TWI463007B - Aqueous cleaning composition for post chemical mechanical planarization - Google Patents
Aqueous cleaning composition for post chemical mechanical planarization Download PDFInfo
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本發明係關於一種含水清洗組合物，特別是關於一種用於積體電路製程中化學機械平坦化(CMP)處理之含水清洗組合物。This invention relates to an aqueous cleaning composition, and more particularly to an aqueous cleaning composition for chemical mechanical planarization (CMP) treatment in an integrated circuit process.
關於半導體元件，現今正朝向更小線寬、更高積體密度的方向發展。然而，當積體電路最小線寬降至0.25微米或以下時，因金屬導線本身的電阻以及介電層寄生電容所引起的時間延遲(RC delay)，已成為影響元件運算速度的主要關鍵。為了提高元件的運算速度，目前針對0.13微米以下之高階製程，業界已逐漸改採銅金屬導線以取代傳統的鋁銅合金導線，此製程即簡稱為「銅製程」。Regarding semiconductor devices, today, the direction is progressing toward a smaller line width and a higher integrated density. However, when the minimum line width of the integrated circuit is reduced to 0.25 micrometers or less, the RC delay caused by the resistance of the metal wire itself and the parasitic capacitance of the dielectric layer has become a key factor affecting the operation speed of the component. In order to improve the computing speed of components, the current industry has gradually changed the copper metal wire to replace the traditional aluminum-copper alloy wire for the high-order process below 0.13 micron. This process is referred to as the "copper process".
化學機械平坦化(Chemical Mechanical Planarization，簡稱CMP)係透過研磨液中之研磨顆粒(包含如二氧化矽、氧化鋁、二氧化鈰、二氧化鋯等)與化學助劑(包含如pH緩衝劑、氧化劑等)相配合，以磨耗表面材質，藉此使得表面不平坦之較高處因受壓相對較大而產生較高的移除速率，表面不平坦之較低處，則因受壓相對較小而有較慢的移除速率，從而達成全域性平坦化之目的。將CMP技術應用於銅金屬導線製程中，不但可克服晶圓因銅金屬蝕刻不易而難以定義圖案的問題，且研磨後形成一全域性平坦化(global planarity)的平面，有助於多層導線化製程的進行。Chemical Mechanical Planarization (CMP) is used to pass abrasive particles (including, for example, cerium oxide, aluminum oxide, cerium oxide, zirconium dioxide, etc.) and chemical auxiliaries (including, for example, pH buffers, Oxidizers, etc. are matched to abrade the surface material, so that the higher part of the surface is not flat due to the relatively high pressure, resulting in a higher removal rate, and the lower surface is uneven, because the pressure is relatively higher. Small and slower removal rate for global flattening. Applying CMP technology to the copper metal wire process can not only overcome the problem that the wafer is difficult to define the pattern due to copper metal etching, but also forms a global planarity plane after grinding, which is helpful for multi-layer wire. The process is carried out.
於CMP過程中，研磨液內的大量細微研磨顆粒和化學助劑，以及晶圓磨耗所剝離的碎屑可能會附著於晶圓表面。一般晶圓在研磨之後常見的污染物為金屬離子、有機化合物或研磨顆粒等，若 無有效的清洗程序以去除上述污染物，則將影響後續製程的進行並降低元件的良率及可靠度。因此，CMP製程之後續清洗程序，已成為能否成功應用CMP於半導體製程之關鍵技術。During the CMP process, a large amount of fine abrasive particles and chemical auxiliaries in the slurry, as well as debris from wafer abrasion, may adhere to the wafer surface. Common contaminants after wafer grinding are metal ions, organic compounds or abrasive particles, etc. Without an effective cleaning procedure to remove the above contaminants, subsequent processes will be affected and component yield and reliability will be reduced. Therefore, the subsequent cleaning process of the CMP process has become a key technology for successfully applying CMP to semiconductor processes.
在銅製程用的研磨液中，多會使用苯并***(benzotriazole，簡稱BTA)或其衍生物作為腐蝕抑制劑。於銅製程晶圓研磨後所產生的污染物中，以BTA有機殘留物最難以去除，主要原因為BTA是以化學吸附方式鍵結於銅導線上。傳統僅利用靜電斥力、超音波震盪及聚乙烯醇(PVA)刷子刷洗等物理方式以去除BTA，不易有良好的清洗效果。In the polishing liquid for copper processing, benzotriazole (BTA) or a derivative thereof is often used as a corrosion inhibitor. Among the contaminants produced after the copper wafer is ground, the most common BTA organic residue is removed. The main reason is that BTA is bonded to the copper wire by chemical adsorption. Traditionally, only physical methods such as electrostatic repulsion, ultrasonic vibration, and polyvinyl alcohol (PVA) brush cleaning have been used to remove BTA, which is not easy to have a good cleaning effect.
