TW201915159A - Composition for surface treatment, method for producing composition for surface treatment, surface treatment method, and method for producing semiconductor substrate - Google Patents

Abstract

A composition for surface treatment according to the present invention is used for treating the surface of an object to be polished after polishing, the composition for surface treatment including: a water-soluble polymer having a constituent unit derived from glycerin; an acid; and water, wherein the composition for surface treatment has a pH of 5 or lower.

Description

表面處理組合物、表面處理組合物的製造方法、表面處理方法及半導體基板的製造方法Surface treatment composition, method for producing surface treatment composition, surface treatment method, and method for producing semiconductor substrate

本發明係關於表面處理組合物、表面處理組合物的製造方法、表面處理方法及半導體基板的製造方法。The present invention relates to a surface treatment composition, a method for producing a surface treatment composition, a surface treatment method, and a method for producing a semiconductor substrate.

近幾年，隨著半導體基板表面的多層線路化，在製造裝置時，利用將半導體基板研磨平坦化的所謂化學機械研磨(chemical mechanical polishing；CMP)技術。CMP是使用包含氧化矽或氧化鋁、二氧化鈰等的研磨粒、防蝕劑、界面活性劑等的組合物(漿料)，將半導體基板等的研磨對象物(被研磨物)的表面平坦化的方法，研磨對象物(被研磨物)為矽、多晶矽、矽氧化膜(氧化矽)、矽氮化物或金屬等所形成的線路、插塞等。In recent years, with the multilayering of the surface of a semiconductor substrate, a so-called chemical mechanical polishing (CMP) technique for planarizing a semiconductor substrate has been used in manufacturing a device. CMP is a composition (slurry) using abrasive grains, an anti-corrosion agent, a surfactant, or the like containing cerium oxide, aluminum oxide, cerium oxide, or the like, and planarizes the surface of an object to be polished (object to be polished) such as a semiconductor substrate. In the method, the object to be polished (the object to be polished) is a line, a plug, or the like formed of tantalum, polycrystalline germanium, tantalum oxide film (yttria), tantalum nitride or metal.

在CMP步驟之後的半導體基板表面，殘留大量的雜質(缺陷)。雜質，包含：來自CMP所使用的研磨用組合物的研磨粒、金屬、抗蝕劑、界面活性劑等的有機物；研磨對象物的含有矽的材料；因研磨金屬線路或插塞等所產生的含有矽的材料、金屬等；以及從各種墊片所產生的墊片屑等的有機物等。A large amount of impurities (defects) remain on the surface of the semiconductor substrate after the CMP step. The impurities include: abrasive grains derived from the polishing composition used for CMP, organic substances such as metals, resists, and surfactants; materials containing ruthenium for polishing objects; and those produced by grinding metal wires or plugs, etc. Materials containing bismuth, metals, etc.; and organic matter such as gasket chips generated from various gaskets.

半導體基板表面被該等雜質污染，則會對半導體的電特性造成不良影響，可能降低裝置可靠度。因此，在CMP步驟之後導入清洗步驟，期望從半導體基板表面去除該等雜質。When the surface of the semiconductor substrate is contaminated by such impurities, the electrical characteristics of the semiconductor are adversely affected, and the reliability of the device may be lowered. Therefore, the cleaning step is introduced after the CMP step, and it is desirable to remove the impurities from the surface of the semiconductor substrate.

可用於如此的清洗步驟的清洗液(清洗用組合物)，例如，在日本特開2012-74678號公報(對應美國專利申請公開第2013/174867號說明書)，揭示可藉由含有聚羧酸或羥基羧酸、磺酸型陰離子性界面活性劑、羧酸型陰離子性界面活性劑、及水的半導體基板用的清洗用組合物，不會腐蝕基板表面，而可去除異物。A cleaning liquid (cleaning composition) which can be used in such a washing step, for example, is disclosed in Japanese Laid-Open Patent Publication No. 2012-74678 (corresponding to the specification of U.S. Patent Application Publication No. 2013/174867), The cleaning composition for a hydroxycarboxylic acid, a sulfonic acid type anionic surfactant, a carboxylic acid type anionic surfactant, and a water semiconductor substrate can remove foreign matter without corroding the surface of the substrate.

但是，在該上述文獻的技術，在清洗已研磨的研磨對象物時，有無法充分去除缺陷的問題。However, in the technique of the above document, when the object to be polished is cleaned, there is a problem that the defect cannot be sufficiently removed.

在此，本發明者們，針對已研磨的研磨對象物的種類與缺陷種類的關係進行研究。結果發現，包含可良好地使用於作為半導體基板的氮化矽、氧化矽或多晶矽的已研磨的研磨對象物，容易附著有機物殘渣，如此的有機物殘渣可能成為破壞半導體裝置的原因。Here, the inventors of the present invention studied the relationship between the type of the object to be polished and the type of the defect. As a result, it has been found that the object to be polished which is satisfactorily used for tantalum nitride, cerium oxide or polycrystalline silicon as a semiconductor substrate is likely to adhere to organic residue, and such organic residue may cause destruction of the semiconductor device.

本發明是有鑑於上述課題而完成，以提供可充分去除存在於已研磨的研磨對象物表面的有機物殘渣的手段為目標。The present invention has been made in view of the above problems, and aims to provide a means for sufficiently removing organic residue remaining on the surface of a polished object to be polished.

本發明者們，有鑑於上述課題，專心進行研究。結果發現，藉由使用包含：具有來自甘油的構成單位的水溶性高分子、酸、及水，且pH為5以下的表面處理組合物，可有效提升去除已研磨的研磨對象物表面的有機物殘渣的效果，而完成本發明。The inventors of the present invention have focused their research in view of the above problems. As a result, it has been found that by using a surface treatment composition comprising a water-soluble polymer having a constituent unit derived from glycerin, an acid, and water and having a pH of 5 or less, the organic residue on the surface of the ground object to be polished can be effectively removed. The effect of the invention is completed.

以下，說明本發明的實施的形態。再者，本發明並非限定於以下的實施形態。此外，在本說明書，此外，若無特別提及，操作及物性等的測定是在室溫(20℃以上、25℃以下)/相對濕度40%RH以上、50%RH以下的條件進行。Hereinafter, embodiments of the present invention will be described. Furthermore, the present invention is not limited to the following embodiments. In addition, in the present specification, unless otherwise mentioned, measurement of handling, physical properties, and the like is performed under the conditions of room temperature (20 ° C or more, 25 ° C or less) / relative humidity of 40% RH or more and 50% RH or less.

此外，在本說明書，在化合物的具體名的記述「(甲基)丙烯酸」是表示「丙烯酸」及「甲基丙烯酸」，「(甲基)丙烯酸酯」是表示「丙烯酸酯」及「甲基丙烯酸酯」。In addition, in the present specification, the description of the specific name of the compound "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid", and "(meth)acrylic acid ester" means "acrylic acid ester" and "methyl group". Acrylate".

［有機物殘渣］ 在本說明書，所謂有機物殘渣，是表示附著在已研磨的研磨對象物(以下亦簡稱為「清洗對象物」)表面的異物中，由有機低分子化合物、高分子化合物等的有機物或有機鹽等所組成的成分。[Organic Residue] In the present specification, the organic residue is an organic substance such as an organic low molecular compound or a polymer compound, which is attached to a foreign matter on the surface of the object to be polished (hereinafter also referred to as "cleaning target"). Or an ingredient composed of an organic salt or the like.

附著在清洗對象物的有機物殘渣，可列舉，例如，在後述的研磨步驟或可任意設置的沖洗研磨步驟所使用的墊片所產生的墊片屑、或是來自在研磨步驟所使用的研磨用組合物或在沖洗研磨步驟所使用的沖洗研磨用組合物中所包含的添加劑的成分等。The organic residue adhering to the object to be cleaned may, for example, be a gasket scrap generated by a gasket used in a polishing step to be described later or a rinsing step which can be arbitrarily set, or may be used for polishing used in the polishing step. The composition or the component of the additive contained in the rinsing and polishing composition used in the rinsing and polishing step.

由於有機物殘渣與其他的異物，顏色及形狀有很大的差異，因此異物是否為有機物殘渣的判斷，可藉由SEM觀察以目視進行，如有需要時，可藉由能量分散型X射線分析裝置(EDX)進行元素分析。Since the organic residue and other foreign matter have a large difference in color and shape, the determination of whether the foreign matter is an organic residue can be visually observed by SEM observation, and if necessary, by an energy dispersive X-ray analyzer (EDX) for elemental analysis.

［已研磨的研磨對象物］ 在本說明書，所謂已研磨的研磨對象物，是指在研磨步驟被研磨後的研磨對象物。研磨步驟，並無特別限制，以CMP步驟為佳。[Abraded object to be polished] In the present specification, the object to be polished refers to an object to be polished which is polished after the polishing step. The polishing step is not particularly limited, and a CMP step is preferred.

本發明的一形態相關的表面處理組合物，用於減低殘留在包含氮化矽(以下亦簡稱為「SiN」)、氧化矽、或多晶矽(以下亦簡稱為「Poly-Si」)的已研磨的研磨對象物表面的有機物殘渣為佳。包含氧化矽的已研磨的研磨對象物，可列舉，例如，使用原矽酸四乙酯作為前驅物所生成的TEOS(tetraethyl orthosilicate：原矽酸四乙酯)型氧化矽面(以下，亦簡稱為「TEOS」)、HDP (high density plasma：高密度電漿)膜、USG (undoped silicate glass：無摻雜矽酸玻璃)膜、PSG (phosphorus silicate glass：磷矽酸玻璃)膜、BPSG (boron-phospho silicate glass：硼磷矽酸玻璃)膜、RTO (rapid thermal oxidation：快速熱氧化)膜等。The surface treatment composition according to one aspect of the present invention is for use in reducing the amount of the remaining surface-containing composition containing tantalum nitride (hereinafter also referred to as "SiN"), yttrium oxide, or polycrystalline germanium (hereinafter also referred to as "Poly-Si"). The organic residue on the surface of the object to be polished is preferably. The polished object to be polished containing cerium oxide, for example, a TEOS (tetraethyl orthosilicate) type cerium oxide surface produced by using tetraethyl orthosilicate as a precursor (hereinafter, also referred to as abbreviated as a precursor) "TEOS"), HDP (high density plasma) film, USG (undoped silicate glass) film, PSG (phosphorus silicate glass) film, BPSG (boron) -phospho silicate glass: borophosphoric acid glass) film, RTO (rapid thermal oxidation) film, and the like.

已研磨的研磨對象物，以已研磨的半導體基板為佳，以CMP後的半導體基板為更佳。其理由在於，特別是有機物殘渣可能會成為半導體裝置破壞的原因，因此已研磨的研磨對象物為已研磨的半導體基板時，半導體基板的清洗步驟，需要盡可能的去除有機物殘渣。The polished object to be polished is preferably a polished semiconductor substrate, and more preferably a semiconductor substrate after CMP. The reason for this is that the organic residue may cause damage to the semiconductor device. Therefore, when the polished object to be polished is a polished semiconductor substrate, it is necessary to remove the organic residue as much as possible in the cleaning step of the semiconductor substrate.

包含氮化矽、氧化矽或多晶矽的已研磨的研磨對象物，並無特別限制，可列舉氮化矽、氧化矽及多晶矽各自單獨形成的已研磨的研磨對象物；除了氮化矽、氧化矽或多晶矽之外，在表面露出該等之外的材料的狀態的已研磨的研磨對象物等。在此，作為前者，可列舉，例如，半導體基板的氮化矽基板、氧化矽基板或多晶矽基板。此外，關於後者，氮化矽、氧化矽或多晶矽之外的材料，並無特別限制，可列舉，例如，鎢等。該已研磨的研磨對象物的具體例，可列舉具有在鎢上形成氮化矽膜、氧化矽膜、或多晶矽膜的構造的已研磨的半導體基板，或是具有鎢的部分、氮化矽膜、氧化矽膜、多晶矽膜全部露出的構造的已研磨的半導體基板等。The object to be polished which includes tantalum nitride, cerium oxide or polycrystalline germanium is not particularly limited, and examples thereof include a polished object to be polished which is formed by each of tantalum nitride, cerium oxide and polycrystalline germanium; In addition to the polycrystalline silicon, a polished object to be polished or the like in a state in which the materials other than the above are exposed on the surface. Here, as the former, for example, a tantalum nitride substrate, a tantalum oxide substrate, or a polycrystalline germanium substrate of a semiconductor substrate may be mentioned. Further, the latter, the material other than tantalum nitride, cerium oxide or polycrystalline germanium is not particularly limited, and examples thereof include tungsten and the like. Specific examples of the object to be polished include a polished semiconductor substrate having a structure in which a tantalum nitride film, a hafnium oxide film, or a polysilicon film is formed on tungsten, or a portion having tungsten or a tantalum nitride film. A polished semiconductor substrate having a structure in which all of the yttrium oxide film and the polysilicon film are exposed.

在此，就發揮本發明的效果的觀點而言，本發明的一形態相關的已研磨的研磨對象物，以包含多晶矽為佳。Here, from the viewpoint of exerting the effects of the present invention, it is preferable that the object to be polished according to one aspect of the present invention contains polycrystalline germanium.

［表面處理組合物］ 本發明的一形態是一種表面處理組合物，包含：具有來自甘油的構成單位的水溶性高分子；酸；及水，且pH為5以下，其可用於處理已研磨的研磨對象物表面。[Surface Treatment Composition] One aspect of the present invention is a surface treatment composition comprising: a water-soluble polymer having a constituent unit derived from glycerin; an acid; and water, and having a pH of 5 or less, which can be used for treating the ground Polish the surface of the object.

本發明的一形態相關的表面處理組合物，特別適合使用在表面處理步驟，作為用於選擇性去除有機物殘渣的有機物殘渣降低劑。The surface treatment composition according to one aspect of the present invention is particularly suitably used in a surface treatment step as an organic residue reducing agent for selectively removing organic residue.

本發明者們推測，藉由本發明解決上述課題的機構如下。The inventors have estimated that the mechanism for solving the above problems by the present invention is as follows.

