TWI568806B - Coating composition containing polysilazane - Google Patents
Coating composition containing polysilazane Download PDFInfo
- Publication number
- TWI568806B TWI568806B TW100100458A TW100100458A TWI568806B TW I568806 B TWI568806 B TW I568806B TW 100100458 A TW100100458 A TW 100100458A TW 100100458 A TW100100458 A TW 100100458A TW I568806 B TWI568806 B TW I568806B
- Authority
- TW
- Taiwan
- Prior art keywords
- molecular weight
- perhydropolyazane
- coating
- composition
- oxide film
- Prior art date
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- 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
-
- 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
Description
本發明係關於在半導體之製程中用於使氧化矽質膜形成之被覆組成物者。更具體而言，係關於在半導體之製程作為絕緣膜使用之用於使氧化矽質膜形成之含聚矽氮烷被覆組成物。The present invention relates to a coating composition for forming a cerium oxide film in a semiconductor process. More specifically, it relates to a polyazoxide-containing coating composition for forming a cerium oxide film which is used as an insulating film in a semiconductor process.
近來，於半導體裝置係開始要求更高的積體密度，同時可相應之製造技術正被改良。並且，在該等半導體裝置的製造過程之一的使絕緣膜形成之步驟，係變得有必要埋設窄隙。Recently, higher integration densities have been demanded in semiconductor devices, and corresponding manufacturing techniques are being improved. Further, in the step of forming an insulating film in one of the manufacturing processes of the semiconductor devices, it is necessary to embed a narrow gap.
要埋設如此之窄隙，已知使用含全氫聚矽氮烷被覆組成物。全氫聚矽氮烷係基本骨架由Si-N、Si-H、N-H鍵所構成之聚合物，具有藉由在含氧及/或水蒸氣之氣體環境燒製而Si-N鍵被Si-O鍵取代，得到純度高之氧化矽質膜這樣的特徵。To embed such a narrow gap, it is known to use a perhydropolyazane-containing coating composition. A polymer composed of Si-N, Si-H, and NH bonds, having a basic structure of a perhydropolyazane, having a Si-N bond by Si- in a gas atmosphere containing oxygen and/or water vapor. The O bond is substituted to obtain a characteristic of a ruthenium oxide film having a high purity.
然而，隨著半導體所被要求之積體密度變得更高，間隙開始變得更窄。以往所知之全氫含聚矽氮烷被覆組成物一般而言，雖道是埋設性優良，但為了要達成近來所要求之高積體密度，係開始有改良之必要。具體而言，在以往之被覆組成物，要使埋設性與塗布性兼顧開始變得困難。However, as the bulk density required for semiconductors becomes higher, the gap begins to become narrower. The perhydrogen-containing polyazane-coated composition known in the prior art is generally excellent in embedding property, but it is necessary to improve the high-density density required in recent years. Specifically, in the conventional coated composition, it is difficult to achieve both the embedding property and the coating property.
如此問題的原因之一，已知有全氫聚矽氮烷的分子量分布。例如，於專利文獻1係揭示有使用重量平均分子量為4000至8000，重量平均分子量及數量平均分子量之比為3.0至4.0之全氫聚矽氮烷的旋轉塗布玻璃(spin on glass)組成物。此外，於專利文獻2，係揭示有重量平均分子量為3000至6000之含聚矽氮烷旋轉塗布玻璃。再者，於專利文獻3係揭示有聚苯乙烯換算分子量為700以下之聚矽氮烷量為總聚矽氮烷量之10%以下的氧化矽系被覆膜形成用塗布液。該等係皆為欲控制聚矽氮烷之分子量分布，改良塗布性等者。One of the causes of such a problem is known to have a molecular weight distribution of perhydropolyazane. For example, Patent Document 1 discloses a spin on glass composition using a perhydropolyazane having a weight average molecular weight of 4000 to 8000 and a weight average molecular weight and a number average molecular weight of 3.0 to 4.0. Further, Patent Document 2 discloses a polyazide-containing spin-coated glass having a weight average molecular weight of 3,000 to 6,000. In addition, Patent Document 3 discloses a coating liquid for forming a cerium oxide-based coating film in which the amount of polyazane in a polystyrene-converted molecular weight of 700 or less is 10% or less of the total amount of polyazane. These are all intended to control the molecular weight distribution of polyazane, improve coating properties and the like.
根據本發明人等之探討，若使用重量平均分子量小的全氫聚矽氮烷則埋設性有提升之傾向，但塗布時變得容易產生條紋，相對地若使用重量平均分子量大的全氫聚矽氮烷，則條紋的產生受抑制且塗布性改良，但埋設性有劣化之傾向。結果未充分埋設至窄隙的深部，容易發生塗布後燒製使氧化矽質膜形成時，間隙深部的氫氟酸所致之蝕刻率變大這樣的問題而有如此之問題點。如此之問題點係在僅有專利文獻1至3所記載之分子量分布之控制時則不充分，期望更進一步的改良。According to the investigation by the inventors of the present invention, when perhydropolyazane having a small weight average molecular weight is used, the embedding property tends to be improved, but streaks are likely to occur during coating, and relatively all hydrogen condensation having a large weight average molecular weight is used. In the case of decane, the generation of streaks is suppressed and the coating property is improved, but the embedding property tends to be deteriorated. As a result, the problem is not sufficiently buried in the deep portion of the narrow gap, and the problem that the etching rate due to hydrofluoric acid in the deep portion is increased when the cerium oxide film is formed by firing after coating is likely to occur. Such a problem is insufficient when only the control of the molecular weight distribution described in Patent Documents 1 to 3 is insufficient, and further improvement is desired.
[專利文獻1]日本特開2001-319927號說明書[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-319927
[專利文獻2]日本特開2005-150702號說明書[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-150702
[專利文獻3]日本特開平8-269399號說明書[Patent Document 3] Japanese Patent Application Laid-Open No. Hei 8-269399
[專利文獻4]日本專利第1474685號說明書[Patent Document 4] Japanese Patent No. 1474685
[專利文獻5]日本專利第2613787號說明書[Patent Document 5] Japanese Patent No. 2613787
如上所述，以往之被覆組成物係在近來所要求之於欲對具有窄隙之基板使氧化矽質膜形成時，無法充分地兼顧埋設性與塗布性。本發明之目的係有鑒於如此之問題點，而提供可充分地埋設窄隙，換言之為縱橫比大的間隙、且塗布時不產生條紋，用於使半導體裝置之氧化矽質膜形成的被覆組成物。As described above, in the conventional coating composition, when it is required to form a cerium oxide film for a substrate having a narrow gap, the embedding property and the coating property cannot be sufficiently achieved. The object of the present invention is to provide a coating which can sufficiently embed a narrow gap, in other words, a gap having a large aspect ratio and which does not generate streaks during coating, for forming a cerium oxide film of a semiconductor device. Things.
本發明所致之被覆組成物，其為含全氫聚矽氮烷與溶劑而成之被覆組成物，其特徵為該全氫聚矽氮烷之分子量分布曲線在分子量800至2,500之範圍、與分子量3,000至8,000之範圍各具有極大值，且重量平均分子量Mw與數量平均分子量Mn之比Mw/Mn為6至12。The coated composition of the present invention is a coated composition comprising perhydropolyazane and a solvent, characterized in that the molecular weight distribution curve of the perhydropolyazane is in the range of molecular weight 800 to 2,500, and The molecular weight ranges from 3,000 to 8,000 each have a maximum value, and the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is from 6 to 12.
此外，本發明所致之氧化矽質膜之形成方法，其特徵為含有以下步驟：於具有凹凸之基板的表面上塗布被覆組成物之塗布步驟，該被覆組成物為含全氫聚矽氮烷與溶劑而成之被覆組成物，其中該全氫聚矽氮烷之分子量分布曲線在分子量800至2,500之範圍、與分子量3,000至8,000之範圍各具有極大值，且重量平均分子量Mw與數量平均分子量Mn之比Mw/Mn為6至12；及將完成塗布之基板在小於1000℃之氧氣環境或含水蒸氣之氧化氣體環境進行加熱處理使前述組成物轉化為二氧化矽膜之硬化步驟。Further, a method for forming a ruthenium oxide film according to the present invention is characterized in that the method comprises the step of applying a coating composition on a surface of a substrate having irregularities, wherein the coating composition is a perhydropolyazoxide containing a coating composition formed with a solvent, wherein the molecular weight distribution curve of the perhydropolyazane has a maximum value in a range of a molecular weight of 800 to 2,500 and a molecular weight of 3,000 to 8,000, and a weight average molecular weight Mw and a number average molecular weight. The ratio Mn of Mw/Mn is 6 to 12; and the hardening step of converting the above-mentioned composition into a cerium oxide film by heat-treating the coated substrate in an oxygen atmosphere of less than 1000 ° C or an oxidizing gas atmosphere containing water vapor.
