TWI529794B - Etch resistant alumina based coatings - Google Patents
Etch resistant alumina based coatings Download PDFInfo
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以下揭示案是關於微電子裝置之製造,具體言之(但不排他地)關於能夠使用光微影技術在基板上形成結構之層。詳言之,本發明是關於製造可用於光微影應用以及隨後蝕刻製程中以在基板上形成所需結構之材料以及塗膜的方法,以及其應用。 The following disclosure relates to the fabrication of microelectronic devices, and in particular (but not exclusively) to layers that are capable of forming structures on a substrate using photolithography. In particular, the present invention relates to methods of fabricating materials and coating films useful in photolithographic applications and subsequent etching processes to form desired structures on substrates, and applications thereof.
為滿足對較小電子產品之需求,不斷地努力增加封裝式微電子裝置之效能,同時使印刷電路板上之所述裝置的面積最小。 In order to meet the demand for smaller electronic products, there is an ongoing effort to increase the performance of packaged microelectronic devices while minimizing the area of the devices on the printed circuit board.
在不斷微型化中,難以降低高效能裝置之高度以及表面積尺寸(亦即密度)。一種除減小線寬外增加微電子裝置之組件密度的方法在於將一個裝置或積體電路(integrated circuit;IC)置於另一者上。實際上,此舉是藉由導電基板穿孔(through substrate via)將晶粒上之主動電路層(active circuit layer)與同一或不同晶粒上之另一主動電路層電耦合來達成。在半導體工業中,所述者最通常被稱為矽穿孔(through silicon via;TSV)。 In the current miniaturization, it is difficult to reduce the height of the high-performance device and the surface area size (ie, density). One method of increasing the density of components of a microelectronic device in addition to reducing the line width is to place one device or an integrated circuit (IC) on the other. In practice, this is accomplished by electrically coupling the active circuit layer on the die to another active circuit layer on the same or different die by a through substrate via. In the semiconductor industry, the latter is most commonly referred to as through silicon via (TSV).
此等垂直互連將相鄰或接近於晶粒一側之結合襯墊或其他導電元件與相鄰或接近於晶粒另一側之導電元件電耦合。舉例而言,經由後段製程(back-end-of-the-line;BEOL)或「後通孔方法(via last method)」、經由矽晶圓互連處理(例如)是藉由自晶圓背面至正面上之結合襯墊 形成深通孔來建構,所述晶圓含有大部分用於特定設計之電路。所形成之通孔常常在一端封閉,接著用導電材料填充,且在製造流程中進一步加工晶圓後,最後使其變薄以降低最終晶粒之厚度,足以獲得穿透基板互連。經由前段製程(front-end-of-the-line;FEOL)或「先通孔方法(via first method)」處理,在製造設計電路之前,在很大程度上形成通孔。所述「後通孔方法」更具挑戰性,因為一般而言,通孔與「先通孔方法」所產生之通孔相比深得多,且此等通孔之形成包含蝕刻或雷射加工穿過諸如矽以及氧化矽之層堆疊。 These vertical interconnects electrically couple bond pads or other conductive elements adjacent or adjacent to one side of the die to conductive elements adjacent or adjacent to the other side of the die. For example, via a back-end-of-the-line (BEOL) or a "via last method", via a germanium wafer interconnect process (for example) by backing from the wafer Bonding pad to the front Deep vias are formed for construction, and the wafer contains most of the circuitry for a particular design. The vias are often closed at one end, then filled with a conductive material, and further processed in the fabrication process, and finally thinned to reduce the thickness of the final die, sufficient to achieve a through substrate interconnection. Through-front-end-of-the-line (FEOL) or "via first method" processing, vias are formed to a large extent before the design circuit is fabricated. The "back via method" is more challenging because, in general, the vias are much deeper than the vias produced by the "first via method", and the formation of such vias includes etching or laser Processing through a layer stack such as tantalum and tantalum oxide.