傳統金屬層間介電層(inter-metal dielectric layer)及鎢栓塞(W plug)於CMP製程後，經常使用氨水溶液、檸檬酸水溶液及/或含氟化合物進行清洗。然而，氨水溶液會不均勻地侵蝕銅金屬表面，而造成粗糙化的現象；檸檬酸水溶液對銅溶解力太差且對污染物的去除率仍有改善空間；氫氟酸等含氟化合物則不僅會使銅表面粗糙化，且為避免其危害人體與環境，需付出更多成本於人員安全防護及廢液處理。因此，上述清洗溶液並不適用於含銅金屬導線之晶圓。Conventional inter-metal dielectric layers and tungsten plugs are often cleaned using an aqueous ammonia solution, an aqueous citric acid solution, and/or a fluorine-containing compound after the CMP process. However, the aqueous ammonia solution will not uniformly erode the surface of the copper metal, causing roughening; the aqueous solution of citric acid has poor solubility to copper and still has room for improvement of the removal rate of pollutants; the fluorine-containing compound such as hydrofluoric acid is not only The copper surface will be roughened, and in order to avoid harm to the human body and the environment, more cost is required for personnel safety protection and waste liquid treatment. Therefore, the above cleaning solution is not suitable for wafers containing copper metal wires.
為了避免使用氨水，業經建議將含氮化合物溶液使用於清洗組合物中。其中，Naghshineh等人之美國專利第6,492,308號揭示一種用於清洗含銅積體電路的清洗液，其係由一C1 -C10 之氫氧化四烷基銨(quaternary ammonium hydroxide)、一極性有機胺及一腐蝕抑制劑組成，其中該極性有機胺可選自單乙醇胺等。Chen等人之美國專利第8,063,006號(台灣專利第I282363號)揭示一種用 於清洗積體電路製程中化學機械平坦化後之含銅導線晶圓的水相清洗組合物，其由一含氮雜環有機鹼、一醇胺及水組成。然而，先前技術中的清洗組合物在晶圓表面造成的粗糙度影響尚有進步空間，尤其對於含銅導線的晶圓，如何適當控制胺對金屬的蝕刻性，減少晶圓研磨後所產生的汙染物，以及降低含銅導線晶圓表面上各種不同組份區域的總和缺陷數等，仍為待解決的課題。In order to avoid the use of aqueous ammonia, it has been proposed to use a nitrogen-containing compound solution for use in the cleaning composition. No. 6,492,308 to Naghshineh et al. discloses a cleaning solution for cleaning a copper-containing integrated circuit comprising a C 1 -C 10 quaternary ammonium hydroxide, a polar organic An amine and a corrosion inhibitor composition, wherein the polar organic amine may be selected from the group consisting of monoethanolamine and the like. An aqueous phase cleaning composition for cleaning a copper-containing wire wafer after chemical mechanical planarization in an integrated circuit process is disclosed in US Patent No. 8,063,006 (Taiwan Patent No. I282363), which is incorporated herein by reference. It consists of a cyclic organic base, a monolamine and water. However, there is still room for improvement in the effect of the cleaning composition of the prior art on the surface of the wafer, especially for wafers containing copper wires, how to properly control the etchability of the amine to the metal, and reduce the occurrence of wafer polishing. Contaminants, as well as the number of total defects in various component areas on the surface of copper-containing wire wafers, remain a problem to be solved.
此外，隨著半導體晶圓製程的進展，金屬導線寬度已縮小到14奈米，新的平坦化製程仍有許多待克服的問題，包括例如奈米線寬的晶圓表面經製程處理後表面粗糙度可能變差，以及線寬縮小後銅導線晶圓之電性測試(open/short test)及可靠度測試(reliability test)結果變差等等。因此，產業界對於晶圓清洗製程仍需一較先前技術更能有效去除殘留於銅導線晶圓表面上的污染物並降低晶圓表面的缺陷數的清洗組合物。In addition, as the semiconductor wafer process progresses, the width of the metal wire has been reduced to 14 nm. There are still many problems to be overcome in the new planarization process, including rough surface of the wafer surface, such as nanowire width. The degree may be deteriorated, and the open/short test and the reliability test result of the copper wire wafer are deteriorated after the line width is reduced. Therefore, the industry still needs a cleaning composition that is more effective than the prior art in removing contaminants remaining on the surface of the copper wire wafer and reducing the number of defects on the surface of the wafer.
本發明即針對前述需求所為之研發成果，提供一種用於後化學機械平坦化之含水清洗組合物，可有效去除污染物及降低晶圓表面的缺陷數，並可維持較佳的晶圓表面粗糙度。The present invention provides an aqueous cleaning composition for post-chemical mechanical planarization in response to the above-mentioned needs, which can effectively remove contaminants and reduce the number of defects on the wafer surface, and can maintain a good wafer surface roughness. degree.
本發明之一目的在於提供一種用於後化學機械平坦化之含水清洗組合物，其係包含至少二種含氮化合物、一界面活性劑、及水。其中，該界面活性劑係乙氧化硫醇(ethoxylated mercaptan)，且該含氮化合物的總濃度為至少約100 ppm，該乙氧化硫醇的濃度為至少約10 ppm。視需要地，該含水清洗組合物可更包含一有機物配位體。It is an object of the present invention to provide an aqueous cleaning composition for post chemical mechanical planarization comprising at least two nitrogen-containing compounds, a surfactant, and water. Wherein, the surfactant is ethoxylated mercaptan, and the total concentration of the nitrogen-containing compound is at least about 100 ppm, and the concentration of the ethoxylated mercaptan is at least about 10 ppm. Optionally, the aqueous cleaning composition may further comprise an organic ligand.
