TWI851333B - Resist layer removing composition and method for removing resist layer using the same - Google Patents
Resist layer removing composition and method for removing resist layer using the same Download PDFInfo
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Abstract
Description
本發明是關於一種去阻層組成物及使用其之去阻層方法，特別是適用於深紫外光微影製程之去阻層組成物及使用其之去阻層方法。 The present invention relates to a resist removal layer composition and a resist removal layer method using the same, in particular to a resist removal layer composition suitable for deep ultraviolet lithography process and a resist removal layer method using the same.
微影製程為製備半導體的重要技術，其是透過已刻好圖案的光罩及阻層，將電路圖案「轉印」至晶圓上的過程。更具體而言，微影製程係先將阻層均勻塗佈在形成於基板上之絕緣層上；接著，選擇性地對阻層進行曝光及顯影，以形成圖案化阻層；再以圖案化阻層作為遮罩，對導電金屬膜或絕緣膜進行蝕刻，進而將電路圖案轉移至阻層下層；最後使用去阻層組成物將不必要的阻層去除，並重複上述步驟完成半導體晶片。 The lithography process is an important technology for preparing semiconductors. It is a process of "transferring" the circuit pattern to the wafer through the patterned mask and resist layer. More specifically, the lithography process is to first evenly coat the resist layer on the insulating layer formed on the substrate; then, selectively expose and develop the resist layer to form a patterned resist layer; then, use the patterned resist layer as a mask to etch the conductive metal film or the insulating film, thereby transferring the circuit pattern to the lower layer of the resist layer; finally, use the resist removal composition to remove the unnecessary resist layer, and repeat the above steps to complete the semiconductor chip.
然而，習知的去阻層組成物無法有效地同時去除晶圓或晶背上的阻層及金屬離子，或需要仰賴多個步驟方能進行阻層與金屬離子的去除與清潔，因而造成製程時間及晶圓缺陷增加、或製程速度及良率降低，對於半導體的生產造成諸多不良影響。 However, the known resist removal compositions cannot effectively remove the resist and metal ions on the wafer or wafer backside at the same time, or require multiple steps to remove and clean the resist and metal ions, which results in increased process time and wafer defects, or reduced process speed and yield, causing many adverse effects on semiconductor production.
由於習知技術存在上述的問題，因此，亟須提出一種新穎的去阻層組成物及使用其之去阻層方法，以消除或緩和上述問題。 Since the prior art has the above-mentioned problems, it is urgent to propose a novel deblocking layer composition and a deblocking layer method using the same to eliminate or alleviate the above-mentioned problems.
有鑑於此，根據本發明的第一態樣，提出一種去阻層組成物，包括一酸類以及一溶劑，酸類之含量為0.1-30wt%，且溶劑之含量為30-99.5wt%。其中，酸類係選自由甲酸、乙酸、乙二酸(Oxalic acid)、三氟乙酸(Trifluoroacetic acid)、甲磺酸(Methanesulfonic acid)、乙磺酸(Ethanesulfonic acid)、硝酸及鹽酸所組成之群組中的一種或多種；溶劑係選自由丙二醇甲醚醋酸酯(Propylene glycol methyl ether acetate)、丙二醇甲醚(Propylene glycol methyl ether)、異丙醇、甲基異丁基甲醇(Methyl isobutyl carbinol)、甲基正戊酮(Methyl n-amy ketone)、環己酮(Cyclohexanone)、二甲基亞碸(Dimethyl sulfoxide)、苯甲醚(Anisole)、乙二醇、乳酸乙酯(Ethyl lactate)及γ-丁內酯(Gamma-butyrolactone)所組成之群組中的一種或多種。 In view of this, according to the first aspect of the present invention, a deblocking layer composition is proposed, including an acid and a solvent, wherein the content of the acid is 0.1-30wt%, and the content of the solvent is 30-99.5wt%. The acid is one or more selected from the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid, nitric acid and hydrochloric acid; the solvent is one or more selected from the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, isopropyl alcohol, methyl isobutyl carbinol, methyl n-amy ketone, cyclohexanone, dimethyl sulfoxide, anisole, ethylene glycol, ethyl lactate and gamma-butyrolactone.