形成穿透基板互連之複雜性在於難以執行蝕刻來在基板中產生如此深的狹窄孔。此等高縱橫比通孔常常形成於0.75-1.5毫米厚度基板上且應展現最小程度之側壁粗糙度以允許隨後製造步驟成功。封閉通孔可藉由經由光微影技術所產生之圖案蝕刻孔來形成。所述蝕刻主要在感應耦合電漿(inductive coupled plasma;ICP)反應器中進行,其中形成所述通孔之條件可能需要大量時間。另外,孔之深度難以控制且除非適當地保護,否則蝕刻劑可能會損傷基板上之特徵。 The complexity of forming a through-substrate interconnect is that it is difficult to perform etching to create such a deep narrow hole in the substrate. These high aspect ratio vias are often formed on a 0.75-1.5 mm thick substrate and should exhibit minimal sidewall roughness to allow subsequent fabrication steps to be successful. The closed vias can be formed by etching holes through a pattern created by photolithography. The etching is mainly performed in an inductive coupled plasma (ICP) reactor in which the conditions for forming the via holes may require a large amount of time. In addition, the depth of the holes is difficult to control and the etchant may damage features on the substrate unless properly protected.
通孔亦可藉由在基板中雷射加工孔來形成。穿過基板之高縱橫比通孔之雷射加工並不適合於許多應用。孔之深度難以控制,從而導致通孔過淺或過深。雷射加工亦為產生可影響晶圓中之鄰近結構的熱區之高溫製程且需要移除所產生之殘餘物。因此,在基板中蝕刻或雷射加工深的高 縱橫比孔可能在許多應用中有困難。 The via holes can also be formed by laser processing holes in the substrate. Laser processing of high aspect ratio vias through the substrate is not suitable for many applications. The depth of the hole is difficult to control, resulting in a shallow or too deep through hole. Laser processing is also a high temperature process that creates a hot zone that can affect adjacent structures in the wafer and requires removal of the resulting residue. Therefore, the etching or laser processing in the substrate is deep Aspect ratio holes can be difficult in many applications.
形成深的高縱橫比結構之第二複雜性在於所述結構之圖案完整性。特定層之圖案化常常藉由由基板之光阻劑旋塗、光阻劑曝光、光阻劑顯影、基板蝕刻以及光阻劑移除組成之多步製程執行。執行深通孔之蝕刻可能在蝕刻期間需要極厚光阻劑,因為環境亦會引起光阻劑之不當降解。因此,待蝕刻基板與防止基板之不當蝕刻之塗膜之間的蝕刻速率差應儘可能大。另外,根據所消耗之時間以及由使用所述厚抗蝕劑引起之ICP反應器的污染,塗覆所述厚抗蝕劑可能不切實際。因此,蝕刻用於圖案化之抗蝕劑以及基板的選擇性很重要。 A second complication of forming a deep high aspect ratio structure is the pattern integrity of the structure. Patterning of a particular layer is often performed by a multi-step process consisting of photoresist spin coating, photoresist exposure, photoresist development, substrate etching, and photoresist removal. Execution of deep via etch may require extremely thick photoresist during etching as the environment may also cause undue degradation of the photoresist. Therefore, the difference in etching rate between the substrate to be etched and the coating film for preventing improper etching of the substrate should be as large as possible. Additionally, coating the thick resist may be impractical depending on the time consumed and contamination of the ICP reactor caused by the use of the thick resist. Therefore, it is important to etch the resist for patterning and the selectivity of the substrate.
另外,具有高蝕刻選擇性之材料或硬質罩幕已用於線寬為65奈米以及65奈米以下之特徵的光微影形成中。因為在光微影加工期間圖案之線寬變化可由反射離開半導體基板上之下伏層的光之光學干涉引起,所以使用抗反射塗膜(anti-reflective coating;ARC)來避免此影響。為使所需加工步驟最少,在單個層中組合硬質罩幕層與ARC之性質是有益的。關於技術現狀,參考美國公開專利申請案第2008/0206578號。 In addition, materials with high etch selectivity or hard masks have been used in the formation of photolithography with features of line widths of 65 nm and below. Since the change in line width of the pattern during photolithography can be caused by optical interference of light reflected off the underlying layer on the semiconductor substrate, an anti-reflective coating (ARC) is used to avoid this effect. In order to minimize the number of processing steps required, it is beneficial to combine the properties of the hard mask layer with the ARC in a single layer. Regarding the state of the art, reference is made to U.S. Patent Application Serial No. 2008/0206578.
