TWI503878B - Acidic post-cmp cleaning composition - Google Patents
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本發明係有關一種酸性清潔組成物，其可有效地去除半導體晶圓表面，尤其是去除銅製程化學機械研磨後晶圓表面上的污染物，以利於後續薄膜沉積、微影等製程的進行。The invention relates to an acidic cleaning composition, which can effectively remove the surface of the semiconductor wafer, in particular to remove contaminants on the surface of the wafer after chemical processing of the copper process, so as to facilitate subsequent processes such as film deposition and lithography.
於深次微米半導體製造中，通常使用銅鑲嵌法於低k介電層中形成導電銅線及通孔。鑲嵌法中的一項重要步驟為化學機械研磨(CMP)步驟，該步驟係用來移除高於介電層表面的過量銅。In deep sub-micron semiconductor fabrication, conductive damascene and vias are typically formed in a low-k dielectric layer using a copper damascene process. An important step in the damascene process is the chemical mechanical polishing (CMP) step, which is used to remove excess copper above the surface of the dielectric layer.
化學機械研磨或化學機械平坦化是一種利用化學性研漿與機械式研磨來研磨晶圓表面的技術。化學機械研磨製程雖為先進半導體製程的關鍵技術，但在無塵室中卻屬高污染性製程(dirty process)。由於化學機械研磨製程中必須將研漿(slurry)引入至晶圓表面進行研磨，研漿中包含約5-10%，30-100奈米之微細研磨粉體(abrasive)，種類包括SiO2 、Al2 O3 、CeO2 、ZrO2 等；此外還必須加入化學助劑，例如pH緩衝劑或有機酸等；氧化劑，例如雙氧水、硝酸鐵、碘酸鉀等；另外還必須加入苯并***(Benzotriazole，BTA)作為腐蝕抑制劑來保護金屬銅表面；且必須加入界面活性劑幫助粉體在水溶液中的懸浮穩定性。故晶圓經過研磨之後，晶圓表面勢必殘留大量之研磨粉體、金屬離子、吸附的化學反應副產品銅-苯并***錯合物及其他不純物之污染。若無有效地利用清潔液來去除此外來之污染物，則將對電路電性與後續的鍍 膜附著、微影等製程有影響，故化學機械研磨後的清洗製程至為重要。Chemical mechanical polishing or chemical mechanical planarization is a technique that uses chemical slurry and mechanical grinding to polish the surface of a wafer. Although the chemical mechanical polishing process is a key technology for advanced semiconductor processes, it is a highly polluting process in clean rooms. Since the slurry must be introduced into the surface of the wafer for grinding in the chemical mechanical polishing process, the slurry contains about 5-10%, 30-100 nm of fine abrasive powder, the type includes SiO 2 , Al 2 O 3 , CeO 2 , ZrO 2 , etc.; in addition, chemical additives such as pH buffers or organic acids must be added; oxidizing agents such as hydrogen peroxide, ferric nitrate, potassium iodate, etc.; benzotriazole must also be added (Benzotriazole, BTA) acts as a corrosion inhibitor to protect the metallic copper surface; and a surfactant must be added to aid in the suspension stability of the powder in aqueous solution. Therefore, after the wafer is polished, a large amount of abrasive powder, metal ions, adsorbed chemical reaction by-product copper-benzotriazole complex and other impurities are likely to remain. If the cleaning liquid is not effectively used to remove the other contaminants, it will affect the electrical properties of the circuit and the subsequent coating adhesion, lithography, etc., so the cleaning process after chemical mechanical polishing is important.
習知清潔技術係使清潔溶液(例如以氫氧化銨為主之鹼性溶液)流動於晶圓表面上，並配合使用超高頻音波、噴射或刷除來移除污染物，同時會使用各類型之界面活性劑(包含離子型或非離子型)，藉以有效潤濕晶圓表面，降低其表面張力有助於粉體之去除。然而，熟知此技藝者皆知含胺之清潔液具有臭味，且所釋放的胺可能毒害晶圓製造廠內放置的光阻。因此鹼性清潔液的用途有限。Conventional cleaning technology allows a cleaning solution (such as an ammonium hydroxide-based alkaline solution) to flow on the surface of the wafer and use ultra-high frequency sound waves, jets or brushes to remove contaminants, and Types of surfactants (including ionic or non-ionic) to effectively wet the surface of the wafer and reduce its surface tension to aid in powder removal. However, it is well known to those skilled in the art that amine-containing cleaning fluids have an odor and that the released amine may poison the photoresist placed in the wafer fabrication facility. Therefore, the use of alkaline cleaning liquids is limited.