表面處理組合物，藉由表面處理組合物所含有的各成分與已研磨的研磨對象物的表面及異物的化學性相互作用，而具有去除已研磨的研磨對象物表面的異物的功能，或使之容易去除的功能。The surface treatment composition has a function of removing foreign matter on the surface of the ground object to be polished by chemical interaction between each component contained in the surface treatment composition and the surface of the object to be polished and foreign matter, or Easy to remove features.

包含在表面處理組合物中的具有來自甘油的構成單位的水溶性高分子，在已研磨的研磨對象物的表面形成親水層，此外，在有機物殘渣的表面亦形成親水層。形成親水層的有機物殘渣，由於與親水化的已研磨的研磨對象物的表面具有親和性，因此會在表面處理步驟中附著在已研磨的研磨對象物表面。之後，藉由清洗等的製程，可容易地去除已研磨的研磨對象物表面的親水層，已研磨的研磨對象物表面的有機物殘渣亦被去除。即，根據本發明，可提供能夠充分去除存在於已研磨的研磨對象物的表面的有機物殘渣的手段。The water-soluble polymer having a constituent unit derived from glycerin contained in the surface treatment composition forms a hydrophilic layer on the surface of the polished object to be polished, and a hydrophilic layer is also formed on the surface of the organic residue. The organic residue forming the hydrophilic layer adheres to the surface of the polished object to be polished in the surface treatment step because of its affinity with the surface of the hydrophilized polished object to be polished. Thereafter, the hydrophilic layer on the surface of the polished object to be polished can be easily removed by a process such as cleaning, and the organic residue on the surface of the polished object to be polished is also removed. That is, according to the present invention, it is possible to provide a means capable of sufficiently removing the organic residue remaining on the surface of the object to be polished.

再者，上述機構是基於推測，其對錯並不會對本發明的技術範圍造成影響。Furthermore, the above mechanism is based on speculation that its right or wrong does not affect the technical scope of the present invention.

以下，說明關於包含在表面處理組合物中的各成分。Hereinafter, each component contained in the surface treatment composition will be described.

［具有來自甘油的構成單位的水溶性高分子］ 本發明的一形態的表面處理組合物，包含：水溶性高分子，其具有來自甘油的構成單位。[Water-soluble polymer having a constituent unit derived from glycerin] The surface treatment composition according to one aspect of the present invention includes a water-soluble polymer having a constituent unit derived from glycerin.

具有來自甘油的構成單位的水溶性高分子之較佳的例子，可列舉選自由聚甘油(參照下述化學式(1))、環氧乙烷變性聚甘油、磺酸變性聚甘油(參照例如下述化學式(2)、(3))、膦酸變性聚甘油(參照例如下述化學式(4)、(5))、聚甘油-4-乙烯基安息香酸酯(苯乙烯基變性聚甘油)、及聚甘油脂肪酸酯所組成之群之至少1種。Preferred examples of the water-soluble polymer having a constituent unit derived from glycerin include polyglycerol (see the following chemical formula (1)), ethylene oxide-modified polyglycerin, and sulfonic acid-modified polyglycerol (see, for example, Chemical formulas (2) and (3)), phosphonic acid-denatured polyglycerol (see, for example, the following chemical formulas (4) and (5)), polyglycerol-4-vinylbenzoate (styrene-based modified polyglycerol), And at least one of the group consisting of polyglycerin fatty acid esters.

[化1](1)(2)(3)(4)(5)[Chemical 1] (1) (2) (3) (4) (5)

上述化學式(1)～(5)中的m及n，分別獨立表示，重覆單位的數量，上述化學式(2)～(5)中的M，分別獨立表示氫原子、鈉(Na)、鉀(K)或銨(NH₄ ⁺ )。m and n in the above chemical formulas (1) to (5) independently represent the number of repeating units, and M in the above chemical formulas (2) to (5) independently represent a hydrogen atom, sodium (Na), and potassium. (K) or ammonium (NH ₄ ⁺ ).

再者，上述化學式(2)～(5)中的複數個M，可彼此相同，亦可彼此不同。例如，上述化學式(2)中M可全部均為鈉(Na)，亦可為氫原子、鈉(Na)、鉀(K)及銨(NH₄ ⁺ )的2種以上的組合。此外，例如，上述化學式(3)中的m個M可全部均為鈉(Na)，亦可為氫原子、鈉(Na)、鉀(K)及銨(NH₄ ⁺ )的2種以上的組合。Further, the plurality of M in the above chemical formulas (2) to (5) may be the same as each other or different from each other. For example, all of M in the above chemical formula (2) may be sodium (Na), and may be a combination of two or more of a hydrogen atom, sodium (Na), potassium (K), and ammonium (NH ₄ ⁺ ). Further, for example, all of m M in the above chemical formula (3) may be sodium (Na), or may be two or more of a hydrogen atom, sodium (Na), potassium (K), and ammonium (NH ₄ ⁺ ). combination.

聚甘油脂肪酸酯之例子，可列舉，例如，聚甘油脂肪酸(C10-13)酯、聚甘油脂肪酸(C10)酯、聚甘油脂肪酸(C8)酯、聚甘油脂肪酸(C3)酯、十甘油月桂酸酯(十甘油脂肪酸(C12)酯)、十甘油硬脂酸酯(十甘油脂肪酸(C18)酯)、十甘油油酸酯(十甘油脂肪酸(C18)酯)等。Examples of the polyglycerin fatty acid esters include, for example, polyglycerin fatty acid (C10-13) ester, polyglycerin fatty acid (C10) ester, polyglycerin fatty acid (C8) ester, polyglycerin fatty acid (C3) ester, and ten glycerin laurel An acid ester (decaglycerin fatty acid (C12) ester), decaglyceryl stearate (decaglycerin fatty acid (C18) ester), decaglyceryl oleate (decaglycerin fatty acid (C18) ester), and the like.

該等具有來自甘油的構成單位的水溶性高分子之中，以聚甘油脂肪酸酯為佳。Among these water-soluble polymers having a constituent unit derived from glycerin, a polyglycerin fatty acid ester is preferred.

聚甘油脂肪酸酯，有聚甘油部分為直鏈結構者，亦有聚甘油部分為分枝結構者，均可沒有限制地使用，惟以分枝結構為佳。分枝結構時，可認為由於聚甘油部分的複數OH基的配置較直鏈結構者的配置更立體，更容易附著於有機物殘渣，且更容易在有機物殘渣表面形成親水層，而容易進行有機物殘渣的去除。Polyglycerol fatty acid esters, those having a polyglycerol moiety as a linear structure, and those having a polyglycerol moiety as a branched structure, can be used without limitation, but a branched structure is preferred. In the case of the branched structure, it is considered that the arrangement of the complex OH groups of the polyglycerol moiety is more three-dimensional than that of the linear structure, and it is more likely to adhere to the organic residue, and it is easier to form a hydrophilic layer on the surface of the organic residue, and it is easy to carry out the organic residue. Removal.

此外，關於聚甘油脂肪酸酯的聚甘油部分，來自甘油的構成單位的數量，並無特別限制，以3以上、20以下為佳，以5以上、15以下為更佳。Further, the number of constituent units derived from glycerin in the polyglycerin portion of the polyglycerin fatty acid ester is not particularly limited, and is preferably 3 or more and 20 or less, and more preferably 5 or more and 15 or less.

再者，聚甘油脂肪酸酯的脂肪酸部分的碳數，亦無特別限制，以2以上、20以下為佳，以6以上、15以下為更佳，以9以上、14以下為進一步更佳。Further, the carbon number of the fatty acid portion of the polyglycerin fatty acid ester is not particularly limited, and is preferably 2 or more and 20 or less, more preferably 6 or more and 15 or less, and still more preferably 9 or more and 14 or less.

上述具有來自甘油的構成單位的水溶性高分子，可以單獨或組合2種以上使用。The water-soluble polymer having a constituent unit derived from glycerin may be used alone or in combination of two or more.

具有來自甘油的構成單位的水溶性高分子的含量(濃度)(2種以上時為其合計量)，並無特別限制，相對於表面處理組合物的總量，以0.01g/kg以上為佳。具有來自甘油的構成單位的水溶性高分子的含量為0.01g/kg以上時，則可更加提升本發明的效果。The content (concentration) of the water-soluble polymer having a constituent unit derived from glycerin (in total of two or more kinds thereof) is not particularly limited, and is preferably 0.01 g/kg or more based on the total amount of the surface treatment composition. . When the content of the water-soluble polymer having a constituent unit derived from glycerin is 0.01 g/kg or more, the effects of the present invention can be further enhanced.

就同樣的觀點而言，具有來自甘油的構成單位的水溶性高分子的含量(濃度)，相對於表面處理組合物的總量，以0.02g/kg以上為佳，以0.05g/kg以上為更佳，以0.06g/kg以上為進一步更佳，以0.08g/kg以上為又進一步更佳，以0.1g/kg以上為特佳，以0.5g/kg以上為最佳。此外，具有來自甘油的構成單位的水溶性高分子的含量(濃度)，相對於表面處理組合物的總量，以5g/kg以下為佳。具有來自甘油的構成單位的水溶性高分子的含量(濃度)為5g/kg以下時，則容易去除表面處理後的具有來自甘油的構成單位的水溶性高分子本身。就同樣的觀點而言，具有來自甘油的構成單位的水溶性高分子的含量(濃度)，相對於表面處理組合物的總量，以4g/kg以下為更佳，以3g/kg以下為進一步更佳，以2g/kg以下為特佳。From the same viewpoint, the content (concentration) of the water-soluble polymer having a constituent unit derived from glycerin is preferably 0.02 g/kg or more, and 0.05 g/kg or more, based on the total amount of the surface treatment composition. More preferably, it is more preferably 0.06 g/kg or more, further preferably 0.08 g/kg or more, particularly preferably 0.1 g/kg or more, and most preferably 0.5 g/kg or more. Further, the content (concentration) of the water-soluble polymer having a constituent unit derived from glycerin is preferably 5 g/kg or less based on the total amount of the surface treatment composition. When the content (concentration) of the water-soluble polymer having a constituent unit derived from glycerin is 5 g/kg or less, it is easy to remove the water-soluble polymer itself having a constituent unit derived from glycerin after the surface treatment. From the same viewpoint, the content (concentration) of the water-soluble polymer having a constituent unit derived from glycerin is more preferably 4 g/kg or less based on the total amount of the surface treatment composition, and further preferably 3 g/kg or less. More preferably, it is particularly good at 2 g/kg or less.

具有來自甘油的構成單位的水溶性高分子的重量平均分子量，以800以上為佳。重量平均分子量為800以上時，則可更加提升去除異物的效果。推測其理由在於，具有來自甘油的構成單位的水溶性高分子被覆清洗對象物或異物時的被覆性變得更良好，可更加提升異物從清洗對象物表面的去除作用或異物對清洗對象物表面的再附著抑制作用。就同樣的觀點而言，重量平均分子量，以超過3,000為佳。此外，具有來自甘油的構成單位的水溶性高分子的重量平均分子量的上限值，並無特別限制，以2,000,000以下為佳，以1,000,000以下為更佳，以500,000以下為進一步更佳。重量平均分子量，可使用凝膠滲透層析(GPC)裝置，以聚乙二醇換算而求得，具體而言，可藉由實施例所記載的方法測定。The weight average molecular weight of the water-soluble polymer having a constituent unit derived from glycerin is preferably 800 or more. When the weight average molecular weight is 800 or more, the effect of removing foreign matter can be further enhanced. The reason for this is that the coating property of the water-soluble polymer having a constituent unit derived from glycerin is more excellent when the object to be cleaned or the foreign matter is coated, and the removal of foreign matter from the surface of the object to be cleaned or the surface of the object to be cleaned can be further enhanced. Reattachment inhibition. From the same point of view, the weight average molecular weight is preferably more than 3,000. In addition, the upper limit of the weight average molecular weight of the water-soluble polymer having a constituent unit derived from glycerin is not particularly limited, and is preferably 2,000,000 or less, more preferably 1,000,000 or less, still more preferably 500,000 or less. The weight average molecular weight can be determined by a gel permeation chromatography (GPC) apparatus in terms of polyethylene glycol, and specifically, it can be measured by the method described in the examples.

具有來自甘油的構成單位的水溶性高分子，可使用市售品，亦可使用合成品。合成時的製造方法，並無特別限制，可採用習知的聚合法。A commercially available product can be used as the water-soluble polymer having a constituent unit derived from glycerin, and a synthetic product can also be used. The production method at the time of the synthesis is not particularly limited, and a conventional polymerization method can be employed.

［酸］ 本發明的一形態的表面處理組合物包含酸。再者，在本說明書，下述離子性分散劑，與在此所述的作為添加劑的酸被視為不同之物。酸的添加目的主要是調整表面處理組合物的pH。[Acid] The surface treatment composition of one aspect of the present invention contains an acid. Further, in the present specification, the following ionic dispersant is considered to be different from the acid as an additive described herein. The purpose of the acid addition is mainly to adjust the pH of the surface treatment composition.

此外，已研磨的研磨對象物包含氮化矽、氧化矽、或多晶矽時，推測酸可執行使該已研磨的研磨對象物的表面、異物表面等帶正電荷的功能。因此，對具有可帶正電荷的性質的異物或清洗對象物使用表面處理組合物時，可藉由添加酸，更加促進靜電的排斥效果，而更加提升表面處理組合物去除異物的效果。Further, when the object to be polished includes tantalum nitride, cerium oxide, or polycrystalline germanium, it is presumed that the acid can function to positively charge the surface of the polished object to be polished, the surface of the foreign matter, and the like. Therefore, when a surface treatment composition is used for a foreign matter having a positively chargeable property or a cleaning target, the effect of removing the foreign matter can be further enhanced by the addition of an acid to further promote the repulsion effect of the static electricity.

酸，可使用無機酸或有機酸的任一種。無機酸，並無特別限制，可列舉，例如，硫酸、硝酸、硼酸、碳酸、次亞磷酸、亞磷酸及磷酸等。有機酸，並無特別限制，可列舉甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、安息香酸、乙醇酸、水楊酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸、及乳酸等的羧酸、甲磺酸、乙磺酸、以及2-羥乙磺酸(isethionic acid)等。As the acid, any of an inorganic acid or an organic acid can be used. The inorganic acid is not particularly limited, and examples thereof include sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid. The organic acid is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, and 2-ethylbutyric acid. 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, Carboxylic acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, and lactic acid, carboxylic acid, methanesulfonic acid, ethanesulfonic acid, and 2-hydroxyethanesulfonate Acid (isethionic acid) and the like.