鑒於先前技術在圖案化以及蝕刻材料以能夠形成深的高縱橫比結構以及窄線寬方面之缺點,不斷需要開發新穎材料,其實質上減少形成圖案之材料的降解,改良對基板上所展示之設計的保護且改良深的高縱橫比以及其他通孔、孔以及結構之製造效率以及對其的控制。 In view of the shortcomings of prior art in patterning and etching materials to enable the formation of deep high aspect ratio structures and narrow line widths, there is a continuing need to develop novel materials that substantially reduce degradation of the patterned material and improve the display on the substrate. The design protects and improves the deep aspect ratio and the manufacturing efficiency and control of other through holes, holes and structures.
本發明之一目的在於提供用於需要高度抗蝕刻硬質罩幕之應用的新穎組合物,其在半導體製造製程中在用於蝕刻所需基板之環境中充分維持其厚度以及性質。 It is an object of the present invention to provide a novel composition for applications requiring a highly etch-resistant hard mask that sufficiently maintains its thickness and properties in an environment for etching a desired substrate in a semiconductor fabrication process.
本發明之另一目的在於提供基於氧化鋁聚合物以及鋁與有機矽氧化物之共聚物的新穎材料組合物,其符合硬質罩幕之需求。 Another object of the present invention is to provide a novel material composition based on an alumina polymer and a copolymer of aluminum and an organic cerium oxide, which meets the requirements of a hard mask.
本發明之另一目的在於提供一種在基板上製備硬質罩幕塗膜之方法。 Another object of the present invention is to provide a method of preparing a hard mask coating film on a substrate.
本發明之第四個目的在於提供一種溶劑系統,其使所述氧化鋁聚合物以及鋁與有機矽氧化物之共聚物穩定足以允許較長存放期而對其效能無不利限制。 A fourth object of the present invention is to provide a solvent system which stabilizes the alumina polymer and the copolymer of aluminum and organic cerium oxide sufficient to allow for a longer shelf life without unduly limiting its performance.
另一目的在於提供本發明之硬質罩幕,其亦充當半導體或尤其TSV製程中之抗反射塗膜以及硬質罩幕(蝕刻罩幕)。根據創新之抗反射塗膜意謂硬質罩幕亦充當底部抗反射塗膜。 Another object is to provide a hard mask of the present invention that also acts as an anti-reflective coating and a hard mask (etch mask) in semiconductor or especially TSV processes. According to the innovative anti-reflective coating, the hard mask also acts as a bottom anti-reflective coating.
再一目的在於提供積體電路中之層,其具有接近矽之熱膨脹係數(coefficient of thermal expansion;CTE)值。 A further object is to provide a layer in an integrated circuit having a coefficient of thermal expansion (CTE) value close to 矽.
最後,一目的在於提供具有如此好的光學性質以致將能夠實現良好微影加工以及膜之非犧牲性質的材料,此意謂硬質罩幕在裝置中可具有永久性光學功能。 Finally, it is an object to provide a material that has such good optical properties that it will enable good lithography and non-sacrificial properties of the film, which means that the hard mask can have a permanent optical function in the device.
本文主張以及描述此等以及其他目的,其與現有材料以及方法一起藉由本發明來達成。 This and other objects are claimed and described herein, which are achieved by the present invention in conjunction with existing materials and methods.
本發明是基於在半導體蝕刻製程中在基板上形成保 護性硬質罩幕層之觀點,其包括藉由溶液沈積將氧化鋁聚合物之溶液或膠態分散液塗覆於所述基板上之步驟,所述溶液或分散液是藉由在水以及催化劑存在下在溶劑或溶劑混合物中使至少一種氧化鋁前驅物之單體水解以及縮合來獲得。 The invention is based on forming a guarantee on a substrate in a semiconductor etching process The viewpoint of a protective hard mask layer comprising the step of applying a solution or a colloidal dispersion of an alumina polymer onto the substrate by solution deposition, the solution or dispersion being by water and a catalyst Obtained by hydrolyzing and condensing a monomer of at least one alumina precursor in a solvent or solvent mixture in the presence.
