WO2009110449A1 - シリカ質膜の製造に用いる浸漬用溶液およびそれを用いたシリカ質膜の製造法 - Google Patents
シリカ質膜の製造に用いる浸漬用溶液およびそれを用いたシリカ質膜の製造法 Download PDFInfo
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- WO2009110449A1 WO2009110449A1 PCT/JP2009/053931 JP2009053931W WO2009110449A1 WO 2009110449 A1 WO2009110449 A1 WO 2009110449A1 JP 2009053931 W JP2009053931 W JP 2009053931W WO 2009110449 A1 WO2009110449 A1 WO 2009110449A1
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- dipping
- substrate
- siliceous film
- film
- solution
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1212—Zeolites, glasses
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/20—Wet processes, e.g. sol-gel process
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
Definitions
- the present invention relates to a dipping solution used in a process for producing a siliceous film in an electronic device, and a method for producing a siliceous film using the same. More specifically, the present invention is used to form a shallow trench isolation structure or insulating film formed for insulation in an electronic device using a polysilazane compound in the manufacture of an electronic device such as a semiconductor element. The present invention also relates to a dipping solution and a method for manufacturing a shallow trench isolation structure or an insulating film using the dipping solution.
- an isolation region In general, in an electronic device such as a semiconductor device, semiconductor elements such as transistors, resistors, and others are arranged on a substrate, but they need to be electrically insulated. Therefore, a region for separating the elements is required between these elements, which is called an isolation region. Conventionally, this isolation region is generally performed by selectively forming an insulating film on the surface of a semiconductor substrate.
- a trench isolation structure is a structure in which a fine groove is formed on the surface of a semiconductor substrate and an insulator is filled in the groove to electrically separate elements formed on both sides of the groove.
- Such a structure for element isolation is an element isolation structure that is effective for achieving the high degree of integration required in recent years because the isolation region can be made narrower than in the conventional method.
- Examples of a method for forming such a trench isolation structure include a CVD method and a high density plasma CVD method (see, for example, Patent Document 1).
- a CVD method and a high density plasma CVD method (see, for example, Patent Document 1).
- voids are formed in the grooves, which are required recently, for example, in the case of embedding a fine groove of 100 nm or less. These structural defects cause damage to the physical strength and insulating properties of the substrate.
- Patent Documents 1 to 4 As a method for suppressing such cracks, a method using polysilazane instead of silicon hydroxide has been studied (for example, Patent Documents 1 to 4). These methods attempt to prevent cracks due to volume shrinkage by using polysilazane which has a smaller volume shrinkage when converted to silicon dioxide.
- the method of forming a trench isolation structure by applying a composition containing polysilazane and embedding a groove and then processing in an oxidizing atmosphere to form high-purity and dense silicon dioxide has excellent composition permeability. Therefore, there is an advantage that voids hardly occur.
- the film quality in the trench is not uniform, and the film quality tends to deteriorate as it goes deeper in the trench. Furthermore, the distribution of the film properties with respect to the trench depth was particularly remarkable in the low-temperature processed film and the fine trench having a high aspect ratio. Since the circuit density of advanced devices is increasing, a new process capable of obtaining uniform film quality even inside a fine trench has been desired.
- a dipping solution according to the present invention is a dipping solution for dipping a substrate coated with a polysilazane composition before firing in the production process of a siliceous film, and comprises hydrogen peroxide, alcohol, a surfactant, and its It is characterized by comprising a bubble adhesion preventing agent selected from the group consisting of a mixture and a solvent different from the alcohol.
- the method for producing a siliceous film according to the present invention includes: An application step of applying a composition comprising a polysilazane compound on the surface of a substrate having irregularities; It comprises a dipping step of dipping the coated substrate in the dipping solution, and a curing step of converting the polysilazane compound into a siliceous film by heat-treating the dipped substrate.
- the present invention even when the aspect ratio of the trench is very high or the trench width is very narrow, a uniform film quality can be obtained up to the inside of the trench. Even in next-generation devices that require a higher aspect ratio, a polysilazane-based coating-type insulating film material can be extended as an effective technology. In addition, since the adhesion of bubbles is suppressed when using the immersion solution, there is no demerit of using the immersion solution.
- the immersion solution in the present invention is used for immersing a substrate coated with a polysilazane composition before firing in the production process of a siliceous film described later.
