TWI572490B - A stripping liquid composition, and a method of removing the polymer film using the release liquid composition - Google Patents
A stripping liquid composition, and a method of removing the polymer film using the release liquid composition Download PDFInfo
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本發明係關於一種剝離液組成物，更詳而言，係關於一種適用於剝離經雷射處理之高分子膜的剝離液組成物。 The present invention relates to a stripping liquid composition, and more particularly to a stripping liquid composition suitable for stripping a laser-treated polymer film.
晶片封裝技術歷經變遷，隨著晶片面積與封裝面積之比越來越接近、適用頻率增加、耐熱性能提升、導線數增多、導線間距減小、重量減小、可靠性提升與無鉛製程發展，習知利用引線鍵合(Wire Bonding)等方式連接晶片與印刷基板的作法，存在著佈線數量有限、晶片間的佈線較長、輸入輸出緩衝器、數據傳輸速度難以提高以及需要較高驅動能力等問題，使2D配置各種IC的做法漸漸為三維晶片(3D IC)封裝技術所取代。 The chip packaging technology has undergone changes, as the ratio of wafer area to package area is getting closer, the applicable frequency is increased, the heat resistance is improved, the number of wires is increased, the wire pitch is reduced, the weight is reduced, the reliability is improved, and the lead-free process is developed. It is known that the method of connecting a wafer and a printed substrate by wire bonding or the like has a problem that the number of wires is limited, the wiring between the wafers is long, the input/output buffer, the data transmission speed is difficult to be improved, and the high driving capability is required. The practice of enabling 2D to configure various ICs has gradually been replaced by three-dimensional chip (3D IC) packaging technology.
3D IC透過直通矽晶穿孔(Through-Silicon Via，TSV)封裝技術，能以最短的距離連接多個晶片，不僅縮短晶片間的佈線長度，更可提高數據傳輸速度並降低耗電量。此外，相較於現有的印刷基板，以晶圓使用經半導體技術加工而得之矽轉接板更可實現佈線的高密度化。因此，目前多使用矽材料的矽轉接板做為安裝IC的基板。 The 3D IC can connect multiple wafers with the shortest distance through the Through-Silicon Via (TSV) packaging technology, which not only shortens the wiring length between the wafers, but also increases the data transmission speed and reduces the power consumption. In addition, compared with the conventional printed circuit board, it is possible to increase the density of the wiring by using the yoke plate which is processed by the semiconductor technology. Therefore, a ruthenium adapter plate using a ruthenium material is currently used as a substrate on which an IC is mounted.
在晶圓薄化的製程中，進行晶背研磨(Grinding)的製程 時，由於晶圓厚度驟減，將導致晶圓強度不足，易造成晶圓在製程運送過程中容易因捲曲而造成脆裂。因此，在晶圓薄化前，通常係先將晶圓以高分子膜(如，環氧樹脂)以暫時性貼合(Temporary Bonding)方式承載於玻璃承載板(Carrier)上，再繼續進行後續製程。 In the process of wafer thinning, the process of crystal back grinding (Grinding) is carried out. At the time of the wafer thickness reduction, the wafer strength is insufficient, which may cause the wafer to be easily cracked due to curl during the process of the process. Therefore, before the wafer is thinned, the wafer is usually loaded on a glass carrier with a polymer film (eg, epoxy resin) in a temporary bonding manner, and then continues. Process.
又，由於於製程最後仍須將薄化後的晶圓自玻璃承載板上分離(De-bonding)，因此，通常會以雷射處理高分子膜，使經處理之高分子膜膨脹，以使晶圓與玻璃承載板間產生縫細使空氣進入而剝離。通常以雷射將高分子膜剝離薄化後的晶圓後，玻璃承載板容易殘留有剝離不完全之高分子膜，必須清洗完全才能繼續回收使用。 Moreover, since the thinned wafer must be de-bonded from the glass carrier plate at the end of the process, the polymer film is usually treated by laser to expand the treated polymer film so that the processed polymer film is expanded. A fine seam is formed between the wafer and the glass carrier plate to allow air to enter and peel off. Usually, after the polymer film is peeled off by the laser, the glass carrier sheet is likely to have a polymer film which is not completely peeled off, and must be completely cleaned before being recycled.