詳言之,較佳氧化鋁前驅物具有通式AlXn(OR1)3-n In particular, preferred alumina precursors have the general formula AlX n (OR 1 ) 3-n
其中R1是獨立地由氫、直鏈烷基、分支鏈烷基、環狀烷基以及芳基的族群中選出;X是獨立地由氯基、溴基、碘基、酯基、尤其醯基、硫酸酯基、硫基以及硝基所構成的族群中選出;n為介於0-3之間的整數;或(R2)mAlXn(OR1)2-n Wherein R 1 is independently selected from the group consisting of hydrogen, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an aryl group; X is independently a chloro group, a bromo group, an iodine group, an ester group, and especially an anthracene. Selected from the group consisting of a sulfhydryl group, a thio group, and a nitro group; n is an integer between 0 and 3; or (R 2 ) m AlX n (OR 1 ) 2-n
其中R1是獨立地由直鏈烷基、分支鏈烷基、環狀烷基以及芳基的族群中選出;R2是獨立地由羧酸、α-羥基羧酸、羧酸鹽、β-二酮、酯以及β-酮酯的族群中選出。 Wherein R 1 is independently selected from the group consisting of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an aryl group; and R 2 is independently a carboxylic acid, an α-hydroxycarboxylic acid, a carboxylate, β- Selected from the group of diketones, esters, and β-ketoesters.
更特定言之,本發明之主要特徵為技術方案1之表徵部分中所述之內容。 More specifically, the main feature of the present invention is the content described in the characterizing portion of the first aspect.
本發明獲得相當大的優點。因此,本發明之各種實施例適用於在TSV製程中製造硬質罩幕以在半導體基板上 形成高縱橫比通孔結構。此外,塗覆包含在微機電系統之製造中提供硬質罩幕以及在光微影圖案化中以抗反射塗膜形式執行。本發明材料亦可用於在雙金屬鑲嵌互連製造中提供硬質罩幕以及抗反射塗膜。 The invention achieves considerable advantages. Accordingly, various embodiments of the present invention are suitable for fabricating a hard mask on a semiconductor substrate in a TSV process A high aspect ratio via structure is formed. Furthermore, the coating comprises providing a hard mask in the manufacture of the MEMS and performing it in the form of an anti-reflective coating in photolithographic patterning. The materials of the present invention can also be used to provide hard masks and anti-reflective coatings in the fabrication of dual damascene interconnects.
隨後,將藉助於實施方式,參看隨附圖式來更仔細地檢驗本發明。 Subsequently, the invention will be examined more closely with the aid of the embodiments, with reference to the accompanying drawings.
基於以上討論,較佳實施例包涵新穎氧化鋁聚合物以及有機矽氧烷與氧化鋁之共聚物的製備溶液,其可在普通半導體製程中用於製造硬質罩幕塗膜。 Based on the above discussion, the preferred embodiment encompasses a preparation solution of a novel alumina polymer and a copolymer of an organic siloxane and alumina which can be used in the manufacture of a hard mask film in a conventional semiconductor process.
由多種無機或有機鋁前驅物合成組合物。組合物亦可視情況包含與鋁前驅物共聚合之有機矽烷前驅物。 The composition is synthesized from a variety of inorganic or organoaluminum precursors. The composition may also optionally comprise an organodecane precursor copolymerized with an aluminum precursor.
材料之組成可經選擇以使得其產生之材料可視情況使用普通光微影技術圖案化或吸收光微影製程中所用之所需波長之光。 The composition of the material can be selected such that the material from which it is produced can be patterned or absorbed by conventional photolithography techniques using light of the desired wavelength used in the photolithographic process.
所述材料藉由在溶劑中使含鋁前驅物與所添加之引起前驅物水解且縮合以產生寡聚以及聚合物質的水反應來製備。 The material is prepared by reacting an aluminum-containing precursor with a solvent which causes hydrolysis and condensation of the precursor to produce an oligomeric and polymeric substance in a solvent.
根據一實施例,使用多種不同前驅物(一種以上),此使得在調節更適合於應用之材料性質方面具有較大靈活性。 According to one embodiment, a plurality of different precursors (more than one) are used, which allows for greater flexibility in adjusting the material properties that are more suitable for the application.
所獲得之材料可使用無機酸或有機酸、β-二酮或β-二酮酯物質來膠溶以賦予在溶液狀態下改良之儲存穩定性。 The material obtained can be peptized using a mineral acid or an organic acid, a β-diketone or a β-diketone ester material to impart improved storage stability in a solution state.