- a polysilazane composition when a polysilazane composition is heated and fired, an oxidation reaction occurs and a siliceous film is formed.
- the polysilazane composition filled in the groove formed on the substrate is also oxidized in the same manner as the surface portion, and a uniform siliceous film is formed.
- the dipping solution according to the present invention comprises hydrogen peroxide, a bubble adhesion preventing agent, and a solvent. Each component will be described as follows.
- Hydrogen peroxide is well known as a general oxidizing agent.
- the oxidation of polysilazane that is, the formation of a siliceous film, is achieved exclusively by baking, and the oxidation of polysilazane is not governed by hydrogen peroxide in the dipping solution. Rather, it acts auxiliary to uniformly oxidize the entire coating film formed from the polysilazane composition.
- the oxygen source is quickly diffused without depending on the film thickness. It is thought that it is important that the oxygen source reacts quickly with polysilazane.
- preliminary oxidation is performed by immersing the applied polysilazane film in a hydrogen peroxide solution, and a uniform film quality can be obtained even inside a fine trench.
- a hydrogen peroxide aqueous solution is generally used for preparing the immersion solution. It is preferable that the immersion solution is blended with an aqueous solution so as to obtain a desired hydrogen peroxide concentration.
- hydrogen peroxide obtained by electrolysis of an aqueous solution of ammonium hydrogen sulfate or hydrolysis of peroxo acid can be directly blended into the dipping solution, but it is easier to use the aqueous solution.
- the content of hydrogen peroxide in the dipping solution is preferably large from the viewpoint of obtaining a uniform fired film, but is preferably below a certain level in consideration of the safety of workers handling the dipping solution. . From such a viewpoint, the content of hydrogen peroxide in the entire composition is preferably 30 to 60% by weight, and more preferably 30 to 35% by weight.
- the immersion solution according to the present invention comprises a bubble adhesion preventive agent.
- the bubble adhesion preventing agent in the dipping solution has an action of reducing bubbles adhering when the substrate is dipped in the dipping solution. Bubbles adhering to the substrate in the dipping solution remain even after being subsequently removed from the dipping solution, resulting in an increase in the surface area of the substrate. The larger the surface area, the easier it is for dust and the like mixed from the environment to adhere, which may eventually lead to defects in the siliceous film formed.
- the generation of the bubbles can be reduced by the bubble adhesion preventing agent, and the quality of the final siliceous film can be improved. Furthermore, there is also an effect of making the siliceous film after firing more uniform.
- the bubble adhesion preventing agent used in the present invention is selected from the group consisting of alcohols, surfactants, and mixtures thereof.
- Alcohol and surfactant can be used in combination, or only one of them can be used. Further, a plurality of types can be selected and combined from any one of alcohol and surfactant.
- alcohol refers to an alcohol in which at least one of hydrogen contained in a hydrocarbon is substituted with a hydroxyl group.
- preferred alcohols in the present invention are monools, diols, or triols in which a hydrogen atom of a saturated hydrocarbon having 1 to 3 carbon atoms is substituted with 1 to 3 hydroxyl groups from the viewpoints of handleability and foam adhesion reduction.
- it has the effect of reducing the surface tension to suppress the generation of bubbles, has a low boiling point to prevent it from remaining on the siliceous film to be formed, and has low reactivity with other components such as hydrogen peroxide. It is desirable. For this reason, it is preferable to use a relatively low molecular weight alcohol. More specifically, it is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, and mixtures thereof.
- a surfactant can be used as the bubble adhesion preventing agent in the present invention.
- Various surfactants are known, and any one can be used as necessary.
- the surfactant is mixed into the formed siliceous film to deteriorate the physical properties of the insulating film, such as the dielectric constant.
- Nonionic surfactants are rarely used.
- polyoxyethylene alkyl ether is one of the preferred surfactants.
- the content of the bubble adhesion inhibitor in the dipping solution is preferably larger from the viewpoint of reducing the adhesion of bubbles and obtaining a uniform fired film, but from the viewpoint of mixing organic substances into the siliceous film serving as an insulator. Is preferably not more than the upper limit.
- the bubble adhesion preventing agent is alcohol, its content is preferably 1 to 20% by weight, and more preferably 1 to 10% by weight.
- the bubble adhesion preventing agent is a surfactant, particularly a nonionic surfactant, its content is preferably 10.1 to 20% by weight, and preferably 0.1 to 10% by weight. More preferred.