目前習知技術上的清潔液尚有，使用包括羥胺、烷基醇胺(alkanolamine)和整合劑(包括鄰苯二酚)的清潔液(如美國專利第5,672,577號所揭示)。或是使用包括親核性胺化合物、烷基醇胺化合物和抗蝕劑(包括沒食子酸)的清潔液(如美國專利第7,144,848號所揭示)。或是使用包括至少一種界面活性劑以降低化學機械研磨後之半導體晶圓表面上的缺陷計數的清潔液(如美國專利第7,208,049號所揭示)。或是使用包括二羧酸及/或其鹽等無氟水性組成物的清潔液(如美國專利第6,627,546號所揭示)。或是使用包括檸檬酸銨以及抗蝕劑(包括抗壞血酸和半胱胺酸)的清潔液(如美國專利第7,087,564號所揭示)。There are currently known cleaning solutions for use in the art, including cleaning solutions including hydroxylamine, alkanolamine and integrators (including catechol) (as disclosed in U.S. Patent No. 5,672,577). Or a cleaning solution comprising a nucleophilic amine compound, an alkyl alcohol amine compound, and a resist (including gallic acid) (as disclosed in U.S. Patent No. 7,144,848). Or a cleaning fluid comprising at least one surfactant to reduce the count of defects on the surface of the semiconductor wafer after chemical mechanical polishing (as disclosed in U.S. Patent No. 7,208,049). Or a cleaning solution comprising a fluorine-free aqueous composition such as a dicarboxylic acid and/or a salt thereof (as disclosed in U.S. Patent No. 6,627,546). Or a cleaning solution comprising ammonium citrate and a resist comprising ascorbic acid and cysteine (as disclosed in U.S. Patent No. 7,087,564).
為了在半導體後段製程中，有效地去除銅製程化學機械研磨後之半導體晶圓表面上的污染物，以利於後續製程進行。經廣泛研究，本案發明者發現具有某些特殊組成之清潔組成物可實現本發明之目的，並將所得結果 陳述於下文中。In order to effectively remove the contaminants on the surface of the semiconductor wafer after the copper chemical mechanical polishing in the semiconductor back-end process, the subsequent processes are facilitated. After extensive research, the inventors of the present invention found that cleaning compositions having certain special compositions can achieve the object of the present invention and the results obtained. It is stated below.
據此，本發明之目的係在提供一種化學機械平坦化後用之酸性清潔組成物，其可有效地去除半導體晶圓表面上的污染物，尤其是銅製程化學機械研磨後之半導體晶圓表面上殘留的苯并***和氧化銅(殘留在銅層上)及銅渣(殘留在氟化矽酸鹽玻璃(FSG)介電層上)等污染物，而且該酸性清潔組成物可降低銅的蝕刻，因此可避免表面粗糙度增加的問題，以利於後續薄膜沉積、微影等製程的進行。Accordingly, it is an object of the present invention to provide an acid cleaning composition for chemical mechanical planarization which is effective for removing contaminants on the surface of a semiconductor wafer, particularly a surface of a semiconductor wafer after chemical processing of a copper process. Contaminants such as residual benzotriazole and copper oxide (residing on the copper layer) and copper slag (residing on the ferric silicate glass (FSG) dielectric layer), and the acidic cleaning composition can reduce copper The etching can avoid the problem of increased surface roughness, so as to facilitate subsequent film deposition, lithography and the like.
為了達到上述目的，本發明提供一種化學機械平坦化後用之酸性清潔組成物，其pH值介於1~5之間，包括：至少一種多胺多羧酸及/或其鹽類；至少一種羥基羧酸及/或其鹽類；以及其餘者實質上為水，其中該酸性清潔組成物係適合用於移除從半導體晶圓表面上的污染物，特別是移除留存在化學機械研磨後之半導體晶圓表面上之金屬及非金屬化合物等顆粒。In order to achieve the above object, the present invention provides an acidic cleaning composition for chemical mechanical planarization having a pH of between 1 and 5, comprising: at least one polyamine polycarboxylic acid and/or a salt thereof; at least one a hydroxycarboxylic acid and/or a salt thereof; and the remainder being substantially water, wherein the acidic cleaning composition is suitable for removing contaminants from the surface of the semiconductor wafer, particularly after removal from chemical mechanical polishing Particles such as metals and non-metallic compounds on the surface of the semiconductor wafer.
本發明的化學機械平坦化後用之酸性清潔組成物更包括至少一種界面活性劑，該界面活性劑不但可使該酸性清潔組成物更具有潤濕能力，而且亦可調控銅層的蝕刻率。The acidic cleaning composition for chemical mechanical planarization of the present invention further comprises at least one surfactant, which not only makes the acidic cleaning composition more wettable, but also regulates the etching rate of the copper layer.
本發明的化學機械平坦化後用之酸性清潔組成物更包括氫氧化四甲基銨、氫氧化胺、氫氧化四丁基銨、氫氧化四乙基銨、氫氧化苯甲基三甲基胺、氫氧化二甲基二乙基銨、氫氧化四丙基銨、磷氮環化合物(例如BEMP)、或胺類(例如三甲胺)。The acidic cleaning composition for chemical mechanical planarization of the present invention further comprises tetramethylammonium hydroxide, amine hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, benzyltrimethylammonium hydroxide. , dimethyldiethylammonium hydroxide, tetrapropylammonium hydroxide, a phosphorus-nitrogen ring compound (for example, BEMP), or an amine (for example, trimethylamine).