所形成之氧化鋁聚合材料的主鏈由重複單元-Al-O-組 成,其可雜有(interrupted)視情況存在之與鋁配位的自有機酸或β-二酮衍生之配位體。 The main chain of the formed alumina polymeric material is composed of repeating units -Al-O-group It may be interrupted by an organic acid or a β-diketone-derived ligand coordinated to aluminum as the case may be.
根據一較佳實施例,上述種類之組合物可用作半導體製造中之硬質罩幕。其將具有高含量之鋁(原子)。 According to a preferred embodiment, the above-described composition can be used as a hard mask in the manufacture of semiconductors. It will have a high content of aluminum (atoms).
此外,材料可使用帶有可在沈積後藉由曝光來活化之官能基的有機酸、β-二酮或β-二酮酯物質來膠溶(peptize),從而允許藉由光微影技術使硬質罩幕材料圖案化。 Further, the material may be peptized using an organic acid, β-diketone or β-diketone ester material having a functional group which can be activated by exposure after deposition, thereby allowing photolithography to be used by photolithography. The hard mask material is patterned.
另外,材料可使用帶有吸收光微影應用中所用之波長(193-460奈米)的光之官能基之有機酸、β-二酮或β-二酮酯物質來膠溶,從而允許材料用於需要抗反射塗膜之應用中。因此,所形成之所述氧化鋁聚合材料的主鏈由雜有自膠溶劑衍生之官能基的重複單元-Al-O-組成。 Alternatively, the material may be peptized using an organic acid, beta-diketone or beta-diketone ester material having a functional group that absorbs light (193-460 nm) used in photolithography applications, thereby allowing materials Used in applications where an anti-reflective coating is required. Therefore, the main chain of the formed alumina polymeric material is composed of a repeating unit -Al-O- mixed with a functional group derived from a colloidal solvent.
所述材料可進一步藉由在溶劑中使上述鋁前驅物以及有機矽前驅物與引起前驅物水解且縮合以產生寡聚以及聚合物質之水反應來製備。 The material can be further prepared by reacting the above-described aluminum precursor and organic ruthenium precursor in a solvent with water which causes hydrolysis and condensation of the precursor to produce oligomerization and polymeraceous matter.
使用帶有可在沈積後藉由曝光而活化之官能基的有機矽前驅物允許使硬質罩幕材料圖案化。類似地,使用帶有吸收光微影應用中所用之波長(193-460奈米)的光之基團之有機矽前驅物允許材料用於需要抗反射塗膜之應用中。 The use of an organic germanium precursor with a functional group that can be activated by exposure after deposition allows the hard mask material to be patterned. Similarly, the use of organic germanium precursors with groups of light that absorbs wavelengths (193-460 nm) used in photolithography applications allows materials to be used in applications requiring antireflective coatings.
因此,所形成之氧化鋁聚合材料的主鏈由可雜有對於鋁前驅物所提及之膠溶劑(β-二酮、β-二酮酯或有機酸)以及矽烷前驅物上之有機取代基的重複單元-Al-O-以及 -Si-O-組成。 Thus, the backbone of the formed alumina polymeric material is miscible with the peptizer (β-diketone, β-diketone or organic acid) mentioned for the aluminum precursor and the organic substituent on the decane precursor. Repeat unit - Al-O- and -Si-O- composition.
接著所獲得之含有自前驅物反應回收之反應產物的溶液可在標準微影製造製程中作為硬質罩幕層塗覆於半導體裝置上。 The resulting solution containing the reaction product recovered from the precursor reaction can then be applied to the semiconductor device as a hard mask layer in a standard lithography manufacturing process.
可在眾多半導體應用中以及尤其在微影製程中應用所述溶液之方法由以下組成: The method of applying the solution in a wide variety of semiconductor applications, and particularly in lithography processes, consists of the following:
1.藉助於旋塗、縫塗、噴塗、滾塗或其他用於在液相狀態下使材料沈積之塗佈技術將溶液塗覆於半導體組件或基板之表面上。 1. Applying a solution to the surface of a semiconductor component or substrate by means of spin coating, slit coating, spray coating, roll coating or other coating technique for depositing material in a liquid phase.