本發明之含水清洗組合物不但可用於銅製程之化學機械平坦化後的清洗步驟，亦可用於普通矽晶圓之化學機械平坦化後的清洗步驟。The aqueous cleaning composition of the present invention can be used not only for the cleaning step after the chemical mechanical planarization of the copper process, but also for the cleaning step after the chemical mechanical planarization of the conventional tantalum wafer.
為使本發明之上述目的、技術特徵及優點能更明顯易懂，下文係以部分具體實施態樣進行詳細說明。The above described objects, technical features and advantages of the present invention will become more apparent from the following detailed description.
以下將具體地描述根據本發明之部分具體實施態樣；惟，在不背離本發明之精神下，本發明尚可以多種不同形式之態樣來實踐，不應將本發明保護範圍解釋為限於說明書所陳述者。此外，除非文中有另外說明，於本說明書中(尤其是在後述專利申請範圍中)所使用之「一」、「該」及類似用語應理解為包含單數及複數形式。The invention will be described in detail below with reference to the specific embodiments of the present invention. The invention may be practiced in various different forms without departing from the spirit and scope of the invention. The person stated. In addition, the terms "a", "an" and "the"
本案發明人研究發現，當於化學機械平坦化操作之後的清洗步驟中組合使用含氮化合物與乙氧化硫醇時，可達到令人滿意的污染物去除率，有效降低晶圓表面的缺陷數，並可維持較佳的晶圓表面粗糙度。The inventors of the present invention have found that when a nitrogen-containing compound and ethoxylated mercaptan are used in combination in the cleaning step after the chemical mechanical planarization operation, a satisfactory contaminant removal rate can be achieved, and the number of defects on the wafer surface can be effectively reduced. It can maintain a good wafer surface roughness.
因此，本發明係提供一含水清洗組合物，其係包含至少二種含氮化合物、乙氧化硫醇、以及水，該含氮化合物的總濃度為約100 ppm至10,000 ppm，該乙氧化硫醇的濃度為約10 ppm至600 ppm。其中，於不受理論限制之情形下，咸信於本發明組合物中，乙氧化硫醇係扮演界面活性劑之角色，以潤濕欲清洗的表面，降低其表面張力，有助於去除吸附或嵌入的研磨顆粒，亦可降低表面之 金屬污染。Accordingly, the present invention provides an aqueous cleaning composition comprising at least two nitrogen-containing compounds, ethoxylated mercaptans, and water, the total concentration of the nitrogen-containing compound being from about 100 ppm to 10,000 ppm, the ethoxylated mercaptan The concentration is about 10 ppm to 600 ppm. Wherein, without being bound by theory, it is believed that in the composition of the present invention, ethoxylated thiol acts as a surfactant to wet the surface to be cleaned, reduce its surface tension, and help to remove adsorption. Or embedded abrasive particles, which can also reduce the surface Metal pollution.
於不受理論限制之情形下，咸信於本發明組合物中，所使用之含氮化合物可調整清洗組合物之鹼度，確保化學機械拋光時所用的研磨顆粒與晶圓表面保持有效之電負相斥力，利於去除研磨顆粒。此外，於銅製程中，更可避免使用氨水所致之銅表面嚴重粗糙化的問題。一般而言，該含氮化合物可選自以下群組：醇胺、雜環胺、及四級銨。Without being bound by theory, it is believed that the nitrogen-containing compound used in the composition of the present invention can adjust the alkalinity of the cleaning composition to ensure that the abrasive particles used in chemical mechanical polishing maintain an effective electrical power on the wafer surface. Negative phase repulsion helps to remove abrasive particles. In addition, in the copper process, the problem of severe roughening of the copper surface caused by the use of ammonia water can be avoided. In general, the nitrogen-containing compound can be selected from the group consisting of an alcohol amine, a heterocyclic amine, and a quaternary ammonium.