根據本發明之被覆組成物，可兼顧含聚矽氮烷化合物被覆組成物之塗布性與埋設性，更且亦可改善所得之氧化矽質膜的膜物性。According to the coating composition of the present invention, both the coatability and the embedding property of the polyazide-containing compound-coated composition can be achieved, and the film properties of the obtained cerium oxide film can be improved.
以下，就本發明的實施形態詳細地說明。Hereinafter, embodiments of the present invention will be described in detail.
本發明所致之被覆組成物，係含全氫聚矽氮烷與可將其全氫聚矽氮烷溶解之溶劑而成。The coating composition of the present invention comprises a perhydropolyazane and a solvent which can dissolve the perhydropolyazane.
用於本發明之全氫聚矽氮烷，係如後述一般需要具有特定之分子量及分子量分布，但其結構並無特別限定，只要不損及本發明之效果可選擇任意結構者。為無機化合物之全氫聚矽氮烷，係具有僅由矽、氮、及氫構成，藉由燒製而使氧化矽質膜形成時不純物不易混入之特徵。如此之全氫聚矽氮烷的具體結構係可以下述一般式(I)表示。The perhydropolyazane used in the present invention is generally required to have a specific molecular weight and molecular weight distribution as described later, but the structure thereof is not particularly limited, and any structure can be selected as long as the effects of the present invention are not impaired. The perhydropolyazane which is an inorganic compound has a characteristic of being composed only of ruthenium, nitrogen, and hydrogen, and the ruthenium oxide film is formed by firing to prevent impurities from being mixed. The specific structure of such a perhydropolyazane can be represented by the following general formula (I).
-(SiH2-NH)n- (I)-(SiH 2 -NH) n - (I)
式中，n係表示聚合度之數。In the formula, n is the number of degrees of polymerization.
另外在不損及本發明之效果的範圍，亦可少量含有(I)式之氫的部分或全部被取代成烷基、烯基、環烷基、芳基、烷矽基、烷胺基或烷氧基等之聚矽氮烷化合物。Further, in a range not impairing the effects of the present invention, a part or all of hydrogen containing a small amount of the formula (I) may be substituted with an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkyl fluorenyl group, an alkylamino group or A polyazane compound such as an alkoxy group.
本發明所致之聚矽氮烷組成物，雖係含前述之全氫聚矽氮烷而成者，但其全氫聚矽氮烷之分子量分布曲線係在分子量800至2,500之區域、與分子量3,000至8,000之區域具有極大值者。此時，於這兩個極大值之間係存在一個以上，較佳為一個的極小值。The polyazane component resulting from the present invention is a mixture of the above-mentioned perhydropolyazane, but the molecular weight distribution curve of the perhydropolyazane is in the region of molecular weight 800 to 2,500, and molecular weight. The area of 3,000 to 8,000 has a great value. At this time, there is one or more, preferably one, minimum values between the two maximum values.
具有如此之分子量分布曲線的全氫聚矽氮烷，雖係可用任意方法進行調製，但最簡單係可藉由混合分子量相對地大的全氫聚矽氮烷、與分子量相對地小的全氫聚矽氮烷而獲得。更具體地說，較佳為藉由將重量平均分子量800至2,500，尤其1,000至2,200的全氫聚矽氮烷(以下，為簡單化以低分子量聚矽氮烷稱之)、與重量平均分子量3,000至8,000，尤其3,500至7,000的全氫聚矽氮烷(以下，為簡單化以高分子量聚矽氮烷稱之)混合而獲得。此係雖無特別限定混合前的全氫聚矽氮烷之合成方法，但可藉由例如專利文獻4或5所記載之方法而合成。The perhydropolyazane having such a molecular weight distribution curve can be prepared by any method, but the simplest is by mixing a perhydropolyazane having a relatively large molecular weight and a total hydrogen having a relatively small molecular weight. Obtained by polyazane. More specifically, it is preferred to use a perhydropolyazane having a weight average molecular weight of 800 to 2,500, especially 1,000 to 2,200 (hereinafter, simplification is referred to as a low molecular weight polyazane), and a weight average molecular weight. It is obtained by mixing 3,000 to 8,000, especially 3,500 to 7,000 of perhydropolyazane (hereinafter, simplification is referred to as high molecular weight polyazane). Although the method of synthesizing the perhydropolyazane before mixing is not particularly limited, it can be synthesized by, for example, the method described in Patent Document 4 or 5.
不僅全氫聚矽氮烷，高分子化合物由於在分子量分布具有範圍，在將分子量不同的兩種高分子化合物混合時、混合前後，有時分子量分布的極大值之位置會變化。此係尤其在兩種高分子化合物之分子量分布的極大值分子量相近時容易發生，藉由混合，具極大值的分子量有接近的傾向。視情形極大值亦可能變成一個。然而，將具有如前所述之重量平均分子量的兩種全氫聚矽氮烷混合時，因分子量差為大，一般而言極大值係不變成一個。此外，在本案發明中，由於認為藉由使具有二個極大值之間的分子量之成分減少而展現本發明的效果，故有必要至少混合兩種全氫聚矽氮烷使兩個極大值之間具有極小值。In addition to the perhydropolyazane, the polymer compound has a range of molecular weight distribution, and when the two polymer compounds having different molecular weights are mixed, the position of the maximum value of the molecular weight distribution may change before and after mixing. This is particularly likely to occur when the molecular weight distributions of the two polymer compounds have similar molecular weights, and by mixing, the molecular weight having a maximum value tends to be close. The maximum value may also become one depending on the situation. However, when two perhydropolyazane having a weight average molecular weight as described above is mixed, the molecular weight difference is large, and generally the maximum value does not become one. Further, in the invention of the present invention, since it is considered that the effect of the present invention is exhibited by reducing the component having a molecular weight between two maximum values, it is necessary to mix at least two perhydropolyazane to make two maximum values. There is a minimum between the two.
本發明中，為了達成目的分子量分布而混合兩種全氫聚矽氮烷時，各全氫聚矽氮烷的分子量分布係以窄者為佳。此係因所混合之任一者、或兩者的全氫聚矽氮烷之分子量分布若廣，則分布曲線的兩個極大值之間不易顯出極小值，此外本發明的效果亦有變小之傾向之故。具體而言，就進行混合前的兩種全氫聚矽氮烷之各者，重量平均分子量Mw與數量平均分子量Mn之比Mw/Mn較佳為1.1至1.8。In the present invention, when two kinds of perhydropolyazane are mixed in order to achieve the desired molecular weight distribution, the molecular weight distribution of each perhydropolyazane is preferably narrow. In this case, if the molecular weight distribution of the perhydropolyazane of either of the two or both of them is wide, the minimum value between the two maximum values of the distribution curve is less likely to be exhibited, and the effect of the present invention is also changed. The reason for the small tendency. Specifically, the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is preferably from 1.1 to 1.8 in terms of each of the two perhydropolyazane before mixing.
要使全氫聚矽氮烷的分子量分布狹窄，由除去全氫聚矽氮烷所含之高分子量成分、及/或低分子量成分而進行係為簡便。以如此之除去高分子量成分、及/或低分子量成分的簡單方法而言，舉出利用溶解度的分子量依存性之方法。亦即，全氫聚矽氮烷，一般而言係有分子量越大溶解度越低、分子量越小溶解度越高之傾向。利用如此之溶解度差，使該全氫聚矽氮烷溶解於具有可溶解該全氫聚矽氮烷之一部分的程度的溶解性之溶劑，藉由過濾分離不溶性成分，而可分別成當作不溶性成分被過濾分離之高分子量成分、與溶解於溶劑中之低分子量成分。亦即，若除去被過濾分離之不溶性成分則係除去高分子量成分，若除去溶解之成分則係除去低分子量成分。In order to narrow the molecular weight distribution of the perhydropolyazane, it is convenient to remove the high molecular weight component and/or the low molecular weight component contained in the perhydropolyazane. A simple method of removing the high molecular weight component and/or the low molecular weight component in this way is a method of utilizing the solubility dependence of the molecular weight. That is, the perhydropolyazane generally has a tendency that the higher the molecular weight, the lower the solubility, and the lower the molecular weight, the higher the solubility. By using such a difference in solubility, the perhydropolyazane is dissolved in a solvent having a solubility to dissolve a part of the perhydropolyazane, and the insoluble component is separated by filtration to be insoluble. The high molecular weight component which is separated by filtration and the low molecular weight component dissolved in the solvent. That is, when the insoluble component separated by filtration is removed, the high molecular weight component is removed, and when the dissolved component is removed, the low molecular weight component is removed.