於本發明的一實施例中，去阻層組成物可更包括一界面活性劑，界面活性劑之含量可為0.001-3wt%。於本發明的一實施例中，界面活性劑可選自由陰離子界面活性劑及非離子型界面活性劑所組成之群組中的一種或多種。上述的陰離子界面活性劑例如為中日合成化學的SINONATE系列、3M的Novec系列；非離子型界面活性劑例如為日信化學的OLFINE E系列、磐亞的PANNOX系列、AIR PRODUCTS的Surfynol系列以及Triton X-100。 In one embodiment of the present invention, the deblocking layer composition may further include a surfactant, and the content of the surfactant may be 0.001-3wt%. In one embodiment of the present invention, the surfactant may be selected from one or more of the group consisting of anionic surfactants and non-ionic surfactants. The above-mentioned anionic surfactants are, for example, the SINONATE series of Sino-Nippon Synthetic Chemical and the Novec series of 3M; the non-ionic surfactants are, for example, the OLFINE E series of Nissin Chemical, the PANNOX series of Pan Asia, the Surfynol series of AIR PRODUCTS, and Triton X-100.
於本發明的一實施例中，上述去阻層組成物之清潔能力可大於90%，例如清潔能力大於95%、98%或99%，或者是例如清潔能力大於99.80%。 In one embodiment of the present invention, the cleaning ability of the above-mentioned deblocking layer composition may be greater than 90%, for example, the cleaning ability is greater than 95%, 98% or 99%, or for example, the cleaning ability is greater than 99.80%.
於本發明的一實施例中，取一第一重量之去阻層組成物放置於室溫的抽氣櫃經過24小時後，得到一第二重量之去阻層組成物，第一重量與第二重量之變化量可小於50%，例如第一重量與第二重量之變化量小於40%或30%。 In one embodiment of the present invention, a first weight of a de-blocking layer composition is placed in a vacuum chamber at room temperature for 24 hours to obtain a second weight of a de-blocking layer composition. The variation between the first weight and the second weight may be less than 50%, for example, the variation between the first weight and the second weight is less than 40% or 30%.
於本發明的一實施例中，取一初始重量之矽晶圓破片浸泡於去阻層組成物72小時後，得到一終點重量之矽晶圓破片，初始重量與終點重量之變化量可小於1g，例如初始重量與終點重量之變化量小於0.5g、0.3g、0.1g、0.01g、0.005g或0.001g。 In one embodiment of the present invention, a silicon wafer fragment of an initial weight is soaked in a resist removal composition for 72 hours to obtain a silicon wafer fragment of an end-point weight. The change between the initial weight and the end-point weight may be less than 1g, for example, the change between the initial weight and the end-point weight is less than 0.5g, 0.3g, 0.1g, 0.01g, 0.005g or 0.001g.
於本發明的一實施例中，取去阻層組成物存放四週後，得到一存放後的去阻層組成物，去阻層組成物與存放後的去阻層組成物之濃度變化可小於10%，例如去阻層組成物與存放後的去阻層組成物之濃度變化小於8%、5%、3%、2%或1%。 In one embodiment of the present invention, after the deblocking layer composition is stored for four weeks, a deblocking layer composition after storage is obtained, and the concentration change between the deblocking layer composition and the deblocking layer composition after storage can be less than 10%, for example, the concentration change between the deblocking layer composition and the deblocking layer composition after storage is less than 8%, 5%, 3%, 2% or 1%.
於本發明的一實施例中，去阻層組成物於一低溫溫度之下係為非結晶且不會相分離，上述低溫溫度可介於0℃至50℃之間，例如低溫溫度介於0℃至40℃之間、3℃至40℃之間、或5℃至30℃之間，或者是例如低溫溫度約為5℃。 In one embodiment of the present invention, the deblocking layer composition is non-crystalline and does not phase separate at a low temperature, and the low temperature may be between 0°C and 50°C, for example, the low temperature is between 0°C and 40°C, between 3°C and 40°C, or between 5°C and 30°C, or for example, the low temperature is about 5°C.
於本發明的一實施例中，去阻層組成物可與一複合材料相容，複合材料可選自由304不銹鋼(SUS 304)、聚二醚酮(PolyEtherEtherKetone,PEEK)、聚四氟乙烯(PolyTetraFluoroEthylene,PTFE)、聚全氟烷氧基聚合物(PolyFluoroAlkoxy,PFA)、聚氯三氟乙烯聚合物(PolyChloroTriFluoroEthylene,PCTFE)、聚丙烯、聚苯硫醚(PolyPhenylene Sulfide,PPS)、全氟化彈性體(PerFluoro elastomer,PF S-10)、全氟化彈性體(KALREZ6375UP S-10)及玻璃纖維所組成之群組中的一種或多種。 In one embodiment of the present invention, the deblocking layer composition is compatible with a composite material, and the composite material can be selected from one or more of the group consisting of 304 stainless steel (SUS 304), polyether ketone (PEEK), polytetrafluoroethylene (PTFE), polyperfluoroalkoxy polymer (PFA), polychlorotrifluoroethylene polymer (PCTFE), polypropylene, polyphenylene sulfide (PPS), perfluoroelastomer (PF S-10), perfluoroelastomer (KALREZ6375UP S-10) and glass fiber.