該等之中，就使已研磨的研磨對象物的表面及異物的表面帶正電荷的效果更良好，而提升異物去除性的觀點而言，以馬來酸或硝酸為更佳，以馬來酸為進一步更佳。Among these, the effect of positively charging the surface of the object to be polished and the surface of the foreign matter is better, and from the viewpoint of improving the removal of foreign matter, maleic acid or nitric acid is more preferable, and Malay is preferred. The acid is further better.

再者，酸可以單獨或組合2種以上使用。Further, the acid may be used singly or in combination of two or more.

相對於表面處理組合物的總量，酸的含量，以0.01質量%以上為佳。酸的含量為0.01質量%以上時，可更加提升去除異物的效果。推測其理由在於，使已研磨的研磨對象物的表面及異物表面帶正電荷的效果更良好。就同樣的觀點而言，相對於表面處理組合物的總量，酸的含量，以0.02質量%以上為佳，以0.03質量%以上為進一步更佳，以0.05質量%以上為又進一步更佳，以0.1質量%以上為特佳。此外，相對於表面處理組合物的總量，酸的含量，以5質量%以下為佳。酸的含量為5質量%以下時，就減低成本的觀點而言，乃是較佳。就同樣的觀點而言，相對於表面處理組合物的總量，酸的含量，以3質量%以下為更佳，以1質量%以下為進一步更佳。The content of the acid is preferably 0.01% by mass or more based on the total amount of the surface treatment composition. When the acid content is 0.01% by mass or more, the effect of removing foreign matter can be further enhanced. The reason is presumed to be that the effect of positively charging the surface of the object to be polished and the surface of the foreign matter is more excellent. From the same viewpoint, the content of the acid is preferably 0.02% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.05% by mass or more, based on the total amount of the surface treatment composition. It is particularly preferable to be 0.1% by mass or more. Further, the content of the acid is preferably 5% by mass or less based on the total amount of the surface treatment composition. When the acid content is 5% by mass or less, it is preferable from the viewpoint of reducing the cost. From the same viewpoint, the content of the acid is preferably 3% by mass or less, more preferably 1% by mass or less, based on the total amount of the surface treatment composition.

［分散媒］ 本發明的一形態相關的表面處理組合物，必須包含水作為分散媒(溶劑)。分散媒，具有使各成分分散或溶解的功能。分散媒，以僅有水為更佳。此外，為了分散或溶解各成分，分散媒亦可為水與有機溶劑的混合溶劑。此時，可使用的有機溶劑之例子，可列舉可與水混合的有機溶劑的丙酮、乙腈、乙醇、甲醇、異丙醇、甘油、乙二醇、丙二醇等。此外，亦可不與水混合而使用該等有機溶劑將各成分分散或溶解之後，再與水混合。該等有機溶劑，可以單獨或組合2種以上使用。[Dispersion Medium] The surface treatment composition according to one aspect of the present invention must contain water as a dispersion medium (solvent). The dispersing medium has a function of dispersing or dissolving each component. Disperse the media, preferably with water only. Further, in order to disperse or dissolve each component, the dispersion medium may be a mixed solvent of water and an organic solvent. In this case, examples of the organic solvent which can be used include acetone, acetonitrile, ethanol, methanol, isopropanol, glycerin, ethylene glycol, propylene glycol and the like which are organic solvents which can be mixed with water. Further, the components may be dispersed or dissolved without using water and mixed with water, and then mixed with water. These organic solvents may be used alone or in combination of two or more.

水，就清洗對象物的污染或阻礙其他的成分的作用的觀點而言，以盡可能不含雜質的水為佳。例如，以過渡金屬離子的合計含量在100ppb以下的水為佳。在此，可藉由，例如，使用離子交換樹脂去除雜質離子，以過濾器去除異物，及藉由蒸餾等的操作，而提升水的純度。具體而言，水，以使用，例如，去離子水(離子交換水)、純水、超純水、蒸餾水為佳。The water is preferably water containing no impurities as far as possible from the viewpoint of contamination of the object to be cleaned or hindering the action of other components. For example, water having a total content of transition metal ions of 100 ppb or less is preferred. Here, the purity of water can be improved by, for example, removing ion ions using an ion exchange resin, removing foreign matter by a filter, and operating by distillation or the like. Specifically, water is preferably used, for example, deionized water (ion exchange water), pure water, ultrapure water, or distilled water.

［pH］ 本發明的一形態的表面處理組合物的pH為5以下。pH為5以下，則對具有可帶正電荷之性質的異物或清洗對象物使用表面處理組合物時，可使清洗對象物表面或異物表面更確實地以正電荷帶電，藉由靜電斥力，能夠得到更高的異物去除效果。pH超過5時，則難以得到異物的去除效果。該pH，以4以下為佳，以3以下為進一步更佳，以未滿3為又進一步更佳，以2.5以下為特佳。此外，表面處理組合物的pH，以1以上為佳。使pH為1以上，可更加減低成本。[pH] The surface treatment composition of one embodiment of the present invention has a pH of 5 or less. When the pH is 5 or less, when a surface treatment composition is used for a foreign matter having a positively chargeable property or a cleaning target, the surface of the object to be cleaned or the surface of the foreign object can be more positively charged with a positive charge, and by electrostatic repulsion, Get a higher foreign matter removal effect. When the pH exceeds 5, it is difficult to obtain a foreign matter removal effect. The pH is preferably 4 or less, further preferably 3 or less, further preferably less than 3, and particularly preferably 2.5 or less. Further, the pH of the surface treatment composition is preferably 1 or more. When the pH is 1 or more, the cost can be further reduced.

再者，表面處理組合物的pH值，可藉由pH計(株式會社掘場製造所製，產品名︰LAQUA(註冊商標))確認。In addition, the pH value of the surface treatment composition can be confirmed by a pH meter (manufactured by Horiba, Ltd., product name: LAQUA (registered trademark)).

調整pH值時，本發明的一形態相關的表面處理組合物以外的成分，可能會成為異物的原因，因此以盡可能不添加為佳。因此，表面處理組合物，較佳為僅使用上述具有來自甘油的構成單位的水溶性高分子、酸、水及按照需要所添加的離子性分散劑而調製。但是，僅以該等難以得到所期望的pH時，在不阻礙本發明的效果的範圍內，亦可使用任意地添加的鹼等其他的添加劑而調整。When the pH is adjusted, components other than the surface treatment composition according to one aspect of the present invention may cause foreign matter, and therefore it is preferable to not add as much as possible. Therefore, the surface treatment composition is preferably prepared by using only the above-described water-soluble polymer having a constituent unit derived from glycerin, an acid, water, and an ionic dispersant added as needed. However, in the case where it is difficult to obtain the desired pH, it is also possible to adjust it by using other additives such as an alkali to be added, insofar as the effect of the present invention is not inhibited.

［離子性分散劑］ 本發明的一形態的表面處理組合物，以進一步包含離子性分散劑為佳。離子性分散劑，可有利於使用表面處理組合物去除異物。因此，包含離子性分散劑的表面處理組合物，在已研磨的研磨對象物的表面處理(沖洗研磨、清洗等)，可充分去除殘留在已研磨的研磨對象物表面的異物(包含有機物殘渣等的雜質)。再者，在本說明書，所謂「離子性分散劑」，僅限於不具有來自甘油的構成單位者。即，若離子性分散劑為具有來自甘油的構成單位的高分子，則歸類在「具有來自甘油的構成單位的水溶性高分子」。[Ionic dispersing agent] The surface treatment composition of one embodiment of the present invention preferably further contains an ionic dispersing agent. An ionic dispersant can facilitate the removal of foreign matter using a surface treatment composition. Therefore, the surface treatment composition containing an ionic dispersing agent can completely remove the foreign matter (including organic residue, etc.) remaining on the surface of the polished object to be polished on the surface of the object to be polished (flushing, washing, etc.). Impurities). In addition, in the present specification, the "ionic dispersing agent" is limited to those having no constituent unit derived from glycerin. In other words, when the ionic dispersant is a polymer having a constituent unit derived from glycerin, it is classified as "a water-soluble polymer having a constituent unit derived from glycerin".

離子性分散劑之例子，可列舉具有磺酸(鹽)基的高分子化合物；具有磷酸(鹽)基的高分子化合物；具有膦酸(鹽)基的高分子化合物；具有羧酸(鹽)基的高分子化合物；聚乙烯基吡咯酮(polyvinyl pyrrolidone, PVP)、聚乙烯基咪唑(polyvinylimidazole, PVI)、聚乙烯基咔唑(polyvinylcarbazole)、聚乙烯基己內醯胺(polyvinyl caprolactam)、聚乙烯基哌啶(polyvinylpiperidine)、聚丙烯醯嗎啉(polyacryloyl morpholine, PACMO)等的包含氮原子的水溶性高分子；聚乙烯醇(polyvinyl alcohol, PVA)、羥乙基纖維素(hydroxyethyl cellulose, HEC)等。Examples of the ionic dispersant include a polymer compound having a sulfonic acid (salt) group, a polymer compound having a phosphate (salt) group, a polymer compound having a phosphonic acid (salt) group, and a carboxylic acid (salt). Base polymer compound; polyvinyl pyrrolidone (PVP), polyvinylimidazole (PVI), polyvinylcarbazole, polyvinyl caprolactam, poly A water-soluble polymer containing a nitrogen atom such as polyvinylpiperidine or polyacryloyl morpholine (PACMO); polyvinyl alcohol (PVA), hydroxyethyl cellulose (HEC) )Wait.

再者，在本說明書，所謂「磺酸(鹽)基」是表示磺酸基(-SO₃ H))或磺酸鹽基(-SO₃ M² ，在此M² 是有機或無機的陽離子)。同樣地，「磷酸(鹽)基」是表示磷酸基或磷酸鹽基，膦酸(鹽)基是表示膦酸或膦酸鹽基，羧酸(鹽)基是表示羧酸基或羧酸鹽基。Further, in the present specification, the "sulfonic acid (salt) group" means a sulfonic acid group (-SO ₃ H) or a sulfonate group (-SO ₃ M ² , where M ² is an organic or inorganic cation. ). Similarly, "phosphoric acid (sodium) group" means a phosphate group or a phosphate group, a phosphonic acid (salt) group means a phosphonic acid or a phosphonate group, and a carboxylic acid (salt) group means a carboxylic acid group or a carboxylate group. base.

該等之中，以具有磺酸(鹽)基的高分子化合物為佳。以下，說明關於具有磺酸(鹽)基的高分子化合物。Among these, a polymer compound having a sulfonic acid (salt) group is preferred. Hereinafter, a polymer compound having a sulfonic acid (salt) group will be described.

＜具有磺酸(鹽)基的高分子化合物＞ 本發明的一形態相關的表面處理組合物，上述離子性分散劑，以具有磺酸(鹽)基的高分子化合物為佳。具有磺酸(鹽)基的高分子化合物(在本說明書中亦簡稱為「含有磺酸基的高分子」)，容易有利於使用表面處理組合物去除異物。因此，包含上述含有磺酸基的高分子的表面處理組合物，在已研磨的研磨對象物的表面處理(沖洗研磨、清洗等)，具有更加容易去除殘留在已研磨的研磨對象物表面的異物(包含有機物殘渣等的雜質)的效果。<Polymer compound having a sulfonic acid (salt) group> The surface treatment composition according to one aspect of the present invention, wherein the ionic dispersant is preferably a polymer compound having a sulfonic acid (salt) group. The polymer compound having a sulfonic acid (salt) group (also referred to simply as "polymer having a sulfonic acid group" in the present specification) is easy to facilitate the removal of foreign matter by using a surface treatment composition. Therefore, the surface treatment composition containing the above-mentioned sulfonic acid group-containing polymer has a surface treatment (rinsing, washing, or the like) of the object to be polished, and it is easier to remove foreign matter remaining on the surface of the object to be polished. (The effect of containing impurities such as organic residue).

該含有磺酸基的高分子，藉由磺酸(鹽)基以外的部分(即，含有磺酸基的高分子的聚合物鏈的部分)與異物(特別是疏水性成分)的親和性，可形成微胞(micell)。因此，認為藉由該微胞溶解或分散在表面處理組合物中，可有效地去除疏水性成分的異物。The sulfonic acid group-containing polymer has affinity with a foreign substance (particularly a hydrophobic component) by a portion other than the sulfonic acid (salt) group (that is, a portion of the polymer chain of the polymer having a sulfonic acid group). A microcell can be formed. Therefore, it is considered that the foreign matter of the hydrophobic component can be effectively removed by dissolving or dispersing the micelle in the surface treatment composition.

此外，在酸性條件下，已研磨的研磨對象物表面為陽離子性時，磺酸(鹽)基藉由陰離子化而變得容易吸附在該已研磨的研磨對象物表面。其結果，認為已研磨的研磨對象物表面成為受到上述含有磺酸基的高分子覆蓋的狀態。另一方面，含有磺酸基的高分子的磺酸(鹽)基容易吸附在殘留的異物(特別是容易帶陽離子性者)，因此異物的表面會帶陰離子性。因此，其表面成為陰離子性的異物與吸附在已研磨的研磨對象物的表面之含有磺酸基的高分子之陰離子化的磺酸(鹽)基會靜電排斥。此外，異物為陰離子性時，異物本身與存在於已研磨的研磨對象物的陰離子化的磺酸(鹽)基會靜電排斥。因此，認為利用如此的靜電排斥，可更有效地去除異物。Further, when the surface of the object to be polished is cationic under acidic conditions, the sulfonic acid (salt) group is easily adsorbed on the surface of the polished object by anionization. As a result, it is considered that the surface of the object to be polished is covered with the polymer containing the sulfonic acid group. On the other hand, the sulfonic acid (salt) group of the polymer containing a sulfonic acid group is easily adsorbed to a residual foreign matter (particularly, it is easy to carry a cationic property), and therefore the surface of the foreign matter is anionic. Therefore, the anisotropic foreign matter on the surface thereof and the anionized sulfonic acid (salt) group of the sulfonic acid group-containing polymer adsorbed on the surface of the polished object to be polished are electrostatically repelled. Further, when the foreign matter is anionic, the foreign matter itself is electrostatically repelled with the anionized sulfonate group present in the polished object to be polished. Therefore, it is considered that the use of such electrostatic repulsion can remove foreign matter more effectively.

