TW201632247A - Composition capable of absorbing pollutant in photomask and applications thereof - Google Patents
Composition capable of absorbing pollutant in photomask and applications thereof Download PDFInfo
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本發明涉及一種可吸收光罩中污染物質的組合物，特別是一種可吸收有機污染物質與氨氣及硫氧化合物等無機污染物質的組合物，以及該組合物在光罩上的應用。The present invention relates to a composition for absorbing contaminants in a reticle, and more particularly to a composition for absorbing organic pollutants and inorganic pollutants such as ammonia and sulphur oxides, and the use of the composition on a reticle.
依據目前的半導體元件製造技術，半導體元件的電路圖案是透過微影(lithography)製程將電路圖案轉印至矽晶圓的表面，具體而言是利用特定波長的光源投射通過光罩(photomask)的方式，將電路圖案轉印至矽晶圓的表面。為了在實現在單位面積上倍增半導體元件例如電晶體的數目，縮小半導體電路的線寬為其主要的技術方案，目前以波長193奈米的深紫外光（DUV）做為微影製程的曝光光源，可令半導體電路的最小線寬達到7~10奈米(nanometer, nm)。According to the current semiconductor device manufacturing technology, the circuit pattern of the semiconductor device is to transfer the circuit pattern to the surface of the germanium wafer through a lithography process, specifically, using a light source of a specific wavelength to project through a photomask. In a way, the circuit pattern is transferred to the surface of the germanium wafer. In order to achieve the number of semiconductor elements, such as transistors, multiplied by the unit area, the line width of the semiconductor circuit is reduced as its main technical solution. At present, deep ultraviolet light (DUV) with a wavelength of 193 nm is used as an exposure light source for the lithography process. The minimum line width of the semiconductor circuit can reach 7~10 nanometer (nm).
由於半導體元件的微小化，在半導體元件的製造過程中，光罩的缺陷會造成矽晶圓表面之電路圖案的扭曲或變形，即使只有奈米尺寸例如20nm~200nm的缺陷都會導致半導體電路圖案的損害。已知造成光罩缺陷的原因之一在於光罩的表面受到污染微粒(contamination particles)的污染；為了維持光罩在使用期間的品質，習知之一種方法係在光罩的表面設置一種光罩保護薄膜(pellicle)，用以防止污染物質掉落在光罩表面進而形成污染微粒。Due to the miniaturization of semiconductor components, defects in the mask may cause distortion or deformation of the circuit pattern on the surface of the wafer during the manufacturing process of the semiconductor device, even if only defects having a nanometer size such as 20 nm to 200 nm may cause a semiconductor circuit pattern. damage. One of the reasons known to cause reticle defects is that the surface of the reticle is contaminated by contamination particles; in order to maintain the quality of the reticle during use, a conventional method is to provide a reticle protection on the surface of the reticle. A pellicle is used to prevent contaminants from falling on the surface of the reticle to form contaminating particles.
然而，即使具有上述的光罩保護薄膜，實務上仍然無法完全避免污染物質對光罩表面所造成的污染，光罩之污染物質的來源或產生原因包括來自環境和內腔中產生的污染物質，前述的環境包括無塵室(clean room)、光罩的儲存環境(storage environment)和微影製程中的設備及化學品；這些化學物或汙染物仍可能經由光罩保護膜的通氣孔或薄膜而進入光罩的內腔中。另一方面，用於將光罩保護薄膜黏著於光罩表面的黏著劑以及光罩本身的框架黏著劑之中所含的成分，也會在微影製程中因為氣體逸出(outgassing)或其他原因而生成污染物質，一般而言有機(organic)的污染物質、無機(inorganic)的污染物質例如氨氣與硫氧化合物或其他污染物質會沈積或附著於光罩的表面逐漸形成一種薄霧(haze)，當污染物質(例如硫酸銨)累積至某一程度將會形成較大的結晶(crystal)或是微粒(particle)，進而在微影製程中與光罩的電路圖案一起聚焦並轉印至矽晶圓的表面，造成電路圖案的扭曲或變形。因此，如何在光罩的使用期間更為有效的吸收污染物質以預防薄霧的產生，已成為業界致力解決的問題之一。However, even with the above-mentioned reticle protective film, it is practically impossible to completely avoid the pollution caused by the pollutant on the surface of the reticle. The source or cause of the pollutant of the reticle includes the pollutants generated from the environment and the cavity, The foregoing environment includes a clean room, a storage environment for the reticle, and equipment and chemicals in the lithography process; these chemicals or contaminants may still pass through the vent or film of the reticle protective film. And into the inner cavity of the reticle. On the other hand, the adhesive contained in the adhesive for adhering the reticle protective film to the surface of the reticle and the frame adhesive of the reticle itself may also be outgassing or other in the lithography process. Causes of the formation of pollutants, generally organic pollutants, inorganic pollutants such as ammonia and sulphur oxides or other pollutants will deposit or adhere to the surface of the reticle to form a mist ( Haze), when a pollutant (such as ammonium sulfate) accumulates to a certain extent, it will form a large crystal or particle, and then focus and transfer with the circuit pattern of the reticle in the lithography process. As for the surface of the wafer, distortion or distortion of the circuit pattern is caused. Therefore, how to absorb pollutants more effectively during the use of the mask to prevent the generation of mist has become one of the problems that the industry is trying to solve.