適用於本發明組合物作為含氮化合物之醇胺的例子包括，但不限於，選自以下群組者：乙醇胺(monoethanolamine)、二乙醇胺(diethanolamine)、三乙醇胺(triethanolamine)、丙醇胺(propanolamine)、異丙醇胺(isopropanolamine)、二異丙醇胺(diisopropanolamine)、N-甲基乙醇胺(N-methylethanolamine)、N-甲基二乙醇胺(N-methyldiethanolamine)、二甘醇胺(diglycolamine)、2-胺基-1-丙醇(2-amino-1-propanol)、3-胺基-1-丙醇(3-amino-1-propanol)、2-胺乙醇(2-aminoethanol)、2-二甲基胺乙醇(2-dimethylaminoethanol)、2-(N-甲胺基)乙醇(2-(N-methylamino)ethanol)、2-(2-胺乙基胺基)乙醇(2-(2-aminoethylamino)ethanol)、參(羥甲基)胺甲烷(tris(hydroxymethyl)aminomethane)、二羥乙甘胺酸(bicine)、三羥乙甘胺酸(tricine)、及其組合。於以下實施例中，所例示使用之醇胺為乙醇胺、二乙醇胺、三乙醇胺、二甘醇胺、2-胺基-1-丙醇、3-胺基-1-丙醇、2-胺乙醇、2-(N-甲胺基)乙醇與參(羥甲基)胺甲烷。當使用醇胺作為本發明組合物之含氮化合物時，除可提 供所欲研磨顆粒移除的效果以外，更可對金屬層表面進行均勻性的蝕刻，使得蝕刻後金屬導線的表面粗糙度不致產生惡化。Examples of alcoholamines suitable for use as the nitrogen-containing compound in the compositions of the present invention include, but are not limited to, those selected from the group consisting of: monoethanolamine, diethanolamine, triethanolamine, propanolamine. ), isopropanolamine, diisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, diglycolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-aminoethanol, 2- 2-dimethylaminoethanol, 2-(N-methylamino)ethanol, 2-(2-aminoethylamino)ethanol (2-(2-) Aminoethylamino)ethanol), tris(hydroxymethyl)aminomethane, bicine, tricine, and combinations thereof. In the following examples, the alcohol amines exemplified are ethanolamine, diethanolamine, triethanolamine, diglycolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-aminoethanol. , 2-(N-methylamino)ethanol and cis (hydroxymethyl)amine methane. When an alcoholamine is used as the nitrogen-containing compound of the composition of the present invention, In addition to the effect of removing the desired abrasive particles, the surface of the metal layer can be uniformly etched so that the surface roughness of the metal wires after etching does not deteriorate.
適用於本發明組合物作為含氮化合物之雜環胺的例子包括，但不限於，選自以下群組者：六氫吡(piperazine)、2-(1-六氫吡)乙醇(2-(1-piperazinyl)ethanol)、2-(1-六氫吡)乙胺(2-(1-piperazinyl)ethylamine)、1-(2-羥乙基)六氫吡(1-(2-hydroxyethyl)piperazine)、1-(2-胺乙基)六氫吡(1-(2-aminoethyl)piperazine)、及其組合。於以下實施例中，所示範使用之雜環胺為六氫吡。當使用雜環胺作為本發明組合物之含氮化合物時，由於雜環胺之雜環上氮原子的未共用電子對可與金屬原子(如銅)進行配位鍵結，從而除可提供所欲研磨顆粒移除的效果以外，更可避免已脫離金屬導線的有機污染物再次化學吸附。Examples of heterocyclic amines suitable for use in the compositions of the present invention as nitrogen-containing compounds include, but are not limited to, those selected from the group consisting of hexahydropyridyl (piperazine), 2-(1-hexahydropyridyl) ) 2-(1-piperazinyl)ethanol, 2-(1-hexahydropyridyl) Ethylamine (2-(1-piperazinyl)ethylamine), 1-(2-hydroxyethyl)hexahydropyridyl (1-(2-hydroxyethyl)piperazine), 1-(2-aminoethyl)hexahydropyridyl (1-(2-aminoethyl)piperazine), and combinations thereof. In the following examples, the heterocyclic amine used in the demonstration is hexahydropyridyl . When a heterocyclic amine is used as the nitrogen-containing compound of the composition of the present invention, the unshared electron pair of the nitrogen atom on the heterocyclic ring of the heterocyclic amine can be coordinately bonded to a metal atom such as copper, thereby providing a In addition to the effect of particle removal, it is also possible to avoid re-chemical adsorption of organic contaminants that have been detached from the metal wires.
適用於本發明組合物作為含氮化合物之四級銨的例子包括，但不限於，選自以下群組者：氫氧化四甲基銨(tetramethylammonium hydroxide，TMAH)、氫氧化四乙基銨(tetraethylammonium hydroxide，TEAH)、氫氧化四丙基銨(tetrapropylammonium hydroxide，TPAH)、氫氧化四丁基銨(tetrabutylammonium hydroxide，TBAH)、氫氧化參(2-羥乙基)甲基銨(tris(2-hydroxyethyl)methylammonium hydroxide，THEMAH)、氫氧化三甲基十六基銨(cetyltrimethylammonium hydroxide，CTAH)、膽鹼(choline)、及其組合。於以下實施例中，所示範使用之含氮化合物為氫氧化四甲基銨、氫氧化四乙基銨、氫氧化 參(2-羥乙基)甲基銨、氫氧化三甲基十六基銨與膽鹼。當使用四級銨作為本發明組合物之含氮化合物時，除可提供所欲研磨顆粒移除的效果以外，並可有效提供本發明組合物所需之鹼度，確保化學機械拋光時所用的研磨顆粒與晶圓表面保持有效之電負相斥力，利於去除研磨顆粒。Examples of quaternary ammonium salts suitable for use in the compositions of the present invention as nitrogen-containing compounds include, but are not limited to, those selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (tetraethylammonium hydroxide). Hydroxide, TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), 2-hydroxyethylammonium hydroxide (trisethyl 2-hydroxyethyl) Methylammonium hydroxide, THEMAH), cetyltrimethylammonium hydroxide (CTAH), choline, and combinations thereof. In the following examples, the nitrogen-containing compounds used as exemplified are tetramethylammonium hydroxide, tetraethylammonium hydroxide, and hydroxide. Reference to (2-hydroxyethyl)methylammonium, trimethylhexadecyl ammonium hydroxide and choline. When quaternary ammonium is used as the nitrogen-containing compound of the composition of the present invention, in addition to providing the effect of removing the desired abrasive particles, the alkalinity required for the composition of the present invention can be effectively provided to ensure the use in chemical mechanical polishing. The abrasive particles maintain an effective electrical and negative repulsive force on the wafer surface to facilitate removal of abrasive particles.