在此，全氫聚矽氮烷之溶解性係視使用之溶劑而異，因此以某溶劑除去高分子量成分後，亦可使用溶解性不同的另一溶劑除去低分子量，進一步使分子量分布的寬度狹窄。在如此之方法，雖常有不能完全地除去高分子量成分或低分子量成分之情況，但為了使不同分子量，亦即不同聚合度的化合物之混合物即高分子化合物的分子量分布狹窄，係簡便且有效的方法。以用於如此之用途的溶劑而言，例如以碳氫化合物為合適。例如若為烷類，隨著碳數變多有可溶解分子量更大的全氫聚矽氮烷之傾向。一般而言，可使用碳數5至10左右的碳氫化合物。Here, the solubility of the perhydropolyazane varies depending on the solvent to be used. Therefore, after removing the high molecular weight component in a certain solvent, the solvent having a different solubility may be used to remove the low molecular weight and further increase the width of the molecular weight distribution. narrow. In such a method, although it is often impossible to completely remove the high molecular weight component or the low molecular weight component, it is simple and effective in order to narrow the molecular weight distribution of the polymer compound having a different molecular weight, that is, a mixture of different polymerization degrees. Methods. For the solvent used for such use, for example, a hydrocarbon is suitable. For example, in the case of an alkane, as the carbon number increases, there is a tendency to dissolve a perhydropolyazane having a larger molecular weight. In general, hydrocarbons having a carbon number of about 5 to 10 can be used.
此外，為使高分子化合物之分子量分布狹窄，亦可藉由一般所用之層析法等而分離成全氫聚矽氮烷之各分子量。但是，若使用層析法則處理時間可能會變長，從生產效率的觀點看來以利用對前述溶劑之溶解性差的方法為佳。Further, in order to narrow the molecular weight distribution of the polymer compound, each molecular weight of the perhydropolyazane may be separated by a conventionally used chromatography method or the like. However, if chromatography is used, the treatment time may become long, and from the viewpoint of productivity, it is preferred to use a method which is inferior in solubility to the aforementioned solvent.
還有，不僅進行用於使全氫聚矽氮烷之分子量分布狹窄的處理，藉由進行合成方法或合成原料的調整而合成分子量分布窄的全氫聚矽氮烷亦為有效。Further, in addition to the treatment for narrowing the molecular weight distribution of the perhydropolyazane, it is also effective to synthesize a perhydropolyazane having a narrow molecular weight distribution by performing a synthesis method or adjustment of a synthetic raw material.
另外，在混合兩種全氫聚矽氮烷前，於除去各全氫聚矽氮烷所含之高分子量成分或低分子量成分時，較佳為將低分子量全氫聚矽氮烷之高分子量成分，又，高分子量全氫聚矽氮烷之低分子量成分除去。藉由如此地減少對應於分子量分布曲線的兩個極大值之中間區域之成分，更強烈地展現本發明之效果。Further, in order to remove the high molecular weight component or the low molecular weight component contained in each perhydropolyazane before mixing the two perhydropolyazane, the high molecular weight of the low molecular weight perhydropolyazane is preferred. The component, in turn, is removed by the low molecular weight component of the high molecular weight perhydropolyazane. The effect of the present invention is more strongly exhibited by thus reducing the composition of the intermediate portion corresponding to the two maximum values of the molecular weight distribution curve.
以如上之方法準備具有不同分子量之全氫聚矽氮烷，混合該等時，其混合比較佳為低分子量聚矽氮烷與高分子量聚矽氮烷之重量比為3:7至6:4，更佳為4:6至6:4。混合比若在此範圍外，則有時塗布性與埋設性之平衡會因而變差。The perhydropolyazane having different molecular weights is prepared in the above manner, and when mixed, the mixing ratio of the low molecular weight polyazane to the high molecular weight polyazane is preferably from 3:7 to 6:4. More preferably 4:6 to 6:4. If the mixing ratio is outside this range, the balance between coatability and embedding may be deteriorated.
本發明中具有特定分子量分布之全氫聚矽氮烷，係如前所述一般，以藉由混合分子量不同的兩種全氫聚矽氮烷而獲得為簡便，但亦可藉由其他方法而獲得。例如，藉由準備具有較廣之分子量分布的全氫聚矽氮烷，然後以層析法除去分子量在2,500至3,000附近之中間區域成分，而可達成期望之分子量分布。The perhydropolyazane having a specific molecular weight distribution in the present invention is generally obtained by mixing two kinds of perhydropolyazane having different molecular weights as described above, but may be further by other methods. obtain. For example, a desired molecular weight distribution can be achieved by preparing a perhydropolyazane having a broad molecular weight distribution and then removing an intermediate component having a molecular weight of around 2,500 to 3,000 by chromatography.
此外，用於本發明之全氫聚矽氮烷係需要其重量平均分子量Mw與數量平均分子量Mn之比Mw/Mn為6至12，較佳為7至10。如此之比Mw/Mn係如前所述一般，在混合兩種全氫聚矽氮烷的情形，在將低分子量全氫聚矽氮烷、與高分子量全氫聚矽氮烷以3:7至6:4之重量比混合時可達成。Further, the perhydropolyazane used in the present invention requires a ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 6 to 12, preferably 7 to 10. The ratio of Mw/Mn is as described above. In the case of mixing two perhydropolyazane, the low molecular weight perhydropolyazane and the high molecular weight perhydropolyazane are 3:7. A weight ratio of 6:4 can be achieved when mixing.
本發明所致之被覆組成物，係含有前述之可溶解全氫聚矽氮烷的溶劑而成。以如此之溶劑而言，只要係可溶解前述之各成分者則無特別限定，但以較佳之溶劑的具體例而言，舉出下列者：(a)芳香族化合物，例如苯、甲苯、二甲苯、乙苯、二乙苯、三甲苯、三乙苯等，(b)飽和烴化合物，例如正戊烷、異戊烷、正己烷、異己烷、正庚烷、異庚烷、正辛烷、異辛烷、正壬烷、異壬烷、正癸烷、異癸烷等，(c)脂環式烴化合物，例如乙基環己烷、甲基環已烷、環己烷、環己烯、對薄荷烷、十氫萘、雙戊烯、檸檬烯等，(d)醚類，例如二丙醚、二丁醚、二乙醚、甲基三級丁基醚、苯甲醚等，及(e)酮類、例如甲基異丁基酮)等。該等之中，更佳為(b)飽和烴化合物、(c)脂環式烴化合物(d)醚類、及(e)酮類。The coating composition according to the present invention is obtained by containing the above-mentioned solvent capable of dissolving perhydropolyazane. The solvent is not particularly limited as long as it can dissolve the above-mentioned respective components. However, specific examples of preferred solvents include the following: (a) aromatic compounds such as benzene, toluene, and Toluene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, etc., (b) saturated hydrocarbon compounds such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane , isooctane, n-decane, isodecane, n-decane, isodecane, etc., (c) alicyclic hydrocarbon compounds such as ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexane Alkene, p-menthane, decalin, dipentene, limonene, etc., (d) ethers such as dipropyl ether, dibutyl ether, diethyl ether, methyl tertiary butyl ether, anisole, etc., and e) a ketone such as methyl isobutyl ketone or the like. Among these, (b) a saturated hydrocarbon compound, (c) an alicyclic hydrocarbon compound (d) ether, and (e) a ketone are more preferable.
該等之溶劑，為調整溶劑的蒸發速度、為降低對人體之有害性、或為調製各成分之溶解性，而係亦可使用經混合適當之兩種以上者。These solvents may be used by adjusting the evaporation rate of the solvent, reducing the harmfulness to the human body, or preparing the solubility of each component.
用於本發明之被覆組成物，係視需要亦可含有其他之添加劑成分。如此之成分，可舉出例如黏度調整劑、交聯促進劑等。此外，以用於半導體裝置時，鈉之聚集(gathering)效果等為目的，亦可含有磷化合物，例如參(三甲基矽基)磷酸酯等。The coating composition used in the present invention may contain other additive components as needed. Examples of such a component include a viscosity modifier, a crosslinking accelerator, and the like. Further, for the purpose of use in a semiconductor device, a glycation effect of sodium or the like may be contained, for example, a phosphorus compound such as ginseng (trimethylsulfonyl) phosphate.