根據本發明的第二態樣，提出一種使用上述去阻層組成物之去阻層方法，包含步驟：提供形成有一阻層之基板及上述去阻層組成物；以及使去阻層組成物與阻層接觸以移除阻層。 According to the second aspect of the present invention, a method for removing a resist layer using the resist layer removal composition is proposed, comprising the steps of: providing a substrate having a resist layer formed thereon and the resist layer removal composition; and bringing the resist layer removal composition into contact with the resist layer to remove the resist layer.
於本發明的一實施例中，可以浸泡或噴灑方式使去阻層組成物與阻層接觸，藉此移除阻層。 In one embodiment of the present invention, the barrier layer can be removed by bringing the barrier layer removal composition into contact with the barrier layer by immersion or spraying.
於本發明的一實施例中，基板可為矽晶圓基板。 In one embodiment of the present invention, the substrate may be a silicon wafer substrate.
於本發明的一實施例中，阻層可為含有錫、銦、銻金屬或其金屬氧化物的光阻層，阻層特別可為含有錫金屬或其金屬氧化物的光阻層。 In one embodiment of the present invention, the resist layer may be a photoresist layer containing tin, indium, antimony metal or its metal oxide, and the resist layer may be a photoresist layer containing tin metal or its metal oxide in particular.
於本發明的一實施例中，阻層可為圖案化阻層或尚未圖案化阻層。 In one embodiment of the present invention, the barrier layer may be a patterned barrier layer or a non-patterned barrier layer.
下文將配合圖式並詳細說明，使本發明的其他目的、優點、及新穎特徵更明顯。 The following will be accompanied by drawings and detailed descriptions to make other purposes, advantages, and novel features of the present invention more obvious.
10:基板 10: Substrate
20:阻層 20: Barrier layer
30:去阻層組成物 30: Remove the barrier layer composition
40:噴頭 40: Spray head
圖1A至圖1B顯示使用本發明的去阻層組成物的去阻層方法之示意圖。 Figures 1A and 1B are schematic diagrams showing a method for removing the barrier layer using the barrier layer composition of the present invention.
圖2顯示本發明實施例1及比較例2之去阻層組成物在室溫抽氣櫃經過不同時間之重量變化量示意圖。 Figure 2 shows a schematic diagram of the weight change of the deblocking layer composition of Example 1 and Comparative Example 2 of the present invention in a vacuum cabinet at room temperature after different periods of time.
以下提供本發明的不同實施例。這些實施例是用於說明本發明的技術內容，而非用於限制本發明的權利範圍。一實施例的一特徵可透過合適的修飾、置換、組合、分離以應用於其他實施例。 Different embodiments of the present invention are provided below. These embodiments are used to illustrate the technical content of the present invention, rather than to limit the scope of the present invention. A feature of an embodiment can be applied to other embodiments through appropriate modification, replacement, combination, and separation.
應注意的是，在本文中，除了特別指明者之外，具備「一」元件不限於具備單一的該元件，而可具備一或更多的該元件。 It should be noted that, in this document, unless otherwise specified, "having an element" is not limited to having a single element, but may have one or more elements.
此外，在本文中，除了特別指明者之外，「第一」、「第二」等序數，只是用於區別具有相同名稱的多個元件，並不表示它們之間存在位階、層級、執行順序、或製程順序。一「第一」元件與一「第二」元件可能一起出現在同一構件中，或分別出現在不同構件中。序數較大的一元件的存在不必然表示序數較小的另一元件的存在。 In addition, in this article, unless otherwise specified, ordinal numbers such as "first" and "second" are only used to distinguish multiple components with the same name, and do not indicate the existence of a hierarchy, level, execution order, or process order between them. A "first" component and a "second" component may appear together in the same component, or appear separately in different components. The existence of a component with a larger ordinal number does not necessarily indicate the existence of another component with a smaller ordinal number.
在本文中，除了特別指明者之外，所謂的特徵甲「或」(or)或「及/或」(and/or)特徵乙，是指甲單獨存在、乙單獨存在、或甲與乙同時存在；所謂的特徵甲「及」(and)或「與」(and)或「且」(and)特徵乙，是指甲與乙同時存在；所謂的「包括」、「包含」、「具有」、「含有」，是指包括但不限於此。 In this document, unless otherwise specified, the so-called feature A "or" or "and/or" feature B means that A exists alone, B exists alone, or A and B exist at the same time; the so-called feature A "and" or "and" or "and" feature B means that A and B exist at the same time; the so-called "include", "include", "have", "contain" means including but not limited to these.