2.視情況藉由穿過罩幕使乾燥塗膜曝露於所選波長之光下來圖案化所述塗膜,且使非曝光區顯影。 2. The coating film is optionally patterned by exposing the dried coating film to light of a selected wavelength through a mask and developing the non-exposed areas.
3.使所塗覆之層固化以在單個層中獲得硬質罩幕。隨後進行微影製程,其中需要在既定裝置中建構其他層。 3. Curing the applied layer to obtain a hard mask in a single layer. The lithography process is then carried out, in which other layers need to be constructed in a given device.
現轉向較佳前驅物,可注意到,在一實施例中,使用具有以下通式之前驅物(下文為「前驅物1」) Turning now to a preferred precursor, it can be noted that in one embodiment, a precursor having the following general formula (hereinafter "Precursor 1") is used.
AlXn(OR1)3-n AlX n (OR 1 ) 3-n
其中R1是獨立地由氫、直鏈烷基、分支鏈烷基、環狀烷基以及芳基的族群中選出;X是獨立地由氯基、溴基、碘基、酯基、尤其醯基、硫酸酯基、硫基以及硝基所構成的族群中選出;n為介於0-3之間的整數。 Wherein R 1 is independently selected from the group consisting of hydrogen, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an aryl group; X is independently a chloro group, a bromo group, an iodine group, an ester group, and especially an anthracene. Selected from the group consisting of a base, a sulfate group, a sulfur group, and a nitro group; n is an integer between 0 and 3.
進一步假定在n=3之情況下,亦包含諸如水合物以 及醚複合物之複合物。 Further assuming that in the case of n=3, such as hydrate is also included And a complex of ether complexes.
在第二個實施例中,使用具有以下通式之另一前驅物(下文為「前驅物2」) In the second embodiment, another precursor having the following general formula (hereinafter referred to as "precursor 2") is used.
(R2)mAlXn(OR1)2-n (R 2 ) m AlX n (OR 1 ) 2-n
其中R1是獨立地由直鏈烷基、分支鏈烷基、環狀烷基以及芳基的族群中選出;R2是獨立地由羧酸、α-羥基羧酸、羧酸鹽、β-二酮、酯以及β-酮酯的族群中選出;X是獨立地由氯基、溴基、碘基、酯基、尤其醯基、硫酸酯基、硫基以及硝基所構成的族群中選出;且m為介於0與2之間的整數;且n是由3-m確定之整數。 Wherein R 1 is independently selected from the group consisting of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an aryl group; and R 2 is independently a carboxylic acid, an α-hydroxycarboxylic acid, a carboxylate, β- Selected from the group of diketones, esters, and β-ketoesters; X is independently selected from the group consisting of a chloro group, a bromo group, an iodine group, an ester group, especially a thiol group, a sulfate group, a thio group, and a nitro group. And m is an integer between 0 and 2; and n is an integer determined by 3-m.
進一步假定在m=0之情況下,亦包含諸如水合物以及醚複合物之複合物。 It is further assumed that in the case of m = 0, a complex such as a hydrate and an ether complex is also included.
在第三個實施例中,使用具有以下通式之前驅物(下文為「前驅物3」) In the third embodiment, a precursor having the following general formula (hereinafter referred to as "precursor 3") is used.
(R3)k-Si-X4-k (R 3 ) k -Si-X 4-k
其中R3是獨立地由直鏈烷基、分支鏈烷基、環狀烷基、烯基(直鏈、環狀以及分支鏈)、炔基、環氧基、丙烯酸酯基、烷基丙烯酸酯基、雜環基、雜芳族基、芳族基(由1-6個環組成)、烷基芳族基(由1-6個環組成)、氰基烷基、異氰酸酯基烷基、胺基烷基、硫烷基、烷基胺基甲酸酯基、 烷基脲、烷氧基、醯氧基、羥基、氫以及氯-官能基的族群中選出,至少一個R3為所述前驅物中充當活化潛伏光活性催化劑時可反應之官能基的基團;X是獨立地由羥基、烷氧基、醯基、氯基、溴基、碘基以及烷基胺基的族群中選出;且n為介於0與3之間的整數。 Wherein R 3 is independently from linear alkyl, branched alkyl, cyclic alkyl, alkenyl (linear, cyclic, and branched), alkynyl, epoxy, acrylate, alkyl acrylate a heterocyclic group, a heteroaromatic group, an aromatic group (consisting of 1 to 6 rings), an alkylaromatic group (consisting of 1 to 6 rings), a cyanoalkyl group, an isocyanatoalkyl group, an amine Selected from the group of alkyl, sulfalkyl, alkyl urethane, alkyl urea, alkoxy, decyloxy, hydroxy, hydrogen, and chloro-functional groups, at least one R 3 being the precursor a group acting as a functional group reactive when a latent photoactive catalyst is activated; X is independently selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group, a chloro group, a bromo group, an iodine group, and an alkylamine group; And n is an integer between 0 and 3.