目前在封裝製程中，用以去除高分子膜的剝離液通常由有機鹼與極性溶劑所組成。然而，該剝離液去除玻璃上經過雷射光處理過的高分子膜效果不佳，容易造成高分子膜的殘留。或者雖可去除高分子膜，卻也同樣損傷玻璃承載板，使該玻璃承載板無法重複使用造成成本上的浪費。 Currently, in the packaging process, the stripping solution for removing the polymer film is usually composed of an organic base and a polar solvent. However, the stripping solution removes the laser-treated polymer film on the glass, which is not effective, and easily causes the polymer film to remain. Or, although the polymer film can be removed, the glass carrier plate is also damaged, so that the glass carrier plate cannot be reused, resulting in cost waste.
因此，目前業界仍亟待開發一種不損傷玻璃承載板，又能有效剝離高分子膜之剝離液組成物。 Therefore, at present, the industry still needs to develop a stripping liquid composition which can effectively peel off the polymer film without damaging the glass carrier sheet.
本發明提供一種剝離液組成物，係包括：無機鹼，以該剝離液組成物之總重計，該無機鹼之含量為5至25%；胺類化合物，以該剝離液組成物之總重計，該胺類化合物之含量為5至30%；極性溶劑，以該剝離液組成物之總重計，該極性溶劑之含量為5至60%；以及水性介質。 The present invention provides a stripping liquid composition comprising: an inorganic base, the inorganic base content is 5 to 25% based on the total weight of the stripping liquid composition; and an amine compound, based on the total weight of the stripping liquid composition The content of the amine compound is 5 to 30%; the polar solvent is 5 to 60% by weight based on the total weight of the stripping liquid composition; and an aqueous medium.
為使本發明之剝離液組成物發揮良好的剝離效果，本發明復提供一種去除高分子膜之方法，係包括：以前述之剝離液組成物去除形成於承載板上之高分子膜。 In order to achieve a good peeling effect of the stripping liquid composition of the present invention, the present invention provides a method for removing a polymer film, comprising: removing a polymer film formed on a carrier sheet by the above-described stripping liquid composition.
於本發明之方法中，係於剝離物組成物在50至90℃之溫度條件下，去除該高分子膜。於較佳實施例中，係於60至70℃之溫度條件下，去除該高分子膜。 In the method of the present invention, the polymer film is removed at a temperature of 50 to 90 ° C in the stripper composition. In a preferred embodiment, the polymeric film is removed at a temperature of from 60 to 70 °C.
於本發明之方法中，該高分子膜為環氧樹脂膜。於較佳實施例中，該高分子膜係經雷射處理之環氧樹脂膜。 In the method of the present invention, the polymer film is an epoxy resin film. In a preferred embodiment, the polymeric film is a laser treated epoxy film.
於本發明之方法中，係以沖洗或浸泡方式去除形成於該承載板上之高分子膜。 In the method of the present invention, the polymer film formed on the carrier sheet is removed by rinsing or immersion.
於前述方法中，無論以沖洗或浸泡方式去除形成於該承載板上之高分子膜，皆能以毛刷刷洗該承載板，輔助去除形成於該承載板上之高分子膜。 In the above method, the carrier film can be brushed by a brush to remove the polymer film formed on the carrier plate, whether the polymer film formed on the carrier plate is removed by rinsing or immersion.
於本發明之剝離液組成物及去除高分子膜之方法中，該無機鹼係選自鹼金屬氫氧化物所構成之群組中之至少一者。於較佳實施例中，該鹼金屬氫氧化物係選自氫氧化鈉及氫氧化鉀所構成群組中之至少一者。 In the peeling liquid composition of the present invention and the method for removing the polymer film, the inorganic base is at least one selected from the group consisting of alkali metal hydroxides. In a preferred embodiment, the alkali metal hydroxide is selected from at least one of the group consisting of sodium hydroxide and potassium hydroxide.