此外，在本文中，除了特別指明者之外，一數值可涵蓋該數值的±10%的範圍，特別是該數值±5%的範圍。除了特別指明者之外，一數值範圍是由較小端點數、較小四分位數、中位數、較大四分位數、及較大端點數所定義的多個子範圍所組成。 In addition, in this document, unless otherwise specified, a numerical value may cover a range of ±10% of the numerical value, in particular, a range of ±5% of the numerical value. Unless otherwise specified, a numerical range is composed of multiple sub-ranges defined by the lower end point, the lower quartile, the median, the upper quartile, and the upper end point.
實施例1之配方 Formula of Example 1
本實施例之去阻層組成物包括酸類以及溶劑，將上述酸類以及溶劑均勻混合，形成去阻層組成物。其中，酸類之含量為5~20wt%、溶劑之含量為40~95wt%。此外，上述的酸類係為甲酸、乙酸、乙二酸、三氟乙酸、甲磺酸、乙磺酸、硝酸及鹽酸所組成之群組中的一種或多種，溶劑係為丙二醇甲醚醋酸 酯、丙二醇甲醚、異丙醇、甲基異丁基甲醇、甲基正戊酮、環己酮、二甲基亞碸、苯甲醚、乙二醇、乳酸乙酯及γ-丁內酯所組成之群組中的一種或多種。 The deblocking layer composition of this embodiment includes acids and solvents, and the acids and solvents are uniformly mixed to form a deblocking layer composition. The content of the acids is 5-20wt%, and the content of the solvent is 40-95wt%. In addition, the acids are one or more of the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid, nitric acid and hydrochloric acid, and the solvent is one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, isopropyl alcohol, methyl isobutyl carbinol, methyl n-amyl ketone, cyclohexanone, dimethyl sulfoxide, anisole, ethylene glycol, ethyl lactate and γ-butyrolactone.
實施例2之配方 Formula of Example 2
本實施例之去阻層組成物之製備方法與實施例1相同，差異在於本實施例之酸類之含量為0.1~15wt%、溶劑之含量為50~99.5wt%。此外，本實施例的酸類係為甲酸、乙酸、乙二酸、三氟乙酸、甲磺酸、乙磺酸、硝酸及鹽酸所組成之群組中的一種或多種，溶劑係為丙二醇甲醚醋酸酯、丙二醇甲醚、異丙醇、甲基異丁基甲醇、甲基正戊酮、環己酮、二甲基亞碸、苯甲醚、乙二醇、乳酸乙酯及γ-丁內酯所組成之群組中的一種或多種。 The preparation method of the deblocking layer composition of this embodiment is the same as that of embodiment 1, except that the content of the acid in this embodiment is 0.1-15wt%, and the content of the solvent is 50-99.5wt%. In addition, the acid in this embodiment is one or more of the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid, nitric acid and hydrochloric acid, and the solvent is one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, isopropyl alcohol, methyl isobutyl carbinol, methyl n-amyl ketone, cyclohexanone, dimethyl sulfoxide, anisole, ethylene glycol, ethyl lactate and γ-butyrolactone.
實施例3之配方 Formula of Example 3
本實施例之去阻層組成物之製備方法與實施例1相同，差異在於本實施例之去阻層組成物還包括界面活性劑，且本實施例之酸類之含量為0.1~15wt%、溶劑之含量為50~99.5wt%、界面活性劑之含量為0.001~3wt%。此外，本實施例的酸類係為甲酸、乙酸、乙二酸、三氟乙酸、甲磺酸、乙磺酸所組成之群組中的一種或多種，溶劑係為丙二醇甲醚醋酸酯、丙二醇甲醚、甲基正戊酮、環己酮、二甲基亞碸、苯甲醚、乳酸乙酯及γ-丁內酯所組成之群組中的一種或多種，且界面活性劑係為SINONATE系列、3M的Novec系列所組成之群組中的一種或多種。 The preparation method of the deblocking layer composition of this embodiment is the same as that of Example 1, except that the deblocking layer composition of this embodiment further includes a surfactant, and the content of the acid in this embodiment is 0.1-15wt%, the content of the solvent is 50-99.5wt%, and the content of the surfactant is 0.001-3wt%. In addition, the acid in this embodiment is one or more of the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, and ethanesulfonic acid, the solvent is one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, methyl n-amyl ketone, cyclohexanone, dimethyl sulfoxide, anisole, ethyl lactate, and γ-butyrolactone, and the surfactant is one or more of the group consisting of SINONATE series and 3M's Novec series.