此外，前述之各成分的含有量，雖係視目的組成物的用途而改變，但全氫聚矽氮烷的含有率較佳為10至25重量%，更佳為設為12至22重量%。一般而言全氫聚矽氮烷的含量若過高則被覆組成物的黏度變高、埋設性或塗布性有劣化之傾向，又若過低則所形成之氧化矽質膜的厚度有不足之傾向。Further, the content of each component described above varies depending on the use of the intended composition, but the content of perhydropolyazane is preferably 10 to 25% by weight, more preferably 12 to 22% by weight. . In general, if the content of the perhydropolyazane is too high, the viscosity of the coating composition tends to be high, the embedding property or the coating property tends to be deteriorated, and if it is too low, the thickness of the cerium oxide film formed is insufficient. tendency.
氧化矽質膜之製造法Method for producing cerium oxide film
根據本發明之氧化矽質膜之製造法，可於具有溝或孔洞等之縫隙的基板上，形成充分地埋設至縫隙之深部、膜面平坦、膜質亦均勻的被覆膜。因此，電子裝置的電晶體部分或電容器部分的作為平坦化絕緣膜(前金屬(pre-metal)絕緣膜)而形成，再於帶有溝之基板上使氧化矽質膜形成並將溝埋封，亦可形成槽隔離(trench isolation)結構。以下基於使槽隔離結構形成之方法說明本發明。According to the method for producing a ruthenium oxide film of the present invention, a coating film which is sufficiently buried in a deep portion of the slit, has a flat film surface, and has a uniform film quality can be formed on a substrate having a slit such as a groove or a hole. Therefore, the transistor portion or the capacitor portion of the electronic device is formed as a planarization insulating film (pre-metal insulating film), and the yttrium oxide film is formed on the grooved substrate and the trench is buried. It is also possible to form a trench isolation structure. The invention is described below based on a method of forming a trench isolation structure.
(A)塗布步驟(A) Coating step
本發明所致之被覆組成物，係適於形成基板上的槽隔離結構者。於使槽隔離結構形成時，準備具有期望之構圖案的矽等之基板。要形成此溝，雖可使用任意方法，但藉由例如以下所示之方法可使其形成。The coated composition of the present invention is suitable for forming a trench isolation structure on a substrate. When the trench isolation structure is formed, a substrate having a desired pattern or the like is prepared. To form the groove, any method can be used, but it can be formed by, for example, the method shown below.
首先，於矽基板表面藉由例如熱氧化法使二氧化矽膜。在此，使其形成之二氧化矽膜的厚度一般為5至30 nm。First, a ruthenium dioxide film is formed on the surface of the ruthenium substrate by, for example, thermal oxidation. Here, the thickness of the cerium oxide film formed is generally 5 to 30 nm.
視需要於所形成之二氧化矽膜上藉由例如減壓CVD法使氮化矽膜形成。該氮化矽膜係可作為之後的蝕刻步驟中之光罩、或後述之研磨步驟中之終止層而使其發揮功能者。氮化矽膜，於使其形成時，一般係以100至400 nm的厚度使其形成。A tantalum nitride film is formed on the formed hafnium oxide film by, for example, a reduced pressure CVD method as needed. The tantalum nitride film can be used as a photomask in a subsequent etching step or a termination layer in a polishing step to be described later. The tantalum nitride film is generally formed to have a thickness of 100 to 400 nm when it is formed.
於如此使其形成之二氧化矽膜或氮化矽膜之上塗布光阻。視需要使光阻膜乾燥或硬化後，以期望的圖案進行曝光及顯影使圖案形成。曝光的方法係可以光罩曝光、掃描曝光等任意的方法來進行。此外，光阻從解析度等之觀點來看，亦可選擇任意者使用。The photoresist is coated on the ruthenium dioxide film or the tantalum nitride film thus formed. The photoresist film is dried or hardened as needed, and then exposed and developed in a desired pattern to form a pattern. The exposure method can be carried out by any method such as mask exposure or scanning exposure. Further, the photoresist may be selected from any viewpoint from the viewpoint of resolution and the like.
將所形成之光阻膜當作光罩，依序蝕刻氮化矽膜及在其下之二氧化矽膜。藉此操作而於氮化矽膜及二氧化矽膜形成期望之圖案。The formed photoresist film is used as a mask, and the tantalum nitride film and the ceria film under it are sequentially etched. By this operation, a desired pattern is formed on the tantalum nitride film and the hafnium oxide film.
將經形成圖案之氮化矽膜及二氧化矽膜作為光罩，乾蝕刻矽基板，使槽隔離溝形成。The patterned tantalum nitride film and the hafnium oxide film are used as a photomask, and the germanium substrate is dry-etched to form a trench isolation trench.
所形成之槽隔離溝的寬度，係由將光阻膜曝光的圖案所決定。半導體元件中槽隔離溝雖係視目的之半導體元件而不同，但寬度係一般為0.02至10 μm，較佳為0.05至5 μm，深度係200至1000 nm，較佳為300至700 nm。本發明所致之方法，與以往之槽隔離結構的形成方法相比，由於可均勻地埋設至更窄、更深的部分，故係適於使更窄、更深的槽隔離結構形成的情況者。尤其，在以往之氧化矽質膜形成用組成物或氧化矽質膜的形成方法，係難以形成均勻的氧化矽質膜至溝的深部分，溝的寬度一般為0.5 μm以下，尤其0.1 μm以下，於形成縱橫比為5以上之槽隔離結構時，藉由使用本發明所致之氧化矽質膜形成用組成物而可使其均一地形成溝內的氧化矽質膜。The width of the trench isolation trench formed is determined by the pattern in which the photoresist film is exposed. The trench isolation trenches in the semiconductor element differ depending on the intended semiconductor element, but the width is generally 0.02 to 10 μm, preferably 0.05 to 5 μm, and the depth is 200 to 1000 nm, preferably 300 to 700 nm. The method according to the present invention is suitable for forming a narrower and deeper trench isolation structure because it can be uniformly buried to a narrower and deeper portion than the conventional method of forming a trench isolation structure. In particular, in the conventional method for forming a cerium oxide film-forming composition or a cerium oxide film, it is difficult to form a uniform cerium oxide film to a deep portion of the groove, and the width of the groove is generally 0.5 μm or less, particularly 0.1 μm or less. When a trench isolation structure having an aspect ratio of 5 or more is formed, the ruthenium oxide film in the trench can be uniformly formed by using the composition for forming a ruthenium oxide film according to the present invention.
接著，於如此所準備之矽基板上，使氧化矽質膜的材料所成之前述被覆組成物的塗膜形成。Next, on the substrate thus prepared, a coating film of the coating composition formed of the material of the cerium oxide film is formed.
被覆組成物係可以任意的方法塗布於基板上。具體而言，舉出旋轉塗布、簾式塗布、浸漬塗布、及其他。該等之中，從塗膜面的均一性等之觀點來看特佳為旋轉塗布。The coating composition can be applied to the substrate by any method. Specifically, spin coating, curtain coating, dip coating, and the like are mentioned. Among these, spin coating is particularly preferred from the viewpoint of uniformity of the coating film surface and the like.
為兼顧氧化矽質膜形成用組成物塗布後之槽溝埋設性及塗布性，所塗布之塗膜的厚度一般為10至1,000 nm，較佳為50至800 nm。In order to achieve both the groove embedding property and the coating property after application of the composition for forming a cerium oxide film, the thickness of the applied coating film is generally from 10 to 1,000 nm, preferably from 50 to 800 nm.
塗布的條件雖視組成物的濃度、溶劑、或塗布方法等而改變，但舉出以旋轉塗布為例則係如以下所述。The conditions of the coating vary depending on the concentration of the composition, the solvent, the coating method, and the like. However, the spin coating is exemplified as follows.
最近係為了改善製造之產率，常於大型基板使元件形成，但為了要於8吋以上的矽基板均一地使氧化矽質膜形成用組成物的塗膜形成，組合多個階段的旋轉塗布係為有效。In order to improve the production yield, a device is often formed on a large substrate. However, in order to uniformly form a coating film of a composition for forming a cerium oxide film on a ruthenium substrate of 8 Å or more, a plurality of stages of spin coating are combined. Is valid.
首先，於矽基板的中心部、或基板整面，以平均地形成塗膜的方式，於含中心部之數處，一般係每一塊矽基板滴下0.5至20cc的組成物。First, a coating film is formed on the center of the substrate or the entire surface of the substrate so that a composition of 0.5 to 20 cc is dropped on each of the ruthenium substrates at the center portion.