於本發明之剝離液組成物及剝離方法中，該極性溶劑係選自由二甲基碸(Dimethyl sulfoxide)、二乙二醇單丁醚(Diethylene glycol monobutyl ether)、苯甲醇(Benzyl alcohol)、N,N-二甲基乙醯胺(Dimethylacetamide)、N,N-二甲基甲醯胺(Dimethylformamide)、與N-甲基-2-吡咯酮(N-Methyl-2-Pyrrolidone)、γ-丁內酯(gamma-butyrolacton)及N,N-二甲基咪唑(N,N-dimethylimidazol)所構成群組中之 至少一者。 In the stripping liquid composition and the stripping method of the present invention, the polar solvent is selected from the group consisting of Dimethyl sulfoxide, Diethylene glycol monobutyl ether, Benzyl alcohol, and N. , N-Dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone, γ-butyl In the group consisting of gamma-butyrolacton and N,N-dimethylimidazol At least one.
於本發明之剝離液組成物及剝離方法中，該胺類化合物係選自烷醇胺及烷基胺所構成群組中之至少一者。於較佳實施例中，該胺類化合物係選自單乙醇胺(Monoethanolamine)、異丙醇胺(Monoisopropanolamine)、三乙醇胺(Triethanolamine)、N-甲基二乙醇胺(N-Methyldiethanolamine)及異丁醇胺(Isobutanolamine)所構成群組中之至少一者。 In the peeling liquid composition and the peeling method of the present invention, the amine compound is at least one selected from the group consisting of an alkanolamine and an alkylamine. In a preferred embodiment, the amine compound is selected from the group consisting of Monoethanolamine, Monoisopropanolamine, Triethanolamine, N-Methyldiethanolamine, and Isobutanolamine. (Isobutanolamine) at least one of the group consisting of.
於本發明之剝離液組成物及剝離方法中，該水性介質為去離子水或純水。 In the stripping liquid composition and the stripping method of the present invention, the aqueous medium is deionized water or pure water.
此外，於本發明之剝離液組成物及剝離方法中，復包括界面活性劑，以該剝離液組成物之總重計，該界面活性劑之含量為0.01至1%。於較佳實施例中，該界面活性劑係選自非離子型界面活性劑、陰離子型界面活性劑所構成群組中之至少一者。 Further, in the stripping liquid composition and the peeling method of the present invention, a surfactant is further included, and the content of the surfactant is 0.01 to 1% based on the total weight of the stripping liquid composition. In a preferred embodiment, the surfactant is selected from at least one of the group consisting of a nonionic surfactant and an anionic surfactant.
本發明之剝離液組成物中係以無機鹼在不損傷承載板的輕微地腐蝕程度下，藉由微蝕承載板表面高分子膜，達到良好的去除高分子膜之效果。此外，由前可知，由於本發明之剝離液組成物係藉由胺類化合物輔佐無機鹼，達到去除高分子膜之效果。因此，本發明之剝離液組成物可於不添加及不含有機鹼之情況下，即在有效地去除高分子膜之情況下，亦達到不損傷承載板之功效。 The stripping liquid composition of the present invention achieves a good effect of removing the polymer film by micro-etching the polymer film on the surface of the carrier plate by the inorganic base without slightly damaging the carrier plate. Further, as described above, since the stripping liquid composition of the present invention is supplemented with an inorganic base by an amine compound, the effect of removing the polymer film is achieved. Therefore, the stripping liquid composition of the present invention can achieve the effect of not damaging the carrier sheet without adding or containing an organic base, that is, in the case of effectively removing the polymer film.
以下係藉由特定之具體實施例進一步說明本發明之實施方式，熟習此技藝之人士可由本說明書所揭示之內容瞭解本發明之其他優點與功效。本發明之實施例如下所示，但本發明並不限於這些實施例。另外，於本文中所使用之術語「微蝕」，係意指雖蝕表面但僅造成以承載板之總表面積計，1%以下之承載板表面因腐蝕而發生產生凹穴、缺口或下陷等損傷。於本發明中所述之胺類化合物係意指一級、二級、三級胺類化合物，但不包括四級銨鹽類化合物。 The embodiments of the present invention are further described by the specific embodiments thereof, and those skilled in the art can understand the other advantages and effects of the present invention from the disclosure of the present disclosure. The embodiment of the present invention is shown below, but the present invention is not limited to these embodiments. In addition, the term "microetching" as used herein means that, although the surface is etched, only the surface area of the carrier plate is less than 1%, and the surface of the carrier plate is corroded to cause pockets, notches or depressions. damage. The amine compound described in the present invention means a primary, secondary or tertiary amine compound, but does not include a quaternary ammonium salt compound.
