1373536 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種自基材如含鋁基材選擇性移除金屬如 Ta或TaN之溶液。本發明亦揭示一種選擇性移除金屬塗層 而不會實質上損害下面基材之經暴露金屬之方法。 【先前技術】 半導體裝置之製造通常包括形成多層，包括均勻光阻劑 塗膜在導電金屬層上方。形成在基材上作為擴散障壁層之 導電金屬層之非限制性例包括鋁、鈦 '鎢、鈕及銅者以及 氧化物、硼化物、氮化物、碳化物及其合金。此等導電金 屬膜通常形成為擴散障壁物以防止金屬内之金屬擴散入位 於基材上之下面介電質層内。例如，障壁層通常形成在含 矽介電質層（如Si〇2或ShN4)與A1或Cu金屬層之間。 頃發現鈕(Ta)及氮化鈕（TaN)對用於半導體加工之傳統以1373536 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a solution for selectively removing a metal such as Ta or TaN from a substrate such as an aluminum-containing substrate. The present invention also discloses a method of selectively removing a metal coating without substantially damaging the exposed metal of the underlying substrate. [Prior Art] The fabrication of a semiconductor device generally involves forming a plurality of layers including a uniform photoresist coating film over the conductive metal layer. Non-limiting examples of conductive metal layers formed on the substrate as diffusion barrier layers include aluminum, titanium 'tungsten, knobs and copper, as well as oxides, borides, nitrides, carbides, and alloys thereof. These conductive metal films are typically formed as diffusion barriers to prevent metal within the metal from diffusing into the underlying dielectric layer on the substrate. For example, the barrier layer is typically formed between a germanium-containing dielectric layer (e.g., Si〇2 or ShN4) and an A1 or Cu metal layer. It has been found that the button (Ta) and the nitride button (TaN) are used in the tradition of semiconductor processing.
Ti為主擴散障壁物至少局部為優異替代物，因為此等材料 在高達溫度為·20〇1下為有效擴散障壁物。在裝置製造中 增加使用Ta導致需要-種方法或剝離溶液以自基材移除h 或TaN層。 例如，在進行已知步驟以得微電路包括光㈣後，金屬 自—微祕之特定區如MTaN層之移除通常係藉有機剝離 ;谷液完成。 輕金屬自㈣材之化學移除為—餘難實施之方法。此 至少因為㈣大部分化學侵飯有高度抗性並需要—種可給 予氣離子以利心層之溶解之劑。近來1氧化劑嘗試濕 98708.doc 1373536 加工其上具有含钽層之電子組件之方法。例如，美國公告 專利申請案2002/0 11 9245A1說明一種钽氧化溶液，其包含 氧化劑如過氧化氫或臭氧及氟離子產生劑如HF或緩衝HF 供濕加工電子組件。 熟悉此技藝者當可明白，氟離子產生劑如氫氟酸（HF)溶 液容易侵蝕經暴露金屬如鋁。因此，基材通常在加工期間 會嚴重地腐蝕而可損壞至難以修護地步。 因此，對此加工使用替代方法如機械磨蝕，有時稱為 "化學機械拋光"（CMP)，其可移除鈕而導致基材受損，特 別是當任何低於整個基材者覆蓋Ta或TaN時。 其他移除Ta及TaN之方法包括喷濺蝕刻。不像CMP，當 整個基材覆蓋Ta或TaN時，其最常使用，喷濺蝕刻通常可 使用於圖案化蝕刻，因為極特定區可以各向異性方式移 除。與喷濺相關之固有缺點，包括由喷濺移除之材料可再 沉積在經暴露表面上之可能性，使得此技術之用途受到限 制。 鑑於上述，需要自基材移除金屬俾可克服至少部分一種 以上與有關技藝相關之缺點。例如，本發明之若干態樣係 關於自基材選擇性化學移除金屬而對基材最低損害或甚至 無損害。 【發明内容】 一典型態樣係關於自含鋁基材選擇性移除金屬之溶液。 此溶液包含：至少一種酸，如HF或缓衝HF，至少一種包 含氟離子之成分如nh4f、乙二醇及水。此等成分之組合 98708.doc 1373536 溶液之量存在。 用於剝離溶液之添加 本文所述溶液視需要可包含通常 劑0例如，溶液可包令_接丨ν μ β ^ 種以上選自界面活性劑、抗腐蝕Ti is the main diffusion barrier and is at least partially an excellent alternative because these materials are effective diffusion barriers up to a temperature of 20 〇1. The increased use of Ta in device fabrication results in the need for a method or stripping solution to remove the h or TaN layer from the substrate. For example, after performing a known procedure to obtain a microcircuit comprising light (4), the removal of a particular region of the metal, such as the MTaN layer, is typically by organic stripping; the valley liquid is completed. The chemical removal of light metals from (four) materials is a difficult method to implement. This is at least because (4) most of the chemical insults are highly resistant and require an agent that can give the gas ions to dissolve the layers. Recently, an oxidant attempted wet 98708.doc 1373536 to process a method having an electronic component containing a ruthenium layer thereon. For example, U.S. Patent Application Serial No. 2002/0 11 9245 A1, which is incorporated herein by reference in its