接著，為了將經滴下之組成物擴展至矽基板整面，以較低速且短時間，例如旋轉速度50至500rpm、0.5至10秒鐘而使其旋轉(預旋轉)。Next, in order to spread the dripped composition to the entire surface of the crucible substrate, it is rotated (pre-rotated) at a lower speed and for a short time, for example, a rotation speed of 50 to 500 rpm, 0.5 to 10 seconds.
接著，為了使塗膜成為期望之厚度，以較高速，例如旋轉速度500至4500rpm、0.5至800秒鐘而使其旋轉(主旋轉)。Next, in order to make the coating film a desired thickness, it is rotated (main rotation) at a relatively high speed, for example, a rotation speed of 500 to 4500 rpm for 0.5 to 800 seconds.
再者，為了減低在矽基板之周邊部分的塗膜之遽增、且將塗膜中之溶劑盡可能地乾燥，以相對於前述主旋轉之旋轉速度快500rpm以上之旋轉速度，例如旋轉速度1000至5000rpm、5至300秒鐘而使其旋轉(終旋轉)。Further, in order to reduce the increase in the coating film in the peripheral portion of the substrate, and to dry the solvent in the coating film as much as possible, the rotation speed is faster than the rotation speed of the main rotation by 500 rpm or more, for example, the rotation speed of 1000. It is rotated (final rotation) to 5000 rpm for 5 to 300 seconds.
該等之塗布條件係視使用之基板的大小、或目的之半導體素子的性能等而適當調整。The coating conditions are appropriately adjusted depending on the size of the substrate to be used, the performance of the semiconductor element to be used, and the like.
(B)硬化步驟(B) hardening step
塗布被覆組成物後，可視需要付諸預烘焙步驟。在預烘焙步驟，係以塗膜中所含溶劑之完全除去、與塗膜之前硬化為目的者。尤其在使用含聚矽氮烷組成物之本發明的氧化矽質膜之形成方法中，係藉由進行預烘焙處理，提升所形成之氧化矽質膜的緻密性，因此較佳為組合預烘焙步驟。After the coated composition is applied, the pre-baking step can be carried out as needed. In the prebaking step, it is intended to completely remove the solvent contained in the coating film and to harden the coating film. In particular, in the method of forming a ruthenium oxide film of the present invention using a polyazide-containing composition, the pre-baking treatment is performed to enhance the density of the formed cerium oxide film, so that it is preferable to combine pre-baking. step.
通常，在預烘焙步驟係於實質上採取以固定溫度進行加熱之方法。此外，於硬化時係為了防止塗膜收縮、縫隙部分變成凹痕、於縫隙內部產生空隙，而較佳為控制預烘焙步驟中之溫度、經時地使其上升同時進行預烘焙。預烘焙步驟中之溫度通常係在50℃至400℃，較佳為在100至300℃之範圍內。預烘焙步驟之需要的時間一般係10秒鐘至30分鐘，較佳為30秒鐘至10分鐘。Typically, the pre-baking step is essentially a method of heating at a fixed temperature. Further, in order to prevent shrinkage of the coating film, formation of dents in the slit portion, and generation of voids in the slit during curing, it is preferred to control the temperature in the prebaking step and raise it over time while prebaking. The temperature in the prebaking step is usually in the range of 50 ° C to 400 ° C, preferably in the range of 100 to 300 ° C. The time required for the pre-baking step is generally from 10 seconds to 30 minutes, preferably from 30 seconds to 10 minutes.
要使預烘焙步驟中之溫度經時地上升，舉出使基板所被放置之氣體環境的溫度階段性地上升之方法、或使溫度單調增加地上升之方法。在此，預烘焙步驟中之最高預烘焙溫度，由從被覆膜除去溶劑之觀點來看，一般設定成比用於氧化矽質膜形成用組成物之溶劑的沸點更高的溫度。In order to increase the temperature in the prebaking step over time, a method of gradually increasing the temperature of the gas atmosphere in which the substrate is placed or a method of increasing the temperature monotonically increases is mentioned. Here, the highest prebaking temperature in the prebaking step is generally set to a temperature higher than the boiling point of the solvent for the cerium oxide film forming composition from the viewpoint of removing the solvent from the coating film.
另外，本發明所致之方法中，於組合預烘焙步驟時，將變得比預烘焙更高溫的基板降低溫度前，以將較佳為50℃以上、預烘焙時之最高溫度以下的溫度之基板付諸硬化步驟為佳。由將降低溫度前之基板付諸硬化步驟，可節省再度使溫度上升之能量與時間。Further, in the method of the present invention, at the time of lowering the temperature of the substrate which is higher than the prebaking, the temperature is lower than the maximum temperature at the time of prebaking, preferably at 50 ° C or higher. The substrate is preferably subjected to a hardening step. By applying the hardening step to the substrate before the temperature is lowered, the energy and time for again increasing the temperature can be saved.
接著，為了使含聚矽氮烷塗膜轉化成氧化矽質膜使其硬化，將基板整體進行加熱，付諸硬化步驟。通常，一般係將基板整體投入硬化爐等並進行加熱。Next, in order to convert the polyazide-containing coating film into a cerium oxide film and harden it, the entire substrate is heated and subjected to a hardening step. Usually, the entire substrate is usually placed in a curing furnace or the like and heated.
硬化係較佳為使用硬化爐或加熱板，在含水蒸氣之惰性氣體或氧氣體環境下進行。水蒸氣於使聚矽氮烷充分轉化成氧化矽質膜(亦即二氧化矽)係為重要，較佳為設為30%以上、更佳為50%以上、最佳為70%以上。尤其水蒸氣濃度若為80%以上，則有機化合物對氧化矽質膜之轉化變得容易進行，空隙等缺陷產生變少，氧化矽質膜之特性改良故佳。於使用惰性氣體作為氣體環境氣體時，使用氮、氬、或氦等。The hardening is preferably carried out using a hardening furnace or a hot plate in an inert gas or oxygen atmosphere containing water vapor. The steam is important for sufficiently converting the polyazane to a cerium oxide film (i.e., cerium oxide), and is preferably 30% or more, more preferably 50% or more, and most preferably 70% or more. In particular, when the water vapor concentration is 80% or more, the conversion of the organic compound to the cerium oxide film is facilitated, defects such as voids are reduced, and the properties of the cerium oxide film are improved. When an inert gas is used as the gaseous ambient gas, nitrogen, argon, helium or the like is used.
為使其硬化之溫度條件，係視使用之氧化矽質膜形成用組成物的種類、或步驟的組合方式而改變。然而，溫度高者，聚矽氮烷轉化成氧化矽質膜之速度有變快之傾向，此外，溫度低者，矽基板之氧化或結晶結構之改變所致之對裝置特性之不良影響有變小之傾向。由如此之觀點而言，在本發明中之硬化步驟，係通常以1000℃以下，較佳為400至700℃進行加熱。在此，至目標溫度之昇溫時間一般係1至100℃/分鐘，到達目標溫度之後的硬化時間一般係1分鐘至10小時，較佳為15分鐘至3小時。視需要亦可使硬化溫度或硬化氣體環境的組成階段性地改變。藉由此加熱，聚矽氮烷轉化成二氧化矽而成為氧化矽質膜。The temperature conditions for hardening are changed depending on the type of the composition for forming a cerium oxide film to be used or the combination of steps. However, at higher temperatures, the rate at which polyazane is converted to a ruthenium oxide film tends to increase. In addition, the lower temperature, the adverse effect on the device characteristics due to the oxidation or crystal structure of the ruthenium substrate changes. Small tendency. From such a viewpoint, the hardening step in the present invention is usually carried out at 1000 ° C or lower, preferably 400 to 700 ° C. Here, the temperature rise time to the target temperature is generally 1 to 100 ° C / minute, and the hardening time after reaching the target temperature is generally 1 minute to 10 hours, preferably 15 minutes to 3 hours. The composition of the hardening temperature or the hardened gas environment may be changed stepwise as needed. By this heating, the polyazide is converted into cerium oxide to form a cerium oxide film.
本發明所致之氧化矽質膜的形成方法，雖係以前述之各步驟為必要者，但視需要亦可組合研磨步驟或蝕刻步驟等之進一步的步驟。The method for forming the cerium oxide film according to the present invention may be carried out by the above-described respective steps, but a further step such as a polishing step or an etching step may be combined as necessary.
若使用各例說明本發明則係如以下所述。The invention will be described below using the examples.