根據本發明，係於含水清潔組合物中合併使用至少二種含氮化合物，即可使用醇胺、雜環胺及四級銨中之二者或三者；舉例言之，可合併使用醇胺與雜環胺，亦可合併使用醇胺與四級銨，或可合併使用雜環胺與四級銨，更可合併使用醇胺、雜環胺與四級銨；於此，本發明之含水清潔組合物亦可同時包含至少二種醇胺、至少二種雜環胺、及/或至少二種四級銨，例如合併使用二乙醇胺(醇胺)、三乙醇胺(醇胺)、六氫吡(雜環胺)、及氫氧化四甲基銨(四級銨)。於此技術領域中具有通常知識者，根據本案說明書的揭露，可藉由不同含氮化合物之使用搭配，有效清除晶圓表面上的汙染物。According to the present invention, at least two nitrogen-containing compounds are used in combination in an aqueous cleaning composition, that is, two or three of an alcohol amine, a heterocyclic amine and a quaternary ammonium can be used; for example, an alcohol amine can be used in combination. With a heterocyclic amine, an alcohol amine and a quaternary ammonium may be used in combination, or a heterocyclic amine and a quaternary ammonium may be used in combination, and an alcohol amine, a heterocyclic amine and a quaternary ammonium may be used in combination; The cleaning composition may also comprise at least two alkanolamines, at least two heterocyclic amines, and/or at least two quaternary ammoniums, for example, a combination of diethanolamine (alcoholamine), triethanolamine (alcoholamine), hexahydropyridinium. (Heterocyclic amine), and tetramethylammonium hydroxide (quaternary ammonium). Those having ordinary skill in the art, according to the disclosure of the present specification, can effectively remove contaminants on the surface of the wafer by using a combination of different nitrogen-containing compounds.
於實際使用本發明之含水清洗組合物時，含氮化合物的總濃度通常為例如約100 ppm至約10,000 ppm，以提供調整組合物酸鹼值以及輕微蝕刻金屬的效果，較佳為約500 ppm至約5,000 ppm。然而，為節省生產、運輸及倉儲成本，含水清洗組合物的製造者通常會以濃縮液形式提供清洗組合物，再於使用端稀釋至所欲之使用濃度；所以，亦可以濃縮形式提供本發明含水清洗組合物，於使用時，再稀釋至所需之使用濃度。因此，於本發明含水清洗組合中，含氮化合物的總濃度為至少約100 ppm，較佳為至少約 500ppm。In the actual use of the aqueous cleaning compositions of the present invention, the total concentration of the nitrogen-containing compound is typically, for example, from about 100 ppm to about 10,000 ppm to provide an effect of adjusting the pH of the composition and slightly etching the metal, preferably about 500 ppm. Up to approximately 5,000 ppm. However, in order to save production, transportation and storage costs, the manufacturer of the aqueous cleaning composition typically provides the cleaning composition in the form of a concentrate which is then diluted to the desired concentration at the end of use; therefore, the invention may also be provided in a concentrated form. The aqueous cleaning composition is diluted to the desired concentration at the time of use. Accordingly, in the aqueous cleaning combination of the present invention, the total concentration of the nitrogen-containing compound is at least about 100 ppm, preferably at least about 500ppm.
可用於本發明之含水清洗組合物中的乙氧化硫醇通常具有如下化學式(I)：H(OCH2 CH2 )n SR1 其中，R1 為烴基，且n為1至100。The ethoxylated thiol which can be used in the aqueous cleaning composition of the present invention generally has the following chemical formula (I): H(OCH 2 CH 2 ) n SR 1 wherein R 1 is a hydrocarbon group and n is from 1 to 100.
本文中所使用的「烴基」可理解為包含脂肪族、環脂肪族及芳香族。舉例言之，「烴基」可為例如，但不限於，烷基、烯基、炔基、環烷基、芳基、芳烷基以及烷芳基，前述基團可為支鏈或非支鏈的、未經取代或經取代的。As used herein, "hydrocarbyl" is understood to include aliphatic, cycloaliphatic, and aromatic. For example, "hydrocarbyl" may be, for example, but not limited to, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, and alkaryl, the foregoing groups may be branched or unbranched , unsubstituted or substituted.