- the immersion solution according to the present invention comprises a solvent. This solvent dissolves the hydrogen peroxide and the bubble adhesion preventive agent uniformly.
- the alcohol used as the bubble adhesion preventing agent is a liquid and can generally act as a solvent, but in the present invention, alcohol is not included in the solvent. That is, the “solvent” in the present invention is selected from those other than the alcohol.
- the solvent can be arbitrarily selected as long as it can uniformly dissolve the above-mentioned components, but water is preferably used. In order to prevent impurities from adhering to the substrate, it is preferable to use one having a high purity, for example, distilled water or deionized water.
- blending hydrogen peroxide or surfactant as aqueous solution for example is also a solvent of the solution for immersion in this invention.
- the immersion solution according to the present invention is prepared by mixing and uniformly dissolving the above components. At this time, the order of mixing is not particularly limited. Moreover, since the solution for immersion after preparation contains the hydrogen peroxide which is comparatively inferior, when storing, you should store in a cool dark place.
- a composition containing a polysilazane compound is applied on the surface of an uneven substrate, and (b) a coated substrate is described above. It is immersed in a dipping solution, and (c) the substrate after dipping is heat-treated to convert the polysilazane compound into a silicon dioxide film.
- substrate used is not specifically limited, For example, a bare silicon, the silicon wafer which formed the thermal oxide film and the silicon nitride film as needed, etc. are mentioned. In the present invention.
- a substrate having irregularities provided with grooves and holes corresponding to a semiconductor element or the like to be finally manufactured is used. These are irregularities corresponding to a trench isolation structure, a contact hole and the like, and various ones are selected as necessary.
- a silicon substrate having a desired groove pattern is generally used.
- An arbitrary method can be used for forming the groove.
- the groove can be formed by the following method.
- a silicon dioxide film is formed on the surface of a silicon substrate by, for example, a thermal oxidation method.
- the thickness of the silicon dioxide film formed here is generally 5 to 30 nm.
- a silicon nitride film is formed on the formed silicon dioxide film by, for example, a low pressure CVD method.
- This silicon nitride film can function as a mask in a later etching process or a stop layer in a polishing process described later.
- the silicon nitride film is generally formed with a thickness of 100 to 400 nm when formed.
- An arbitrary photoresist is applied on the silicon dioxide film or silicon nitride film thus formed.
- the photoresist film is dried or cured as necessary, and then exposed and developed with a desired pattern to form a pattern.
- the exposure method can be performed by any method such as mask exposure or scanning exposure. Also, any photoresist can be selected and used from the viewpoint of resolution and the like.
- the silicon nitride film and the underlying silicon dioxide film are sequentially etched. By this operation, a desired pattern is formed on the silicon nitride film and the silicon dioxide film.
- the silicon substrate is dry-etched to form trench isolation grooves.
- the width of the trench isolation groove to be formed is determined by the pattern for exposing the photoresist film.
- the trench / isolation groove in the semiconductor element varies depending on the target semiconductor element, but the width is generally 0.02 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m, and the depth is 200 to 1000 nm, preferably 300 to 700 nm.
- the method according to the present invention makes it possible to uniformly embed a narrower and deeper portion than a conventional trench isolation structure formation method, so that a narrower and deeper trench isolation structure is formed. It is suitable for forming. In particular, in the conventional method for forming a siliceous film, it has been difficult to form a uniform siliceous film up to a deep part of the groove.
- the groove width is generally 0.5 ⁇ m or less, particularly 0.1 ⁇ m or less, and the aspect ratio is 5
- the siliceous film in the groove can be formed uniformly by using the dipping solution according to the present invention.
- a polysilazane composition serving as a material for the siliceous film is applied on the silicon substrate thus prepared to form a coating film.
- a polysilazane composition a conventionally known arbitrary polysilazane compound dissolved in a solvent can be used.
- the polysilazane compound used for this invention is not specifically limited, As long as the effect of this invention is not impaired, it can select arbitrarily.
- These may be either inorganic compounds or organic compounds.
- these polysilazanes as the inorganic polysilazane, for example, the general formula (I): And having a molecular weight of 690 to 2000, 3 to 10 SiH 3 groups in one molecule, and an element ratio by chemical analysis of Si: 59 to 61 N: 31 to 34 and H: 6.5 to 7.5, and perhydropolysilazane having a polystyrene-reduced average molecular weight in the range of 3,000 to 20,000.