再者，已研磨的研磨對象物不容易帶電荷時，推測是藉由與上述不同的機構去除異物。首先，認為異物(特別是疏水性成分)是藉由疏水性的相互作用而成為容易附著在疏水性的已研磨的研磨對象物，之狀態。在此，含有磺酸基的高分子的聚合物鏈的部分(疏水性結構部位)因其疏水性，而朝向已研磨的研磨對象物的表面側，另一方面，親水性結構部位的陰離子化的磺酸(鹽)基等則是朝向已研磨的研磨對象物表面側的相反側。推測已研磨的研磨對象物表面藉此成為被陰離子化的磺酸(鹽)基被覆的狀態，而成為親水性。其結果，認為異物(特別是疏水性成分)與上述已研磨的研磨對象物之間不容易發生疏水性的相互作用，而能夠更加抑制異物的附著。Further, when the object to be polished is not easily charged, it is presumed that the foreign matter is removed by a mechanism different from the above. First, it is considered that a foreign matter (particularly a hydrophobic component) is in a state of being easily adhered to a hydrophobic polished object by hydrophobic interaction. Here, the portion (hydrophobic structural portion) of the polymer chain of the polymer having a sulfonic acid group is oriented toward the surface side of the object to be polished due to its hydrophobicity, and on the other hand, anionization of the hydrophilic structure portion The sulfonic acid (salt) group or the like is on the opposite side to the surface side of the object to be polished. It is presumed that the surface of the object to be polished which has been polished is in a state of being covered with an anionized sulfonic acid (salt) group, and is hydrophilic. As a result, it is considered that the hydrophobic interaction between the foreign matter (particularly the hydrophobic component) and the polished object to be polished is less likely to occur, and the adhesion of the foreign matter can be further suppressed.

然後，吸附在已研磨的研磨對象物表面的具有來自甘油的構成單位的水溶性高分子及含有磺酸基的高分子，可進一步藉由進行水洗等，而容易地去除。Then, the water-soluble polymer and the sulfonic acid group-containing polymer having a constituent unit derived from glycerin adsorbed on the surface of the polished object to be polished can be easily removed by washing with water or the like.

含有磺酸基的高分子，只要是具有複數磺酸(鹽)基者，並無特別限制，可使用習知的化合物。含有磺酸基的高分子之例子，可列舉將成為基質(base)的高分子化合物磺化而得到的高分子化合物，或將具有磺酸(鹽)基的單體共聚合而得到的高分子化合物等。The polymer having a sulfonic acid group is not particularly limited as long as it has a complex sulfonic acid (salt) group, and a conventional compound can be used. Examples of the polymer having a sulfonic acid group include a polymer compound obtained by sulfonating a polymer compound which is a base, or a polymer obtained by copolymerizing a monomer having a sulfonic acid (salt) group. Compounds, etc.

更具體而言，可列舉含有磺酸(鹽)基的聚乙烯醇(磺酸變性聚乙烯醇)、聚苯乙烯磺酸、聚苯乙烯磺酸鈉等的含有磺酸(鹽)基的聚苯乙烯、含有磺酸(鹽)基的聚乙酸乙烯酯(磺酸變性聚乙酸乙烯酯)，含有磺酸(鹽)基的聚酯、(甲基)丙烯酸-含有磺酸(鹽)基的單體之共聚物等的含有(甲基)丙烯酸基的單體-含有磺酸(鹽)基的單體之共聚物等。上述含有磺酸基的高分子，可以單獨或組合2種以上使用。該等高分子所具有的磺酸基的至少一部分，亦可為鹽的形態。作為鹽的例子，可列舉鈉鹽、鉀鹽等的鹼金屬鹽、鈣鹽、鎂鹽等的第2族元素的鹽、胺鹽、銨鹽等。特別是已研磨的研磨對象物是CMP步驟後的半導體基板時，就極力去除基板表面的金屬的觀點而言，以銨鹽為佳。More specifically, a sulfonic acid (salt) group-containing polycondensation such as a polyvinyl alcohol (sulfonic acid-modified polyvinyl alcohol) containing a sulfonic acid (salt) group, polystyrenesulfonic acid or sodium polystyrenesulfonate Styrene, polyvinyl acetate containing sulfonic acid (salt) group (sulfonic acid denatured polyvinyl acetate), polyester containing sulfonic acid (salt) group, (meth)acrylic acid containing sulfonic acid (salt) group A (meth)acryl group-containing monomer such as a monomer copolymer or a copolymer of a sulfonic acid (salt) group-containing monomer. The above-mentioned sulfonic acid group-containing polymer may be used alone or in combination of two or more. At least a part of the sulfonic acid group which these polymers have may be in the form of a salt. Examples of the salt include a salt of a Group 2 element such as an alkali metal salt such as a sodium salt or a potassium salt, a calcium salt or a magnesium salt, an amine salt or an ammonium salt. In particular, when the object to be polished is a semiconductor substrate after the CMP step, an ammonium salt is preferred from the viewpoint of removing the metal on the surface of the substrate as much as possible.

此外，含有磺酸基的高分子為含有磺酸基的聚乙烯醇時，就溶解性的觀點而言，皂化度以80%以上為佳，以85%以上為更佳(上限100%)。Further, when the sulfonic acid group-containing polymer is a sulfonic acid group-containing polyvinyl alcohol, the degree of saponification is preferably 80% or more from the viewpoint of solubility, and more preferably 85% or more (upper limit: 100%).

在本發明，含有磺酸基的高分子的重量平均分子量，以1,000以上為佳。重量平均分子量為1,000以上時，可更加提高去除異物的效果。推測其理由在於，被覆已研磨的研磨對象物及異物時的被覆性更良好，而更加提升從清洗對象物表面去除異物的作用或抑制有機物殘渣對已研磨的研磨對象物表面的再附著的作用。就同樣的觀點而言，重量平均分子量，以2,000以上為更佳，以8,000以上為進一步更佳。In the present invention, the weight average molecular weight of the polymer having a sulfonic acid group is preferably 1,000 or more. When the weight average molecular weight is 1,000 or more, the effect of removing foreign matter can be further enhanced. The reason for this is that the coating property of the object to be polished and the foreign matter is more excellent, and the effect of removing foreign matter from the surface of the object to be cleaned or the effect of suppressing the reattachment of the organic residue on the surface of the object to be polished is suppressed. . From the same viewpoint, the weight average molecular weight is more preferably 2,000 or more, and still more preferably 8,000 or more.

此外，含有磺酸基的高分子的重量平均分子量，以100,000以下為佳。重量平均分子量為100,000以下時，可更加提高去除異物的效果。推測其理由在於，在清洗步驟後的含有磺酸基的高分子的去除性變得更良好。就同樣的觀點而言，重量平均分子量，以50,000以下為更佳，以40,000以下為進一步更佳。Further, the weight average molecular weight of the polymer having a sulfonic acid group is preferably 100,000 or less. When the weight average molecular weight is 100,000 or less, the effect of removing foreign matter can be further enhanced. The reason is presumed to be that the removal property of the sulfonic acid group-containing polymer after the washing step is further improved. From the same viewpoint, the weight average molecular weight is more preferably 50,000 or less, and still more preferably 40,000 or less.

該重量平均分子量，可藉由凝膠滲透層析儀(GPC)測定，具體而言，是藉由實施例所述的方法測定。The weight average molecular weight can be measured by a gel permeation chromatography (GPC), specifically, by the method described in the examples.

含有磺酸基的高分子，亦可使用市售品，可使用，例如，日本合成化學工業株式會社製GOHSENX (註冊商標) L-3226、GOHSENX (註冊商標) CKS-50、東亞合成株式會社製ARON (註冊商標) A-6012、A-6016A、A-6020、東曹有機化學株式會社製PolyNaSS (註冊商標) PS-1等。For the polymer containing a sulfonic acid group, a commercially available product can be used, and it can be used, for example, GOHSENX (registered trademark) L-3226, GOHSENX (registered trademark) CKS-50, manufactured by Nippon Synthetic Chemical Co., Ltd., manufactured by Toagosei Co., Ltd. ARON (registered trademark) A-6012, A-6016A, A-6020, PolyNaSS (registered trademark) PS-1 manufactured by Tosoh Organic Chemical Co., Ltd., etc.

相對於表面處理組合物的總量，含有磺酸基的高分子的含量(濃度)，以0.01g/kg以上為佳。含有磺酸基的高分子的含量為0.01g/kg以上時，則可更加提升去除異物的效果。推測其理由在於，含有磺酸基的高分子被覆已研磨的研磨對象物及異物時，能夠以更多的面積進行被覆。藉此，特別是由於異物變得容易形成微胞，因此可藉由該微胞的溶解．分散而提升去除異物的效果。此外，推測藉由增加磺酸(鹽)基的數量，能夠更強地顯現靜電的吸附或排斥效果。就同樣的觀點而言，相對於表面處理組合物的總量，含有磺酸基的高分子的含量(濃度)，以0.03g/kg以上為佳，以0.05g/kg以上為更佳。此外，含有磺酸基的高分子的含量(濃度)，相對於表面處理組合物的總量，以5g/kg以下為佳含有磺酸基的高分子的含量(濃度)，在5g/kg以下，則可更加提高去除異物的效果。該理由推測係在清洗步驟後的含有磺酸基的高分子的去除性更良好。就同樣的觀點而言，含有磺酸基的高分子的含量，相對於表面處理組合物的總量，以3g/kg以下為更佳，以2g/kg以下為進一步更佳，以1g/kg以下為特佳。The content (concentration) of the polymer having a sulfonic acid group is preferably 0.01 g/kg or more based on the total amount of the surface treatment composition. When the content of the polymer having a sulfonic acid group is 0.01 g/kg or more, the effect of removing foreign matter can be further enhanced. The reason for this is presumed to be that when the polymer containing a sulfonic acid group is coated with the object to be polished and the foreign matter, it can be coated with a larger area. Thereby, especially since the foreign matter becomes easy to form the micelle, it can be dissolved by the micelle. Disperse and enhance the effect of removing foreign matter. Further, it is presumed that by increasing the number of sulfonic acid (salt) groups, the adsorption or repulsion effect of static electricity can be more strongly exhibited. From the same viewpoint, the content (concentration) of the polymer having a sulfonic acid group is preferably 0.03 g/kg or more, and more preferably 0.05 g/kg or more, based on the total amount of the surface treatment composition. In addition, the content (concentration) of the polymer having a sulfonic acid group is preferably 5 g/kg or less based on the total amount of the surface treatment composition, and the content (concentration) of the polymer containing a sulfonic acid group is 5 g/kg or less. , the effect of removing foreign matter can be further improved. This reason is presumed to be more excellent in the removal property of the sulfonic acid group-containing polymer after the washing step. From the same viewpoint, the content of the polymer having a sulfonic acid group is preferably 3 g/kg or less, more preferably 2 g/kg or less, and 1 g/kg, based on the total amount of the surface treatment composition. The following is especially good.

根據本發明的一形態，相對於離子性分散劑的總質量，離子性分散劑中的含有磺酸基的高分子的含量，以超過80質量%為佳(上限100質量%)。含有磺酸基的高分子的含量，相對於包含在表面處理組合物中的離子性分散劑的總質量為超過80質量%時，則可更加提升去除異物的效果。推測其理由在於，能夠降低清洗步驟後可能成為異物的原因的含有磺酸基的高分子以外的離子性分散劑的量。此外，推測含有磺酸基的高分子被覆已研磨的研磨對象物及異物時，能夠抑制被含有磺酸基的高分子以外的離子性分散劑妨礙被覆。就同樣的觀點而言，含有磺酸基的高分子的含量，相對於包含在表面處理組合物中的離子性分散劑的總質量，以超過95質量%為佳。在此情形，可顯著地提升去除異物的效果。According to one aspect of the present invention, the content of the sulfonic acid group-containing polymer in the ionic dispersant is preferably more than 80% by mass based on the total mass of the ionic dispersant (upper limit: 100% by mass). When the content of the sulfonic acid group-containing polymer is more than 80% by mass based on the total mass of the ionic dispersant contained in the surface treatment composition, the effect of removing foreign matter can be further enhanced. The reason is presumed to be that the amount of the ionic dispersing agent other than the sulfonic acid group-containing polymer which may cause foreign matter after the washing step can be reduced. In addition, when it is estimated that the sulfonic acid group-containing polymer coats the polished object to be polished and the foreign matter, it is possible to suppress the ionic dispersant other than the polymer containing a sulfonic acid group from interfering with the coating. From the same viewpoint, the content of the polymer having a sulfonic acid group is preferably more than 95% by mass based on the total mass of the ionic dispersant contained in the surface treatment composition. In this case, the effect of removing foreign matter can be remarkably improved.

再者，含有磺酸基的高分子的含量，相對於包含在表面處理組合物的離子性分散劑的總質量，以100質量%為特佳。即，包含在表面處理組合物中的離子性分散劑，以僅為含有磺酸基的高分子為特佳。Further, the content of the polymer having a sulfonic acid group is particularly preferably 100% by mass based on the total mass of the ionic dispersant contained in the surface treatment composition. That is, the ionic dispersant contained in the surface treatment composition is particularly preferred as a polymer containing only a sulfonic acid group.

再者，在本說明書，所謂「高分子化合物」，是指其重量平均分子量為1,000以上的化合物。In the present specification, the term "polymer compound" means a compound having a weight average molecular weight of 1,000 or more.

［其他的添加劑］ 本發明的一形態的表面處理組合物，在不阻礙本發明的效果的範圍內，亦可按照需要以任意比例含有其他的添加劑。惟，本發明的一形態相關的表面處理組合物的必須成分以外的成分，由於可能成為異物的原因，以盡可能不添加為佳。因此，必須成分以外的成分，其添加量以盡可能的少為佳，以不包含為更佳。其他的添加劑，可列舉，例如，研磨粒、鹼、防腐劑、溶存氣體、還原劑、氧化劑及烷醇胺類等。其中，為了更加提升去除異物的效果，表面處理組合物，以實質上不含研磨粒為佳。在此，所謂「實質上不含研磨粒」，是指相對於表面處理組合物的總量，研磨粒的含量為0.01質量%以下。[Other Additives] The surface treatment composition according to one aspect of the present invention may contain other additives in an arbitrary ratio as needed within a range not inhibiting the effects of the present invention. However, components other than the essential components of the surface treatment composition according to one aspect of the present invention are preferably not added as much as possible because they may become foreign matter. Therefore, it is necessary to add a component other than the component as much as possible, and it is preferable to not include it. Examples of other additives include abrasive grains, alkalis, preservatives, dissolved gases, reducing agents, oxidizing agents, and alkanolamines. Among them, in order to further enhance the effect of removing foreign matter, the surface treatment composition preferably contains substantially no abrasive particles. Here, the term "substantially free of abrasive grains" means that the content of the abrasive grains is 0.01% by mass or less based on the total amount of the surface treatment composition.