使用本發明化學機械平坦化後用之酸性清潔組成物可有效地去除銅製程化學機械研磨後之晶圓表面上殘留的污染物，如研磨粒、金屬及非金屬化合物等顆粒，且不致使金屬表面粗糙。The use of the acidic cleaning composition for chemical mechanical planarization of the present invention can effectively remove residual contaminants on the surface of the wafer after chemical mechanical polishing, such as abrasive grains, metal and non-metal compounds, without causing metal rough surface.
由本發明下述之實施方式，本發明的前述及其他目的、特徵、觀點及優點將會更加明瞭。The above and other objects, features, aspects and advantages of the present invention will become apparent from
下面將以更加詳細的方式描述本發明的較佳實施例。Preferred embodiments of the present invention will now be described in more detail.
為求方便說明，本文所用之「半導體晶圓」係指微電子、積體電路等中所使用的半導體晶圓。For the convenience of description, "semiconductor wafer" as used herein refers to a semiconductor wafer used in microelectronics, integrated circuits, and the like.
本文所用之「污染物」一詞係相當於反應副產物、金屬殘留物及存在於研漿中之化學品等物料。The term "contaminant" as used herein refers to materials such as by-products of reaction, metal residues, and chemicals present in the slurry.
本文所用之「介電層」一詞係指介電常數小於約3.5的介電材料層，例如含矽有機聚合物、含矽有機/無機混成材料、有機矽酸鹽玻璃(OSG)、四乙氧基矽烷(TEOS)、氟化矽酸鹽玻璃(FSG)、二氧化矽、或摻碳氧化物(CDO)玻璃。As used herein, the term "dielectric layer" means a layer of dielectric material having a dielectric constant of less than about 3.5, such as a ruthenium containing organic polymer, a ruthenium containing organic/inorganic hybrid material, an organosilicate glass (OSG), a tetrazine. Oxy decane (TEOS), fluorite silicate glass (FSG), cerium oxide, or carbon doped oxide (CDO) glass.
本發明化學機械平坦化後用之酸性清潔組成物，包括：至少一種多胺多羧酸及/或其鹽類；至少一種羥基羧酸及/或其鹽類；至少一種界面活性劑；以及其餘者實質上為水。The acidic cleaning composition for chemical mechanical planarization of the present invention comprises: at least one polyamine polycarboxylic acid and/or a salt thereof; at least one hydroxycarboxylic acid and/or a salt thereof; at least one surfactant; and the rest The person is essentially water.
本發明之化學機械平坦化後用之酸性清潔組成物係利用氨水或氫氧化四甲基銨來調整其pH值，該pH值介於1~5之間，較佳為2~4，而此pH值係利用適合之pH參考電極來測定。The acidic cleaning composition for chemical mechanical planarization of the present invention uses ammonia water or tetramethylammonium hydroxide to adjust the pH thereof, and the pH is between 1 and 5, preferably 2 to 4, and this is The pH is determined using a suitable pH reference electrode.
本發明所使用之多胺多羧酸係選自於由單胺多羧酸、二胺多羧酸及三胺多羧酸所組成的群組，較佳為三胺五羧酸，例如為乙三胺五乙酸(ethylene triamine pentaacetic acid)、二乙三胺五乙酸(diethylene triamine pentaacetic acid)、或三乙三胺五乙酸(triethylene triamine pentaacetic acid)，而適合之多胺多羧酸的鹽類包括鹼金屬鹽、鹼土金屬鹽及銨鹽，而所使用之多胺多羧酸或其鹽類的含量約為0.001~10重量%，較佳約為0.0025~5重量%。The polyamine polycarboxylic acid used in the present invention is selected from the group consisting of monoamine polycarboxylic acids, diamine polycarboxylic acids, and triamine polycarboxylic acids, preferably triamine pentacarboxylic acid, such as B. Ethylene triamine pentaacetic acid, diethylene triamine pentaacetic acid, or triethylene triamine pentaacetic acid, and suitable salts of polyamine polycarboxylic acids include The alkali metal salt, the alkaline earth metal salt and the ammonium salt are used in an amount of from 0.001 to 10% by weight, preferably from 0.0025 to 5% by weight, based on the polyamine polycarboxylic acid or a salt thereof.
本發明所使用之羥基羧酸，較佳係選自於由蘋果酸、酒石酸、乳酸及檸檬酸所組成的群組，而其適合之鹽類包括鹼金屬、鹼土金屬及銨鹽，而所使用之羥基羧酸或其鹽類的含量約為0.05~20重量%，較佳約為0.2~5重量%。The hydroxycarboxylic acid used in the present invention is preferably selected from the group consisting of malic acid, tartaric acid, lactic acid and citric acid, and suitable salts thereof include alkali metals, alkaline earth metals and ammonium salts, and are used. The content of the hydroxycarboxylic acid or a salt thereof is about 0.05 to 20% by weight, preferably about 0.2 to 5% by weight.