- Examples of other polysilazanes include, for example, a general formula: (Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group directly connected to silicon such as a fluoroalkyl group other than these groups. Represents a carbon group, an alkylsilyl group, an alkylamino group, or an alkoxy group, provided that at least one of R 1 , R 2, and R 3 is a hydrogen atom. Examples thereof include polysilazane having a number average molecular weight of about 100 to 50,000 or a modified product thereof. These polysilazane compounds can be used in combination of two or more.
- the polysilazane composition used in the present invention comprises a solvent capable of dissolving the polysilazane compound.
- the solvent used here is different from the solvent used for the dipping solution.
- Such a solvent is not particularly limited as long as it can dissolve each of the above-mentioned components.
- Specific examples of preferable solvents include the following: (A) Aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, etc.
- solvents can be used in combination of two or more as appropriate in order to adjust the evaporation rate of the solvent, to reduce the harmfulness to the human body, or to adjust the solubility of each component.
- the polysilazane composition used in the present invention may contain other additive components as necessary.
- examples of such components include viscosity modifiers and crosslinking accelerators.
- a phosphorus compound such as tris (trimethylsilyl) phosphate may be contained for the purpose of obtaining a sodium gettering effect when used in a semiconductor device.
- the content of each of the above components varies depending on the intended use of the composition, but the content of the polysilazane compound is 0.1 to 40% by weight in order to form a siliceous material having a sufficient film thickness. It is preferably 0.5 to 20% by weight, more preferably 5 to 20% by weight. Usually, when the content of the polysilazane compound is 5 to 20% by weight, a generally preferred film thickness, for example, 2000 to 8000 mm can be obtained.
- a conventionally known method such as a spin coating method, a dip method, a spray method, or a transfer method may be used. Of these, the spin coating method is particularly preferred.
- the coated substrate is preheated (prebaked) to remove (dry) the excess organic solvent from the coating film formed on the substrate surface as necessary, and then immersed in the dipping solution described above. Soaked. Since the preheating is not intended to cure the polysilazane, it is generally performed by heating at a low temperature for a short time. Specifically, it is carried out by heating at 70 to 150 ° C., preferably 100 to 150 ° C. for 1 to 10 minutes, preferably 3 to 5 minutes.
- the temperature for dipping in the dipping solution that is, the temperature of the dipping solution is not particularly limited, but is generally 20 to 50 ° C., preferably 20 to 30 ° C.
- the immersion time varies depending on the film thickness, the type of polysilazane compound, or the concentration of the immersion solution, but is generally 1 to 30 minutes, preferably 10 to 30 minutes. At this time, bubbles are less likely to adhere to the substrate in the immersion solution according to the present invention. For this reason, since adhesion of dust or the like in the subsequent process is reduced, final substrate defects are reduced.
- the substrate is heat-treated, and the polysilazane composition on the surface is cured and converted into a siliceous film.
- the heat treatment is preferably performed in an atmosphere containing water vapor, oxygen, or a mixed gas thereof, that is, in an oxidizing atmosphere.
- the oxygen content is preferably 1% or more, more preferably 10% or more, based on the volume.
- inert gas such as nitrogen and helium, may be mixed in atmosphere.
- the heat treatment when the heat treatment is performed in an atmosphere containing water vapor, it is preferably 0.1% or more, more preferably 1% or more based on the volume. In the present invention, it is particularly preferable to perform firing in a mixed gas atmosphere containing oxygen and water vapor.
- the temperature of the heat treatment must be such that the polysilazane compound can be added to the siliceous film.
- the heat treatment is preferably performed at 400 to 1,200 ° C., more preferably at 400 to 700 ° C.
- the heating time can be appropriately selected according to the heating temperature, but is generally 0.5 to 5 hours, preferably 0.5 to 1 hour. Further, by performing the heat treatment under a high humidity condition, it is possible to reduce the temperature necessary for the conversion and shorten the necessary time.
- a uniform siliceous film is formed up to the inside of the recess on the substrate.
- a siliceous film is uniformly formed even inside a trench isolation groove having a high aspect ratio, and a high-quality trench isolation structure can be obtained.
- the polysilazane composition was applied to a TEG substrate whose surface was coated with a silicon nitride liner layer by spin coating.
- the application conditions were a rotation speed of 1000 rpm and a rotation time of 20 seconds.
- the film thickness was about 0.6 ⁇ m.