entirety, discloses a sulp Those skilled in the art will appreciate that fluoride ion generators such as hydrofluoric acid (HF) solutions tend to attack exposed metals such as aluminum. Therefore, the substrate is often severely corroded during processing and can be damaged to the point where it is difficult to repair. Therefore, alternative methods such as mechanical abrasion, sometimes referred to as "chemical mechanical polishing" (CMP), which removes the button and causes damage to the substrate, especially when any substrate below the substrate is covered, Ta or TaN. Other methods of removing Ta and TaN include sputter etching. Unlike CMP, which is most commonly used when the entire substrate is covered with Ta or TaN, sputter etching can often be used for patterned etching because very specific regions can be removed anisotropically. The inherent disadvantages associated with sputtering, including the possibility that materials removed by sputtering can be deposited on the exposed surface, limit the use of this technique. In view of the above, the need to remove the metal ruthenium from the substrate overcomes at least some of the above-mentioned disadvantages associated with the related art. For example, several aspects of the invention relate to the selective chemical removal of metal from a substrate with minimal or no damage to the substrate. SUMMARY OF THE INVENTION A typical aspect relates to a solution for selectively removing a metal from an aluminum-containing substrate. The solution comprises: at least one acid such as HF or buffered HF, at least one fluoride-containing component such as nh4f, ethylene glycol and water. Combination of these ingredients 98708.doc 1373536 The amount of solution is present. Addition to the stripping solution The solution described herein may contain a usual agent 0 as needed, for example, the solution may be _ 丨 ν μ β ^ more than one selected from the group of surfactants, corrosion resistant
劑、PH改質劑等之添加劑。在一具體例中，此等視需要成 分可以取多5重罝。/〇溶液之量存在。可視需要加入揭示溶 液之界面活性劑之非限制如i包括#長02至012之直鏈與支 鏈第一、第二及第三胺、醯胺、氟碳及烷基乙氧化物包 括陰離子、非離子、陽離子及兩性離子界面活性劑及其混 α物。遠界©活性劑之例可發現於公告美國專利巾請案US 2002/0119245 A1 ， 2〇〇2年 8月 29 日公告及US 20〇3/〇114〇14 A1，2003年6月19日公告，其迸入本文供參考。在一具體 例中’界面活性劑為辛胺（c8)。可使用之其他界面活性劑 包括氟碳界面活性劑如範圍為3M®之Fc、醯胺及烷基乙氧 化物。 抗腐蝕劑之例包括苯并三唑及焦兒茶酚。 可用以保持溶液之PH為低於7，如低於6，甚至低於5， 及低於4之pH改質劑之非限制例包括任何適當酸，如選自 鹽酸、硫酸、醋酸及磷酸之酸及其混合物。 在一具體例中，揭示一種自含鋁基材選擇性移除Ta或 TaN之溶液，其中溶液，以溶液之重量％計包含：卜2〇 重量％ HF、1-4〇重量％ Nh4F、4〇_95重量％乙二醇，及視 需要界面活性劑，其餘包含水。 本文亦揭示一種使用任何前述溶液自基材選擇性移除金 屬之方法。例如，此方法包括將基材與前述溶液（例如， 98708.doc •10· 1373536 塗佈基材與所述溶液之接觸可使用分批式程序，例如，藉 浸潰基材於含有溶液之浴内一段足以移除金屬之時間實 施〇 或者，接觸基材可使用連續式程序實施。在此具體例 中，一種以上基材可在可移除金屬之速率下通過含溶液之 容器。 一種或二種此類過程可在單或多步驟程序令發生。此 外，亦可使用包含連續式及分批式之混合物之過程。 不論所用之實際過程如何，機械作用通常可相同。例 如，加工溶液可包含—旦移除塗膜，π,以暴露基材時足 以與基材表面反應之量之複合劑。有機_金屬複合物可在 剝離介質内為*溶性’其可防止基材受侵襲，但在進—步 加工時可隨後移除。例如，㉟乙醇鹽複合物可溶於水令並 可用清洗移除，接著酸性移除塗膜。 J中此過耘包括暴露基材至定時浸潰於渴 學浴内或自化學噴射工且之啥Α+古？丨— 耵具之噴射，直到完全移除金屬為 止。該過程可為多步驟，以致可為剝離-檢視-剝離-檢視循 環，直到Μ移除為止。雖料續式系統在半導體工^ 通常很稀少，惟一旦餅姓令π〜Λ Α & 、 —’ ν 5又疋之、，且件成立剝離時間時， 其可如上述般操作。 除了操作實例以外，或降非萁；社ηΗ 戎除非另予指明，須知 明書及請求項之砉+ 士々V曰 ^ ^ ^ 碩之表不成伤罝、反應條件等之數目可在所右 情況下由術語"約"改變。