［異物去除效果］ 本發明的一形態相關的表面處理組合物，去除已研磨的研磨對象物表面上的異物(有機物殘渣)的效果越高越佳。即，使用表面處理組合物進行已研磨的研磨對象物的表面處理時，殘存在表面的異物(有機物殘渣)的數量越少越佳。具體而言，使用表面處理組合物表面處理已研磨的研磨對象物時，異物(有機物殘渣)的數量，以6000個以下為佳，以3000個以下為更佳，以2000個以下為進一步佳，以1500個以下為特佳，以1000個以下為最佳。另一方面，由於上述異物(有機物殘渣)的數量越少越佳，故其下限並無特別限制，實質上為50個。[Forebody Removal Effect] The surface treatment composition according to one aspect of the present invention has a higher effect of removing foreign matter (organic residue) on the surface of the object to be polished. In other words, when the surface treatment composition is subjected to the surface treatment of the polished object to be polished, the smaller the number of foreign matter (organic residue) remaining on the surface, the better. Specifically, when the surface to be polished is surface-treated with the surface-treated composition, the amount of the foreign matter (organic residue) is preferably 6,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less. It is particularly good for 1,500 or less, and 1000 or less is the best. On the other hand, since the number of the foreign matter (organic residue) is preferably as small as possible, the lower limit is not particularly limited, and is substantially 50.

再者，上述異物(有機物殘渣)的數量，是藉由實施例所述的方法進行表面處理之後，採用實施例所述的方法測定之值。Further, the amount of the above-mentioned foreign matter (organic residue) was measured by the method described in the examples, and then measured by the method described in the examples.

［表面處理組合物的製造方法］ 上述表面處理組合物的製造方法，並無特別限制。例如，可藉由將具有來自甘油的構成單位的水溶性高分子、酸、及水混合而製造。即，根據本發明的其他形態，可提供一種上述表面處理組合物的製造方法，其包含將具有來自甘油的構成單位的水溶性高分子、酸及水混合。上述具有來自甘油的構成單位的水溶性高分子的種類、添加量等，如上所述。再者，本發明的一形態相關的表面處理組合物的製造方法，按照需要，亦可進一步混合上述離子性分散劑、其他的添加劑、水以外的分散媒等。該等的種類、添加量等，如上所述。[Method for Producing Surface Treatment Composition] The method for producing the surface treatment composition is not particularly limited. For example, it can be produced by mixing a water-soluble polymer having a constituent unit derived from glycerin, an acid, and water. That is, according to another aspect of the present invention, a method for producing the surface treatment composition comprising mixing a water-soluble polymer having a constituent unit derived from glycerin, an acid, and water can be provided. The type, addition amount, and the like of the water-soluble polymer having a constituent unit derived from glycerin are as described above. Further, in the method for producing a surface treatment composition according to one aspect of the present invention, the ionic dispersant, other additives, a dispersion medium other than water, or the like may be further mixed as needed. The types, addition amounts, and the like are as described above.

上述各成分的添加順序、添加方法，並無特別限制。可將上述各成分，整批地或各自地、階段地或連續地添加。此外，混合方法，亦無特別限制，可使用習知的方法。較佳的是上述表面處理組合物的製造方法包含以下步驟：將具有來自甘油的構成單位的水溶性高分子、酸、水、及按照需要添加的離子性分散劑，依序添加，在水中攪拌。再者，上述表面處理組合物的製造方法，亦可進一步包含以下步驟：以使pH成為5以下之方式測定並調整表面處理組合物的pH。The order of addition and the method of addition of each component described above are not particularly limited. The above components may be added in whole batch or individually, in stages or continuously. Further, the mixing method is also not particularly limited, and a conventional method can be used. Preferably, the method for producing a surface treatment composition comprises the steps of: sequentially adding a water-soluble polymer having a constituent unit derived from glycerin, an acid, water, and an ionic dispersant added as needed, and stirring in water. . Further, the method for producing the surface treatment composition may further comprise the step of measuring and adjusting the pH of the surface treatment composition so that the pH is 5 or less.

［表面處理方法］ 本發明的另一形態是一種表面處理方法，其包含使用上述表面處理組合物表面處理已研磨的研磨對象物。在本說明書，所謂表面處理方法，是指減低在已研磨的研磨對象物表面的異物的方法，是進行廣義的清洗之方法。[Surface Treatment Method] Another aspect of the present invention provides a surface treatment method comprising surface-treating a polished object to be polished using the surface treatment composition. In the present specification, the surface treatment method refers to a method of reducing foreign matter on the surface of the object to be polished, and is a method of performing generalized cleaning.

根據本發明的一形態相關的表面處理方法，可充分去除殘留在已研磨的研磨對象物的表面異物。即，根據本發明的另一形態，提供一種表面處理方法，其係使用上述表面處理組合物表面處理已研磨的研磨對象物，降低已研磨的研磨對象物表面的異物的方法。According to the surface treatment method according to one aspect of the present invention, the foreign matter remaining on the surface of the object to be polished can be sufficiently removed. That is, according to another aspect of the present invention, there is provided a surface treatment method for surface-treating a polished object to be polished using the surface treatment composition to reduce foreign matter on the surface of the object to be polished.

本發明的一形態相關的表面處理方法，是使本發明的表面處理組合物直接接觸已研磨的研磨對象物，藉由如此方法而進行。A surface treatment method according to an aspect of the present invention is carried out by directly contacting the surface treatment composition of the present invention with the object to be polished.

表面處理方法，主要可列舉(I)採用沖洗研磨處理的方法、(II)採用清洗處理的方法。即，本發明的一形態相關的表面處理，以採用沖洗研磨或清洗而進行為佳。沖洗研磨處理及清洗處理，是為了去除已研磨的研磨對象物表面上的異物(粒子、金屬污染、有機物殘渣、墊片屑等)，得到潔淨的表面而實施。以下說明關於上述(I)及(II)。The surface treatment method mainly includes (I) a method using a rinsing treatment, and (II) a method using a cleaning treatment. That is, the surface treatment according to one aspect of the present invention is preferably carried out by rinsing or washing. The rinsing and polishing treatment and the cleaning treatment are performed to remove foreign matter (particles, metal contamination, organic residue, gasketings, and the like) on the surface of the object to be polished, thereby obtaining a clean surface. The following description of the above (I) and (II).

(I)沖洗研磨處理 本發明相關的表面處理組合物，可良好地使用於沖洗研磨處理。沖洗研磨處理的目的，是針對研磨對象物進行最終研磨(精加工研磨)之後，去除研磨對象物表面上的異物，並且在安裝有研磨墊片的研磨定盤(platen)上進行。此時，藉由使本發明相關的表面處理組合物直接接觸已研磨的研磨對象物，而進行沖洗研磨處理。其結果，已研磨的研磨對象物表面的異物，可藉由研磨墊片所產生的摩擦力(物理性作用)及表面處理組合物所產生的化學作用而被去除。異物之中，特別是粒子、有機物殘渣等，容易藉由物理性作用去除。因此，在沖洗研磨處理中，在研磨定盤上利用與研磨墊片的摩擦，藉此可有效地去除粒子、有機物殘渣等。(I) Rinse grinding treatment The surface treatment composition according to the present invention can be suitably used for the rinsing and polishing treatment. The purpose of the rinsing and polishing treatment is to remove the foreign matter on the surface of the object to be polished after the final polishing (finishing polishing) of the object to be polished, and to perform the polishing on the platen on which the polishing pad is attached. At this time, the surface treatment composition according to the present invention is subjected to a rinse polishing treatment by directly contacting the ground object to be polished. As a result, the foreign matter on the surface of the object to be polished can be removed by the frictional force (physical action) generated by the polishing pad and the chemical action generated by the surface treatment composition. Among the foreign matters, in particular, particles, organic residue, and the like are easily removed by physical action. Therefore, in the rinsing and polishing process, friction with the polishing pad is utilized on the polishing platen, whereby particles, organic residue, and the like can be effectively removed.

具體而言，沖洗研磨處理可如下進行：將研磨步驟後的已研磨的研磨對象物表面設置在研磨裝置的研磨定盤，使研磨墊片與已研磨的研磨對象物接觸，一邊對該接觸部分供給表面處理組合物(沖洗研磨用組合物)，一邊使已研磨的研磨對象物與研磨墊片相對滑動。Specifically, the rinsing and polishing treatment may be performed by providing the surface of the polished object to be polished after the polishing step to the polishing plate of the polishing apparatus, and bringing the polishing pad into contact with the object to be polished, while the contact portion is The surface treatment composition (flush polishing composition) is supplied while sliding the polished object to be polished and the polishing pad.

沖洗研磨處理，可使用單面研磨裝置、雙面研磨裝置的任一種而進行。此外，上述研磨裝置，除了研磨用組合物的射出噴嘴之外，較佳為亦具備沖洗研磨用組合物的射出噴嘴。研磨裝置的沖洗研磨處理時的運轉條件並無特別限制，只要是該業者可適宜設定。The rinsing and polishing treatment can be carried out using either a single-side polishing apparatus or a double-side polishing apparatus. Further, in addition to the injection nozzle of the polishing composition, the polishing apparatus preferably further includes an injection nozzle for rinsing and polishing the composition. The operating conditions at the time of the rinsing and polishing treatment of the polishing apparatus are not particularly limited, and may be appropriately set as long as the manufacturer can.

(II)清洗處理 本發明相關的表面處理組合物，可良好地使用於清洗處理。清洗處理的目的，是針對研磨對象物進行最終研磨(精加工研磨)之後，或進行上述沖洗研磨處理之後，去除已研磨的研磨對象物表面的異物而進行。再者，清洗處理與上述沖洗研磨處理，是根據進行該等處理的場所分類，清洗處理，是將已研磨的研磨對象物從研磨定盤上取下之後所進行的表面處理。在清洗處理，亦可藉由使本發明相關的表面處理組合物直接接觸已研磨的研磨對象物，而去除該對象物表面的異物。(II) Cleaning treatment The surface treatment composition according to the present invention can be suitably used for the cleaning treatment. The purpose of the cleaning process is to perform the final polishing (finishing polishing) on the object to be polished, or to perform the above-described rinsing and polishing process, and then remove the foreign matter on the surface of the object to be polished. Further, the cleaning process and the above-described rinsing and polishing process are classified according to the location at which the processes are performed, and the cleaning process is a surface treatment performed after the polished object to be polished is removed from the polishing platen. In the cleaning treatment, foreign matter on the surface of the object may be removed by directly contacting the surface treatment composition according to the present invention to the object to be polished.

作為進行清洗處理的方法的一例，可列舉(i)在保持已研磨的研磨對象物的狀態下，使清洗刷與已研磨的研磨對象物的單面或雙面接觸，一邊對該接觸部分供給表面處理組合物，一邊以清洗刷擦拭清洗對象物表面的方法；(ii)使已研磨的研磨對象物浸漬在表面處理組合物中，進行超音波處理、攪拌等的方法(浸漬式)等。在該方法，研磨對象物表面的異物，可藉由清洗刷的摩擦力或超音波處理、攪拌等所產生的機械力、及表面處理組合物所產生的化學作用而被去除。As an example of the method of performing the cleaning treatment, (i) the contact portion is supplied while the cleaning brush is in contact with one or both sides of the object to be polished while holding the object to be polished. The surface treatment composition is a method of wiping the surface of the object to be cleaned with a cleaning brush; (ii) a method of immersing the object to be polished in the surface treatment composition, and performing a method such as ultrasonic treatment, stirring, or the like (immersion type). In this method, the foreign matter on the surface of the object to be polished can be removed by the frictional force of the cleaning brush, the mechanical force generated by ultrasonic treatment, stirring, or the like, and the chemical action generated by the surface treatment composition.

在上述(i)的方法，使表面處理組合物(清洗用組合物)接觸已研磨的研磨對象物的方法，並無特別限定，可列舉一邊使表面處理組合物從噴嘴流動到已研磨的研磨對象物，一邊使已研磨的研磨對象物高速旋轉的旋轉式；將表面處理組合物噴霧在已研磨的研磨對象物而進行清洗的噴霧式等。In the method of the above (i), the method of bringing the surface treatment composition (cleaning composition) into contact with the polished object to be polished is not particularly limited, and examples thereof include flowing the surface treatment composition from the nozzle to the ground polishing. The object is a rotary type in which the object to be polished is rotated at a high speed, and a spray type or the like in which the surface treatment composition is sprayed on the polished object to be polished and washed.

就可以短時間有效地去除污染的觀點而言，清洗處理，以採用旋轉式、噴霧式等為佳，以旋轉式為更佳。From the viewpoint of effectively removing the contamination in a short time, the cleaning treatment is preferably a rotary type, a spray type or the like, and a rotary type is more preferable.

用於進行如此的清洗處理的裝置，有將收容在卡匣(cassette)的複數片已研磨的研磨對象物同時進行表面處理的批次式清洗裝置；將1片已研磨的研磨對象物安裝在支架而進行表面處理的枚葉式清洗裝置等。就縮短清洗時間的觀點而言，以使用枚葉式清洗裝置的方法為佳。The apparatus for performing such a cleaning process includes a batch type cleaning apparatus that simultaneously performs surface treatment on a plurality of pieces of the polished object to be polished accommodated in a cassette; and one piece of the object to be polished is attached to the object to be polished. A leaf type cleaning device that performs surface treatment with a holder. From the viewpoint of shortening the cleaning time, a method using a lobed type cleaning device is preferred.

再者，用於進行清洗處理的裝置，可列舉具備清洗裝置的研磨裝置，其可將已研磨的研磨對象物從研磨定盤取下之後，將該對象物以清洗刷進行擦拭。藉由使用如此的研磨裝置，可更有效地進行已研磨的研磨對象物的清洗處理。Further, the apparatus for performing the cleaning treatment includes a polishing apparatus including a cleaning device that can remove the polished object to be polished from the polishing platen, and then wipe the object with a cleaning brush. By using such a polishing apparatus, the cleaning process of the object to be polished can be performed more efficiently.

如此的研磨裝置，可使用具有保持已研磨的研磨對象物的支架、可改變旋轉數的馬達、清洗刷等的一般的研磨裝置。研磨裝置，可使用單面研磨裝置或雙面研磨裝置的任一種。再者，在CMP步驟之後，進行沖洗研磨步驟時，該清洗處理使用與沖洗研磨步驟所使用的研磨裝置相同的裝置進行，可更有效率，因而較佳。As such a polishing apparatus, a general polishing apparatus having a holder for holding a polished object to be polished, a motor capable of changing the number of rotations, a cleaning brush, and the like can be used. As the polishing apparatus, any one of a single-side polishing apparatus or a double-side polishing apparatus can be used. Further, when the rinsing and polishing step is performed after the CMP step, the cleaning treatment is carried out using the same apparatus as the polishing apparatus used in the rinsing and polishing step, which is more efficient and therefore preferable.

清洗刷，並無特別限制，使用樹脂製的刷子為佳。樹脂製刷子的材質，並無特別限制，可列舉，例如，PVA(聚乙烯醇)。清洗刷，使用PVA製海綿為更佳。The cleaning brush is not particularly limited, and a resin brush is preferred. The material of the resin brush is not particularly limited, and examples thereof include PVA (polyvinyl alcohol). It is better to use a PVA sponge for the cleaning brush.

清洗條件，並無特別限制，可按照清洗對象物的種類、及去除對象的有機物殘渣的種類及量，適宜設定。例如，清洗刷的轉數，以10rpm(0.17s^-1 ，60rpm=1s^-1 ，以下相同)以上、200rpm(3.3s^-1 )以下為佳。清洗對象物的轉數，以10rpm(0.17s^-1 )以上、100rpm(1.7s^-1 )以下為佳。對清洗對象物施加的壓力(研磨壓力)，分別以0.5psi(3.4kPa，1psi=6894.76Pa，以下相同)以上、10psi(68.9kPa)以下為佳。對研磨墊片供給表面處理組合物的方法，亦無特別限制，可使用，例如，藉由幫浦等連續供給的方法(澆注)。表面處理組合物的供給量，並無特別限制，以表面處理組合物可隨時覆蓋清洗刷及清洗對象物表面的供給量為佳，以10mL/分以上、5000mL/分以下為更佳。清洗時間，亦無特別限制，使用本發明的一形態相關的表面處理組合物的步驟，以5秒以上、180秒以下為佳。在如此的範圍，可更有效地去除異物。The cleaning conditions are not particularly limited, and may be appropriately set depending on the type of the object to be cleaned and the type and amount of the organic residue to be removed. For example, the number of revolutions of the cleaning brush is preferably 10 rpm (0.17 s ^-1 , 60 rpm = 1 s ^-1 , the same applies hereinafter) or more, and 200 rpm (3.3 s ^-1 ) or less. Number of revolutions of the cleaning object to 10rpm (0.17s ^-1) or more, 100rpm (1.7s ^-1) or less is preferable. The pressure (grinding pressure) applied to the object to be cleaned is preferably 0.5 psi (3.4 kPa, 1 psi = 6974.76 Pa, the same or less) or more, and 10 psi (68.9 kPa) or less. The method of supplying the surface treatment composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying a pump or the like (casting) can be used. The amount of the surface treatment composition to be supplied is not particularly limited, and the surface treatment composition can preferably cover the surface of the cleaning brush and the object to be cleaned at any time, preferably 10 mL/min or more and 5000 mL/min or less. The washing time is not particularly limited, and the step of using the surface treatment composition according to one aspect of the present invention is preferably 5 seconds or longer and 180 seconds or shorter. In such a range, foreign matter can be removed more effectively.

清洗時的表面處理組合物的溫度，並無特別限制，通常可為室溫(25℃)好，在不損及性能的範圍，亦可加溫到40℃以上、70℃以下的程度。The temperature of the surface treatment composition at the time of washing is not particularly limited, and it is usually room temperature (25 ° C), and can be heated to a temperature of 40 ° C or more and 70 ° C or less in a range not impairing performance.

在上述(ii)的方法，關於藉由浸漬的清洗方法的條件，並無特別限制，可使用習知的手法。In the method of the above (ii), the conditions of the cleaning method by the immersion are not particularly limited, and a conventional method can be used.

在以上述(i)(ii)的方法進行清洗處理之前、之後或其雙方，亦可進行使用水的清洗。Washing with water may be performed before, after, or both of the cleaning treatment by the method (i) (ii) above.

此外，清洗後的已研磨的研磨對象物(清洗對象物)，較佳為藉由旋轉乾燥機等將附著在表面的水滴甩落使其乾燥。此外，亦可藉由吹氣乾燥使清洗對象物表面乾燥。In addition, it is preferable that the object to be polished (the object to be cleaned) after the cleaning is dropped by a spin dryer or the like to be dried. Further, the surface of the object to be cleaned may be dried by blowing air.

［半導體基板的製造方法］ 當已研磨的研磨對象物為已研磨的半導體基板時，可良好地適用本發明的一形態相關的表面處理方法。即，已研磨的研磨對象物為已研磨的半導體基板，根據本發明的另一形態，提供一種半導體基板的製造方法，包含使用上述表面處理組合物對該已研磨的半導體基板進行表面處理。[Manufacturing Method of Semiconductor Substrate] When the object to be polished is a polished semiconductor substrate, a surface treatment method according to one aspect of the present invention can be suitably applied. That is, the polished object to be polished is a polished semiconductor substrate, and according to another aspect of the present invention, there is provided a method of producing a semiconductor substrate comprising surface-treating the polished semiconductor substrate using the surface treatment composition.

關於適用該製造方法的半導體基板的細節，如以上藉由上述表面處理組合物表面處理的已研磨的研磨對象物的說明。The details of the semiconductor substrate to which the manufacturing method is applied are as described above for the polished object to be polished by the surface treatment composition.

此外，半導體基板的製造方法，只要是包含使用本發明的一形態相關的表面處理組合物對已研磨的半導體基板的表面進行表面處理的步驟(表面處理步驟)，就無特別限制。該製造方法，可列舉，例如，用於形成已研磨的半導體基板的研磨步驟及清洗步驟的方法。此外，作為另一例子，可列舉除了研磨步驟及清洗步驟之外，在研磨步驟及清洗步驟之間具有沖洗研磨步驟的方法。以下說明該等各步驟。Further, the method for producing a semiconductor substrate is not particularly limited as long as it is a step (surface treatment step) of surface-treating the surface of the polished semiconductor substrate using the surface treatment composition according to one aspect of the present invention. The manufacturing method includes, for example, a method for forming a polishing step and a cleaning step of the polished semiconductor substrate. Further, as another example, a method of having a rinsing and polishing step between the polishing step and the cleaning step in addition to the polishing step and the cleaning step may be mentioned. The steps are described below.

＜研磨步驟＞ 包含於半導體基板的製造方法的研磨步驟，是研磨半導體基板而形成已研磨的半導體基板的步驟。<Polishing Step> The polishing step included in the method of manufacturing the semiconductor substrate is a step of polishing the semiconductor substrate to form a polished semiconductor substrate.

研磨步驟，只要是研磨半導體基板的步驟，並無特別限制，以化學機械研磨步驟為佳。此外，研磨步驟，可為單一步驟所組成的研磨步驟，亦可為複數步驟所組成的研磨步驟。由複數步驟組成的研磨步驟，可列舉，例如，在預備研磨步驟(粗研磨步驟)之後進行精加工研磨步驟的步驟，或在1次研磨步驟之後，進行一次或兩次以上的2次研磨步驟，之後進行精加工研磨步驟的步驟等。使用本發明相關的表面處理組合物的表面處理步驟，以在上述精加工研磨步驟之後進行為佳。The polishing step is not particularly limited as long as it is a step of polishing the semiconductor substrate, and a chemical mechanical polishing step is preferred. In addition, the grinding step may be a grinding step consisting of a single step, or a grinding step consisting of a plurality of steps. The grinding step consisting of a plurality of steps may, for example, be a step of performing a finishing grinding step after the preliminary grinding step (coarse grinding step) or two or more grinding steps after one grinding step. Then, the steps of finishing the polishing step and the like are performed. It is preferred to carry out the surface treatment step of the surface treatment composition according to the present invention after the above-described finishing polishing step.

研磨用組合物，可按照半導體基板的特性，適宜使用習知的研磨用組合物。研磨用組合物，並無特別限制，例如，可良好地使用包含研磨粒、酸鹽、分散媒、及酸的等。該研磨用組合物的具體例，可列舉包含磺酸修飾膠態氧化矽、水及馬來酸的研磨用組合物等。As the polishing composition, a conventional polishing composition can be suitably used in accordance with the characteristics of the semiconductor substrate. The polishing composition is not particularly limited, and for example, abrasive grains, acid salts, a dispersion medium, an acid, and the like can be preferably used. Specific examples of the polishing composition include a polishing composition containing a sulfonic acid-modified colloidal cerium oxide, water, and maleic acid.

研磨裝置，可使用安裝有保持具有研磨對象物的基板等的支架及可改變轉數的馬達等，且具有可黏貼研磨墊片(研磨布)的研磨定盤的一般的研磨裝置。研磨裝置，可使用單面研磨裝置或雙面研磨裝置的任一種。As the polishing apparatus, a general polishing apparatus having a holder for holding a substrate having an object to be polished and the like, a motor capable of changing the number of revolutions, and the like, and having a polishing plate to which a polishing pad (abrasive cloth) can be attached can be used. As the polishing apparatus, any one of a single-side polishing apparatus or a double-side polishing apparatus can be used.

研磨墊片，可無特別限制地使用一般的不織布、聚氨酯、及多孔質氟樹脂等。研磨墊片，以施行可積存研磨液的溝加工為佳。As the polishing pad, a general non-woven fabric, a polyurethane, a porous fluororesin or the like can be used without particular limitation. It is preferable to grind the spacer to perform the processing of the groove in which the slurry can be accumulated.

研磨條件亦無特別限制，例如，研磨定盤的轉數及研磨頭(載體)轉數，以10rpm以上、100rpm以下為佳，對研磨對象物施加的壓力(研磨壓力)，以0.5psi(3.4kPa)以上、10psi(68.9kPa)以下為佳。對研磨墊片供給研磨用組合物的方法，亦無特別限制，可使用，例如，藉由幫浦等連續供給的方法(澆注)。研磨用組合物的供給量，並無特別限制，以研磨用組合物可隨時覆蓋研磨墊片的供給量為佳，以10mL/分以上、5000mL/分以下為更佳。研磨時間，亦無特別限制，關於使用研磨用組合物的步驟，以5秒以上、180秒以下為佳。The polishing conditions are not particularly limited. For example, the number of revolutions of the polishing platen and the number of revolutions of the polishing head (carrier) are preferably 10 rpm or more and 100 rpm or less, and the pressure (grinding pressure) applied to the object to be polished is 0.5 psi (3.4). Above kPa), preferably 10 psi (68.9 kPa) or less. The method of supplying the polishing composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying a pump or the like (casting) can be used. The amount of the polishing composition to be supplied is not particularly limited, and the polishing composition can be applied to the polishing pad at any time, preferably 10 mL/min or more and 5000 mL/min or less. The polishing time is not particularly limited, and the step of using the polishing composition is preferably 5 seconds or longer and 180 seconds or shorter.

＜表面處理步驟＞ 所謂表面處理步驟，是指使用本發明相關的表面處處理組合物減低已研磨的研磨對象物表面的異物的步驟。在半導體基板的製造方法，作為表面處理步驟，可進行沖洗研磨步驟及清洗步驟，亦可僅進行沖洗研磨步驟，亦可僅進行清洗步驟。<Surface Treatment Step> The surface treatment step refers to a step of reducing the foreign matter on the surface of the polished object to be polished using the treatment composition at the surface according to the present invention. In the method of manufacturing a semiconductor substrate, as the surface treatment step, a rinse polishing step and a cleaning step may be performed, and only the rinse polishing step may be performed, or only the cleaning step may be performed.

(沖洗研磨步驟) 在半導體基板的製造方法，沖洗研磨步驟，可設於研磨步驟及清洗步驟之間。沖洗研磨步驟，是藉由本發明的一形態相關的表面處理方法(沖洗研磨處理方法)減低已研磨的研磨對象物(已研磨的半導體基板)表面的異物的步驟。(Rinsing and Polishing Step) In the method of manufacturing a semiconductor substrate, the rinsing and polishing step may be provided between the polishing step and the cleaning step. The rinsing and polishing step is a step of reducing the foreign matter on the surface of the polished object to be polished (the polished semiconductor substrate) by the surface treatment method (flushing and polishing method) according to one aspect of the present invention.

在沖洗研磨步驟，除了供給本發明相關的表面處理組合物代替供給研磨用組合物以外，研磨裝置、研磨墊片及沖洗研磨的條件，可適用與上述研磨步驟相同的裝置及條件。In the rinsing and polishing step, the same apparatus and conditions as those of the above-described polishing step can be applied, except that the surface treatment composition according to the present invention is supplied instead of the supply of the polishing composition, the conditions of the polishing apparatus, the polishing pad, and the rinsing.

使用於沖洗研磨步驟的沖洗研磨方法的細節，如上述沖洗研磨處理的說明所述。The details of the rinsing and grinding method used in the rinsing and grinding step are as described in the above description of the rinsing and grinding treatment.

(清洗步驟) 在半導體基板的製造方法，清洗步驟，可設於研磨步驟之後，亦可設於沖洗研磨步驟之後。清洗步驟，是藉由本發明的一形態相關的表面處理方法(清洗方法)減低已研磨的研磨對象物(已研磨的半導體基板)表面的異物的步驟。(Cleaning Step) In the method of manufacturing the semiconductor substrate, the cleaning step may be provided after the polishing step or after the rinsing step. The cleaning step is a step of reducing the foreign matter on the surface of the polished object to be polished (the polished semiconductor substrate) by the surface treatment method (cleaning method) according to one aspect of the present invention.

使用於清洗步驟的清洗方法的細節，如上述清洗方法的說明所述。The details of the cleaning method used in the cleaning step are as described in the above description of the cleaning method.

尚文詳細地說明了本發明相關的實施形態，惟此僅為說明且例示而並非限定，本發明的範圍應以附件的專利申請範圍所解釋。The present invention is described in detail with reference to the accompanying drawings and claims

本發明包含下述態樣及形態。 1. 一種表面處理組合物，用於處理已研磨的研磨對象物的表面，包含： 具有來自甘油的構成單位的水溶性高分子； 酸；及 水， pH為5以下； 2. 如上述1.所述之表面處理組合物，其中上述具有來自甘油的構成單位的水溶性高分子為選自由聚甘油、環氧乙烷變性聚甘油、磺酸變性聚甘油、膦酸變性聚甘油、聚甘油-4-乙烯基安息香酸酯(苯乙烯基變性聚甘油)、及聚甘油脂肪酸酯所組成之群之至少1種； 3. 如上述1.或2.所述之表面處理組合物，其中進一步包含離子性分散劑； 4. 如上述3.所述之表面處理組合物，其中上述離子性分散劑為具有磺酸(鹽)基的高分子化合物。 5. 如上述1.至4.之任何一項所述之表面處理組合物，其中上述pH為4以下； 6. 如上述1.至5.之任何一項所述之表面處理組合物，其中實質上不含研磨粒； 7. 如上述1.至6.之任何一項所述之表面處理組合物，其中上述已研磨的研磨對象物包含多晶矽； 8. 一種製造方法，其係如上述1.至7.之任何一項所述之表面處理組合物的製造方法，包含：將上述具有來自甘油的構成單位的水溶性高分子、上述酸、及上述水混合； 9. 一種表面處理方法，包含使用上述1.至7.之任何一項所述之表面處理組合物對已研磨的研磨對象物進行表面處理，降低在已研磨的研磨對象物表面的有機物殘渣； 10. 如上述9.所述之表面處理方法，其中上述表面處理是藉由沖洗研磨或清洗而進行； 11. 一種半導體基板的製造方法，其中已研磨的研磨對象物為已研磨的半導體基板，該製造方法包含藉由上述9.或10.所述之表面處理方法而減低在已研磨的研磨對象物表面的有機物殘渣之表面處理步驟。The present invention encompasses the following aspects and forms. A surface treatment composition for treating a surface of a ground object to be polished, comprising: a water-soluble polymer having a constituent unit derived from glycerin; an acid; and water having a pH of 5 or less; 2. The surface treatment composition, wherein the water-soluble polymer having a constituent unit derived from glycerin is selected from the group consisting of polyglycerol, ethylene oxide modified polyglycerin, sulfonic acid modified polyglycerin, phosphonic acid denatured polyglycerin, and polyglycerin- At least one of the group consisting of 4-vinylbenzoic acid ester (styrene-based modified polyglycerol) and polyglycerol fatty acid ester; 3. The surface treatment composition according to the above 1. or 2., further The surface treatment composition according to the above 3., wherein the ionic dispersant is a polymer compound having a sulfonic acid (salt) group. 5. The surface treatment composition according to any one of the above 1 to 4, wherein the above-mentioned pH is 4 or less; The surface treatment composition according to any one of the above-mentioned items 1 to 6, wherein the ground object to be polished comprises polycrystalline germanium; 8. A manufacturing method, which is as described above The method for producing a surface treatment composition according to any one of the preceding claims, comprising: mixing the water-soluble polymer having a constituent unit derived from glycerin, the acid, and the water; The surface treatment composition according to any one of the above items 1 to 7, wherein the ground object to be polished is subjected to surface treatment to reduce the organic residue on the surface of the ground object to be polished; The surface treatment method described above, wherein the surface treatment is performed by rinsing or cleaning; 11. A method of manufacturing a semiconductor substrate, wherein the ground object to be polished is a ground semiconductor substrate, and the manufacturing method includes 9. The above-described surface treatment or the method of claim 10. The reduction in the surface of the organic residue milled polished surface of the object processing step.

［實施例］ 使用以下的實施例及比較例更詳細地說明本發明。惟，本發明的技術上範圍並非限定於以下的實施例。再者，若無特別提及，「%」及「份」是指「質量%」及「質量份」。此外，在下述實施例，若無特別提及，操作是在室溫(20℃以上、25℃以下)/相對濕度40%RH以上、50%RH以下的條件下進行。[Examples] The present invention will be described in more detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments. In addition, "%" and "parts" mean "% by mass" and "parts by mass" unless otherwise mentioned. Further, in the following examples, unless otherwise specified, the operation was carried out under the conditions of room temperature (20 ° C or more, 25 ° C or less) / relative humidity of 40% RH or more and 50% RH or less.

再者，具有來自甘油的構成單位的水溶性高分子及聚乙烯醇的重量平均分子量，是以凝膠滲透層析儀(GPC)所測定的重量平均分子量(聚乙二醇換算)之值，更具體而言，是以下述裝置及條件測定。 GPC裝置︰株式會社島津製造所製 型式︰Prominence 管柱︰Shim-pack (註冊商標) VP-ODS (株式會社島津JLC製) 移動相 A︰MeOH B：乙酸1%水溶液 流量︰1mL/分 檢測器︰ELSD(蒸發光散射偵測器；Evaporative Light Scattering Detector)檢測器(ELSD-LTII)、temp.：40℃、Gain：8、N₂ GAS：350kPa 烘箱溫度︰40℃ 注入量︰40μL。Further, the weight average molecular weight of the water-soluble polymer and polyvinyl alcohol having a constituent unit derived from glycerin is a value of a weight average molecular weight (in terms of polyethylene glycol) measured by a gel permeation chromatography (GPC). More specifically, it is measured by the following apparatus and conditions. GPC device: manufactured by Shimadzu Corporation. Prominence tube column.. Shim-pack (registered trademark) VP-ODS (manufactured by Shimadzu JLC) Mobile phase A.. MeOH B: 1% aqueous solution of acetic acid: 1 mL/min detector .. ELSD (Evaporative Light Scattering Detector) detector (ELSD-LTII), temp.: 40 ° C, Gain: 8, N ₂ GAS: 350 kPa oven temperature: 40 ° C injection amount: 40 μL.

＜表面處理組合物的調製＞ ［實施例1：表面處理組合物A-1的調製］ 將作為有機酸的濃度30質量%的馬來酸水溶液，以相對於組合物全體100質量份為1.0質量份(以馬來酸0.3質量份)的濃度、使作為具有來自甘油的構成單位的水溶性高中分子的聚甘油(重量平均分子量(Mw)：15,000)成為1.0g/kg的濃度、及使作為離子性分散劑的聚苯乙烯磺酸成為0.25g/kg的濃度，分別與水(去離子水)混合，調製表面處理組合物A-1。對表面處理組合物A-1(液溫︰25℃)，以pH計(株式會社堀場製造所製，產品名︰LAQUA(註冊商標))確認的pH為2.1。<Preparation of surface treatment composition> [Example 1: Preparation of surface treatment composition A-1] The aqueous maleic acid solution having a concentration of organic acid of 30% by mass is 1.0 mass based on 100 parts by mass of the total composition. The concentration of the glycerol (weight average molecular weight (Mw): 15,000) which is a water-soluble high-molecular molecule having a constituent unit derived from glycerin is 1.0% by weight, and is used as a concentration of 0.3 parts by weight of maleic acid. The polystyrenesulfonic acid of the ionic dispersant was brought to a concentration of 0.25 g/kg, and mixed with water (deionized water) to prepare a surface treatment composition A-1. The pH of the surface treatment composition A-1 (liquid temperature: 25 ° C) was confirmed by a pH meter (manufactured by Horiba, Ltd., product name: LAQUA (registered trademark)).

［實施例2：表面處理組合物A-2的調製］ 使用環氧乙烷變性聚甘油(EO變性聚甘油，重量平均分子量︰15,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-2。針對表面處理組合物A-2(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 2: Preparation of surface treatment composition A-2] The same procedure as in Example 1 was carried out except that the polyglycerol was replaced with ethylene oxide-modified polyglycerin (EO-modified polyglycerin, weight average molecular weight: 15,000). The surface treatment composition A-2 was prepared. The pH of the surface treatment composition A-2 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例3：表面處理組合物A-3的調製］ 使環氧乙烷變性聚甘油(EO變性聚甘油，重量平均分子量︰15,000)的濃度成為2.0g/kg，除此之外，與實施例2同樣地調製表面處理組合物A-3。針對表面處理組合物A-3(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 3: Preparation of surface treatment composition A-3] The concentration of ethylene oxide-modified polyglycerol (EO-modified polyglycerol, weight average molecular weight: 15,000) was 2.0 g/kg, and Example 2 The surface treatment composition A-3 was prepared in the same manner. The pH of the surface treatment composition A-3 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例4：表面處理組合物A-4的調製］ 使用磺酸變性聚甘油(重量平均分子量︰10,000~15,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-4。針對表面處理組合物A-4(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 4: Preparation of surface treatment composition A-4] A surface treatment composition was prepared in the same manner as in Example 1 except that the polyglycerin was replaced with a sulfonic acid-modified polyglycerol (weight average molecular weight: 10,000 to 15,000). A-4. The pH of the surface treatment composition A-4 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例5：表面處理組合物A-5的調製］ 使磺酸變性聚甘油(重量平均分子量︰10000-15,000)的濃度成為2.0g/kg，除此之外，與實施例4同樣地調製表面處理組合物A-5。針對表面處理組合物A-5(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 5: Preparation of surface treatment composition A-5] The same procedure as in Example 4 was carried out except that the concentration of the sulfonic acid-modified polyglycerol (weight average molecular weight: 10,000-15,000) was 2.0 g/kg. Surface treatment composition A-5. The pH of the surface treatment composition A-5 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例6：表面處理組合物A-6的調製］ 使用膦酸變性聚甘油(重量平均分子量︰10,000~15,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-6。針對表面處理組合物A-6(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 6: Preparation of surface treatment composition A-6] A surface treatment composition was prepared in the same manner as in Example 1 except that polyglycerol was replaced with phosphonic acid-denatured polyglycerol (weight average molecular weight: 10,000 to 15,000). A-6. The pH of the surface treatment composition A-6 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例7︰表面處理組合物A-7的調製］ 使膦酸變性聚甘油(重量平均分子量：10,000~15,000)的濃度成為2.0g/kg，除此之外，與實施例6同樣地調製表面處理組合物A-7。針對表面處理組合物A-7(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 7: Preparation of surface treatment composition A-7] The same procedure as in Example 6 was carried out except that the concentration of the phosphonic acid-denatured polyglycerol (weight average molecular weight: 10,000 to 15,000) was 2.0 g/kg. Surface treatment composition A-7. The pH of the surface treatment composition A-7 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例8：表面處理組合物A-8的調製］ 使用聚甘油-4-乙烯基安息香酸酯(重量平均分子量︰10,000~15,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-8。針對表面處理組合物A-8(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 8: Preparation of surface treatment composition A-8] The same procedure as in Example 1 except that polyglycerol-4-vinylbenzoate (weight average molecular weight: 10,000 to 15,000) was used instead of polyglycerin. Surface treatment composition A-8 was prepared. The pH of the surface treatment composition A-8 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例9：表面處理組合物A-9的調製］ 使用聚甘油脂肪酸(C10-13)酯(重量平均分子量︰1,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-9。針對表面處理組合物A-8(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 9: Preparation of surface treatment composition A-9] Surface treatment was prepared in the same manner as in Example 1 except that polyglycerol was replaced with polyglycerol fatty acid (C10-13) ester (weight average molecular weight: 1,000). Composition A-9. The pH of the surface treatment composition A-8 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例10︰表面處理組合物A-10的調製］ 使用聚甘油脂肪酸(C10)酯(重量平均分子量︰900)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-10。針對表面處理組合物A-10(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 10: Preparation of surface treatment composition A-10] A surface treatment composition was prepared in the same manner as in Example 1 except that polyglycerol fatty acid (C10) ester (weight average molecular weight: 900) was used instead of polyglycerin. A-10. The pH of the surface treatment composition A-10 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例11︰表面處理組合物A-11的調製］ 使用聚甘油脂肪酸(C8)酯(重量平均分子量︰900)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-11。針對表面處理組合物A-11(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 11: Preparation of surface treatment composition A-11] A surface treatment composition was prepared in the same manner as in Example 1 except that polyglycerol fatty acid (C8) ester (weight average molecular weight: 900) was used instead of polyglycerin. A-11. The pH of the surface treatment composition A-11 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例12：表面處理組合物A-12的調製］ 使用聚甘油脂肪酸(C3)酯(重量平均分子量︰800)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-12。針對表面處理組合物A-12(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 12: Preparation of surface treatment composition A-12] A surface treatment composition was prepared in the same manner as in Example 1 except that the polyglycerol fatty acid (C3) ester (weight average molecular weight: 800) was used instead of the polyglycerin. A-12. The pH of the surface treatment composition A-12 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例13︰表面處理組合物A-13的調製］ 使用十甘油月桂酸酯(重量平均分子量︰1,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-13。針對表面處理組合物A-13(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 13: Preparation of surface treatment composition A-13] The surface treatment composition A was prepared in the same manner as in Example 1 except that the polyglycerol was replaced by decaglyceryl laurate (weight average molecular weight: 1,000). 13. The pH of the surface treatment composition A-13 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例14︰表面處理組合物A-14的調製］ 使用十甘油硬脂酸酯(重量平均分子量︰1,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-14。針對表面處理組合物A-14(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 14: Preparation of surface treatment composition A-14] Surface treatment composition A was prepared in the same manner as in Example 1 except that polyglycerin was replaced by decaglyceryl stearate (weight average molecular weight: 1,000). -14. The pH of the surface treatment composition A-14 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［實施例15︰表面處理組合物A-15的調製］ 使用十甘油油酸酯(重量平均分子量︰1,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物A-15。針對表面處理組合物A-15(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Example 15: Preparation of surface treatment composition A-15] The surface treatment composition A was prepared in the same manner as in Example 1 except that the polyglycerol was replaced by decaglyceryl oleate (weight average molecular weight: 1,000). 15. The pH of the surface treatment composition A-15 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［比較例1︰表面處理組合物C-1的調製］ 沒有使用聚甘油，除此之外，與實施例1同樣地調製表面處理組合物C-1。針對表面處理組合物C-1(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Comparative Example 1: Preparation of Surface Treatment Composition C-1] The surface treatment composition C-1 was prepared in the same manner as in Example 1 except that the polyglycerin was not used. The pH of the surface treatment composition C-1 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

［比較例2：取代表面處理組合物C-2的調製］ 使用聚乙烯醇(重量平均分子量︰15,000)取代聚甘油，除此之外，與實施例1同樣地調製表面處理組合物C-2。針對表面處理組合物C-2(液溫︰25℃)，以與實施例1相同方法確認的pH為2.1。[Comparative Example 2: Preparation of Substituted Surface Treatment Composition C-2] Surface treatment composition C-2 was prepared in the same manner as in Example 1 except that polyvinyl alcohol (weight average molecular weight: 15,000) was used instead of polyglycerin. . The pH of the surface treatment composition C-2 (liquid temperature: 25 ° C) confirmed in the same manner as in Example 1 was 2.1.

＜評價＞ ＜已研磨的研磨對象物(表面處理對象物)的準備＞ 準備藉由下述化學機械研磨(CMP)步驟研磨後的已研磨的氮化矽基板、已研磨的TEOS基板、及已研磨的多晶矽基板、或按照需要進一步藉由下述沖洗研磨步驟處理後的已研磨的氮化矽基板、已研磨的TEOS基板及已研磨的多晶矽基板作為表面處理對象物。<Evaluation> <Preparation of the object to be polished (surface-treated object)> The polished tantalum nitride substrate polished by the following chemical mechanical polishing (CMP) step, the polished TEOS substrate, and the prepared The polished polycrystalline silicon substrate or the polished tantalum nitride substrate, the polished TEOS substrate, and the polished polycrystalline germanium substrate which have been subjected to the following rinsing and polishing step are further subjected to a surface treatment target as needed.

［CMP步驟］ 對半導體基板的氮化矽基板、TEOS基板及多晶矽基板，使用研磨用組合物(組成：磺酸修飾膠態氧化矽(以”Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”, Chem. Commun. 246-247 (2003)所記載的方法製作，一次粒子徑30nm，二次粒子徑60nm)4質量%，濃度30質量的馬來酸水溶液0.018質量%，溶劑︰水)，分別以下述條件進行研磨。在此，氮化矽基板、TEOS基板及多晶矽基板，使用200mm晶圓。[CMP step] For the tantalum nitride substrate, the TEOS substrate, and the polycrystalline germanium substrate of the semiconductor substrate, a polishing composition (constituting: Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups) is used. A method described in Chem. Commun. 246-247 (2003), having a primary particle diameter of 30 nm, a secondary particle diameter of 60 nm) of 4% by mass, a concentration of 30 mass of a maleic acid aqueous solution of 0.018% by mass, and a solvent: water), respectively. The conditions are described for grinding. Here, a 200 mm wafer is used for the tantalum nitride substrate, the TEOS substrate, and the polysilicon substrate.

(研磨裝置及研磨條件) 研磨裝置︰應用材料公司製 MirraMesa 研磨墊片︰NITTA HAAS株式會社製 硬質聚氨酯墊片IC1010 研磨壓力︰2.0psi (13.8kPa) (再者，1psi=6894.76Pa，以下相同) 研磨定盤轉數︰60rpm 研磨頭轉數︰60rpm 研磨用組合物的供給︰澆注 研磨用組合物供給量︰100mL/分 研磨時間︰60秒。(Polishing device and polishing conditions) Grinding device: Mirra Mesa grinding pad made by Applied Materials Co., Ltd.: Hard polyurethane gasket IC1010 manufactured by NITTA HAAS Co., Ltd. Grinding pressure: 2.0 psi (13.8 kPa) (Further, 1 psi = 6974.76 Pa, the same applies hereinafter) Grinding plate rotation number: 60 rpm Grinding head rotation number: 60 rpm Supply of polishing composition: pouring polishing composition supply amount: 100 mL / minute grinding time: 60 seconds.

［沖洗研磨步驟］ 按照需要，對藉由上述CMP步驟研磨後的已研磨的氮化矽基板、已研磨的TEOS基板及已研磨的多晶矽基板，使用沖洗研磨用組合物(組成：聚乙烯醇(重量平均分子量10,000)0.1質量%，溶劑：水，以硝酸調整為pH=2)，以下述條件進行沖洗研磨。[Rinsing and Polishing Step] If necessary, a composition for rinsing and polishing is used for the ground tantalum nitride substrate, the polished TEOS substrate, and the polished polycrystalline ruthenium substrate polished by the CMP step (composition: polyvinyl alcohol ( The weight average molecular weight was 10,000) 0.1% by mass, solvent: water, adjusted to pH = 2 with nitric acid, and rinsing was carried out under the following conditions.

(沖洗研磨裝置及沖洗研磨條件) 研磨裝置︰應用材料公司製 MirraMesa 研磨墊片︰NITTA HAAS株式會社製 硬質聚氨酯墊片IC1010 研磨壓力︰1.0psi (6.89kPa) 研磨定盤轉數︰60rpm 研磨頭轉數︰60rpm 沖洗研磨用組合物的供給︰澆注 沖洗研磨用組合物供給量︰100mL/分 研磨時間︰60秒。(rinsing and polishing device and rinsing and polishing conditions) Grinding device: MirraMesa grinding pad made by Applied Materials Co., Ltd.. Hard polyurethane gasket IC1010 manufactured by NITTA HAAS Co., Ltd. Grinding pressure: 1.0 psi (6.89 kPa) Grinding plate rotation number: 60 rpm Grinding head rotation The number: 60 rpm rinse polishing composition supply: pouring rinse polishing composition supply amount: 100 mL / minute grinding time: 60 seconds.

［清洗步驟］ 使用上述所調製的各表面處理組合物或水(去離子水)，一邊對清洗刷的聚乙烯醇(PVA)製海綿施加壓力，一邊以下述條件擦拭各個已研磨的研磨對象物，藉由如此的清洗方法清洗各已研磨的研磨對象物。[Cleaning step] Using the surface treatment composition prepared above or water (deionized water), while applying pressure to the sponge of polyvinyl alcohol (PVA) of the cleaning brush, each of the polished objects to be polished is wiped under the following conditions. Each of the polished objects to be polished is cleaned by such a cleaning method.

(清洗裝置及清洗條件) 裝置︰應用材料公司製 MirraMesa 清洗刷轉數︰100rpm 清洗對象物(已研磨的研磨對象物)轉數︰50rpm 清洗液的流量︰1000mL/分 清洗時間︰60秒。(Cleaning device and cleaning conditions) Device: MirraMesa cleaning brush rotation number: 100 rpm Cleaning target (ground object to be polished) Number of revolutions: 50 rpm Flow rate of cleaning solution: 1000 mL/min Cleaning time: 60 seconds.

＜評價＞ 針對上述清洗步驟後的各已研磨的研磨對象物，測定下述項目而進行評價。將評價結果一併示於表1。<Evaluation> The following items were measured and evaluated for each of the polished objects to be polished after the above-described washing step. The evaluation results are shown together in Table 1.

［總缺陷數的評價］ 針對進行上述清洗步驟後的已研磨的研磨對象物，測定0.13μm以上的總缺陷數。總缺陷數的測定，使用KLA TENCOR公司製，Surfscan SP2。測定是針對將從已研磨的研磨對象物的單面的外周端部起至寬度5mm為止的部分除外後所剩餘的部分進行。[Evaluation of the total number of defects] The total number of defects of 0.13 μm or more was measured for the object to be polished after the above-described cleaning step. The total number of defects was measured using a Surfa SP2 manufactured by KLA TENCOR. The measurement is performed on the portion remaining from the outer peripheral end portion of one surface of the object to be polished to the width of 5 mm.

［有機物殘渣數的評價］ 針對進行上述清洗處理後的已研磨的研磨對象物，使用株式會社日立高科技公司製，Review SEM RS6000，以SEM觀察測定有機物殘渣的數量。首先，以SEM觀察取樣100個存在於將從已研磨的研磨對象物的單面的外周端部起至寬度5mm為止的部分除外後所剩餘的部分的缺陷。接著，從取樣的100個缺陷，以目視的SEM觀察判別有機物殘渣，確認其數量，算出缺陷中的有機物殘渣的比例(%)。然後，由上述總缺陷數的評價所測定的0.13μm以上的總缺陷數(個)，與藉由SEM觀察所算出的缺陷中的有機物殘渣的比例(%)的乘積，算出有機物殘渣數(個)。[Evaluation of the Number of Organic Residues] The amount of the organic residue was measured by SEM observation using a Review SEM RS6000 manufactured by Hitachi High-Technologies Corporation. First, SEM observation was performed to sample 100 defects existing in the portion remaining from the outer peripheral end portion of one surface of the object to be polished to the width of 5 mm. Next, from the 100 defects sampled, the organic residue was discriminated by visual SEM observation, and the amount thereof was confirmed, and the ratio (%) of the organic residue in the defect was calculated. Then, the number of the total number of defects (number) of 0.13 μm or more and the ratio (%) of the organic residue in the defect calculated by SEM observation by the evaluation of the total number of defects is calculated, and the number of organic residues is calculated. ).

針對各表面處理組合物，使用已研磨的氮化矽基板作為表面處理對象物時、使用已研磨的TEOS基板作為表面處理對象物時、及使用已研磨的多晶矽基板作為表面處理對象物時的有機物殘渣的評價結果分別示於下述表1。For each surface treatment composition, when a polished tantalum nitride substrate is used as a surface treatment target, when a polished TEOS substrate is used as a surface treatment target, and when a polished polycrystalline germanium substrate is used as a surface treatment target, an organic substance is used. The evaluation results of the residue are shown in Table 1 below.

[表1] 表1 [Table 1] Table 1

由上述表1可知，與比較例的表面處理組合物相比，實施例的表面處理組合物可減低已研磨的研磨對象物表面的有機物殘渣。As is apparent from the above Table 1, the surface treatment composition of the example can reduce the organic residue on the surface of the polished object to be polished, as compared with the surface treatment composition of the comparative example.

本發明是基於申請日為西元2017年9月22日的日本專利申請編號第2017-182903號案、及申請日為西元2018年3月14日的日本專利申請編號第2018-046471號案，且其揭示內容的全部以參照的方式納入本說明書。The present invention is based on the Japanese Patent Application No. 2017-182903 filed on September 22, 2017, and the Japanese Patent Application No. 2018-046471, filed on March 14, 2018, The disclosure of the entire contents is incorporated herein by reference.

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Claims (11)

一種表面處理組合物，用於處理已研磨的研磨對象物的表面，包含： 具有來自甘油的構成單位的水溶性高分子； 酸；及 水， pH為5以下。A surface treatment composition for treating a surface of a polished object to be polished, comprising: a water-soluble polymer having a constituent unit derived from glycerin; an acid; and water having a pH of 5 or less. 如申請專利範圍第1項所述之表面處理組合物，其中上述具有來自甘油的構成單位的水溶性高分子為選自由聚甘油、環氧乙烷變性聚甘油、磺酸變性聚甘油、膦酸變性聚甘油、聚甘油-4-乙烯基安息香酸酯(苯乙烯基變性聚甘油)、及聚甘油脂肪酸酯所組成之群之至少1種。The surface treatment composition according to claim 1, wherein the water-soluble polymer having a constituent unit derived from glycerin is selected from the group consisting of polyglycerol, ethylene oxide-modified polyglycerin, sulfonic acid-modified polyglycerin, and phosphonic acid. At least one of a group consisting of denatured polyglycerol, polyglycerol-4-vinylbenzoate (styrene-based modified polyglycerol), and polyglycerin fatty acid ester. 如申請專利範圍第1項所述之表面處理組合物，其中進一步包含離子性分散劑。The surface treatment composition of claim 1, further comprising an ionic dispersant. 如申請專利範圍第3項所述之表面處理組合物，其中上述離子性分散劑為具有磺酸(鹽)基的高分子化合物。The surface treatment composition according to claim 3, wherein the ionic dispersant is a polymer compound having a sulfonic acid (salt) group. 如申請專利範圍第1項所述之表面處理組合物，其中上述pH為4以下。The surface treatment composition according to claim 1, wherein the pH is 4 or less. 如申請專利範圍第1項所述之表面處理組合物，其中實質上不含研磨粒。The surface treatment composition of claim 1, wherein the abrasive particles are substantially free. 如申請專利範圍第1項所述之表面處理組合物，其中上述已研磨的研磨對象物包含多晶矽。The surface treatment composition according to claim 1, wherein the ground object to be polished comprises polycrystalline germanium. 一種製造方法，其係如申請專利範圍第1項所述之表面處理組合物的製造方法，包含：將上述具有來自甘油的構成單位的水溶性高分子、上述酸、及上述水混合。A method for producing a surface treatment composition according to claim 1, comprising: mixing the water-soluble polymer having a constituent unit derived from glycerin, the acid, and the water. 一種表面處理方法，包含使用申請專利範圍第1項所述之表面處理組合物，對已研磨的研磨對象物進行表面處理，降低在已研磨的研磨對象物表面的有機物殘渣。A surface treatment method comprising surface-treating a polished object to be polished using the surface treatment composition according to claim 1 to reduce the organic residue on the surface of the object to be polished. 如申請專利範圍第9項所述之表面處理方法，其中上述表面處理是藉由沖洗研磨或清洗進行。The surface treatment method of claim 9, wherein the surface treatment is performed by rinsing or washing. 一種半導體基板的製造方法，其中已研磨的研磨對象物為已研磨的半導體基板，該製造方法包含藉由申請專利範圍第9項所述之表面處理方法而減低在已研磨的研磨對象物表面的有機物殘渣之表面處理步驟。A method of manufacturing a semiconductor substrate, wherein the ground object to be polished is a polished semiconductor substrate, the method of manufacturing comprising: reducing a surface of the ground object to be polished by the surface treatment method of claim 9 Surface treatment step of organic residue.