- the pattern of the TEG substrate is a line and space in the order of 0.05 ⁇ m, 0.1 ⁇ m, 0.2 ⁇ m, 0.5 ⁇ m, and 1.0 ⁇ m as follows.
- the coated substrate was pre-baked for 3 minutes on a hot plate at 150 ° C.
- the pre-baked polysilazane film was immersed in an immersion solution containing 35% hydrogen peroxide and 10% ethanol for 30 minutes, and then further post-baked for 3 minutes on a hot plate at 150 ° C.
- absorption attributable to the Si—O bond was obtained at a wave number of 1080 cm ⁇ 1 .
- the substrate on which the film was formed was cut in a direction perpendicular to the longitudinal direction of the groove, and then 0.5% wt. It was immersed in an aqueous hydrofluoric acid solution at 23 ° C. for 30 seconds, and then thoroughly washed with pure water and then dried.
- the groove depth of the cross section of the substrate was measured by SEM at 50000 times, and the etching depth was evaluated by observing the deepest portion of the groove from 30 degrees above the elevation angle in the direction perpendicular to the cross section. Those without immersion had a large amount of etching at the bottom of the trench, and the inside of the trench was non-uniform. In the case with the immersion solution treatment, the etching amount at the bottom of the trench was small, and a uniform film inside the trench was a good quality film.
- the polysilazane composition was applied on the TEG substrate, pre-baked, then immersed in a dipping solution, and the number of bubbles on the substrate surface was measured 5 minutes after the start of dipping.
- a solution containing 30% hydrogen peroxide and 10% ethanol (Example) and a 30% hydrogen peroxide solution (Comparative Example) containing no ethanol were used as the immersion solution.
- the obtained results were as shown in Table 1.
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Abstract
Description
最先端デバイスでは回路の高密度化が進んでいるため、微細なトレンチ内部であっても均一な膜質を得ることができる新たなプロセスが望まれていた。
凹凸を有する基板の表面上に、ポリシラザン化合物を含んでなる組成物を塗布する塗布工程、
塗布済み基板を前記の浸漬用溶液に浸漬させる浸漬工程、および
浸漬後の基板を加熱処理してポリシラザン化合物をシリカ質膜に転化させる硬化工程
を含んでなることを特徴とするものである。
本発明における浸漬用溶液は、後述するシリカ質膜の製造過程において、ポリシラザン組成物塗布済み基板を焼成前に浸漬するのに用いるものである。一般に、ポリシラザン組成物を加熱焼成することにより酸化反応が起こり、シリカ質膜が形成される。ここで、焼成前に本発明による浸漬用溶液で処理することにより、例えば基板上に形成された溝に充填されたポリシラザン組成物も表面部と同様に酸化され、均一なシリカ質膜が形成される。
それぞれの成分について説明すると以下の通りである。
過酸化水素は、一般的な酸化剤としてよく知られているものである。しかしながら、本発明においては、ポリシラザンの酸化、すなわちシリカ質膜の形成はもっぱら焼成によって達成されるのであり、浸漬用溶液中の過酸化水素によってポリシラザンの酸化が支配されるわけではない。むしろ、ポリシラザン組成物から形成される塗膜全体を均一に酸化させるために補助的に作用するものである。
このため、本発明においても浸漬用溶液の調製には過酸化水素水溶液が用いられるのが一般的である。所望の過酸化水素濃度となるように浸漬用溶液に水溶液で配合することが好ましい。例えば硫酸水素アンモニウム水溶液の電気分解や、ペルオキソ酸の加水分解などにより得られた過酸化水素を直接浸漬用溶液に配合することもできるが、水溶液を用いる方が簡便である。
本発明による浸漬用溶液は気泡付着防止剤を含んでなる。本発明において、浸漬用溶液中における気泡付着防止剤は、基板を浸漬用溶液に浸漬したときに付着する気泡を減少させる作用がある。浸漬用溶液中において基板に付着した気泡は、その後浸漬用溶液から取り出された後にも残留し、結果的に基板の表面積を増大させる。表面積が大きいほど環境から混入するダストなどが付着しやすくなり、最終的には形成されるシリカ質膜の欠陥になる可能性がある。本発明においては気泡付着防止剤によりこの気泡の発生を減少させ、最終的なシリカ質膜の品質を改良させることができる。さらには、焼成後のシリカ質膜をさらに均一化させる作用もある。
本発明による浸漬用溶液は、溶媒を含んでなる。この溶媒は、前記の過酸化水素および気泡付着防止剤を均一に溶解させるものである。なお、前記気泡付着防止剤として用いられるアルコールは液体であり、一般的に溶媒としても作用し得るものであるが、本発明においてアルコールは溶媒に含めないものとする。すなわち、本発明における「溶媒」は前記アルコール以外のものから選択されるものである。
本発明によるシリカ質膜の製造法は、(a)凹凸を有する基板の表面上に、ポリシラザン化合物を含んでなる組成物を塗布し、(b)塗布済み基板を前記した浸漬用溶液に浸漬させ、さらに(c)浸漬後の基板を加熱処理してポリシラザン化合物を二酸化シリコン膜に転化させることを含んでなる。
用いられる基板の表面材質は特に限定されないが、例えばベアシリコン、必要に応じて熱酸化膜や窒化珪素膜を成膜したシリコンウェハー、などが挙げられる。本発明においては。このような基板に対して、最終的に製造しようとする半導体素子などに対応した溝や孔が設けられた、凹凸を有する基板が用いられる。これらは、トレンチ・アイソレーション構造や、コンタクトホールなどに対応した凹凸であり、必要に応じて種々のものが選択される。
ここで形成させる二酸化シリコン膜の厚さは一般に5~30nmである。
窒化シリコン膜は、形成させる場合には、一般に100~400nmの厚さで形成させる。
(a)芳香族化合物、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン、ジエチルベンゼン、トリメチルベンゼン、トリエチルベンゼン等、(b)飽和炭化水素化合物、例えばn-ペンタン、i-ペンタン、n-ヘキサン、i-ヘキサン、n-ヘプタン、i-ヘプタン、n-オクタン、i-オクタン、n-ノナン、i-ノナン、n-デカン、i-デカン等、(c)脂環式炭化水素化合物、例えばエチルシクロヘキサン、メチルシクロヘキサン、シクロヘキサン、シクロヘキセン、p-メンタン、デカヒドロナフタレン、ジペンテン、リモネン等、(d)エーテル類、例えばジプロピルエーテル、ジブチルエーテル、ジエチルエーテル、メチルターシャリーブチルエーテル(以下、MTBEという)、アニソール等、および(e)ケトン類、例えばメチルイソブチルケトン(以下、MIBKという)等。これらのうち、(b)飽和炭化水素化合物、(c)脂環式炭化水素化合物(d)エーテル類、および(e)ケトン類がより好ましい。
塗布済みの基板は、必要に応じて基板表面に形成された塗布膜から過剰の有機溶媒を除去(乾燥)するために予備加熱(プリベーク)したあと、前記した浸漬用溶液に浸漬される。予備加熱はポリシラザンを硬化させることが目的ではないため、一般に低温で短時間加熱することにより行われる。具体的には70~150℃、好ましくは100~150℃で、1~10分、好ましくは3~5分加熱することにより行われる。
浸漬工程のあと、基板は加熱処理され、表面のポリシラザン組成物が硬化してシリカ質膜に転化される。このとき、加熱処理は好ましくは水蒸気、酸素、またはその混合ガスを含む雰囲気中、すなわち酸化雰囲気中で行われる。本発明においては、特に加熱処理を酸素を含む雰囲気下で焼成することが好ましい。ここで、酸素の含有率は体積を基準として1%以上であることが好ましく、10%以上であることがより好ましい。ここで、本発明の効果を損なわない範囲で、雰囲気中に窒素やヘリウムなどの不活性ガスが混在していてもよい。
本発明においては、特に酸素と水蒸気とを含む混合ガス雰囲気下で焼成を行うことが好ましい。
本発明を諸例を用いて説明すると以下の通りである。
この条件でベアシリコン基板上に塗布を行ったとき、その膜厚は約0.6μmであった。
また、TEG基板のパターンは以下のとおり、0.05μm、0.1μm、0.2μm、0.5μm、および1.0μmの順のライン&スペースである。