囡屮 ^ 奎鱼…， 艾因此，除非另予指明，前述說明 θ與下述凊求項設定之數值參數 数马大約值，其可視希望獲 98708.docAdditives such as agents and pH modifiers. In a specific example, these components may take up to 5 more weights. / The amount of bismuth solution is present. Non-limiting examples of surfactants which may be added to the revealing solution as needed include i. The linear and branched first and second and third amines, decylamine, fluorocarbon and alkyl ethoxylates, including anion 02 to 012, include an anion, Nonionic, cationic and zwitterionic surfactants and their alpha compounds. Examples of the far-end © active agent can be found in the US Patent Applicant US 2002/0119245 A1, Announcement on August 29, 2002 and US 20〇3/〇114〇14 A1, June 19, 2003 Announcement, which is incorporated herein by reference. In a specific example, the surfactant is octylamine (c8). Other surfactants which may be used include fluorocarbon surfactants such as Fc, guanamine and alkyl ethoxylates in the range 3M®. Examples of the anticorrosive agent include benzotriazole and pyrocatechol. Non-limiting examples of pH modifiers that can be used to maintain the pH of the solution below 7, such as below 6, or even below 5, and below 4 include any suitable acid, such as selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid. Acids and mixtures thereof. In a specific example, a solution for selectively removing Ta or TaN from an aluminum-containing substrate is disclosed, wherein the solution comprises, by weight% of the solution: 〇2% by weight HF, 1-4% by weight, Nh4F, 4 〇 _ 95% by weight of ethylene glycol, and if necessary, surfactant, the rest contains water. Also disclosed herein is a method of selectively removing a metal from a substrate using any of the foregoing solutions. For example, the method includes contacting the substrate with the aforementioned solution (eg, 98708.doc • 10·1373536 coated substrate with the solution can be used in a batch process, for example, by dipping the substrate into a bath containing the solution The inner period of time is sufficient to remove the metal or the contacting substrate can be carried out using a continuous procedure. In this embodiment, more than one substrate can be passed through the solution containing container at a rate at which the metal can be removed. Such a process can occur in a single or multi-step procedure. In addition, a process comprising a mixture of continuous and batch can be used. The mechanical action can generally be the same regardless of the actual process used. For example, the processing solution can comprise Once the coating film, π, is removed to expose the substrate in an amount sufficient to react with the surface of the substrate. The organic-metal composite can be *soluble in the release medium, which prevents the substrate from being attacked, but The stepwise processing can be subsequently removed. For example, the 35 ethanol salt complex is soluble in water and can be removed by washing, followed by acid removal of the film. This J in this case includes exposing the substrate to a timed dip Spray in a thirst bath or from a chemical sprayer and 古 古 耵 耵 耵 耵 耵 , 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Until the Μ is removed. Although the continuation system is usually rare in the semiconductor industry, once the pie name is π~Λ Α &, —' ν 5 is again, and the part is set to stripping time, it can be as The above operation. In addition to the operation examples, or the reduction of the number; the company Η Η 戎 unless otherwise specified, the number of the notice and the request item + 士々V曰^ ^ ^ The number of the table is not a scar, the reaction conditions, etc. In the right case, the term "about" is changed. 囡屮^ 奎鱼..., Ai, therefore, unless otherwise specified, the above description θ and the numerical parameter set by the following request are approximate, which is visible. Hope to get 98708.doc