於化學式(I)中，R1 較佳係C1 -C30 烷基、C2 -C30 烯基、C2 -C30 炔基、C3 -C30 環烷基、C5 -C30 芳基、C6 -C30 芳烷基、或C6 -C30 烷芳基，且n為4至20；更佳R1 係C6 -C18 烷基、或C6 -C18 芳烷基，且n為4至12。In the formula (I), R 1 is preferably C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 3 -C 30 cycloalkyl, C 5 -C 30 Aryl, C 6 -C 30 aralkyl, or C 6 -C 30 alkaryl, and n is from 4 to 20; more preferably R 1 is C 6 -C 18 alkyl, or C 6 -C 18 aralkyl Base, and n is 4 to 12.
舉例言之，適用於本發明組合物之乙氧化硫醇之具體實施例包括，但不以此為限，選自以下群組者：乙氧基三級十二基硫醇(ethoxylated tertiary dodecyl mercaptan)、乙氧基正十二烷基硫醇(ethoxylated dodecyl mercaptan)、及乙氧基2-苯基乙基硫醇(ethoxylated 2-phenylethyl mercaptan)、及其組合。市售可用於本發明組合物作為乙氧化硫醇之產品，例如自Shibley Chemicals,Elyria,OH購得的Alcodet 260、Alcodet SK以及Alcodet 218。By way of example, specific examples of ethoxylated thiols suitable for use in the compositions of the present invention include, but are not limited to, those selected from the group consisting of ethoxylated tertiary dodecyl mercaptan ), ethoxylated dodecyl mercaptan, and ethoxylated 2-phenylethyl mercaptan, and combinations thereof. Commercially available products of the present invention are useful as ethoxylated mercaptans such as Alcodet 260, Alcodet SK and Alcodet 218 available from Shibley Chemicals, Elyria, OH.
於實際使用本發明之含水清洗組合物時，乙氧化硫醇的濃度通常為約10ppm至約600ppm，較佳為約50ppm至約300ppm。如 前述，可以以濃縮形式提供本發明含水清洗組合物，於使用時再進行稀釋。因此，於本發明含水清洗組合物中，乙氧化硫醇的濃度為至少約10ppm，較佳為至少約50ppm。When the aqueous cleaning composition of the present invention is actually used, the concentration of the ethoxylated thiol is usually from about 10 ppm to about 600 ppm, preferably from about 50 ppm to about 300 ppm. Such as In the foregoing, the aqueous cleaning composition of the present invention can be provided in a concentrated form and further diluted at the time of use. Accordingly, in the aqueous cleaning compositions of the present invention, the concentration of ethoxylated mercaptans is at least about 10 ppm, preferably at least about 50 ppm.
除含氮化合物與乙氧化硫醇以外，視需要地，可於本發明清洗組合物更包含一有機物配位體。於本文中，「有機物配位體」係指可化學吸附或結合化學機械拋光程序後殘留在晶圓上如BTA之有機物質。適用於本發明清洗組合物之有機物配位體之例子包括，但不限於，選自以下群組者：L-半胱胺酸(L-cysteine)、2,5-二巰基-1,3,4-噻二唑(2,5-dimercapto-1,3,4-thiadiazole)、4,6-二胺基-2-巰基嘧啶(4,6-diamino-2-mercaptopyrimidine)、2-硫尿嘧啶(2-thiouracil)、及其組合，較佳係L-半胱胺酸。當使用時，有機物配位體於本發明組合物之濃度通常為約50ppm至約2,000ppm，較佳為約100ppm至約1,000ppm。於不受理論限制之情形下，咸信有機物配位體可提升如BTA之有機物的飽和溶解度，增進清洗效果。In addition to the nitrogen-containing compound and the ethoxylated mercaptan, the cleaning composition of the present invention may further comprise an organic ligand as needed. As used herein, "organic ligand" refers to an organic substance that remains on a wafer, such as BTA, after being chemically adsorbed or combined with a chemical mechanical polishing procedure. Examples of organic ligands suitable for use in the cleaning compositions of the present invention include, but are not limited to, those selected from the group consisting of L-cysteine, 2,5-dimercapto-1,3, 4-thiazole-1,3,4-thiadiazole, 4,6-diamino-2-mercaptopyrimidine, 2-thiouracil (2-thiouracil), and combinations thereof, preferably L-cysteine. When used, the concentration of the organic ligand in the compositions of the present invention is typically from about 50 ppm to about 2,000 ppm, preferably from about 100 ppm to about 1,000 ppm. Without being bound by theory, the salt organic ligand can enhance the saturation solubility of organic substances such as BTA and improve the cleaning effect.
此外，根據本發明之含水清洗組成物之pH值範圍較佳係大於9，更佳係大於10。Further, the aqueous cleaning composition according to the present invention preferably has a pH in the range of more than 9, more preferably more than 10.