本發明所使用之界面活性劑可為陰離子界面活性劑及非離子界面活性劑，較佳係選自於由烷基磺酸、烷基苯磺酸、烷基硫酸、磺基琥珀酸酯、牛磺酸、壬酚四聚氧乙烯醚硫酸、乙氧基化脂肪醇及其鹽類所組成的群組，而所使用之界面活性劑的含量約為0.001~10重量%，較佳約為0.0025~5重量%。The surfactant used in the present invention may be an anionic surfactant and a nonionic surfactant, and is preferably selected from the group consisting of alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl sulfuric acid, sulfosuccinate, and cattle. a group consisting of sulfonic acid, indophenol tetrapolyoxyethylene ether sulfuric acid, ethoxylated fatty alcohol, and salts thereof, and the surfactant is used in an amount of about 0.001 to 10% by weight, preferably about 0.0025. ~5 wt%.
在銅製程化學機械研磨之後，以本發明酸性清潔組成物清洗整個晶圓，另外，本發明酸性清潔組成物可配合超高頻音波、噴射或刷除裝置一起使用，以更有效地移除污染物。After the copper process chemical mechanical polishing, the entire wafer is cleaned with the acidic cleaning composition of the present invention. In addition, the acidic cleaning composition of the present invention can be used together with an ultra-high frequency sound wave, spray or brushing device to more effectively remove the contamination. Things.
本發明的酸性清潔組成物不僅能藉由有機酸的整合作用來清除沈積在晶片上的金屬或金屬錯合物，亦可 同時清除殘留的研磨顆粒和有機化合物等污染物。本發明的酸性清潔組成物具有優良的清潔效果，只需在常溫下對晶圓表面加以適當地沖刷即可。The acidic cleaning composition of the present invention can not only remove the metal or metal complex deposited on the wafer by the integration of organic acids, but also At the same time, the residual particles such as abrasive particles and organic compounds are removed. The acidic cleaning composition of the present invention has an excellent cleaning effect, and it is only necessary to appropriately flush the surface of the wafer at a normal temperature.
以下實施例將對本發明作進一步之說明，唯非用以限制本發明的範疇。The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
首先配製不同之化學機械平坦化後用之酸性清潔組成物(如表1所示)，並利用氨水或氫氧化四甲基銨來調整該酸性清潔組成物的pH值。First, an acid cleaning composition for different chemical mechanical planarization (as shown in Table 1) was prepared, and the pH of the acidic cleaning composition was adjusted using ammonia water or tetramethylammonium hydroxide.
表1中之將酸性清潔組成物樣品滴落在銅晶圓(Cu wafer)表面上的接觸角係利用CCD攝影機，動態擷取影像，並作分析而測得。表1中之酸性清潔組成物樣品的表面張力係利用去離子水，將該酸性清潔組成物樣品以39:1(重量比)稀釋，然後使用注射器滴落一滴稀釋後酸性清潔組成物樣品，而滴落過程由CCD攝影機記錄，並擷取CCD攝影機在清潔組成物樣品在滴落之前所攝得之影像，並作分析而測得。The contact angle of the sample of the acidic cleaning composition dropped on the surface of the copper wafer in Table 1 was measured by a CCD camera, and the image was dynamically taken and analyzed. The surface tension of the acidic cleaning composition sample in Table 1 was diluted with 39:1 (weight ratio) using deionized water, and then a drop of the diluted acidic cleaning composition sample was dropped using a syringe. The dripping process was recorded by a CCD camera, and the image taken by the CCD camera before cleaning the composition sample was dropped and analyzed for analysis.
接著，分別對配製完成的已稀釋酸性清潔組成物樣 品1至5進行下列四種分析：(1)毯覆式銅晶圓(Cu wafer)的銅損耗率(rate of copper loss)或動態蝕刻率；(2)毯覆式銅晶圓的靜態蝕刻率(static etching rate); (3)毯覆式FSG晶圓(FSG wafer)上殘留的銅；以及(4)毯覆式銅晶圓殘留上的苯并***和氧化銅。Then, the prepared diluted acidic cleaning composition samples are respectively prepared. Products 1 to 5 perform the following four analyses: (1) copper loss rate or dynamic etch rate of a blanket wafer; (2) static etching of a blanket copper wafer (static etching rate); (3) copper remaining on a blanket FSG wafer; and (4) benzotriazole and copper oxide on the blanket copper wafer residue.