本發明之剝離液組成物係包括：以該剝離液組成物之總重計，5至25%之無機鹼、5至30%之胺類化合物、5至60%之極性溶劑以及去離子水。 The stripping liquid composition of the present invention comprises 5 to 25% of an inorganic base, 5 to 30% of an amine compound, 5 to 60% of a polar solvent, and deionized water based on the total weight of the stripping liquid composition.
於本發明之剝離液組成物中，係藉由極性溶劑溶解高分子膜，以達到去除高分子膜之功效。於本發明中，對於極性溶劑的選擇並未有特殊限制，為一般常用的極性溶劑即可，於此便不再贅述。 In the composition of the stripping liquid of the present invention, the polymer film is dissolved by a polar solvent to achieve the effect of removing the polymer film. In the present invention, the selection of the polar solvent is not particularly limited, and it is generally a commonly used polar solvent, and will not be described herein.
於本發明之剝離液組成物中，係藉由無機鹼微蝕玻璃表面，以達到剝離高分子膜之功效。於本發明中，該無機鹼係為鹼金屬氫氧化物。於下述實施例中，係以氫氧化鈉與氫氧化鉀為例，以該鹼金屬氫氧化物剝離高分子膜。 In the stripping liquid composition of the present invention, the surface of the glass is microetched by an inorganic base to achieve the effect of peeling off the polymer film. In the present invention, the inorganic base is an alkali metal hydroxide. In the following examples, sodium hydroxide and potassium hydroxide were exemplified, and the polymer film was peeled off from the alkali metal hydroxide.
於本發明之剝離液組成物中，該胺類化合物係選自烷醇胺或烷基胺類中的至少一種。 In the stripping liquid composition of the present invention, the amine compound is at least one selected from the group consisting of an alkanolamine or an alkylamine.
於較佳實施例中，該胺類化合物係選自一級、二級、 及三級胺類化合物所構成群組中之至少一者。 In a preferred embodiment, the amine compound is selected from the group consisting of primary, secondary, and And at least one of the group consisting of tertiary amine compounds.
於一實施例中，該胺類化合物為三級胺類化合物，其中，該胺類化合物中-OH基團的數目係小於等於3，較佳係選自三乙醇胺(Triethanolamine)、及N-甲基二乙醇胺(N-Methyldiethanolamine)所構成群組中之至少一者。 In one embodiment, the amine compound is a tertiary amine compound, wherein the number of -OH groups in the amine compound is 3 or less, preferably selected from the group consisting of triethanolamine and N-A. At least one of the group consisting of N-Methyldiethanolamine.
於一實施例中，該胺類化合物為單乙醇胺，且以該剝離液組成物之總重計，該單乙醇胺之含量係介於10%至20%。 In one embodiment, the amine compound is monoethanolamine, and the monoethanolamine is present in an amount of from 10% to 20% based on the total weight of the stripper composition.
於本發明之剝離液組成物中，該胺類化合物係用以輔助無機鹼剝離高分子膜，並可延長剝離液組成物之使用壽命。 In the stripping liquid composition of the present invention, the amine compound is used to assist the inorganic base to peel off the polymer film, and the service life of the stripping liquid composition can be prolonged.
本發明之方法係使用本發明之剝離液組成物去除形成於承載板上之高分子膜。於本發明之方法中，對於去除該高分子膜的方式並未有特殊限制，可使用浸泡或沖洗的方式剝離該高分子膜。 The method of the present invention removes the polymer film formed on the carrier sheet using the stripping liquid composition of the present invention. In the method of the present invention, the manner of removing the polymer film is not particularly limited, and the polymer film may be peeled off by immersion or rinsing.
將5重量份之氫氧化鈉、5重量份之異丁醇胺、60重量份之二乙二醇單丁醚溶解於去離子水中，製得本發明實施例1之剝離液組成物，其中，以該剝離液組成物之總重計，該氫氧化鈉之含量為5%、異丁醇胺之含量為5%、二乙二醇單丁醚之含量為60%。 The peeling liquid composition of the first embodiment of the present invention is obtained by dissolving 5 parts by weight of sodium hydroxide, 5 parts by weight of isobutanolamine, and 60 parts by weight of diethylene glycol monobutyl ether in deionized water. The content of the sodium hydroxide was 5%, the content of isobutanolamine was 5%, and the content of diethylene glycol monobutyl ether was 60% based on the total weight of the stripping liquid composition.
重複實施例1之步驟，但使用如表1所示之組成成分， 並依據表2所示之用量製備實施例2至18之剝離液組成物。 The procedure of Example 1 was repeated, but using the components shown in Table 1, The stripping liquid compositions of Examples 2 to 18 were prepared in accordance with the amounts shown in Table 2.
將45wt%之氫氧化鉀溶解於去離子水中，製得比較例 1之剝離液。 Dissolving 45 wt% of potassium hydroxide in deionized water to prepare a comparative example 1 stripping solution.
將1重量份1%之氫氧化四甲基銨(tetramethylammonium hydroxide，TMAH)、96重量份之二甲基亞碸(Dimethyl sulfoxide，DMSO)溶解於去離子水中，製得比較例2之剝離液組成物。 1 part by weight of 1% tetramethylammonium hydroxide (TMAH) and 96 parts by weight of dimethyl sulfoxide (DMSO) were dissolved in deionized water to prepare a stripping solution of Comparative Example 2. Things.
將2重量份2%之氫氧化四甲基銨(tetramethylammonium hydroxide，TMAH)、92重量份之二甲基亞碸(Dimethyl sulfoxide，DMSO)溶解於去離子水中，製得比較例3之剝離液組成物。 2 parts by weight of 2% tetramethylammonium hydroxide (TMAH) and 92 parts by weight of dimethyl sulfoxide (DMSO) were dissolved in deionized water to prepare a stripping solution of Comparative Example 3. Things.
於玻璃承載板上形成環氧樹脂膜，並以雷射光照射該環氧樹脂膜，得到具有經雷射處理的環氧樹脂膜之玻璃承載板。 An epoxy resin film is formed on the glass carrier plate, and the epoxy resin film is irradiated with laser light to obtain a glass carrier plate having a laser-treated epoxy resin film.
依據表2及表3，調整實施例1至18及比較例1至3的剝離液組成物的溫度，分別以實施例1至18及比較例1至3的剝離液組成物以噴灑(Spray)方式，並以毛刷輔助刷洗1分鐘，以去除由前述方法製得之具有經雷射處理的環氧樹脂膜。 The temperatures of the stripping liquid compositions of Examples 1 to 18 and Comparative Examples 1 to 3 were adjusted according to Tables 2 and 3, and the stripping liquid compositions of Examples 1 to 18 and Comparative Examples 1 to 3 were respectively sprayed (Spray). The brush was assisted by a brush for 1 minute to remove the laser-treated epoxy film obtained by the aforementioned method.
並使用Thermo Scientific公司出品之X光光電子能譜儀(型號K-Alpha)進行表面X光光電子能譜分析(X-ray photoelectron spectroscopy/Electron Spectroscopy for chemical Analysis，XPS/ESCA)，測量經本發明之剝離液組成物去除環氧樹脂後，以該玻璃承載板的總表面積計，該玻璃承載板上所殘留的碳含量，以確認是否有環氧樹脂殘留，並將結果記錄於表2及表3。 X-ray photoelectron spectroscopy/Electron Spectroscopy for Chemical Analysis (XPS/ESCA) was performed using an X-ray photoelectron spectrometer (Model K-Alpha) from Thermo Scientific, and the stripping by the present invention was measured. After the liquid composition was removed from the epoxy resin, the amount of carbon remaining on the glass carrier plate was determined based on the total surface area of the glass carrier plate to confirm whether or not epoxy resin remained, and the results are reported in Tables 2 and 3.
