent with SiL into the chamber, where each R is independently selected from the group consisting of H, methyl, and ethyl; L is 1,2,3-triazole, piperidine. , 1-Methylpiperazin, pyrrolidine, and pyrazole, a nitrogen-containing ring selected from the group; one nitrogen in the nitrogen-containing ring directly bonded to a Si atom; the repair agent and the dielectric. A method comprising the step of contacting with the body membrane.</u><u style="single">[12] The method according to [11], further comprising heating the dielectric film after introduction into the chamber and prior to introduction of the repair agent.</u><u style="single">[13] The method according to [11], further comprising reacting the repair agent with the insulating film for a suitable period following the contact step.</u><u style="single">[14] The method according to [13], further comprising annealing the dielectric film following the repair agent reaction step.</u><u style="single">[15] The method according to claim 11, wherein the repair agent is selected from the group consisting of trimethylsilylpyrrolidine, trimethylsilylpyrazole, trimethylsilyl-1,2,3-triazole, trimethylsilylpiperidine, and trimethylsilyl-4-methylpiperazine.</u><u style="single">[16] The method according to [15], wherein the repair agent has a total concentration of metal contaminants of less than 10 ppmw.</u>