將8吋2000 Å銅厚之毯覆式銅晶圓置入後化學機械研磨清洗設備機台(Ontrak Post CMP brush box，Lam Research ,CAUSA)，並在該毯覆式銅晶圓通過毛刷箱(毛刷箱1及毛刷箱2)內部之同時，使用上述表1所示的已稀釋酸性清潔組成物樣品1以300 ml/min的速率對該毯覆式銅晶圓進行沖洗，而清洗時間總共費時50秒(亦即，該毯覆式銅晶圓在毛刷箱1中清洗30秒，隨後進入毛刷箱2中清洗20秒)，然後予以乾燥。接者，使用X-光螢光分析儀(X-ray Fluorescence Spectrometer, XRF)，量測清洗前與清洗後的晶圓上之銅層厚度的變化。此銅層清洗前和清洗後之厚度變化係分別藉由5-點探針及橢圓率測量法來決定，然後取此5-點的平均值。清洗前與清洗後的晶圓上之銅層厚度的差異係以銅損耗率來代表。該些量測值將列於下面表2中。The 8吋2000 Å copper-thick blanket copper wafer was placed in a post-chemical mechanical polishing equipment (Ontrak Post CMP brush box, Lam Research, CAUSA), and the blanket copper wafer was passed through the brush box. While the inside of the brush box 1 and the brush box 2 was simultaneously washed, the blanket copper wafer was washed at a rate of 300 ml/min using the diluted acidic cleaning composition sample 1 shown in Table 1 above. The time takes a total of 50 seconds (i.e., the blanket copper wafer is cleaned in the brush box 1 for 30 seconds, then into the brush box 2 for 20 seconds) and then dried. The X-ray Fluorescence Spectrometer (XRF) was used to measure the change in the thickness of the copper layer on the wafer before and after cleaning. The thickness change before and after cleaning of the copper layer is determined by a 5-point probe and an ellipticity measurement method, respectively, and then the average value of the 5-point is taken. The difference in copper thickness on the wafer before and after cleaning is represented by the copper loss rate. These measurements will be listed in Table 2 below.
除了以已稀釋酸性清潔組成物樣品2取代酸性清潔組成物樣品1以外，重複實施例1之步驟，而所獲得 之量測值將列於下面表2中。The procedure of Example 1 was repeated except that the acid cleaning composition sample 2 was replaced with the diluted acidic cleaning composition sample 2, and obtained The measured values will be listed in Table 2 below.
除了以已稀釋酸性清潔組成物樣品3取代酸性清潔組成物樣品1以外，重複實施例1之步驟，而所獲得之量測值將列於下面表2中。The procedure of Example 1 was repeated except that the acid cleaning composition sample 3 was replaced with the diluted acidic cleaning composition sample 3, and the obtained measurement values are listed in Table 2 below.
除了以已稀釋酸性清潔組成物樣品4取代酸性清潔組成物樣品1以外，重複實施例1之步驟，而所獲得之量測值將列於下面表2中。The procedure of Example 1 was repeated except that the acid cleaning composition sample 4 was replaced with the diluted acidic cleaning composition sample 4, and the obtained measurement values are listed in Table 2 below.
除了以已稀釋酸性清潔組成物樣品5取代酸性清潔組成物樣品1以外，重複實施例1之步驟，而所獲得之量測值將列於下面表2中。The procedure of Example 1 was repeated except that the acid cleaning composition sample 5 was replaced with the diluted acidic cleaning composition sample 5, and the obtained measurement values are listed in Table 2 below.
就上述動態蝕刻試驗的銅損耗率而言，在所有情況下顯示低的銅損耗率，而低的銅損耗率代表以本發明酸 性清潔組成物清洗後，晶圓表面的粗糙度增加很少。表2中顯示樣品1、4、5的銅損耗率低於樣品2、3，而此結果指出可利用界面活性劑及清潔組成物之pH值來調控銅的損耗率。In terms of the copper loss rate of the above dynamic etching test, a low copper loss rate is exhibited in all cases, and a low copper loss rate represents an acid of the present invention. After the cleaning composition is cleaned, the roughness of the wafer surface increases little. Table 2 shows that the copper loss rates of samples 1, 4, and 5 are lower than those of samples 2 and 3, and this result indicates that the pH of the surfactant and the cleaning composition can be utilized to regulate the loss rate of copper.
將8吋2000 Å銅厚之毯覆式銅晶圓浸漬於裝有已稀釋酸性清潔組成物樣品1(如上述表1所示)的圓桶形容器中總共4小時。浸漬之後，以去離子水清洗該毯覆式銅晶圓，並予以乾燥。接者，使用X-光螢光分析儀(X-ray Fluorescence Spectrometer, XRF)，量測浸漬前與浸漬後的晶圓上之銅層厚度的變化。此銅層浸漬前和浸漬後之厚度變化係分別藉由5-點探針及橢圓率測量法來決定，然後取此5-點的平均值。浸漬前與浸漬後的晶圓上之銅層厚度的差異係以靜態蝕刻率來代表。該些量測值將列於下面表3中。A 8 吋 2000 Å copper-thick blanket copper wafer was immersed in a drum-shaped container containing the diluted acidic cleaning composition sample 1 (shown in Table 1 above) for a total of 4 hours. After impregnation, the blanket copper wafer was rinsed with deionized water and dried. Next, the change in the thickness of the copper layer on the wafer before and after the immersion was measured using an X-ray Fluorescence Spectrometer (XRF). The thickness change of the copper layer before and after the immersion is determined by a 5-point probe and an ellipticity measurement method, respectively, and then the average value of the 5-point is taken. The difference in thickness of the copper layer on the wafer before and after immersion is represented by a static etch rate. These measurements will be listed in Table 3 below.