含成例1 低分子量聚矽氮烷之合成Synthesis of Example 1 Low molecular weight polyazane
將400g純度99%以上之二氯矽烷一邊攪拌一邊注入至5kg 0℃的無水吡啶。將此混合物的溫度維持於0℃，同時一邊攪拌1.22kg純度99.9%的氨氣一邊注入至混合物。400 g of methylene chloride having a purity of 99% or more was injected while stirring to 5 kg of anhydrous pyridine at 0 °C. The temperature of this mixture was maintained at 0 ° C while being injected into the mixture while stirring 1.22 kg of ammonia gas having a purity of 99.9%.
一邊將混合物的溫度維持於0℃一邊繼續攪拌進行12小時反應。將乾燥氮吹入反應後之混合物30分鐘，除去過剩的氨，其後從漿體狀之反應混合物過濾分離氯化銨，得到濾液A。將二甲苯混合至所得之濾液A中加熱至50℃，在20 mmHg之減壓下進行蒸餾除去吡啶，作成含重量平均分子量1450的聚合物之20重量%濃度之溶液。The reaction was continued for 12 hours while maintaining the temperature of the mixture at 0 °C. Dry nitrogen was blown into the mixture after the reaction for 30 minutes to remove excess ammonia, and then ammonium chloride was separated by filtration from the slurry-like reaction mixture to obtain a filtrate A. The xylene was mixed until the obtained filtrate A was heated to 50 ° C, and pyridine was distilled off under a reduced pressure of 20 mmHg to prepare a 20% by weight solution of a polymer having a weight average molecular weight of 1450.
將所得之20重量%的二甲苯溶液加熱至50℃，在10mmHg之減壓下進行蒸餾除去二甲苯。將正戊烷加入至所得之無色透明液體中，作成10重量%濃度的白色溶液。將此溶液以過濾精度0.2μm的過濾器進行過濾得到聚合物溶液。將二丁醚混合於此聚合物溶液且加熱至50℃，在20mmHg之減壓下進行蒸餾除去正戊烷，作成含重量平均分子量1100、重量平均分子量Mw與數量平均分子量Mn之比Mw/Mn為1.45之聚合物的20重量%濃度之聚合物溶液1。The obtained 20% by weight xylene solution was heated to 50 ° C, and xylene was distilled off under reduced pressure of 10 mmHg. n-Pentane was added to the obtained colorless transparent liquid to prepare a white solution having a concentration of 10% by weight. This solution was filtered with a filter having a filtration precision of 0.2 μm to obtain a polymer solution. Dibutyl ether was mixed with the polymer solution and heated to 50 ° C, and n-pentane was distilled off under a reduced pressure of 20 mmHg to prepare a ratio MW/Mn of a weight average molecular weight of 1,100, a weight average molecular weight Mw and a number average molecular weight Mn. It is a 20% by weight polymer solution 1 of a polymer of 1.45.
合成例2 高分子量聚矽氮烷之合成Synthesis Example 2 Synthesis of high molecular weight polyazane
與合成例1同樣地進行而調製濾液A，進一步在密閉系統以150℃加熱3小時。冷卻至室溫後，回到常壓，將二甲苯混合至所得之溶液並加熱至50℃，在20 mmHg之減壓下進行蒸餾除去吡啶，並作成含重量平均分子量6000之聚合物的20重量%濃度之溶液。The filtrate A was prepared in the same manner as in Synthesis Example 1, and further heated at 150 ° C for 3 hours in a sealed system. After cooling to room temperature, returning to normal pressure, xylene was mixed to the obtained solution and heated to 50 ° C, and pyridine was distilled off under a reduced pressure of 20 mmHg, and 20 weight of a polymer having a weight average molecular weight of 6000 was prepared. % concentration solution.
將所得之20重量%的二甲苯溶液加熱至50℃，並在10 mmHg之減壓下進行蒸餾除去二甲苯。加入正庚烷至所得之白色粉末，作成10重量%濃度之分散液。使用玻璃過濾器(ADVANTEC東洋股份有限公司製：GF-75(商品名))減壓過濾該分散液，並除去溶劑。將所得之白色粉末溶解於二丁醚，作成含重量平均分子量為6400、重量平均分子量Mw與數量平均分子量Mn之比Mw/Mn為1.22之聚合物的20重量%濃度之聚合物溶液2。The obtained 20% by weight xylene solution was heated to 50 ° C, and xylene was distilled off under reduced pressure of 10 mmHg. n-Heptane was added to the obtained white powder to prepare a dispersion having a concentration of 10% by weight. The dispersion was filtered under reduced pressure using a glass filter (manufactured by ADVANTEC Toyo Co., Ltd.: GF-75 (trade name)), and the solvent was removed. The obtained white powder was dissolved in dibutyl ether to prepare a polymer solution 2 having a concentration of 20% by weight of a polymer having a weight average molecular weight of 6,400, a weight average molecular weight Mw and a number average molecular weight Mn of Mw/Mn of 1.22.
合成例3 超高分子量聚矽氮烷之合成Synthesis Example 3 Synthesis of Ultra High Molecular Weight Polyazane
與合成例1同樣地進行而調製濾液A，在密閉系統以150℃加熱6小時。冷卻至室溫後，回到常壓，將二丁醚混合至所得之溶液並加熱至50℃，在20mmHg之減壓下進行蒸餾除去吡啶，並作成含重量平均分子量9200之聚合物的20重量%濃度之聚合物溶液3。 The filtrate A was prepared in the same manner as in Synthesis Example 1, and heated in a sealed system at 150 ° C for 6 hours. After cooling to room temperature, returning to normal pressure, dibutyl ether was mixed to the obtained solution and heated to 50 ° C, and pyridine was distilled off under a reduced pressure of 20 mmHg, and 20 weight of a polymer having a weight average molecular weight of 9,200 was prepared. % concentration of polymer solution 3.
混合60g之聚合物溶液1與40g之聚合物溶液2。混合後之聚合物溶液，於分子量分布曲線之分子量為6300之位置與650之位置具有極大值，又Mw/Mn為10。 60 g of the polymer solution 1 and 40 g of the polymer solution 2 were mixed. The mixed polymer solution had a maximum value at a molecular weight distribution curve of 6300 and a position at 650, and Mw/Mn was 10.
準備形成有深度0.5μm且具有0.05、0.1、0.2、及0.5μm之寬度的溝、表面被氮化矽內襯層所被覆之基板作為矽基板。於此基板藉由旋轉塗布將所調製之聚合物溶液塗布作為被覆組成物。塗布條件係設為，預旋轉：300rpm/5秒鐘、主旋轉：1000rpm/20秒鐘、終旋轉：1500rpm/10秒鐘。觀察塗布後之膜面後，可確認沒有產生條紋、可達成優良之塗布性。 A substrate having a groove having a width of 0.5 μm and having a width of 0.05, 0.1, 0.2, and 0.5 μm and having a surface covered with a tantalum nitride liner layer as a tantalum substrate was prepared. The prepared polymer solution was applied as a coating composition on the substrate by spin coating. The coating conditions were set to pre-rotation: 300 rpm/5 seconds, main rotation: 1000 rpm/20 seconds, and final rotation: 1500 rpm/10 seconds. After observing the film surface after coating, it was confirmed that no streaks were generated, and excellent coatability was achieved.
進一步將此塗布後之基板在加熱板上150℃預烘焙3分鐘，繼續不使其冷卻而導入至純氧氣體環境下之燒製爐。在燒製爐內以昇溫速度10℃/分鐘至加熱800℃，進一步在水蒸氣濃度80%之氧氣體環境下燒製30分鐘。測定所得之燒製膜的FT-IR後，觀測到歸屬於Si-O鍵之波數1080cm-1之吸收，確認得到氧化矽質膜。另一方面，觀測不到歸屬於N-H鍵及Si-H鍵之波數3380cm-1及2200cm-1之吸收，確認全氫聚矽氮烷已轉化成氧化矽。 Further, the coated substrate was prebaked on a hot plate at 150 ° C for 3 minutes, and further introduced into a firing furnace under a pure oxygen gas atmosphere without cooling. The firing was carried out for 30 minutes in an oxygen gas atmosphere having a water vapor concentration of 80% at a heating rate of 10 ° C / min to 800 ° C. After the FT-IR of the obtained fired film was measured, the absorption of the wave number of 1080 cm -1 attributed to the Si-O bond was observed, and it was confirmed that the cerium oxide film was obtained. On the other hand, the absorption of the wave number 3380 cm -1 and 2200 cm -1 attributed to the NH bond and the Si-H bond was not observed, and it was confirmed that the perhydropolyazane was converted into cerium oxide.