於一方面，本發明提供一種可吸收光罩中污染物質的組合物，包括： 0~50重量百分比(wt%)吸附劑； 50~80 wt%二甲基聚丙氧基甲基氯化銨(Diethyl polypropoxy methylammonium chloride)；以及 0~50 wt%壓克力膠。In one aspect, the present invention provides a composition for absorbing contaminants in a reticle comprising: 0 to 50 weight percent (wt%) of adsorbent; 50 to 80 wt% of dimethylpolypropoxymethylammonium chloride ( Diethyl polypropoxy methylammonium chloride); and 0~50 wt% acrylic glue.
於某些具體實施例中，該吸附劑為硼酸或亞硫酸鈉。In some embodiments, the adsorbent is boric acid or sodium sulfite.
於某些具體實施例中，該吸附劑之含量為20~50 wt%，二甲基聚丙氧基甲基氯化銨之含量為45~80 wt%，且壓克力膠之含量為0~10 wt%。於一較佳具體實施例中，該壓克力膠之含量為1 wt%，更佳為0.9 wt%、0.8 wt%、0.7 wt%、0.6 wt%、0.5 wt%、0.4 wt%、0.3 wt%、0.2 wt%、0.1 wt%，或0 wt%(意思就是可以不要壓克力膠)。In some embodiments, the content of the adsorbent is 20-50% by weight, the content of dimethylpolypropyloxymethylammonium chloride is 45-80 wt%, and the content of the acrylic adhesive is 0~ 10 wt%. In a preferred embodiment, the content of the acrylic adhesive is 1 wt%, more preferably 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt. %, 0.2 wt%, 0.1 wt%, or 0 wt% (meaning that acrylic glue can be used).
於某些具體實施例中，該吸附劑之含量為0~15 wt%，二甲基聚丙氧基甲基氯化銨之含量為25~75 wt%，且壓克力膠之含量為25~75 wt%。於一較佳具體實施例中，該吸附劑之含量為1 wt%，更佳為0.9 wt%、0.8 wt%、0.7 wt%、0.6 wt%、0.5 wt%、0.4 wt%、0.3 wt%、0.2 wt%、0.1 wt%，或0 wt%(意思就是可以不要壓克力膠)。In some embodiments, the content of the adsorbent is 0 to 15 wt%, the content of dimethylpolypropyloxymethyl ammonium chloride is 25 to 75 wt%, and the content of the acrylic adhesive is 25~ 75 wt%. In a preferred embodiment, the adsorbent is present in an amount of 1 wt%, more preferably 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, or 0 wt% (meaning that acrylic glue can be used).
於另一方面，本發明提供一種延長光罩使用期限之方法，包含下列步驟： 提供一光罩，該光罩具有一表面，該表面上結合有一光罩保護膜組件，該光罩保護膜組件係由一框架及結合在框架頂面的透明薄膜構成，使透明薄膜會將框架頂面封閉，使框架具有一內腔壁面，且該光罩保護組件及光罩結合後會形成一內腔； 將一含有20~50 wt%吸附劑、45~80 wt%二甲基聚丙氧基甲基氯化銨以及0~10 wt%壓克力膠的第一組合物塗覆於該光罩保護膜組件的內腔壁面；以及 將一含有0~15 wt%吸附劑、25~75 wt%二甲基聚丙氧基甲基氯化銨以及25~75 wt%壓克力膠的第二組合物塗覆於該光罩保護膜組件之框架底面，可作為與光罩貼合之黏著劑。In another aspect, the present invention provides a method for extending the life of a reticle, comprising the steps of: providing a reticle having a surface having a reticle protective film assembly bonded thereto, the reticle protective film assembly The utility model is composed of a frame and a transparent film combined on the top surface of the frame, so that the transparent film will close the top surface of the frame, so that the frame has an inner cavity wall surface, and the reticle protection component and the reticle are combined to form an inner cavity; Applying a first composition containing 20 to 50 wt% of adsorbent, 45 to 80 wt% of dimethylpolypropoxymethylammonium chloride, and 0 to 10 wt% of acrylic rubber to the mask protective film a lumen wall of the component; and coating a second composition comprising 0-15% by weight of adsorbent, 25-75% by weight of dimethylpolypropyloxymethylammonium chloride, and 25 to 75 wt% of acrylic glue The bottom surface of the frame covering the reticle protective film assembly can serve as an adhesive for bonding to the reticle.
於某些具體實施例中，該方法進一步包含下列步驟： 將一含有20~50 wt%吸附劑、45~80 wt%二甲基聚丙氧基甲基氯化銨以及0~10 wt%壓克力膠的第一組合物塗覆於該光罩保護膜組件之框架頂面，可做為框架與透明薄膜貼合之黏著劑。In some embodiments, the method further comprises the steps of: comprising 20 to 50 wt% of adsorbent, 45 to 80 wt% of dimethylpolypropoxymethylammonium chloride, and 0 to 10 wt% of acrylic The first composition of the adhesive is applied to the top surface of the frame of the reticle protective film assembly, and can be used as an adhesive for bonding the frame to the transparent film.
於又一方面，本發明提供一種延長光罩使用期限的結構，包含： 一光罩，具有一表面； 一光罩保護膜組件，係包含一框架及貼合在框架頂面的一透明薄膜，經由透明薄膜將框架頂面封閉，使光罩保護膜組件具有一內腔壁面；係將光罩保護膜組件結合於光罩表面，使光罩保護膜組件與光罩形成一內腔； 一含有20~50 wt%吸附劑、45~80 wt%二甲基聚丙氧基甲基氯化銨以及0~10 wt%壓克力膠的第一組合物，係塗覆於該光罩保護膜組件的內腔壁面；以及 一含有0~15 wt%吸附劑、25~75 wt%二甲基聚丙氧基甲基氯化銨以及25~75 wt%壓克力膠的第二組合物，係塗覆於該光罩保護膜組件之框架底面，可作為與光罩貼合的黏著劑。In another aspect, the present invention provides a structure for extending the life of a photomask, comprising: a photomask having a surface; and a photomask protective film assembly comprising a frame and a transparent film attached to the top surface of the frame, The top surface of the frame is closed by a transparent film, so that the photomask protective film assembly has a cavity wall surface; the photomask protective film assembly is bonded to the surface of the photomask, and the photomask protective film assembly and the photomask form an inner cavity; a first composition of 20 to 50 wt% of adsorbent, 45 to 80 wt% of dimethylpolypropoxymethylammonium chloride, and 0 to 10 wt% of acrylic adhesive applied to the photomask protective film assembly a lumen wall; and a second composition comprising 0 to 15 wt% of adsorbent, 25 to 75 wt% of dimethylpolypropoxymethylammonium chloride, and 25 to 75 wt% of acrylic glue, The bottom surface of the frame covering the reticle protective film assembly can serve as an adhesive for bonding to the reticle.
於某些具體實施例中，該含有20~50 wt%吸附劑、45~80 wt%二甲基聚丙氧基甲基氯化銨以及0~10 wt%壓克力膠的第一組合物進一步塗覆於該光罩保護膜組件之框架頂面，可作為與透明薄膜貼合的黏著劑。In some embodiments, the first composition comprising 20 to 50 wt% of adsorbent, 45 to 80 wt% of dimethylpolypropoxymethylammonium chloride, and 0 to 10 wt% of acrylic gum is further The top surface of the frame coated on the reticle protective film assembly can be used as an adhesive for bonding to the transparent film.
以下配合圖式所描述的內容係為用於實現本發明上述之目的、實施例、技術特徵及其功效的較佳實施方式，並非用以限定本發明。The following description of the drawings is a preferred embodiment of the present invention, and is not intended to limit the invention.
除非另有定義，否則本文所用之所有的技術與科學術語具有與本發明所屬技術領域中之技術人員通常理解者相同的意義。All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined.
如本文所用，除非上下文明確指示，否則單數形式“一”、“一個”、“該”包含複數對象。因此，例如，提及“一樣本”包含複數個這樣的樣本以及本領域技術人員所知的等同物。As used herein, the singular forms "", "," Thus, for example, reference to "the same" includes a plurality of such references and equivalents as known to those skilled in the art.
如本文所用，術語“污染物質”意指會沈積或附著於光罩的表面而逐漸形成一薄霧的污染物質，當污染物質累積至某一程度將會形成較大的結晶或是微粒。污染物質包括但不限於有機的污染物質與無機的污染物質。該有機的污染物質包含但不限於β-氯乙酸乙酯(β-chloroethyl acetate)、1,3-二噁烷(1,3-Dioxane)、甲苯(toluene)、N-二甲氨基甲基叔丁基異丙基膦(N-dimethylamino methyl-tert-butyl-isopropyl phosphine)、1-丙氧基-2-丙醇(1-propoxy 2-propanol)、三乙基矽烷(triethylsilane)、1,2-丙二醇-2-醋酸鹽(1,2-propanediol, 2-acetate)、S-(3-羥丙基)硫代醋酸鹽 (S-(3-hydroxypropyl)thioacetate)、1-甲基-4-(1-甲基乙烯基)-環己烯(1-methyl-4-(1-methylethenyl)-cyclohexene)、1-丁醇(1- butanol)、苯,1-氯-2-(三氟甲基)- (benzene, 1-chloro-2-(trifluoromethyl)-)、2-丙酮,1-(乙醯氧基) (2-propanone, 1-(acetyloxy))、對二甲苯(p-xylene)、甲基2-丁氧基醋酸鹽(methyl 2-butoxy acetate)、3-庚酮(3-heptanone)、苯乙烯(styrene)、雙環[3.1.0]己-2-烯,2-甲基-5-(1-甲基乙基)- (bicyclo[3.1.0]hex-2-ene, 2-methyl-5-(1-methylethyl)-)、L-高絲胺酸,鄰-丙基(L-homoserine, o-propyl)、苯,1-乙基-2-甲基(benzene, 1-ethyl-2-methyl-)、苯,1,2,4-三甲基(benzene, 1,2,4-trimethyl)、苯,1,4-二乙基(benzene, 1,4-diethyl-)。該無機的污染物質包含但不限於氨氣(NH3 )與硫氧化合物(SOx)，如一氧化硫(SO)、二氧化硫(SO2 )、三氧化硫(SO3 )、一氧化二硫(S2 O)、一氧化硫二聚體(S2 O2 )。