除了以已稀釋酸性清潔組成物樣品2取代酸性清潔組成物樣品1以外，重複實施例6之步驟，而所獲得之量測值將列於下面表3中。The procedure of Example 6 was repeated except that the acid cleaning composition sample 2 was replaced with the diluted acidic cleaning composition sample 2, and the obtained measurement values are listed in Table 3 below.
除了以已稀釋酸性清潔組成物樣品3取代酸性清潔組成物樣品1以外，重複實施例6之步驟，而所獲得之量測值將列於下面表3中。The procedure of Example 6 was repeated except that the acid cleaning composition sample 3 was replaced with the diluted acidic cleaning composition sample 3, and the obtained measurement values are listed in Table 3 below.
除了以已稀釋酸性清潔組成物樣品4取代酸性清 潔組成物樣品1以外，重複實施例6之步驟，而所獲得之量測值將列於下面表3中。In addition to acid dilution with sample 4 of diluted acidic cleaning composition The procedure of Example 6 was repeated except for the cleansing composition sample 1, and the obtained measured values will be listed in Table 3 below.
除了以已稀釋酸性清潔組成物樣品5取代酸性清潔組成物樣品1以外，重複實施例6之步驟，而所獲得之量測值將列於下面表3中。The procedure of Example 6 was repeated except that the acid cleaning composition sample 5 was replaced with the diluted acidic cleaning composition sample 5, and the obtained measurement values are listed in Table 3 below.
就上述靜態蝕刻試驗而言，在所有情況下顯示低的靜態蝕刻率，而低的靜態蝕刻率代表以本發明酸性清潔組成物浸漬後，晶圓表面的粗糙度增加很少。表3中顯示樣品1、5的靜態蝕刻率低於樣品2、3、4，而此結果指出可利用界面活性劑及清潔組成物之pH值來調控銅層的蝕刻率，其中又以樣品5的靜態蝕刻率為最低。For the static etch test described above, a low static etch rate is shown in all cases, while a low static etch rate represents little increase in the roughness of the wafer surface after immersion in the acidic cleaning composition of the present invention. Table 3 shows that the static etch rates of samples 1, 5 are lower than those of samples 2, 3, and 4, and the results indicate that the pH of the surfactant can be adjusted by the pH of the surfactant and the cleaning composition, with sample 5 again. The static etch rate is the lowest.
在應用材料公司製的Mirra研磨機台上對8"毯覆式銅晶圓進行化學機械研磨總共60秒。將研磨墊再整修 機制(polishing pad conditioning)停止，以盡量保留銅渣在研磨墊上。然後在相同的研磨機台之研磨墊上對一個毯覆式FSG晶圓(直徑為200 mm)進行化學機械研磨總共10秒。此時，由上述化學機械研磨後所保留在研磨墊上的銅渣已被毯覆式FSG晶圓沾上。將沾上銅渣之毯覆式FSG晶圓置入後化學機械研磨清洗設備機台(Ontrak)，並在該毯覆式FSG晶圓通過毛刷箱(毛刷箱1及毛刷箱2)內部之同時，使用上述表1所示的已稀釋酸性清潔組成物樣品1以300 ml/min的流速對該毯覆式FSG晶圓進行沖洗，而清洗時間總共費時50秒，然後予以乾燥。接者，使用全反射X-光螢光分析儀(Total reflection X-ray Fluorescence Spectrometer, TXRF)，偵測清洗後之毯覆式FSG晶圓上所殘留之銅渣。所偵測的毯覆式FSG晶圓上3-點(分別為晶圓的中心(0,0)、中心左邊87 mm (87,0)和中心右邊87 mm (-87,0))的Cu-K射線強度將列於下面表4中。Chemical mechanical grinding of 8" blanket copper wafers on a Mirra mill made by Applied Materials for a total of 60 seconds. Refinishing the pads The polishing pad conditioning is stopped to keep the copper slag on the polishing pad as much as possible. A blanket FSG wafer (200 mm diameter) was then chemical mechanically grounded on a polishing pad of the same grinder for a total of 10 seconds. At this time, the copper slag remaining on the polishing pad after the above chemical mechanical polishing has been applied to the blanket FSG wafer. The blanket-mounted FSG wafer with the copper slag is placed in the post-chemical mechanical polishing equipment (Ontrak), and the blanket FSG wafer is passed through the brush box (brush box 1 and brush box 2) While internally, the blanket FSG wafer was rinsed at a flow rate of 300 ml/min using the diluted acidic cleaning composition sample 1 shown in Table 1 above, and the cleaning time took a total of 50 seconds and then dried. In addition, a total reflection X-ray Fluorescence Spectrometer (TXRF) was used to detect the residual copper residue on the cleaned blanket FSG wafer. Cu on the detected blanket-on FSG wafer 3-point (center of the wafer (0,0), 87 mm (87,0) on the left side of the center, and 87 mm (-87,0) on the right side of the center) The -K ray intensity will be listed in Table 4 below.