並以目視觀察玻璃承載板外觀是否發生變化。用如下方法進行評估，並將結果記錄於表2及表3：◎：良好，承載板外觀良好，且表面完全未有經腐蝕而產生的凹穴、缺口或下陷等損傷；○：佳，以承載板之總表面積計，1%以下之承載板表面經腐蝕而產生凹穴、缺口或下陷等損傷；△：尚可，以承載板之總表面積計，1至10%以上之承載板表面經腐蝕而產生凹穴、缺口或下陷等損傷；以及×：差，以承載板之總表面積計，10%以上之承載板表面經腐蝕而產生凹穴、缺口或下陷等損傷。 And visually observe whether the appearance of the glass carrier plate changes. The evaluation was carried out as follows, and the results were recorded in Table 2 and Table 3: ◎: good, the appearance of the carrier plate was good, and the surface was completely free of corrosion, such as pockets, notches or depressions; ○: good, The total surface area of the carrier plate is less than 1% of the surface of the carrier plate is corroded to cause damage such as pockets, notches or depressions; △: Yes, based on the total surface area of the carrier plate, 1 to 10% of the surface of the carrier plate is Corrosion causes damage such as pockets, notches or sags; and ×: Poor, based on the total surface area of the carrier plate, more than 10% of the surface of the carrier plate is corroded to cause damage such as pockets, notches or sags.
如表2及3所示，僅使用無機鹼做為剝離液之比較例1不僅無法有效的去除環氧樹脂，更會過度腐蝕玻璃承載 板使玻璃承載板產生凹穴、缺口或下陷等損傷。又，比較例2及3的剝離液組成物，雖不會損壞承載板，卻無法有效的將環氧樹脂去除。鑒於比較例1至3，本發明的實施例1至18之剝離液組成物，不僅具有良好的環氧樹脂去除效果，更不會損傷承載板。 As shown in Tables 2 and 3, Comparative Example 1 using only an inorganic base as a stripping solution not only failed to effectively remove the epoxy resin, but also excessively corroded the glass bearing. The plate causes the glass carrier plate to cause damage such as pockets, notches or depressions. Further, the peeling liquid compositions of Comparative Examples 2 and 3 did not damage the carrier sheet, but could not effectively remove the epoxy resin. In view of Comparative Examples 1 to 3, the peeling liquid compositions of Examples 1 to 18 of the present invention not only have a good epoxy resin removing effect, but also do not damage the carrier sheet.
如表2及3結果所示，相較於比較例1至3，使用本發明的實施例1至18之剝離液組成物進行剝離，能在不損傷玻璃承載板的情況下有效地去除經雷射處理的環氧樹脂膜。 As shown in the results of Tables 2 and 3, the peeling liquid compositions of Examples 1 to 18 of the present invention were used for peeling as compared with Comparative Examples 1 to 3, and the thunder was effectively removed without damaging the glass carrier plate. A treated epoxy film.
綜上所述，本發明之剝離液組成物得以在不添加有機鹼之情況下，有效控制去除高分子膜，且承載板上不會發生外觀腐蝕之缺失。 In summary, the stripping liquid composition of the present invention can effectively control the removal of the polymer film without adding an organic base, and the absence of appearance corrosion does not occur on the carrier sheet.
上述實施例僅例示說明本發明之原理及其功效，而非用於限制本發明。任何熟習此項技藝之人士均可在不違背本發明之精神及範疇下，對上述實施例進行修飾與改變。因此，本發明之權利保護範圍，應如後述之申請專利範圍所列，在不影響本發明所能產生之功效及所能達成之目的下，均應仍落在本發明所揭示之技術內容得能涵蓋之範圍內。 The above-described embodiments are merely illustrative of the principles of the invention and its effects, and are not intended to limit the invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the present invention should be as set forth in the scope of the claims, and the technical contents disclosed in the present invention should still be obtained without affecting the effects and the objects that can be achieved by the present invention. Can cover the scope.
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