As used herein, the term "contaminant" means a contaminant that will deposit or adhere to the surface of the reticle to gradually form a mist that will form larger crystals or particles when the contaminant accumulates to some extent. Contaminants include, but are not limited to, organic pollutants and inorganic pollutants. The organic pollutants include, but are not limited to, β-chloroethyl acetate, 1,3-dioxane, toluene, N-dimethylaminomethyl N-dimethylamino methyl-tert-butyl-isopropyl phosphine, 1-propoxy 2-propanol, triethylsilane, 1,2 -1,2-propanediol, 2-acetate, S-(3-hydroxypropyl)thioacetate, 1-methyl-4- (1-methyl-4-(1-methylethenyl)-cyclohexene), 1-butanol, benzene, 1-chloro-2-(trifluoromethyl) Base)-(benzene, 1-chloro-2-(trifluoromethyl)-), 2-propanone, 1-propanone, 1-(acetyloxy), p-xylene , methyl 2-butoxy acetate, 3-heptanone, styrene, bicyclo[3.1.0]hex-2-ene, 2-methyl -5-(1-methylethyl)-(bicyclo[3.1.0]hex-2-ene, 2-methyl-5-(1-methylethyl)-), L-homoserine, o-propyl ( L-homoserine, o-propyl), benzene, 1-ethyl-2-methyl (benzene, 1-ethyl-2-methy L-), benzene, 1,2,4-trimethyl, benzene, 1,4-diethyl-benzene. The inorganic pollutants include, but are not limited to, ammonia (NH 3 ) and sulfur oxides (SOx) such as sulfur monoxide (SO), sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), and disulfide (S). 2 O), sulfur monoxide dimer (S 2 O 2 ).
如本文所用，術語“載體”意指可以與一吸附劑結合之化合物，使該吸附劑可與載體一起塗佈於一表面上。較佳地，該載體亦可吸附有機的污染物質。該載體係為離子液體(ionic liquid)，包含但不限於二甲基聚丙氧基甲基氯化銨(Diethyl polypropoxy methylammonium chloride)。As used herein, the term "carrier" means a compound that can be combined with an adsorbent such that the adsorbent can be applied to a surface with a carrier. Preferably, the carrier also adsorbs organic contaminants. The carrier is an ionic liquid including, but not limited to, Diethyl polypropoxy methylammonium chloride.
如本文所用，術語“吸附劑”意指與離子液體結合後可在末端形成一羥基(-OH)的無機酸，並可吸附無機的污染物質如氨氣(NH3 )以及硫氧化合物(SOx)。該吸附劑包含但不限於硼酸與亞硫酸。As used herein, the term "adsorbent" means a mineral acid that combines with an ionic liquid to form a hydroxyl group (-OH) at the end, and which adsorbs inorganic contaminants such as ammonia (NH 3 ) and sulfur oxides (SOx). ). The adsorbent includes, but is not limited to, boric acid and sulfurous acid.
本發明現將參照以下之實施例為更具體地描述，實施例的提供係為示範而非限制之目的。The invention will now be described in more detail with reference to the following examples, which are intended to be illustrative and not limiting.
實施例Example 11 本發明之組合物吸收無機的污染物質能力之分析Analysis of the ability of the composition of the invention to absorb inorganic pollutants
於本實施例中，使用傅立葉轉換遠紅外光譜儀(Fourier-Transform Infrared Spectrometer, FT-IR)測量分析本發明之組合物吸收無機的污染物質之能力。將載體二甲基聚丙氧基甲基氯化銨(樣本1)、載體二甲基聚丙氧基甲基氯化銨以氨氣處理(樣本2)、本發明組合物(含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸)(樣本3)，以及本發明組合物(含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸)以氨氣處理(樣本4)之各樣本分別置於傅立葉轉換遠紅外光譜儀中測量。結果分別如圖1A、1B、1C、1D所示。In this example, the ability of the composition of the present invention to absorb inorganic contaminants was measured using a Fourier-Transform Infrared Spectrometer (FT-IR) measurement. Carrier dimethylpolypropoxymethylammonium chloride (sample 1), carrier dimethylpolypropyloxymethylammonium chloride treated with ammonia (sample 2), composition of the invention (containing 50 wt% of carrier II) Methyl polypropoxymethylammonium chloride with 50 wt% boric acid) (Sample 3), and a composition of the invention (containing 50 wt% of carrier dimethylpolypropyloxymethylammonium chloride and 50 wt% of boric acid) Each sample of ammonia treatment (sample 4) was separately measured in a Fourier transform far infrared spectrometer. The results are shown in Figures 1A, 1B, 1C, and 1D, respectively.
如圖1A、1B所示，載體二甲基聚丙氧基甲基氯化銨在沒有氨氣處理的情況下(樣本1)以及有氨氣處理的情況下(樣本2)，此二樣本皆在波長約3400 cm-1 至3500 cm-1 之處有一吸收波鋒(如箭頭所指處所示，圖1A至圖1F所示為透光率，透光率越低表示吸收率越高)，表示載體二甲基聚丙氧基甲基氯化銨並不會吸收氨氣。As shown in Figures 1A and 1B, the carrier dimethylpolypropoxymethylammonium chloride is in the absence of ammonia treatment (sample 1) and in the case of ammonia treatment (sample 2). The wavelength of about 3400 cm -1 to 3500 cm -1 has an absorption wave front (as indicated by the arrow, the light transmittance is shown in Fig. 1A to Fig. 1F, and the lower the light transmittance, the higher the absorption rate). It indicates that the carrier dimethylpolypropyloxymethylammonium chloride does not absorb ammonia.
此外，如圖1C所示，本發明組合物(含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸)在沒有氨氣處理的情況下(樣本3)，亦在波長約3400 cm-1 至3500 cm-1 之處有一吸收波鋒(如箭頭所指處所示)，表示本發明之組合物尚未吸附有害物質。Furthermore, as shown in Figure 1C, the composition of the invention (containing 50 wt% of carrier dimethylpolypropoxymethylammonium chloride and 50 wt% of boric acid) in the absence of ammonia treatment (sample 3), A wavelength of about 3400 cm -1 to 3500 cm -1 has an absorption wave front (as indicated by the arrow), indicating that the composition of the present invention has not adsorbed harmful substances.
如圖1D所示，將本發明組合物(含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸)以氨氣處理(樣本4)後，在波長約3400 cm-1
至3500 cm-1
之處有二吸收波鋒(如箭頭所指處所示)，顯示本發明之組合物吸附了氨氣，而進行了如下的化學反應：
接著將上述樣本4再以硫氧化合物(SOx)處理(樣本5)後置於傅立葉轉換遠紅外光譜儀中測量。結果如圖1E所示，原本在波長約3400 cm-1
至3500 cm-1
之處的二吸收波鋒(如圖1D所示)消失，而在波長約3500 cm-1
之處具有一吸收波鋒(如圖1E箭頭所指處所示)，顯示本發明之組合物進一步吸附了硫氧化合物，而進行了如下的化學反應：
再接著將上述樣本5以氨氣處理(樣本6)後置於傅立葉轉換遠紅外光譜儀中測量。結果如圖1F所示，在波長約3400 cm-1
至3500 cm-1
之處又出現了二吸收波鋒(如箭頭所指處所示)，顯示本發明之組合物又進一步吸附了氨氣，而進行了如下的化學反應：
由本實施例可知，本發明所提供之組合物可吸收環境中無機的污染物質，特別是氨氣與硫氧化合物。It can be seen from the present examples that the composition provided by the present invention can absorb inorganic pollutants in the environment, particularly ammonia gas and sulfur oxides.
實施例Example 22 本發明之組合物吸收有機的污染物質能力之分析Analysis of the ability of the composition of the invention to absorb organic pollutants
於本實施例中，使用氣相色譜質譜儀(Gas Chromatography-Mass Spectrophotometer, GC-MS)測量分析本發明之組合物吸收有機的污染物質之能力。將未吸收有機揮發氣體之本發明載體二甲基聚丙氧基甲基氯化銨(樣本A)與已吸收有機揮發氣體之本發明載體二甲基聚丙氧基甲基氯化銨(樣本B)分別置於鋁盤上，於90°C加熱2小時後以氦氣作為載氣以氣相色譜質譜儀進行有機揮發氣體含量的分析，以總離子層析圖(Total Ions Chromatography, TIC)的積分面積代表有機揮發氣體之含量。結果顯示，未吸收有機揮發氣體之本發明載體二甲基聚丙氧基甲基氯化銨(樣本A)釋放的有機揮發氣體相對量為3.4 x 107 /g，而已吸收有機揮發氣體之本發明載體二甲基聚丙氧基甲基氯化銨(樣本B)經過加熱後會釋放有機揮發氣體，其釋放的有機揮發氣體相對量為8 x 109 /g。由此可知，本發明之載體二甲基聚丙氧基甲基氯化銨可吸收有機揮發氣體，減少光罩內腔環境中的有機揮發氣體之量。In this example, the ability of the composition of the present invention to absorb organic contaminants was measured using a Gas Chromatography-Mass Spectrophotometer (GC-MS). The carrier of the invention, dimethylpolypropoxymethylammonium chloride (sample A), which does not absorb organic volatile gases, and the carrier of the invention, dimethylpolypropoxymethylammonium chloride (sample B), which have absorbed organic volatile gases They were placed on an aluminum pan and heated at 90 °C for 2 hours. The content of organic volatile gases was analyzed by gas chromatography mass spectrometry using helium as a carrier gas. The total ion chromatogram (TIC) was integrated. The area represents the content of organic volatile gases. The results show that the relative amount of the organic volatile gas released by the carrier dimethylpolypropoxymethylammonium chloride (sample A) of the present invention which does not absorb the organic volatile gas is 3.4 x 10 7 /g, and the present invention which has absorbed the organic volatile gas The carrier, dimethylpolypropoxymethylammonium chloride (sample B), upon heating, releases organic volatile gases, which release a relative amount of organic volatile gas of 8 x 10 9 /g. It can be seen that the carrier of the present invention, dimethylpolypropoxymethylammonium chloride, can absorb organic volatile gases and reduce the amount of organic volatile gases in the environment of the reticle.
另外，將壓克力膠(有機膠，會釋放有機的污染物質)(樣本C)以及含有壓克力膠之本發明載體二甲基聚丙氧基甲基氯化銨(含有33 wt%載體二甲基聚丙氧基甲基氯化銨以及67 wt%壓克力膠)(樣本D)分別置於鋁盤上，於90°C加熱2小時後以氦氣作為載氣以氣相色譜質譜儀進行有機揮發氣體含量的分析，以總離子層析圖(TIC)的積分面積代表有機揮發氣體之含量。結果顯示，壓克力膠(樣本C)釋放的有機揮發氣體相對量為1.1 x 109 /g，而含有壓克力膠之本發明載體二甲基聚丙氧基甲基氯化銨(樣本D)釋放的有機揮發氣體相對量為1.1 x 108 /g。由此可知，含有本發明之載體二甲基聚丙氧基甲基氯化銨的組合物，可減少壓克力膠釋放有機揮發氣體之量。In addition, acrylic glue (organic gel, which will release organic pollutants) (sample C) and the carrier of the invention containing acrylonitrile dimethylpolypropoxymethylammonium chloride (containing 33 wt% of carrier II) Methyl polypropoxymethylammonium chloride and 67 wt% acrylic gel (sample D) were placed on an aluminum pan, heated at 90 ° C for 2 hours, and then gas was used as a carrier gas to gas chromatography mass spectrometer. The analysis of the content of the organic volatile gas is carried out, and the integrated area of the total ion chromatogram (TIC) represents the content of the organic volatile gas. The results showed that the relative amount of organic volatile gas released by the acrylic gel (sample C) was 1.1 x 10 9 /g, while the carrier of the invention, dimethylpolypropoxymethylammonium chloride containing acrylic adhesive (sample D) The relative amount of organic volatile gas released is 1.1 x 10 8 /g. From this, it is understood that the composition containing the carrier dimethylpolypropoxymethylammonium chloride of the present invention can reduce the amount of organic volatile gas released by the acrylic adhesive.
實施例Example 33 本發明之組合物於光罩上的應用Application of the composition of the invention to a photomask
於本實施例中，本發明之組合物係應用於光罩上，以吸收環境中的有機污染物質以及無機污染物質。請結合參閱圖2與圖3，圖2與圖3所示分別為一應用於半導體製程之光罩的平面構造圖及其構造斷面圖。In the present embodiment, the composition of the present invention is applied to a photomask to absorb organic pollutants and inorganic contaminants in the environment. Please refer to FIG. 2 and FIG. 3 together. FIG. 2 and FIG. 3 are respectively a planar structural view of a photomask applied to a semiconductor process and a structural sectional view thereof.
如圖2所示，在本實施例中，光罩10係應用於深紫外光(deep ultraviolet, DUV)微影製程，該光罩10具有一表面11，該表面11上具有一曝光區A1及一非曝光區A2，其中曝光區A1具有在光罩製程(photomask making process)中形成於光罩10之一表面11的電路圖案。As shown in FIG. 2, in the embodiment, the reticle 10 is applied to a deep ultraviolet (DUV) lithography process, and the reticle 10 has a surface 11 having an exposure area A1 and A non-exposed area A2, wherein the exposed area A1 has a circuit pattern formed on one surface 11 of the reticle 10 in a photomask making process.
如圖2及圖3所示，該光罩10的表面11貼合有一光罩保護薄膜組件2，該光罩保護薄膜包括：一透明薄膜21、一框架22、一框架黏著劑23、一薄膜黏著劑24以及一框內黏著層26。該框架黏著劑23係為本發明之組合物的一種配方，含有33 wt%載體二甲基聚丙氧基甲基氯化銨以及67 wt%壓克力膠。該薄膜黏著劑24以及該框內黏著層26亦為本發明之組合物的另一種配方，含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸。該光罩保護膜組件2之透明薄膜21係利用薄膜黏著劑24黏著於框架22的頂面，框架22的底面係利用框架黏著劑23貼合於光罩10的表面11的周圍，以將光罩10之曝光區域遮蔽A1，該透明薄膜21藉由框架22的支撐而不與光罩10接觸，並且在光罩保護膜組件和光罩10之間形成一內腔25，光罩保護膜組件2之框架22的其中一側壁221具有一通氣孔222用以令內腔25的氣壓和環境氣壓保持平衡，通氣孔222設有一過濾膜223用以防止污染物質或微粒侵入內腔25，該框內黏著層26係黏著於框架22形成的內腔壁面。As shown in FIG. 2 and FIG. 3, the surface 11 of the reticle 10 is attached with a reticle protective film assembly 2, and the reticle protective film comprises: a transparent film 21, a frame 22, a frame adhesive 23, and a film. Adhesive 24 and an adhesive layer 26 in the frame. The frame adhesive 23 is a formulation of the composition of the present invention comprising 33 wt% of a carrier of dimethylpolypropoxymethylammonium chloride and 67 wt% of an acrylic gum. The film adhesive 24 and the in-frame adhesive layer 26 are also another formulation of the compositions of the present invention comprising 50 wt% of carrier dimethylpolypropoxymethylammonium chloride and 50 wt% of boric acid. The transparent film 21 of the reticle protective film unit 2 is adhered to the top surface of the frame 22 by the film adhesive 24, and the bottom surface of the frame 22 is attached to the periphery of the surface 11 of the reticle 10 by the frame adhesive 23 to light The exposed area of the cover 10 shields A1, the transparent film 21 is not supported by the frame 22 by the support of the frame 22, and an inner cavity 25 is formed between the reticle protective film assembly and the reticle 10, and the reticle protective film assembly 2 One of the side walls 221 of the frame 22 has a venting hole 222 for balancing the air pressure of the inner cavity 25 with the ambient air pressure. The venting hole 222 is provided with a filtering membrane 223 for preventing intrusion of pollutants or particles into the inner cavity 25. The layer 26 is adhered to the inner wall surface formed by the frame 22.
透過上述方式將本發明之組合物應用於光罩時，含有本發明之組合物的一種配方(33 wt%載體二甲基聚丙氧基甲基氯化銨以及67 wt%壓克力膠)的框架黏著劑23除了提供黏著力之外，這種壓克力膠亦提供了緩衝之效果，可有效預防該光罩10因為該光罩保護膜組件22之加壓而變形，且載體二甲基聚丙氧基甲基氯化銨可有效減少壓克力膠釋放有機揮發氣體之量，預防有機的有害物質釋放至該內腔25中。When the composition of the present invention is applied to a reticle by the above method, a formulation containing the composition of the present invention (33 wt% of carrier dimethylpolypropyloxymethylammonium chloride and 67 wt% of acrylic gum) In addition to providing adhesion to the frame adhesive 23, the acrylic adhesive also provides a cushioning effect, which can effectively prevent the reticle 10 from being deformed by the pressure of the reticle protective film assembly 22, and the carrier dimethyl group Polypropoxymethylammonium chloride can effectively reduce the amount of organic volatile gas released by the acrylic glue and prevent the release of organic harmful substances into the inner cavity 25.
另一方面，含有本發明之組合物的另一種配方(50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸)的薄膜黏著劑24以及該框內黏著層26除了提供黏著力之外，載體二甲基聚丙氧基甲基氯化銨可吸附環境中的有機有害物質，而吸附劑硼酸則可吸附環境中的無機有害物質，特別是氨氣以及硫氧化合物。In another aspect, a film adhesive 24 comprising another formulation of the composition of the invention (50 wt% of carrier dimethylpolypropyloxymethylammonium chloride and 50 wt% of boric acid) and the in-frame adhesive layer 26 are provided in addition to In addition to the adhesion, the carrier dimethylpolypropoxymethylammonium chloride can adsorb organic harmful substances in the environment, while the adsorbent boric acid can adsorb inorganic harmful substances in the environment, especially ammonia gas and sulfur oxides.
由此可知，透過上述方式將本發明之組合物應用於光罩時，可以有效地降低光罩內腔環境中有機污染物質及無機污染物質的沈積，進而防止光罩表面形成薄霧、結晶及/或微粒，而延長光罩之壽命。Therefore, it can be seen that when the composition of the present invention is applied to the reticle by the above manner, the deposition of organic pollutants and inorganic pollutants in the luminal cavity environment can be effectively reduced, thereby preventing mist, crystallization and formation on the surface of the reticle. / or particles, and extend the life of the mask.
此外，上述作為框架黏著劑23、薄膜黏著劑24以及該框內黏著層26的本發明之組合物配方僅為本發明之較佳實施方式之一，並非用以侷限本案之專利範圍。Further, the composition of the composition of the present invention as the frame adhesive 23, the film adhesive 24, and the in-frame adhesive layer 26 is only one of the preferred embodiments of the present invention, and is not intended to limit the scope of the patent.
以上所述之實施例及/或實施方式，僅是用以說明實現本發明技術的較佳實施例及/或實施方式，並非對本發明技術的實施方式作任何形式上的限制，任何熟習本發明技術者，在不脫離本發明內容所揭露之技術手段的範圍，當可作些許之更動或修飾為其他等效的實施例，但仍應視為與本發明實質相同之技術或實施例。The embodiments and/or the embodiments described above are merely illustrative of preferred embodiments and/or implementations of the techniques of the present invention, and are not intended to limit the embodiments of the present invention in any way. A person skilled in the art may make some modifications or modifications to other equivalent embodiments without departing from the spirit and scope of the invention.
(A1)‧‧‧曝光區
(A2)‧‧‧非曝光區
(10)‧‧‧光罩
(11)‧‧‧第一表面
(21)‧‧‧透明薄膜
(22)‧‧‧光罩保護膜組件
(221)‧‧‧側壁
(222)‧‧‧通氣孔
(223)‧‧‧過濾膜
(23)‧‧‧框架黏著劑
(24)‧‧‧薄膜黏著劑
(25)‧‧‧內腔
(26)‧‧‧框內黏著層(A1) ‧ ‧ exposure area
(A2) ‧ ‧ non-exposed areas
(10) ‧‧‧Photomask
(11) ‧‧‧ first surface
(21)‧‧‧Transparent film
(22) ‧‧‧Photomask protective film assembly
(221)‧‧‧ Sidewall
(222) ‧ ‧ vents
(223) ‧‧‧Filter membrane
(23) ‧‧‧Frame Adhesive
(24) ‧‧‧film adhesive
(25) ‧‧‧ lumen
(26) ‧‧‧Adhesive layer in the frame
圖1為本發明組合物以傅立葉轉換遠紅外光譜儀(Fourier-Transform Infrared Spectrometer, FT-IR)分析之結果；圖1A之樣本為載體二甲基聚丙氧基甲基氯化銨(樣本1)；；圖1B之樣本為載體二甲基聚丙氧基甲基氯化銨以氨氣處理(樣本2)；圖1C之樣本為含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸的組合物(樣本3)；圖1D之樣本為含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸的組合物以氨氣處理(樣本4)；圖1E之樣本為含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸的組合物以氨氣處理後再以硫氧化合物(SOx)處理(樣本5)；圖1F之樣本為含有50 wt%載體二甲基聚丙氧基甲基氯化銨與50 wt%硼酸的組合物以氨氣處理後再以硫氧化合物(SOx)處理後再以氨氣處理(樣本6)。Figure 1 is a result of analysis of a composition of the present invention by Fourier-Transform Infrared Spectrometer (FT-IR); the sample of Figure 1A is a carrier of dimethylpolypropyloxymethylammonium chloride (Sample 1); The sample of Figure 1B is a carrier of dimethylpolypropyloxymethylammonium chloride treated with ammonia (sample 2); the sample of Figure 1C is containing 50 wt% of carrier dimethylpolypropoxymethylammonium chloride and 50 a composition of wt% boric acid (sample 3); a sample of FIG. 1D is a composition containing 50 wt% of carrier dimethylpolypropyloxymethylammonium chloride and 50 wt% of boric acid treated with ammonia gas (sample 4); The sample of 1E is a composition containing 50 wt% of carrier dimethylpolypropyloxymethylammonium chloride and 50 wt% of boric acid treated with ammonia gas and then treated with sulfur oxides (SOx) (sample 5); The sample was a composition containing 50 wt% of carrier dimethylpolypropoxymethylammonium chloride and 50 wt% of boric acid, treated with ammonia gas, treated with sulfur oxides (SOx), and treated with ammonia gas (sample 6). .
圖2為本發明組合物應用於光罩時，該光罩之一實施例的平面構造圖。Figure 2 is a plan view showing an embodiment of the reticle when the composition of the present invention is applied to a reticle.
圖3為圖2之光罩在III-III位置的構造斷面圖。Figure 3 is a cross-sectional view showing the structure of the reticle of Figure 2 at the position III-III.
(A1)‧‧‧曝光區 (A1) ‧ ‧ exposure area
(A2)‧‧‧非曝光區 (A2) ‧ ‧ non-exposed areas
(10)‧‧‧光罩 (10) ‧‧‧Photomask
(2)‧‧‧光罩保護膜組件 (2) ‧‧‧Photomask protective film assembly
(11)‧‧‧第一表面 (11) ‧‧‧ first surface
(21)‧‧‧透明薄膜 (21)‧‧‧Transparent film
(22)‧‧‧框架 (22) ‧‧‧Framework
(23)‧‧‧框架黏著劑 (23) ‧‧‧Frame Adhesive
(24)‧‧‧薄膜黏著劑 (24) ‧‧‧film adhesive
(25)‧‧‧內腔 (25) ‧‧‧ lumen
(26)‧‧‧框內黏著層 (26) ‧‧‧Adhesive layer in the frame
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104107825A TW201632247A (en) | 2015-03-11 | 2015-03-11 | Composition capable of absorbing pollutant in photomask and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104107825A TW201632247A (en) | 2015-03-11 | 2015-03-11 | Composition capable of absorbing pollutant in photomask and applications thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201632247A true TW201632247A (en) | 2016-09-16 |
| TWI562820B TWI562820B (en) | 2016-12-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104107825A TW201632247A (en) | 2015-03-11 | 2015-03-11 | Composition capable of absorbing pollutant in photomask and applications thereof |
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| TWI789737B (en) * | 2021-04-09 | 2023-01-11 | 美商微相科技股份有限公司 | Composition for absorbing contaminants in adhesive of photomask protective film and its application |
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| WO2014054530A1 (en) * | 2012-10-04 | 2014-04-10 | 東レ株式会社 | Conductive pattern fabrication method |
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