除了以已稀釋酸性清潔組成物樣品2取代酸性清潔組成物樣品1以外，重複實施例11之步驟，而所獲得之量測值將列於下面表4中。The procedure of Example 11 was repeated except that the acid cleaning composition sample 2 was replaced with the diluted acidic cleaning composition sample 2, and the obtained measurement values are listed in Table 4 below.
除了以已稀釋酸性清潔組成物樣品3取代酸性清潔組成物樣品1以外，重複實施例11之步驟，而所獲得之量測值將列於下面表4中。The procedure of Example 11 was repeated except that the acid cleaning composition sample 3 was replaced with the diluted acidic cleaning composition sample 3, and the obtained measurement values are listed in Table 4 below.
除了以已稀釋酸性清潔組成物樣品4取代酸性清 潔組成物樣品1以外，重複實施例11之步驟，而所獲得之量測值將列於下面表4中。In addition to acid dilution with sample 4 of diluted acidic cleaning composition The procedure of Example 11 was repeated except for the cleansing composition sample 1, and the obtained measured values will be listed in Table 4 below.
除了以已稀釋酸性清潔組成物樣品5取代酸性清潔組成物樣品1以外，重複實施例11之步驟，而所獲得之量測值將列於下面表4中。The procedure of Example 11 was repeated except that the acid cleaning composition sample 5 was replaced with the diluted acidic cleaning composition sample 5, and the obtained measurement values are listed in Table 4 below.
由表4可知，以上述表1所示之酸性清潔組成物樣品1至5中之任何一者清洗之後，毯覆式FSG晶圓上皆無可偵測到的Cu-K射線計數。因此，可證明以本發明酸性清潔組成物樣品1至5中之任何一者清洗之後，皆能有效地將FSG層上的銅殘留物去除。As can be seen from Table 4, after cleaning with any of the acidic cleaning composition samples 1 to 5 shown in Table 1 above, there was no detectable Cu-K ray count on the blanket FSG wafer. Therefore, it can be confirmed that the copper residue on the FSG layer can be effectively removed after washing with any of the acidic cleaning composition samples 1 to 5 of the present invention.
在應用材料公司製的Mirra研磨機台上，以含100 ppm之苯并***的化學性研漿對8"毯覆式銅晶圓進行化學機械研磨總共60秒。將研磨墊再整修機制停止，且不進行去離子水潤洗步驟，以盡量保留殘渣碎片在該毯覆式銅晶圓上。接著，將沾上殘渣碎片之毯覆式銅晶圓浸入含有0.3重量%苯并***之溶液中總共30秒。 然後將該毯覆式銅晶圓置入後化學機械研磨清洗設備機台(Ontrak)，並在該毯覆式銅晶圓通過毛刷箱(毛刷箱1及毛刷箱2)內部之同時，使用上述表1配製所示的已稀釋酸性清潔組成物樣品1以300 ml/min的流速對該毯覆式銅晶圓進行沖洗，而清洗時間總共費時50秒(亦即，該毯覆式銅晶圓在毛刷箱1中清洗30秒，隨後進入毛刷箱2中清洗20秒)，然後予以潤洗及乾燥。接者，使用飛行時間二次離子質譜儀(Time of Flight-Secondary Ion Mass Spectrometry, TOF-SIMS)，偵測清洗前及清洗後之該毯覆式銅晶圓上的殘留物，TOF-SIMS的偵測結果將列於下面表5中。Chemical mechanical grinding of 8" blanket copper wafers with a chemical slurry containing 100 ppm of benzotriazole on a Mirra mill made by Applied Materials for a total of 60 seconds. The polishing pad was refurbished. And do not perform the deionized water rinsing step to keep the residue debris on the blanket copper wafer as much as possible. Then, the blanket copper wafer with the residue fragments is immersed in the benzotriazole containing 0.3% by weight. A total of 30 seconds in the solution. The blanket copper wafer is then placed in a post-chemical mechanical polishing equipment (Ontrak), and while the blanket copper wafer passes through the interior of the brush box (brush box 1 and brush box 2) The blanketed copper wafer was rinsed at a flow rate of 300 ml/min using the diluted acid cleaning composition sample 1 shown in Table 1 above, and the cleaning time took a total of 50 seconds (ie, the blanket type) The copper wafer was cleaned in the brush box 1 for 30 seconds, then washed into the brush box 2 for 20 seconds, then rinsed and dried. Receiver, using Time of Flight-Secondary Ion Mass Spectrometry (TOF-SIMS) to detect residues on the blanket copper wafer before and after cleaning, TOF-SIMS The detection results will be listed in Table 5 below.