浸漬用溶液処理なし 16.9%
浸漬用溶液処理あり 8.0%
全工程終了後の成膜された基板を、溝の長手方向に対して直角の方向で切断した後、0.5%wt.フッ化水素酸水溶液に23℃で30秒浸漬し、その後純水でよく洗浄してから乾燥させた。基板断面の溝部分をSEMにより50000倍で、断面に垂直な方向の仰角30度上方から溝最深部を観察してエッチング量を評価した。浸漬なしのものはトレンチ底部のエッチング量が多く、トレンチ内部が不均一であった。浸漬用溶液処理ありのものは、トレンチ底部のエッチング量が少なく、トレンチ内部が均一な膜が良質な膜であった。
前記と同様にして、TEG基板上にポリシラザン組成物を塗布し、プリベークした後、浸漬用溶液に浸漬し、浸漬開始から5分後の基板表面上の気泡数を計測した。ここで、浸漬用溶液としては、30%の過酸化水素と10%のエタノールを含むもの(実施例)と、エタノールを含まない、30%過酸化水素水(比較例)を用いた。得られた結果は表1に示す通りであった。
気泡付着を評価した後、浸漬後、および焼成後の実施例および比較例のTEG基板表面の欠陥数を表面欠陥検査計(KLA-2115(商品名)、KLAテンコール社製)により評価した。焼成は、400℃、80%水蒸気雰囲気下で30分の条件でおこなった。得られた結果は表1に示す通りであった。なお、このとき参照例として浸漬用溶液に浸漬しないものについても同様の評価を行った。
Claims (10)
- シリカ質膜の製造過程において、ポリシラザン組成物塗布済み基板を焼成前に浸漬させるための浸漬用溶液であって、過酸化水素と、アルコール、界面活性剤、およびその混合物からなる群から選択される気泡付着防止剤と、前記アルコールとは異なる溶媒とを含んでなることを特徴とする浸漬用溶液。
- 前記アルコールが、炭素数1~3の飽和炭化水素の水素が1~3個の水酸基で置換されたモノオール、ジオール、またはトリオールである、請求項1に記載の浸漬用溶液。
- 前記アルコールが、メタノール、エタノール、n-プロパノール、イソプロパノール、およびそれらの混合物からなる群から選択される、請求項1または2に記載の浸漬用溶液。
- 前記界面活性剤がノニオン性界面活性剤である、請求項1に記載の浸漬用溶液。
- 前記ノニオン性界面活性剤がポリオキシエチレンアルキルエーテルである、請求項4に記載の浸漬用溶液。
- 前記アルコールとは異なる溶媒が水である、請求項1~5のいずれか1項に記載の浸漬用溶液。
- 凹凸を有する基板の表面上に、ポリシラザン化合物を含んでなる組成物を塗布する塗布工程、
塗布済み基板を請求項1~6のいずれか1項に記載の浸漬用溶液に浸漬させる浸漬工程、および
浸漬後の基板を加熱処理してポリシラザン化合物をシリカ質膜に転化させる硬化工程
を含んでなることを特徴とする、シリカ質膜の製造法。 - 前記塗布工程と浸漬工程との間に、さらに基板を予備加熱する工程を含んでなる、請求項7に記載のシリカ質膜の製造法。
- 前記硬化工程における加熱処理を水蒸気濃度1%以上の不活性ガスまたは酸素雰囲気下で行う、請求項7または8に記載のシリカ質膜の製造法。
- 前記硬化工程における加熱処理を400℃以上1,200℃以下の温度で行う、請求項7~9のいずれか1項に記載のシリカ質膜の製造法。
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- 2009-03-03 CN CN200980107577XA patent/CN101965629A/zh active Pending
- 2009-03-03 EP EP09716895.9A patent/EP2264744B1/en active Active
- 2009-03-03 KR KR1020107022181A patent/KR101623764B1/ko active IP Right Grant
- 2009-03-03 WO PCT/JP2009/053931 patent/WO2009110449A1/ja active Application Filing
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US8603923B2 (en) | 2013-12-10 |
EP2264744B1 (en) | 2018-05-02 |
EP2264744A1 (en) | 2010-12-22 |
JP5405031B2 (ja) | 2014-02-05 |
JP2009212433A (ja) | 2009-09-17 |
US20130277808A1 (en) | 2013-10-24 |
KR101623764B1 (ko) | 2016-05-24 |
US20110014796A1 (en) | 2011-01-20 |
TW200946453A (en) | 2009-11-16 |
EP2264744A4 (en) | 2016-11-09 |
TWI538884B (zh) | 2016-06-21 |
CN101965629A (zh) | 2011-02-02 |
KR20110116966A (ko) | 2011-10-26 |
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