此外，使用含0.5重量%之氫氟酸與30重量%之氟化銨的水溶液作為蝕刻溶液，在23℃進行蝕刻而測定對於熱氧化氧化矽膜之相對蝕刻率後，為1.48。 Further, an aqueous solution containing 0.5% by weight of hydrofluoric acid and 30% by weight of ammonium fluoride was used as an etching solution, and etching was performed at 23 ° C to measure the relative etching rate for the thermally oxidized cerium oxide film, which was 1.48.
將燒製後之基板以相對溝之長度方向為直角之方向切斷後，浸漬於含0.5重量%之氫氟酸與30重量%之氟化銨的水溶液30秒鐘，進一步用純水充分地洗淨而後使其乾燥。 The fired substrate was cut in a direction perpendicular to the longitudinal direction of the groove, and then immersed in an aqueous solution containing 0.5% by weight of hydrofluoric acid and 30% by weight of ammonium fluoride for 30 seconds, and further washed thoroughly with pure water. Clean it and then dry it.
將基板之截面，藉由掃描型電子顯微鏡，以50,000倍而從垂直於截面之方向的仰角30°上方觀察各溝之最深部，評估蝕刻量。即使溝寬度改變，蝕刻量之改變亦僅有一點點，可確認即使在寬0.05μm之溝的最深部中亦充分地形成有緻密的氧化矽質膜。 The cross section of the substrate was observed by a scanning electron microscope at a depth of 50,000 times from the elevation angle of 30° perpendicular to the cross section, and the amount of etching was evaluated. Even if the groove width was changed, the amount of etching was changed only a little, and it was confirmed that a dense ruthenium oxide film was sufficiently formed even in the deepest portion of the groove having a width of 0.05 μm.
混合40g之聚合物溶液1與60g之聚合物溶液2。混合後之聚合物溶液，係於分子量分布曲線之分子量為6250的位置與680之位置具有極大值，又Mw/Mn為10。 40 g of the polymer solution 1 and 60 g of the polymer solution 2 were mixed. The mixed polymer solution has a maximum value at a position where the molecular weight distribution curve has a molecular weight of 6,250 and a position of 680, and Mw/Mn is 10.
將所調製之聚合物溶液當作被覆組成物，與實施例1同樣地進行，並塗布於矽基板上。觀察塗布後之膜面後，可確認沒有產生條紋、可達成優良之塗布性。 The prepared polymer solution was used as a coating composition, and was applied in the same manner as in Example 1 and applied onto a ruthenium substrate. After observing the film surface after coating, it was confirmed that no streaks were generated, and excellent coatability was achieved.
進一步將此塗布後之基板與實施例1同樣地進行燒製。測定所得之燒製膜的FT-IR後，觀測到歸屬於Si-O鍵之波數1080cm-1之吸收，確認得到氧化矽質膜。另一方面，觀測不到歸屬於N-H鍵及Si-H鍵之波數3380cm-1及2200cm-1之吸收，確認全氫聚矽氮烷已轉化成氧化矽。此外，與實施例1同樣地測定對於熱氧化氧化矽膜之相對蝕刻率後，為1.50。Further, this coated substrate was fired in the same manner as in Example 1. After the FT-IR of the obtained fired film was measured, the absorption of the wave number of 1080 cm -1 attributed to the Si-O bond was observed, and it was confirmed that the cerium oxide film was obtained. On the other hand, the absorption of the wave number 3380 cm -1 and 2200 cm -1 attributed to the NH bond and the Si-H bond was not observed, and it was confirmed that the perhydropolyazane was converted into cerium oxide. Further, in the same manner as in Example 1, the relative etching rate for the thermally oxidized cerium oxide film was measured and found to be 1.50.
將燒製後之基板的截面藉由與實施例1同樣的方法而觀察，並評估蝕刻量。即使溝寬度改變，蝕刻量之改變亦僅有一點點，可確認即使在寬0.05 μm之溝的最深部中亦充分地形成有緻密的氧化矽質膜。The cross section of the fired substrate was observed in the same manner as in Example 1, and the etching amount was evaluated. Even if the groove width was changed, the amount of etching was changed only a little, and it was confirmed that a dense ruthenium oxide film was sufficiently formed even in the deepest portion of the groove having a width of 0.05 μm.
將聚合物溶液1當作被覆組成物，與實施例1同樣地進行，並塗布於矽基板上。觀察塗布後之膜面後，確認從中心部分朝向周邊部分產生複數條紋，同時塗布性不充分。The polymer solution 1 was used as a coating composition, and was applied in the same manner as in Example 1 and applied onto a ruthenium substrate. After observing the film surface after coating, it was confirmed that a plurality of stripes were generated from the center portion toward the peripheral portion, and the coatability was insufficient.
進一步將此塗布後之基板以與實施例1同樣的方法燒製，並以電子顯微鏡觀察截面。在寬0.1 μm以上之溝，係蝕刻量之改變僅有一點點，可確認即使在最深部中亦充分地形成有緻密的氧化矽質膜。但是，在寬0.05 μm之溝的最深部中，蝕刻量大，確認於該部分係未形成緻密的氧化矽質膜。Further, this coated substrate was fired in the same manner as in Example 1, and the cross section was observed with an electron microscope. In the groove having a width of 0.1 μm or more, the amount of etching was changed only a little, and it was confirmed that a dense cerium oxide film was sufficiently formed even in the deepest portion. However, in the deepest portion of the groove having a width of 0.05 μm, the amount of etching was large, and it was confirmed that a dense cerium oxide film was not formed in this portion.
將聚合物溶液2當作被覆組成物，與實施例1同樣地進行，並塗布於矽基板上。觀察塗布後之膜面後，確認沒有產生條紋，可達成優良之塗布性。The polymer solution 2 was used as a coating composition, and was applied in the same manner as in Example 1 and applied onto a ruthenium substrate. After observing the film surface after coating, it was confirmed that no streaks were generated, and excellent coatability was achieved.
進一步將此塗布後之基板，以與實施例1同樣的方法進行燒製，以電子顯微鏡觀察截面。在寬0.2 μm以上之溝，係蝕刻量之改變僅有一點點，可確認即使在最深部中亦充分地形成有緻密的氧化矽質膜。然而，在寬0.05 μm與0.1 μm之溝的最深部中，係蝕刻量大，可確認於該部分係未形成緻密的氧化矽質膜。Further, the coated substrate was fired in the same manner as in Example 1, and the cross section was observed with an electron microscope. In the groove having a width of 0.2 μm or more, the amount of etching was changed only a little, and it was confirmed that a dense cerium oxide film was sufficiently formed even in the deepest portion. However, in the deepest portion of the groove having a width of 0.05 μm and 0.1 μm, the amount of etching was large, and it was confirmed that a dense cerium oxide film was not formed in this portion.
將聚合物溶液3當作被覆組成物，與實施例1同樣地進行，並塗布於矽基板上。觀察塗布後之膜面後，可確認沒有產生條紋、可達成優良之塗布性。The polymer solution 3 was used as a coating composition, and was carried out in the same manner as in Example 1 and applied onto a ruthenium substrate. After observing the film surface after coating, it was confirmed that no streaks were generated, and excellent coatability was achieved.
進一步將此塗布後之基板以與實施例1同樣的方法燒製，並以電子顯微鏡觀察截面。在寬0.2 μm以下之溝，係辨識出空隙，可確認埋設性有改良的空間。Further, this coated substrate was fired in the same manner as in Example 1, and the cross section was observed with an electron microscope. In the groove having a width of 0.2 μm or less, the void is recognized, and the space in which the embedding property is improved can be confirmed.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010001883A JP5172867B2 (en) | 2010-01-07 | 2010-01-07 | Coating composition comprising polysilazane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201132716A TW201132716A (en) | 2011-10-01 |
| TWI568806B true TWI568806B (en) | 2017-02-01 |
Family
ID=44435640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100100458A TWI568806B (en) | 2010-01-07 | 2011-01-06 | Coating composition containing polysilazane |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5172867B2 (en) |
| KR (1) | KR101711662B1 (en) |
| CN (1) | CN102153951B (en) |
| TW (1) | TWI568806B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5970197B2 (en) | 2012-02-08 | 2016-08-17 | メルクパフォーマンスマテリアルズマニュファクチャリング合同会社 | Inorganic polysilazane resin |
| JP6107188B2 (en) * | 2012-03-13 | 2017-04-05 | セントラル硝子株式会社 | Antifogging film forming material, antifogging film forming coating solution, antifogging article, and production method thereof |
| KR101556672B1 (en) | 2012-12-27 | 2015-10-01 | 제일모직 주식회사 | Composition for forming silica based insulating layer, method for manufacturing composition for forming silica based insulating layer, silica based insulating layer and method for manufacturing silica based insulating layer |
| US20140322486A1 (en) * | 2013-04-30 | 2014-10-30 | Shigeto Kobori | Method for preparing modified silica film, coating liquid for the same and modified silica film prepared from the same |
| JP2014213318A (en) * | 2013-04-30 | 2014-11-17 | チェイル インダストリーズインコーポレイテッド | Method for producing modified silica film, coating liquid, and modified silica film |
| JP6104785B2 (en) * | 2013-12-09 | 2017-03-29 | アーゼッド・エレクトロニック・マテリアルズ（ルクセンブルグ）ソシエテ・ア・レスポンサビリテ・リミテ | Perhydropolysilazane, composition containing the same, and method for forming siliceous film using the same |
| JP6198685B2 (en) * | 2014-07-01 | 2017-09-20 | 国立大学法人東京工業大学 | Polybenzoxazine-silica composite and method for producing the same |
| KR101806328B1 (en) * | 2014-10-07 | 2017-12-07 | 삼성에스디아이 주식회사 | Composition for forming silica based layer, silica based layer, and electronic device |
| US10020185B2 (en) | 2014-10-07 | 2018-07-10 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, silica layer, and electronic device |
| KR101833800B1 (en) * | 2014-12-19 | 2018-03-02 | 삼성에스디아이 주식회사 | Composition for forming silica based layer, method for manufacturing silica based layer, and electronic device including the silica based layer |
| KR101837971B1 (en) * | 2014-12-19 | 2018-03-13 | 삼성에스디아이 주식회사 | Composition for forming silica based layer, silica based layer, and electronic device |
| KR20170014946A (en) | 2015-07-31 | 2017-02-08 | 삼성에스디아이 주식회사 | Composition for forming silica layer, method for manufacturing silica layer, and silica layer |
| KR102066271B1 (en) * | 2017-04-18 | 2020-01-14 | 단국대학교 천안캠퍼스 산학협력단 | Sealing method of electrostatic chuck |
| KR102589656B1 (en) * | 2017-09-27 | 2023-10-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Fluorine-containing coating compositions, surface treatment agents and articles |
| CN108329506A (en) * | 2018-03-01 | 2018-07-27 | 苏州维洛克电子科技有限公司 | The preparation method of polyester film containing Perhydropolysilazane-urea coating |
| KR102432933B1 (en) | 2019-05-17 | 2022-08-12 | 삼성에스디아이 주식회사 | Composition for forming silica layer, silica layer and electronic device incorporating silica layer |
| KR102094647B1 (en) * | 2019-10-31 | 2020-03-31 | 화성이엔씨(주) | Two-component pavement agent for heat shielding and non-slip to be paved at room temperature, and preparation method thereof |
| CN110925779A (en) * | 2019-12-11 | 2020-03-27 | 大连东泰产业废弃物处理有限公司 | Method for utilizing perhydropolysilazane-containing waste organic solvent in incinerator |
| JP7222948B2 (en) | 2020-04-23 | 2023-02-15 | 信越化学工業株式会社 | COATING AGENT COMPOSITION FOR FORMING HIGH HARDNESS FILM |
| KR102253483B1 (en) * | 2021-01-13 | 2021-05-20 | (주)에스케이솔라에너지 | Color Photovoltaic Module For Building |
| KR102265267B1 (en) * | 2021-01-13 | 2021-06-17 | (주)에스케이솔라에너지 | Color Photovoltaic Module For Building |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608314A (en) * | 2001-12-27 | 2005-04-20 | 克拉瑞特国际有限公司 | Solvent for treating polysilazane and method of treating polysilazane with the solvent |
| TW200947613A (en) * | 2008-02-29 | 2009-11-16 | Az Electronic Materials Japan | The method for forming siliceous film and siliceous film formed thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2613787B2 (en) | 1987-08-13 | 1997-05-28 | 財団法人石油産業活性化センター | Inorganic silazane high polymer, production method thereof and use thereof |
| JPH03232709A (en) * | 1990-02-09 | 1991-10-16 | Tonen Corp | Polysilazane for silicon nitride fiber and production thereof |
| JP3015104B2 (en) * | 1991-07-16 | 2000-03-06 | 触媒化成工業株式会社 | Semiconductor device and manufacturing method thereof |
| JPH05148720A (en) * | 1991-11-22 | 1993-06-15 | Honda Motor Co Ltd | Polysilazane fiber, its production and ceramic fiber |
| WO1994012448A1 (en) * | 1992-11-26 | 1994-06-09 | Tonen Corporation | Process for producing ceramic product |
| JP3208040B2 (en) | 1995-04-04 | 2001-09-10 | 触媒化成工業株式会社 | Coating solution for forming silica-based film and substrate with film |
| JP5020425B2 (en) * | 2000-04-25 | 2012-09-05 | Ａｚエレクトロニックマテリアルズ株式会社 | Method for embedding fine grooves with siliceous material |
| KR100362834B1 (en) | 2000-05-02 | 2002-11-29 | 삼성전자 주식회사 | Method for forming oxide layer in semiconductor manufacturing process and semiconductor device manufactured by using the same |
| CN100444331C (en) * | 2003-11-11 | 2008-12-17 | 三星电子株式会社 | Spin-on glass composition and method of forming silicon oxide layer in semiconductor manufacturing process using the same |
| DE102004011212A1 (en) * | 2004-03-04 | 2005-09-29 | Clariant International Limited | Perhydropolysilazane-containing coatings for metal and polymer surfaces |
| JP2006054353A (en) * | 2004-08-13 | 2006-02-23 | Az Electronic Materials Kk | Siliceous film having little flat-band shift and its manufacturing method |
| JP4578993B2 (en) * | 2005-02-02 | 2010-11-10 | Ａｚエレクトロニックマテリアルズ株式会社 | Polysilazane treatment solvent and method for treating polysilazane using this solvent |
| JP2009158887A (en) * | 2007-12-28 | 2009-07-16 | Jgc Catalysts & Chemicals Ltd | Semiconductor device and method of manufacturing the same |
| JP5692736B2 (en) * | 2009-10-05 | 2015-04-01 | 株式会社Adeka | Insulating film forming coating liquid and insulating film using the same |
-
2010
- 2010-01-07 JP JP2010001883A patent/JP5172867B2/en active Active
- 2010-12-28 KR KR1020100136639A patent/KR101711662B1/en active IP Right Grant
-
2011
- 2011-01-06 CN CN201110006067.2A patent/CN102153951B/en active Active
- 2011-01-06 TW TW100100458A patent/TWI568806B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608314A (en) * | 2001-12-27 | 2005-04-20 | 克拉瑞特国际有限公司 | Solvent for treating polysilazane and method of treating polysilazane with the solvent |
| TW200947613A (en) * | 2008-02-29 | 2009-11-16 | Az Electronic Materials Japan | The method for forming siliceous film and siliceous film formed thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5172867B2 (en) | 2013-03-27 |
| KR101711662B1 (en) | 2017-03-02 |
| KR20110081043A (en) | 2011-07-13 |
| JP2011142207A (en) | 2011-07-21 |
| TW201132716A (en) | 2011-10-01 |
| CN102153951A (en) | 2011-08-17 |
| CN102153951B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI568806B (en) | Coating composition containing polysilazane | |
| JP6104785B2 (en) | Perhydropolysilazane, composition containing the same, and method for forming siliceous film using the same | |
| JP6060460B2 (en) | Method for forming siliceous film and siliceous film formed by the same method | |
| JP4982659B2 (en) | Method for producing siliceous film and substrate with siliceous film produced thereby | |
| EP2071616B1 (en) | Composition for forming siliceous film and process for producing siliceous film from the same | |
| US8828877B2 (en) | Etching solution and trench isolation structure-formation process employing the same | |
| KR20070028518A (en) | Method for forming trench isolation structure | |
| WO2009110449A1 (en) | Dipping solution for use in production of siliceous film and process for producing siliceous film using the dipping solution | |
| KR20020093069A (en) | Method for sealing fine groove with siliceous material and substrate having siliceous coating formed thereon | |
| EP2637203B1 (en) | Method for forming isolation structure | |
| TW201811671A (en) | Composition for forming silica layer, silica layer, and electronic device | |
| JP2004292642A (en) | Composition for forming porous film, manufacturing method of porous film, porous film, interlayer insulating film and semiconductor device | |
| CN110903764B (en) | Silicon dioxide layer, method for producing same, composition for forming same, and electronic device | |
| CN101512737A (en) | Composition for forming siliceous film and process for producing siliceous film from the same |