本發明之清洗組合物可在常溫下使用。以清洗含銅半導體晶圓為例，將此清洗組合物與含銅半導體晶圓接觸一段有效時間，去除殘留於晶圓表面上的污染物，同時維持銅導線較佳的表面粗糙度。一般而言，當使用濃度較低時，需較長的接觸時間(例如，1至3分鐘)，使用濃度較高時，僅需較短的接觸時間(例如，短於1分鐘)。於實際使用時，使用者可依需要進行調整。The cleaning composition of the present invention can be used at normal temperature. For example, cleaning a copper-containing semiconductor wafer, the cleaning composition is contacted with the copper-containing semiconductor wafer for an effective period of time to remove contaminants remaining on the surface of the wafer while maintaining a preferred surface roughness of the copper conductor. In general, when the concentration is lower, a longer contact time (for example, 1 to 3 minutes) is required, and when the concentration is higher, only a shorter contact time (for example, shorter than 1 minute) is required. In actual use, the user can adjust as needed.
本發明之含水清洗組合物不但可用於清洗經化學機械拋光之含銅半導體晶圓，亦可用於清洗經化學機械拋光之含矽半導體晶圓，展現高度應用性。於實際使用時，可於執行化學機械平坦化之機台上使用本發明清洗組合物，以清洗經平坦化之晶圓表面，亦可於一獨立之清洗機台上使用本發明清洗組合物以清洗經平坦化之晶圓表面。The aqueous cleaning composition of the present invention can be used not only for cleaning chemically mechanically polished copper-containing semiconductor wafers, but also for cleaning chemically and mechanically polished germanium-containing semiconductor wafers, exhibiting high applicability. In practical use, the cleaning composition of the present invention can be used on a machine performing chemical mechanical planarization to clean the surface of the planarized wafer, and the cleaning composition of the present invention can also be used on a separate cleaning machine. Clean the surface of the flattened wafer.
以下實施例將進一步說明本發明，惟非用以限制本發明之範圍，於此技術領域中具通常知識者可輕易達成之修飾及改變均涵蓋於本發明範圍內。The invention is further described in the following examples, which are not intended to limit the scope of the invention, and the modifications and variations which can be readily made by those skilled in the art are within the scope of the invention.
以表1、表2及表3所列成分與用量製備清洗組合物。Sinonate系列界面活性劑係由中日合成化學股份有限公司供應，其中1100HP(聚氧乙烯烷基醚磷酸)、9620P(聚氧乙烯壬基苯基醚磷酸)、1204P(聚氧乙烯烷基醚磷酸)、19P(烷基磷酸)皆為陰離子界面活性劑。Alcodet系列界面活性劑係由美國Rhodia公司提供，218、SK及260組成皆為乙氧化十二基硫醇(CAS.No.：9004-83-5)。BYK系列界面活性劑係由BYK公司提供，187為多官能聚合物的烷基醇銨鹽的溶液，191、194為具親顏料基團(pigment affinic groups)共聚物的溶液，381為聚丙烯酸酯的離子性溶液，380N為非離子性丙烯酸共聚物的溶液。各表格所列的其他化學藥品則可購自Sigma-Aldrich、Alfa Aesar、MERCK、Showa Chemical等藥品供應商之純度99%以上者。The cleaning compositions were prepared in the amounts and amounts listed in Tables 1, 2 and 3. Sinonate series surfactants are supplied by Sino-Japanese Synthetic Chemical Co., Ltd., including 1100HP (polyoxyethylene alkyl ether phosphate), 9620P (polyoxyethylene nonylphenyl ether phosphate), and 1204P (polyoxyethylene alkyl ether phosphate). ), 19P (alkyl phosphate) are all anionic surfactants. Alcodet series surfactants are supplied by Rhodia, USA, and 218, SK and 260 are all oxidized dodecyl mercaptan (CAS. No.: 9004-83-5). BYK series surfactants are supplied by BYK, 187 is a solution of a polyalcohol alkyl alkoxide, 191, 194 is a solution with pigmentary affinic groups, and 381 is a polyacrylate. An ionic solution, 380N is a solution of a nonionic acrylic copolymer. Other chemicals listed in the tables are available from Sigma-Aldrich, Alfa Aesar, MERCK, Showa Chemical and other pharmaceutical suppliers with a purity of more than 99%.
實施例使用的銅空白晶圓(blanket copper wafer)為購自美商 SKW Associates,Inc.，銅膜厚度為1.5微米之銅空白晶圓。Coral空白晶圓(blanket Coral wafer)及TEOS空白晶圓(blanket TEOS wafer)為購自美商SVTC Technologies,L.L.C.，Coral與TEOS為膜厚度各為1.0微米之空白晶圓。The copper copper wafer used in the embodiment is purchased from the US SKW Associates, Inc., a copper blank wafer with a copper film thickness of 1.5 microns. Coral blank wafers and TEOS blank wafers are commercially available from SVTC Technologies, L.L.C., Coral and TEOS as blank wafers each having a film thickness of 1.0 μm.