除了以已稀釋酸性清潔組成物樣品4取代酸性清潔組成物樣品1以外，重複實施例16之步驟，而所獲得之量測值將列於下面表5中。The procedure of Example 16 was repeated except that the acid cleaning composition sample 4 was replaced with the diluted acidic cleaning composition sample 4, and the obtained measurement values are listed in Table 5 below.
除了以已稀釋酸性清潔組成物樣品5取代酸性清潔組成物樣品1以外，重複實施例16之步驟，而所獲得之量測值將列於下面表5中。The procedure of Example 16 was repeated except that the acid cleaning composition sample 5 was replaced with the diluted acidic cleaning composition sample 5, and the obtained measurement values are listed in Table 5 below.
由表5可知，以上述表1所示之酸性清潔組成物樣品1、4及5中之任何一者清洗之後，皆能非常有效地去除化學機械研磨後之毯覆式銅晶圓上所殘留的氧化銅、苯并***及有機氧化物，而其中苯并***殘留物的移除率更高達95%以上。As can be seen from Table 5, after cleaning with any of the acidic cleaning composition samples 1, 4 and 5 shown in Table 1 above, it is possible to very effectively remove the residue on the blanket-copper wafer after chemical mechanical polishing. Copper oxide, benzotriazole and organic oxides, wherein the removal rate of benzotriazole residues is more than 95%.
因此，本發明化學機械平坦化後用之酸性清潔組成物的優點為：在銅製程化學機械研磨之後不但可非常有效地去除晶圓上的銅殘留物及銅層上的氧化銅、苯并***及有機氧化物等殘留物，且同時清洗之後銅的損耗率低而低的銅損耗率代表以本發明酸性清潔組成物清洗後，晶圓表面的粗糙度增加很少，因此利於後續薄膜沉積、微影等製程的進行。Therefore, the acidic cleaning composition used in the chemical mechanical planarization of the present invention has the advantages that not only the copper residue on the wafer but also the copper oxide and benzotriene on the copper layer can be removed very effectively after the copper chemical mechanical polishing. Residues such as azole and organic oxide, and low loss rate of copper after cleaning at the same time, and low copper loss rate means that the surface roughness of the wafer is less increased after cleaning with the acidic cleaning composition of the present invention, thereby facilitating subsequent film deposition. , lithography and other processes.
對所有熟習此技藝者而言，本發明明顯地可以作 出多種修改及變化而不脫離本發明的精神和範圍。因此，本發明包括該些修改及變化，且其皆被包括在下附之申請專利範圍及其均等者中。The present invention is clearly applicable to all those skilled in the art. Various modifications and changes may be made without departing from the spirit and scope of the invention. Therefore, the present invention includes such modifications and variations, and is included in the scope of the appended claims and their equivalents.
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| US6136708A (en) * | 1998-11-06 | 2000-10-24 | Nec Corporation | Method for manufacturing semiconductor device |
| US6444583B2 (en) * | 1998-09-07 | 2002-09-03 | Nec Corporation | Substrate-cleaning method and substrate-cleaning solution |
| US6787480B2 (en) * | 2001-02-21 | 2004-09-07 | Nec Corporation | Manufacturing method of semicondcutor device |
| US20070023731A1 (en) * | 2003-07-30 | 2007-02-01 | Jha Sunil C | Polishing slurries and methods for chemical mechanical polishing |
| US20070232512A1 (en) * | 2006-03-30 | 2007-10-04 | Fujifilm Corporation | Cleaning solution for substrate for use in semiconductor device and cleaning method using the same |
| TW200745384A (en) * | 2006-03-31 | 2007-12-16 | Sanyo Chemical Ind Ltd | Cleaning agent for copper wiring |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6444583B2 (en) * | 1998-09-07 | 2002-09-03 | Nec Corporation | Substrate-cleaning method and substrate-cleaning solution |
| US6136708A (en) * | 1998-11-06 | 2000-10-24 | Nec Corporation | Method for manufacturing semiconductor device |
| US6787480B2 (en) * | 2001-02-21 | 2004-09-07 | Nec Corporation | Manufacturing method of semicondcutor device |
| US7268087B2 (en) * | 2001-02-21 | 2007-09-11 | Nec Electronics Corporation | Manufacturing method of semiconductor device |
| US20070023731A1 (en) * | 2003-07-30 | 2007-02-01 | Jha Sunil C | Polishing slurries and methods for chemical mechanical polishing |
| US20070232512A1 (en) * | 2006-03-30 | 2007-10-04 | Fujifilm Corporation | Cleaning solution for substrate for use in semiconductor device and cleaning method using the same |
| TW200801176A (en) * | 2006-03-30 | 2008-01-01 | Fujifilm Corp | Cleaning solution for substrate for use in semiconductor device and cleaning method using the same |
| TW200745384A (en) * | 2006-03-31 | 2007-12-16 | Sanyo Chemical Ind Ltd | Cleaning agent for copper wiring |
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