實施例4之配方 Formula of Example 4
本實施例之去阻層組成物之製備方法與實施例1相同，差異在於本實施例之去阻層組成物還包括界面活性劑，且本實施例之酸類之含量為0.1~15wt%、溶劑之含量為50~99.5wt%、界面活性劑之含量為0.001~3wt%。此外， 本實施例的酸類係為甲酸、乙酸、乙二酸、三氟乙酸、甲磺酸、乙磺酸所組成之群組中的一種或多種，溶劑係為丙二醇甲醚醋酸酯、丙二醇甲醚、甲基正戊酮、環己酮、二甲基亞碸、苯甲醚、乳酸乙酯及γ-丁內酯所組成之群組中的一種或多種，且界面活性劑係為日信化學的OLFINE E系列、磐亞的PANNOX系列、AIR PRODUCTS的Surfynol系列以及Triton X-100所組成之群組中的一種或多種。 The preparation method of the deblocking layer composition of this embodiment is the same as that of Example 1, except that the deblocking layer composition of this embodiment further includes a surfactant, and the content of the acid in this embodiment is 0.1-15wt%, the content of the solvent is 50-99.5wt%, and the content of the surfactant is 0.001-3wt%. In addition, the acid of this embodiment is one or more of the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, and ethanesulfonic acid, the solvent is one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, methyl n-amyl ketone, cyclohexanone, dimethyl sulfoxide, anisole, ethyl lactate, and γ-butyrolactone, and the surfactant is one or more of the group consisting of Nissin Chemical's OLFINE E series, Pan Asia's PANNOX series, AIR PRODUCTS' Surfynol series, and Triton X-100.
實施例5之配方 Formula of Example 5
本實施例之去阻層組成物之製備方法與實施例1相同，差異在於本實施例之去阻層組成物還包括界面活性劑，且本實施例之酸類之含量為5~20wt%、溶劑之含量為40~95wt%、界面活性劑之含量為0.001~3wt%。此外，本實施例的酸類係為甲酸、乙酸、乙二酸、三氟乙酸、硝酸及鹽酸所組成之群組中的一種或多種，溶劑係為丙二醇甲醚醋酸酯、丙二醇甲醚、異丙醇、甲基異丁基甲醇、苯甲醚、乙二醇、乳酸乙酯及γ-丁內酯所組成之群組中的一種或多種，且界面活性劑係為日信化學的OLFINE E系列、磐亞的PANNOX系列、AIR PRODUCTS的Surfynol系列以及Triton X-100所組成之群組中的一種或多種。 The preparation method of the deblocking layer composition of this embodiment is the same as that of Example 1, except that the deblocking layer composition of this embodiment further includes a surfactant, and the content of the acid in this embodiment is 5-20wt%, the content of the solvent is 40-95wt%, and the content of the surfactant is 0.001-3wt%. In addition, the acid in this embodiment is one or more of the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, nitric acid and hydrochloric acid, the solvent is one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, isopropyl alcohol, methyl isobutyl carbinol, anisole, ethylene glycol, ethyl lactate and γ-butyrolactone, and the surfactant is one or more of the group consisting of Nissin Chemical's OLFINE E series, Pan Asia's PANNOX series, AIR PRODUCTS' Surfynol series and Triton X-100.
實施例6之配方 Formula of Example 6
本實施例之去阻層組成物之製備方法與實施例1相同，差異在於本實施例之酸類之含量為10~30wt%、溶劑之含量為30~90wt%。此外，本實施例的酸類係為甲酸、乙酸、乙二酸、三氟乙酸、甲磺酸、乙磺酸、硝酸及鹽酸所組成之群組中的一種或多種，溶劑係為丙二醇甲醚醋酸酯、丙二醇甲醚、異丙醇、甲基異丁基甲醇、甲基正戊酮、環己酮、二甲基亞碸、苯甲醚、乙二醇、乳酸乙酯及γ-丁內酯所組成之群組中的一種或多種。 The preparation method of the deblocking layer composition of this embodiment is the same as that of embodiment 1, except that the content of the acid in this embodiment is 10-30wt%, and the content of the solvent is 30-90wt%. In addition, the acid in this embodiment is one or more of the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid, nitric acid and hydrochloric acid, and the solvent is one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, isopropyl alcohol, methyl isobutyl carbinol, methyl n-amyl ketone, cyclohexanone, dimethyl sulfoxide, anisole, ethylene glycol, ethyl lactate and γ-butyrolactone.
實施例7之配方 Formula of Example 7
本實施例之去阻層組成物之製備方法與實施例1相同，差異在於本實施例之去阻層組成物還包括界面活性劑，且本實施例之酸類之含量為10~30wt%、溶劑之含量為30~90wt%、界面活性劑之含量為0.001~3wt%。此外，本實施例的酸類係為甲酸、乙酸、乙二酸、三氟乙酸、甲磺酸、乙磺酸所組成之群組中的一種或多種，溶劑係為丙二醇甲醚醋酸酯、丙二醇甲醚、甲基正戊酮、環己酮、二甲基亞碸、苯甲醚、乳酸乙酯及γ-丁內酯所組成之群組中的一種或多種，且界面活性劑係為SINONATE系列、3M的Novec系列所組成之群組中的一種或多種。 The preparation method of the deblocking layer composition of this embodiment is the same as that of embodiment 1, except that the deblocking layer composition of this embodiment further includes a surfactant, and the content of the acid in this embodiment is 10-30wt%, the content of the solvent is 30-90wt%, and the content of the surfactant is 0.001-3wt%. In addition, the acid in this embodiment is one or more of the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, and ethanesulfonic acid, the solvent is one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, methyl n-amyl ketone, cyclohexanone, dimethyl sulfoxide, anisole, ethyl lactate, and γ-butyrolactone, and the surfactant is one or more of the group consisting of SINONATE series and 3M's Novec series.
實施例8之配方 Formula of Example 8
本實施例之去阻層組成物之製備方法與實施例1相同，差異在於本實施例之去阻層組成物還包括界面活性劑，且本實施例之酸類之含量為10~30wt%、溶劑之含量為30~90wt%、界面活性劑之含量為0.001~3wt%。此外，本實施例的酸類係為甲酸、乙酸、乙二酸、三氟乙酸、甲磺酸、乙磺酸所組成之群組中的一種或多種，溶劑係為丙二醇甲醚醋酸酯、丙二醇甲醚、甲基正戊酮、環己酮、二甲基亞碸、苯甲醚、乳酸乙酯及γ-丁內酯所組成之群組中的一種或多種，且界面活性劑係為日信化學的OLFINE E系列、磐亞的PANNOX系列、AIR PRODUCTS的Surfynol系列以及Triton X-100所組成之群組中的一種或多種。 The preparation method of the deblocking layer composition of this embodiment is the same as that of Example 1, except that the deblocking layer composition of this embodiment further includes a surfactant, and the content of the acid in this embodiment is 10-30wt%, the content of the solvent is 30-90wt%, and the content of the surfactant is 0.001-3wt%. In addition, the acid in this embodiment is one or more of the group consisting of formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, and ethanesulfonic acid, the solvent is one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, methyl n-amyl ketone, cyclohexanone, dimethyl sulfoxide, anisole, ethyl lactate, and γ-butyrolactone, and the surfactant is one or more of the group consisting of Nissin Chemical's OLFINE E series, Pan Asia's PANNOX series, AIR PRODUCTS' Surfynol series, and Triton X-100.
比較例1 Comparison Example 1
比較例1為王水，其成分包括濃硝酸以及濃鹽酸，其中濃硝酸與濃鹽酸之比例係為1：3。 Comparative Example 1 is aqua regia, which contains concentrated nitric acid and concentrated hydrochloric acid, with the ratio of concentrated nitric acid to concentrated hydrochloric acid being 1:3.
比較例2 Comparison Example 2
比較例2為習知的去阻層組成物，商品名為OK-73，其成分包括丙二醇單甲基醚(PGME)與丙二醇單甲基醚酯(PGMEA)。 Comparative Example 2 is a known deblocking layer composition, the trade name is OK-73, and its ingredients include propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether ester (PGMEA).
去阻層組成物之清潔能力 Cleaning ability of barrier layer composition
將含有錫金屬或其金屬氧化物之阻層的矽晶圓破片浸泡於實施例1至實施例5或比較例中(室溫、30秒)，再將此溶液以ICP-MS進行分析，進而得到溶液中錫含量及錫(原子/cm2)等數值，如下表1所示。以錫(原子/cm2)數值及實施例1舉例計算清潔能力(%)，計算公式=(((比較例1-空白試驗)-(實施例1-空白試驗))/(比較例1-空白試驗))x100%。 A silicon wafer fragment containing a barrier layer of tin metal or its metal oxide was immersed in Examples 1 to 5 or Comparative Examples (room temperature, 30 seconds), and the solution was analyzed by ICP-MS to obtain the tin content and tin (atoms/cm 2 ) in the solution, as shown in Table 1. The cleaning ability (%) was calculated using the tin (atoms/cm 2 ) value and Example 1, and the calculation formula = (((Comparative Example 1-Blank Test)-(Example 1-Blank Test))/(Comparative Example 1-Blank Test)) x 100%.
去阻層組成物放置於室溫的抽氣櫃之重量變化量 Weight change of the barrier layer removal composition placed in a vacuum cabinet at room temperature
本測試方法係取第一重量之實施例1及比較例2之去阻層組成物置於100毫升燒杯內，並放置於室溫的抽氣櫃經過24小時後，分別得到第二重量之實施例1及比較例2之去阻層組成物，其重量變化量之計算如下式(1)所示。 This test method is to take the first weight of the de-blocking layer composition of Example 1 and Comparative Example 2 and place it in a 100 ml beaker, and place it in a vacuum hood at room temperature for 24 hours, and then obtain the second weight of the de-blocking layer composition of Example 1 and Comparative Example 2, and the weight change is calculated as shown in the following formula (1).
重量變化量=((第一重量-第二重量)/第一重量)x100% (1) Weight change = ((first weight - second weight) / first weight) x 100% (1)
如圖2所示，在經過24小時後，實施例1之去阻層組成物之重量變化量小於30%，比較例2之去阻層組成物之重量變化量小於60%。由此可知，實施例1之去阻層組成物放置於室溫抽氣櫃的耗損量較低，約僅為比較例2的0.5倍，得以減少去阻層組成物之使用量，以節省生產成本。 As shown in Figure 2, after 24 hours, the weight change of the de-blocking layer composition of Example 1 is less than 30%, and the weight change of the de-blocking layer composition of Comparative Example 2 is less than 60%. It can be seen that the de-blocking layer composition of Example 1 is less wasted when placed in a room temperature exhaust cabinet, which is only about 0.5 times that of Comparative Example 2, so that the use of the de-blocking layer composition can be reduced to save production costs.
矽晶圓破片浸泡於去阻層組成物之重量變化量 Weight change of silicon wafer fragments immersed in the resist removal composition
本測試方法係取初始重量之矽晶圓破片在室溫下浸泡於實施例1之去阻層組成物72小時後，矽晶圓破片以超純水清洗並用氮氣乾燥，得到終點重量之矽晶圓破片。 This test method is to take the initial weight of the silicon wafer fragments and soak them in the resist removal composition of Example 1 at room temperature for 72 hours. The silicon wafer fragments are then washed with ultrapure water and dried with nitrogen to obtain the final weight of the silicon wafer fragments.
如上表2所示，本發明實施例1之去阻層組成物與矽晶圓之相容性佳，不會對矽晶圓產生腐蝕性，因此實施例1之去阻層組成物適用於製備矽晶圓半導體。 As shown in Table 2 above, the resist removal composition of Example 1 of the present invention has good compatibility with silicon wafers and will not cause corrosion to silicon wafers. Therefore, the resist removal composition of Example 1 is suitable for preparing silicon wafer semiconductors.
去阻層組成物之濃度變化 Concentration variation of the deblocking layer composition
本測試方法係取實施例1及實施例5至實施例8之去阻層組成物存放兩週及四週後，分別得到實施例1及實施例5至實施例8之存放兩週的第一去阻層組成物及存放四週的第二去阻層組成物，其結果如下表3所示。 This test method is to take the deblocking layer composition of Example 1 and Example 5 to Example 8 and store it for two weeks and four weeks, and then obtain the first deblocking layer composition of Example 1 and Example 5 to Example 8 stored for two weeks and the second deblocking layer composition stored for four weeks, respectively. The results are shown in Table 3 below.
如上表3所示，可以發現本發明實施例1及實施例5至實施例6及實施例8在存放四週後的濃度變化小於3%，具有極佳的穩定性。 As shown in Table 3 above, it can be found that the concentration change of Example 1 and Example 5 to Example 6 and Example 8 of the present invention after storage for four weeks is less than 3%, and has excellent stability.
低溫下去阻層組成物之結晶性及相態 Crystallinity and phase state of barrier layer composition at low temperature
本測試方法係將本發明實施例1之去阻層組成物分別放置於5℃或23℃下存放24小時及48小時，並觀察其結晶性及相態。經過觀察發現，在5℃或23℃下分別存放24小時及48小時後，本發明實施例1之去阻層組成物皆為非結晶 且不會產生相分離。顯示本發明之去阻層組成物對於儲存環境之要求低，具有較佳的穩定性。 This test method is to place the de-blocking layer composition of Example 1 of the present invention at 5°C or 23°C for 24 hours and 48 hours, and observe its crystallinity and phase state. After observation, it was found that after being stored at 5°C or 23°C for 24 hours and 48 hours, the de-blocking layer composition of Example 1 of the present invention is non-crystalline and does not produce phase separation. It shows that the de-blocking layer composition of the present invention has low requirements for the storage environment and has better stability.
去阻層組成物與複合材料之相容性 Compatibility of barrier layer components and composite materials
本測試方法係取初始重量之複合材料浸泡於實施例1及比較例2中，經過24小時或48小時後，將複合材料使用超純水清洗並用氮氣乾燥，分別得到第一重量及第二重量之複合材料，其結果如下表4所示。 This test method is to soak the composite material of the initial weight in Example 1 and Comparative Example 2. After 24 hours or 48 hours, the composite material is washed with ultrapure water and dried with nitrogen to obtain the first weight and second weight composite materials respectively. The results are shown in Table 4 below.
如上表4所示，可發現本發明實施例1之去阻層組成物與上述複合材料的相容性佳，不會損傷上述任一種複合材料，可直接上機使用而無須進行其他更動。 As shown in Table 4 above, it can be found that the deblocking layer composition of Example 1 of the present invention has good compatibility with the above-mentioned composite materials and will not damage any of the above-mentioned composite materials. It can be used directly on the machine without making other changes.
使用上述去阻層組成物之去阻層方法 Deblocking method using the above-mentioned deblocking composition
如圖1A至圖1B所示，使用上述去阻層組成物30之去阻層方法包含步驟：提供形成阻層20之基板10及上述去阻層組成物30；以及使去阻層組成物30與阻層20接觸以移除阻層20。其中，圖1A是顯示透過設置在基板(設置於阻層20下方)及阻層20邊緣處上方及下方的兩個噴頭40噴灑去阻層組成物30，對阻層20的邊緣進行清潔；圖1B是顯示分別透過設置在基板10及阻層20的中心上方及邊緣處下方的兩個噴頭40噴灑去阻層組成物30，清潔阻層20。然而，本發明並不僅限於此。
As shown in FIG. 1A and FIG. 1B , the resist removal method using the resist
於本實施例中，基板10為矽晶圓基板，形成於基板10上的阻層20為含有錫金屬或其金屬氧化物的光阻層，且係透過噴頭40以噴灑方式使去阻層組成物30與阻層20接觸，藉此移除阻層20。
In this embodiment, the
綜上所述，本發明之去阻層組成物可有效去除晶圓或晶背上的阻層及金屬離子，且單一步驟即可同時進行清潔與去除金屬離子，因而具有優異的清潔能力。此外，本發明之去阻層組成物具有長時間存放之重量變化量低、濃度變化低、適用於製備矽晶圓半導體、低溫下為非結晶且不會產生相分離、或與複合材料之相容性佳等優點，可縮短製程時間、減少晶圓缺陷、提升製程速度與良率，對於半導體的生產將帶來諸多益處。 In summary, the resist removal composition of the present invention can effectively remove the resist layer and metal ions on the wafer or wafer back, and can simultaneously clean and remove metal ions in a single step, thus having excellent cleaning ability. In addition, the resist removal composition of the present invention has the advantages of low weight change and concentration change after long-term storage, is suitable for the preparation of silicon wafer semiconductors, is non-crystalline at low temperatures and does not produce phase separation, or has good compatibility with composite materials, etc. It can shorten the process time, reduce wafer defects, and improve the process speed and yield, which will bring many benefits to the production of semiconductors.
20:阻層 20: Barrier layer
30:去阻層組成物 30: Remove the barrier layer composition
40:噴頭 40: Spray head
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200424760A (en) * | 2002-09-30 | 2004-11-16 | Dongjin Semichem Co Ltd | Photoresist remover composition |
| TW200848954A (en) * | 2007-02-20 | 2008-12-16 | Samsung Electronics Co Ltd | Photoresist-stripping composition and method of stripping a photoresist film using the sam |
| TW201126286A (en) * | 2009-09-02 | 2011-08-01 | Wako Pure Chem Ind Ltd | Resist layer removing composition and method for removing a resist layer by using such composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200424760A (en) * | 2002-09-30 | 2004-11-16 | Dongjin Semichem Co Ltd | Photoresist remover composition |
| TW200848954A (en) * | 2007-02-20 | 2008-12-16 | Samsung Electronics Co Ltd | Photoresist-stripping composition and method of stripping a photoresist film using the sam |
| TW201126286A (en) * | 2009-09-02 | 2011-08-01 | Wako Pure Chem Ind Ltd | Resist layer removing composition and method for removing a resist layer by using such composition |
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