以美商卡博特微電子所生產的C8908銅研磨液先將銅空白晶圓研磨20秒，再以美商卡博特微電子所生產的B7601銅阻障層研磨液研磨60秒，使銅膜被移除約0.2微米，再將此經研磨液汙染的銅空白晶圓送入美商Entrepix,Inc.公司所銷售的OnTrak清洗機台，利用以下各表所列的組合物進行清洗；Coral與TEOS空白晶圓則是以美商卡博特微電子所生產的B7601銅阻障層研磨液研磨60秒，使Coral與TEOS膜各被移除約300至500埃(Å)及1000Å，再分別將經研磨液汙染的Coral與TEOS空白晶圓送入美商Entrepix,Inc.公司所銷售的OnTrak清洗機台，利用以下各表所列的組合物進行清洗。清洗時間2分鐘，清洗組合物流量為每分鐘1500毫升。清洗完成後以原子力顯微鏡(AFM)量測晶圓表面粗糙度，另以KLA-Tencor SP 1量測晶圓表面缺陷數。測試結果如表1、表2與表3中所列。The copper blank wafer was first ground for 20 seconds with C8908 copper slurry produced by American Cabot Microelectronics, and then polished with B7601 copper barrier layer slurry produced by American Cabot Microelectronics for 60 seconds to make copper. The film was removed by about 0.2 microns, and the copper blank wafer contaminated with the slurry was sent to the OnTrak cleaning machine sold by Entrepix, Inc., and cleaned using the compositions listed in the following tables; Coral The TEOS blank wafer was ground for 60 seconds with B7601 copper barrier layer slurry produced by Merck & Co. Microelectronics, and the Coral and TEOS films were removed by about 300 to 500 Å and 1000 Å, respectively. The Coral and TEOS blank wafers contaminated with the slurry were separately sent to the OnTrak cleaning machine sold by Entrepix, Inc., and the compositions listed in the following tables were used for cleaning. The cleaning time was 2 minutes and the flow rate of the cleaning composition was 1500 ml per minute. After the cleaning, the surface roughness of the wafer was measured by atomic force microscopy (AFM), and the number of wafer surface defects was measured by KLA-Tencor SP 1. The test results are listed in Table 1, Table 2 and Table 3.
表1結果顯示，合併使用界面活性劑乙氧化硫醇的組合(實施例1至4)於消除各項缺陷的綜合表現，優於使用其他界面活性劑的組合(比較例1至4及5至9)或是未使用界面活性劑的組合(比較例10)。此外，添加使用有機物配位體半胱胺酸則可進一步減少銅缺陷(實施例1、2及4與實施例5至7)。The results in Table 1 show that the combination of the surfactant ethoxylated thiols (Examples 1 to 4) is superior to the combination of other surfactants in eliminating the combined performance of various defects (Comparative Examples 1 to 4 and 5 to 9) Or a combination of surfactants was not used (Comparative Example 10). In addition, the addition of the organic ligand cysteine further reduced copper defects (Examples 1, 2 and 4 and Examples 5 to 7).
表2結果顯示，以2,5-二巰基-1,3,4-噻二唑(實施例9)、4,6-二胺基-2-巰基嘧啶(實施例10)、2-硫尿嘧啶(實施例11)取代L-半胱胺酸，所提供之清洗組成物在缺陷程度和粗糙度綜合表現上，仍可提供相當良好的效果。The results in Table 2 show that 2,5-dimercapto-1,3,4-thiadiazole (Example 9), 4,6-diamino-2-mercaptopyrimidine (Example 10), 2-thiourea The pyrimidine (Example 11) replaces L-cysteine, and the cleaning composition provided still provides a fairly good effect in terms of the overall degree of defect and roughness.
表3結果顯示，選用不同的含氮化合物組合，在適當的鹼度下所提供之含水清洗組合物在缺陷程度綜合表現上，可提供相當良好的效果。The results in Table 3 show that the aqueous cleaning compositions provided at the appropriate alkalinity provide a relatively good effect in the overall performance of the defect levels using different combinations of nitrogen-containing compounds.
上述僅為例示本發明之較佳實施例，不應以此限定本發明。任何參照本發明申請專利範圍及說明書內容所作之簡單變化，皆屬於本發明所涵蓋的範圍。The above is merely illustrative of preferred embodiments of the invention and should not be construed as limiting. Any simple changes made to the scope of the invention and the contents of the specification are within the scope of the invention.
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| TW101140987A TWI463007B (en) | 2012-11-05 | 2012-11-05 | Aqueous cleaning composition for post chemical mechanical planarization |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI463007B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000046423A1 (en) * | 1999-02-05 | 2000-08-10 | Betzdearborn Inc. | Cleaner composition and method of use thereof |
| US20090291873A1 (en) * | 2008-05-22 | 2009-11-26 | Air Products And Chemicals, Inc. | Method and Composition for Post-CMP Cleaning of Copper Interconnects Comprising Noble Metal Barrier Layers |
-
2012
- 2012-11-05 TW TW101140987A patent/TWI463007B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000046423A1 (en) * | 1999-02-05 | 2000-08-10 | Betzdearborn Inc. | Cleaner composition and method of use thereof |
| US20090291873A1 (en) * | 2008-05-22 | 2009-11-26 | Air Products And Chemicals, Inc. | Method and Composition for Post-CMP Cleaning of Copper Interconnects Comprising Noble Metal Barrier Layers |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201418450A (en) | 2014-05-16 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |