WO2010137544A1 - エッチング液およびそれを用いたトレンチ・アイソレーション構造の形成方法 - Google Patents
エッチング液およびそれを用いたトレンチ・アイソレーション構造の形成方法 Download PDFInfo
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- WO2010137544A1 WO2010137544A1 PCT/JP2010/058711 JP2010058711W WO2010137544A1 WO 2010137544 A1 WO2010137544 A1 WO 2010137544A1 JP 2010058711 W JP2010058711 W JP 2010058711W WO 2010137544 A1 WO2010137544 A1 WO 2010137544A1
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- Prior art keywords
- etching solution
- organic solvent
- etching
- isolation structure
- trench isolation
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Images
Classifications
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- 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
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
- H01L21/02222—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
-
- 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
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02321—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer
- H01L21/02323—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of oxygen
- H01L21/02326—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of oxygen into a nitride layer, e.g. changing SiN to SiON
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/76—Making of isolation regions between components
- H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
- H01L21/76224—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using trench refilling with dielectric materials
- H01L21/76229—Concurrent filling of a plurality of trenches having a different trench shape or dimension, e.g. rectangular and V-shaped trenches, wide and narrow trenches, shallow and deep trenches
-
- 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
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
Definitions
- the present invention relates to an etchant for etching a spin-on dielectric layer (hereinafter referred to as SOD film) which is an insulating film in a semiconductor element manufacturing process.
- SOD film spin-on dielectric layer
- 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 trench is formed on the surface of a semiconductor substrate and an insulator is filled in the trench to electrically isolate elements formed on both sides of the trench.
- 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.
- One method for forming such a trench isolation structure is a self-aligned shallow trench isolation process.
- a composition containing an insulating material hereinafter referred to as SOD material
- SOD material an insulating material
- CMP chemical mechanical polishing method
- etching solutions used in such a method have been studied.
- a hydrofluoric acid aqueous solution and a hydrofluoric acid buffer solution As the simplest, there are a hydrofluoric acid aqueous solution and a hydrofluoric acid buffer solution.
- a hydrofluoric acid aqueous solution to which isopropyl alcohol is added Patent Document 1
- a solution in which a hydrofluoric acid salt is dissolved in an organic solvent Patent Document 2
- the etching rate during wet etching may be non-uniform due to the influence of the trench isolation structure.
- the etching rate around the trench is relatively large, and the intermediate portion may be convex, or the trench width may be uneven.
- Such defects in the structure are not preferable in terms of poor insulation characteristics and mechanical strength, and thus need to be improved.
- the etching solution according to the present invention comprises hydrofluoric acid and an organic solvent, wherein the organic solvent has a ⁇ H defined by a Hansen solubility parameter of 4 or more and 12 or less, and a saturated solubility in water at 20 ° C. of 5%. It is the above, It is characterized by the above.
- the method for forming a shallow trench isolation structure includes: An application step of applying a composition containing an insulating material to a substrate surface having a trench structure to form a coating film; A baking process in which the coated substrate is baked to cure the insulating material and form an insulating film;
- the insulating film after polishing comprises hydrofluoric acid and an organic solvent, and ⁇ H defined by the Hansen solubility parameter is 4 or more and 12 or less, and the saturation solubility in water at 20 ° C. is 5%. It is characterized by including the etching process processed with the etching liquid which is the above.
- an etchant that can etch all trenches uniformly and flatly in the trenches is provided. By using this etching solution, it becomes possible to form a shallow trench isolation structure with few defects and excellent insulating properties and mechanical strength.
- the cross-sectional conceptual diagram which shows the process of shallow trench isolation using the etching liquid of this invention.
- Sectional conceptual diagram which shows the process of shallow trench isolation using the conventional etching liquid.
- the trench cross-sectional conceptual diagram after an etching.
- a circuit 2 made of a metal thin film is formed on the substrate 1.
- the substrate can be selected from a semiconductor material such as silicon or any other material.
- a circuit or the like can be formed on the substrate by any method such as etching or printing.
- the cap 3 is formed on the circuit etc. as needed (FIG. 1 (a)).
- the cap 3 is for protecting a circuit and the like during later etching, and can be formed using, for example, a photoresist.
- a uniform metal thin film is formed on the substrate surface, and then the cap 3, that is, a mask is formed on the metal thin film by using a photoresist or the like.
- the circuit 2 can be formed by etching the metal thin film.
- the substrate 1 is etched using the cap 3 thus formed as a mask. By this operation, a desired pattern is transferred to the substrate 1 and a trench isolation structure is formed (FIG. 1B).
- the width and depth of the trench are not particularly limited, but the width is generally 0.02 to 10 ⁇ m, preferably 0.02 to 5 ⁇ m.
- the depth is 200 to 1000 nm, preferably 300 to 700 nm.
- a silicon nitride liner film, a polysilicon film, a silicon oxide film, or the like can be further formed on the surface of the substrate on which the trench is formed by a CVD method, an ALD (Atomic Layer Deposition) method, or the like.
- composition containing an SOD material as a material of the SOD film is applied on a silicon substrate having a trench formed on the surface. This application fills the trench with SOD material.
- the SOD material is preferably selected from the group consisting of polysilazane, hydrogenated silsesquioxane, and mixtures thereof, more preferably polysilazane.
- the polysilazane compound is not particularly limited and can be arbitrarily selected as long as the effects of the present invention are not impaired. These may be either inorganic compounds or organic compounds. Among these polysilazanes, the most preferable ones include those composed of combinations of units represented by the following general formulas (Ia) to (Ic): (Where m1 to m3 are numbers representing the degree of polymerization) Of these, those having a weight average molecular weight in terms of styrene of 700 to 30,000 are particularly preferred.
- 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. A group which is carbon, 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, and n is a number representing the degree of polymerization). Examples thereof include polysilazane having a skeleton composed of the above structural units and 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 composition containing the SOD material used in the present invention comprises a solvent capable of dissolving the SOD material.
- a solvent is not particularly limited as long as it can dissolve each of the above-mentioned components.
- 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 composition containing the SOD material used in the present invention may contain other additive components as necessary.
- such components include cross-linking accelerators that promote the cross-linking reaction of SOD materials such as polysilazane, catalysts for reactions that convert SOD materials into insulators, and viscosity modifiers that adjust the viscosity of the composition. It is done.
- 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 application conditions, firing conditions, and the like.
- the content of the SOD material is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, based on the total weight of the composition.
- the concentration of the SOD material contained in the composition is not limited to this, and any concentration of the composition can be used as long as the trench isolation structure specified in the present invention can be formed.
- the content of various additives other than the SOD material varies depending on the kind of the additive, etc., but the amount added to the SOD material is preferably 0.001 to 40% by weight, preferably 0.005 to 30% by weight. More preferred is 0.01 to 20% by weight.
- the composition can be applied on the substrate by any method. Specific examples include spin coating, curtain coating, dip coating, and others. Of these, spin coating is particularly preferable from the viewpoint of uniformity of the coating surface.
- the thickness of the coating film to be applied that is, the thickness of the coating film in the portion having no trench on the substrate surface is preferably 20 to 150 nm, and more preferably 30 to 100 nm.
- the substrate coated with the composition can be pre-baked. This step aims to remove at least a part of the solvent contained in the coating film.
- the temperature is usually in the range of 50 to 250 ° C., preferably 80 to 200 ° C., and the required time is generally 0.5 to 10 minutes, preferably 1 to 5 minutes. .
- the coating film is baked to convert the entire coating film into the insulator film 4 (FIG. 1 (c)).
- Firing is preferably performed in an inert gas or oxygen atmosphere containing water vapor using a curing furnace or a hot plate.
- the water vapor is important for sufficiently converting an SOD material such as a polysilazane compound into an insulator, and is preferably 1% or more, more preferably 10% or more, and most preferably 20% or more. In particular, when the water vapor concentration is 20% or more, the conversion of the SOD material into an insulator is likely to proceed, the occurrence of defects such as voids is reduced, and the characteristics of the insulating film are improved.
- an inert gas is used as the atmospheric gas, nitrogen, argon, helium, or the like is used.
- the temperature condition for curing varies depending on the type of SOD material to be used and the combination of processes. However, when the temperature is relatively high, the rate at which the SOD material is converted into the insulator film tends to increase, and the lower the temperature, the device characteristics due to the oxidation of the substrate such as silicon or the change of the crystal structure. There is a tendency for adverse effects to be reduced. From such a viewpoint, in the method according to the present invention, heating is usually performed at 1000 ° C. or lower, preferably 300 to 900 ° C.
- the temperature raising time to the target temperature is generally 1 to 100 ° C./min
- the curing time after reaching the target temperature is generally 1 minute to 10 hours, preferably 15 minutes to 3 hours. If necessary, the curing temperature or the composition of the curing atmosphere can be changed stepwise.
- Polishing is generally performed by CMP.
- This polishing by CMP can be performed with a general abrasive and polishing apparatus.
- the polishing agent an aqueous solution in which an abrasive such as silica, alumina, or ceria and other additives are dispersed as required can be used.
- a typical CMP apparatus can be used.
- the silicon dioxide film derived from the polysilazane composition formed on the flat portion on the surface of the cap 3 is almost removed by the polishing treatment, but the insulator film remaining between the adjacent circuits 2 is removed. Further, an etching process is performed using the etching solution according to the present invention. This etching process can be performed in the same manner as in the conventional method except that the etching solution specified in the present invention is used.
- the etching solution used here contains water, hydrofluoric acid, and a specific organic solvent at a content of not more than the solubility in water.
- the content of hydrofluoric acid varies depending on the type of SOD film to be etched, but is preferably 0.06 to 2% by weight, more preferably 0.1 to 1% by weight, based on the total weight of the etching solution. Included in the ratio.
- the specific organic solvent is one having a hydrogen bond strength index ⁇ H defined by Hansen's solubility parameter of 4 or more and 12 or less and a saturated solubility in water of 20 ° C. of 5% by weight or more. is there.
- Specific examples of such an organic solvent include those shown in Table 1.
- the description of “arbitrary” means that the organic solvent is mixed with water at an arbitrary ratio. Two or more of these organic solvents can be used in combination.
- the saturated solubility in water at 20 ° C. is preferably 8% by weight or more, and more preferably 10% by weight or more.
- propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetoacetate, acetone, dimethyl ether, methyl ethyl ketone, and ethylene glycol dimethyl ether are preferable from the viewpoints of handleability and cost, and propylene glycol monomethyl ether and acetone are the effects of the present invention. Is particularly preferred since it is strongly expressed.
- the content of the specific organic solvent contained in the etching solution is generally selected in a range where the components contained in the etching solution are uniformly mixed, and is not particularly limited. However, the greater the content, the stronger the effect of the present invention tends to be expressed. From such a viewpoint, the content of the organic solvent is preferably 1% by weight or more and 5% by weight or more based on the total weight of the etching solution within a range not exceeding the saturation solubility of the organic solvent in water. It is preferable. Moreover, when using the organic solvent whose solubility with respect to water is finite, it is preferable to contain an organic solvent in the ratio close
- the etching rate tends to decrease as the content of the organic solvent in the etching solution increases, so the content of the organic solvent may not be excessively high from the viewpoint of securing the etching rate.
- the content may be equal to or lower than the saturation solubility.
- the content of the organic solvent with respect to the total weight of the etching solution is preferably 95% by weight or less, and more preferably 90% by weight or less. .
- the etching solution according to the present invention contains the above-described hydrofluoric acid and a specific organic solvent, but may contain other components as necessary.
- examples of such other components include ammonium fluoride and phosphoric acid which are considered to assist the etching action, and surfactants which are considered to improve the wettability of the etching solution.
- the insulator film 4 between the circuits 2 is uniformly etched, and the etching is completed at an appropriate timing, so that the surface of the substrate 1 can be obtained.
- a structure filled with an insulator film can be obtained.
- the insulator film can be uniformly removed by etching.
- FIGS. 2A to 2D are the same as those described above, but when a conventional etching solution is used for wet etching, the etching rate varies depending on the location, and FIG. As shown, the central part inside the trench is raised. This does not change even when the cap 3 is removed (FIG. 2 (f)). Therefore, the final semiconductor device often causes poor insulation and insufficient mechanical strength.
- the portion of the insulating film formed on the substrate surface that is in contact with the inner side surface of the trench has a strong tensile stress and therefore tends to be easily etched. Therefore, the etching rate in the portion close to the inner side surface of the trench is increased, and the central portion inside the trench is raised as shown in FIG.
- HF 2 ⁇ ions mainly contribute to the etching reaction. If the contribution of HF 2 ⁇ ions is too large, the above-described non-uniform etching proceeds, whereas in the present invention, a specific organic solvent associates with HF by hydrogen bonding, and ionization to HF 2 ⁇ ions is performed. It is considered that the effective concentration of HF 2 ⁇ is appropriately lowered by suppressing the HF 2 ⁇ .
- the etching solution according to the present invention is suitable for forming the shallow trench isolation as described above, but can also be applied to other applications. Specifically, it can be used for cleaning a contact hole when forming a metal wiring interlayer insulating film (also referred to as IMD) and a premetal insulating film (also referred to as PMD) in the manufacturing process of a semiconductor device.
- IMD metal wiring interlayer insulating film
- PMD premetal insulating film
- the film exposed inside the hole may be non-uniform in the film thickness direction.
- the etching solution according to the present invention the film is uniformly cleaned even if the film quality is non-uniform. be able to. For this reason, when the etching solution according to the present invention is used for cleaning the contact hole, it is not necessary to control the composition of the etching solution and the etching time in order to maintain the shape of the contact hole as in the prior art.
- Examples 1 to 19 and Comparative Examples 1 to 5 First, a silicon substrate having a trench structure on the surface was prepared.
- the trench widths were 80 nm, 190 nm, and 1800 nm, and the depth was 540 nm.
- a solution of polysilazane in dibutyl ether (solid content concentration based on the total weight of the composition is 19% by weight) is spin-coated on the above substrate at 1000 rpm and a part of the solvent at 150 ° C. for 3 minutes. Was removed. At this time, the film thickness of the polysilazane composition coating film in the portion other than the trench structure on the substrate surface was 600 nm.
- H 2 O / (O 2 + H 2 O) 80 mol%
- the undulation height is defined as a difference in height h between a portion where the removal of the SOD film by etching in the trench is the most and a portion where the removal is the smallest.
- PGMEA is propylene glycol monomethyl ether acetate
- PGME is propylene glycol monomethyl ether
- EAA is ethyl acetoacetate
- MEK is methyl ethyl ketone
- EGMEA is ethylene glycol monomethyl ether acetate
- CA is crotonic acid
- PD is 2,4-pentanedione
- IPA represents isopropanol.
- the film shape was defined as A (excellent) when the undulation height was less than 57 nm, B (good) when 57 nm or more and less than 76 nm, and C (inferior) when 76 nm or more.
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Abstract
Description
トレンチ構造を有する基板表面に絶縁材料を含む組成物を塗布して塗膜を形成させる塗布工程、
塗布済みの基板を焼成して、絶縁材料を硬化させ、絶縁膜を形成させる焼成工程、
研磨後の絶縁膜を、フッ酸と有機溶媒とを含んでなり、前記有機溶媒の、ハンセンの溶解度パラメーターによって定義されるδHが4以上12以下であり、20℃の水に対する飽和溶解度が5%以上であるエッチング液で処理するエッチング工程
を含んでなることを特徴とするものである。
このうち、特に好ましいものとしてスチレン換算重量平均分子量が700~30,000であるものが好ましい。
(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。
必要に応じて硬化温度または硬化雰囲気の組成を段階的に変化させることもできる。
基板表面に形成された絶縁膜のトレンチ内側側面に接触している部分は、引っ張り応力が強いため、エッチングされやすい傾向にある。そのため、トレンチ内側側面に近い部分におけるエッチング速度が速くなり、図2(e)に示されるように、トレンチ内部の中央部が盛り上がる。
まず、表面にトレンチ構造を有するシリコン基板を準備した。そのトレンチの幅は80nm、190nm、および1800nmであり、深さは540nmであった。
PGMEAはプロピレングリコールモノメチルエーテルアセテート、
PGMEはプロピレングリコールモノメチルエーテル、
EAAはエチルアセトアセテート、
MEKはメチルエチルケトン、
EGMEAはエチレングリコールモノメチルエーテルアセテート、
CAはクロトン酸、
PDは2,4-ペンタンジオン、
IPAはイソプロパノールを表す。
また、膜形状は、起伏高さが57nm未満をA(優れる)、57nm以上76nm未満をB(良好)、76nm以上をC(劣る)とした。
2 回路
3 キャップ
4 絶縁膜
Claims (8)
- フッ酸と有機溶媒とを含んでなり、前記有機溶媒の、ハンセンの溶解度パラメーターによって定義されるδHが4以上12以下であり、20℃の水に対する飽和溶解度が5重量%以上のものであることを特徴とするエッチング液。
- 前記エッチング液の総重量を基準とした前記フッ酸の含有率が0.06~2重量%である、請求項1に記載のエッチング液。
- 前記有機溶媒が、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、およびエチルアセトアセテートからなる群から選択される、請求項1または2に記載のエッチング液。
- 前記エッチング液の総重量を基準とした前記有機溶媒の含有率が1重量%以上である、請求項1~3のいずれか1項に記載のエッチング液。
- トレンチ構造を有する基板表面に絶縁材料を含む組成物を塗布して塗膜を形成させる塗布工程、
塗布済みの基板を焼成して、絶縁材料を硬化させ、絶縁膜を形成させる焼成工程、
研磨後の絶縁膜を、フッ酸と有機溶媒とを含んでなり、前記有機溶媒の、ハンセンの溶解度パラメーターによって定義されるδHが4以上12以下であり、20℃の水に対する飽和溶解度が5%以上であるエッチング液で処理するエッチング工程
を含んでなることを特徴とするシャロー・トレンチ・アイソレーション構造の形成方法。 - 前記絶縁材料がポリシラザン化合物であり、前記絶縁膜がシリカ質膜である、請求項5に記載のシャロー・トレンチ・アイソレーション構造の形成方法。
- 焼成工程の後、基板上に形成された絶縁膜を研磨する研磨工程をさらに含んでなる、請求項5または6に記載のシャロー・トレンチ・アイソレーション構造の形成方法。
- 研磨を化学的機械的研磨により行う、請求項7に記載のシャロー・トレンチ・アイソレーション構造の形成方法。
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EP10780499.9A EP2437283B1 (en) | 2009-05-25 | 2010-05-24 | Method for forming trench isolation structure |
CN201080022960.8A CN102449746B (zh) | 2009-05-25 | 2010-05-24 | 蚀刻液及用其形成沟槽隔离结构的方法 |
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SG175799A1 (en) | 2011-12-29 |
JP5535583B2 (ja) | 2014-07-02 |
US20120064722A1 (en) | 2012-03-15 |
CN102449746B (zh) | 2015-02-18 |
TW201100591A (en) | 2011-01-01 |
CN102449746A (zh) | 2012-05-09 |
US8828877B2 (en) | 2014-09-09 |
KR20120036878A (ko) | 2012-04-18 |
EP2437283A4 (en) | 2014-05-07 |
EP2437283B1 (en) | 2017-09-20 |
TWI555883B (zh) | 2016-11-01 |
KR101624378B1 (ko) | 2016-05-25 |
JP2011009685A (ja) | 2011-01-13 |
EP2437283A1 (en) | 2012-04-04 |
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