藉由經由水解使用一或多種上述前驅物進行聚合或共聚合所獲得之反應產物將具有由上述前驅物1-3(其中整數n=1)組成之組合物,將構成由以下重複單元組成之通式:-[Al-O1.5]a-[(R2)m-Al-O-]b-[(R3)k-Si-O2/3]c- The reaction product obtained by polymerization or copolymerization using one or more of the above precursors by hydrolysis will have a composition consisting of the above precursors 1-3 (in which the integer n = 1), and the composition consists of the following repeating units. General formula: -[Al-O 1.5 ] a -[(R 2 ) m -Al-O-] b -[(R 3 ) k -Si-O 2/3 ] c -
其中R2以及R3具有與上文相同之含義,且a、b以及c為基於用於獲得上述組合物之前驅物1-3之相對莫耳比的數值。 Wherein R 2 and R 3 have the same meanings as above, and a, b and c are values based on the relative molar ratios of the precursors 1-3 for obtaining the above composition.
所得硬質罩幕塗膜組合物在光阻劑顯影後具有傑出蝕刻效能。高鋁含量對於彼用途為較佳。 The resulting hard mask coating composition has excellent etching performance after photoresist development. High aluminum content is preferred for each use.
在有機矽烷前驅物在材料之水解以及縮合中用作共聚單體之情況下,折衷(trade off)存在以獲得展現足夠蝕刻選擇性之塗膜以及可使用光微影技術圖案化之材料。因此,實際上,20%至95%之Al含量為較佳且40%至90%之Al含量為更佳。 In the case where the organodecane precursor is used as a comonomer in the hydrolysis and condensation of the material, a trade off exists to obtain a coating film exhibiting sufficient etching selectivity and a material that can be patterned using photolithography. Therefore, in practice, 20% to 95% of the Al content is preferable and 40% to 90% of the Al content is more preferable.
為定製較佳組合物之性質,前驅物1至3可經選擇以致: - 一種前驅物將提供與形成深通孔之基板相比足夠的蝕刻選擇性且因此保護由其覆蓋之基板面積;- 一種前驅物將提供足夠存放期且用於控制所得組合物之分子量;- 一種前驅物將提供與形成深通孔之基板的足夠黏著力;- 一種前驅物將提供可藉由將能夠使用光微影技術實現材料之圖案化的潛伏催化劑活化之官能基;以及- 一種前驅物將提供能夠吸收光微影應用中所用之波長的光之官能基。 To tailor the properties of the preferred composition, precursors 1 through 3 can be selected such that: - a precursor will provide sufficient etch selectivity compared to the substrate forming the deep via and thus protect the area of the substrate covered by it; - a precursor will provide sufficient shelf life and be used to control the molecular weight of the resulting composition; A precursor will provide sufficient adhesion to the substrate forming the deep via; - a precursor will provide a functional group that can be activated by a latent catalyst capable of patterning the material using photolithography; and - a precursor The material will provide a functional group capable of absorbing light of the wavelengths used in photolithographic applications.
更特定言之,基團R1可由選自可存在烷氧基、氰基、胺基、酯或羰基官能基之C1-12烷基之有機取代基的族群中選出。所述烷基可視情況經鹵化,帶有至少一個鹵素原子(氟基、氯基、溴基或碘基)。所述烷基可為直鏈、分支鏈或含有環狀種類。含有上述基團之前驅物較佳可藉由蒸餾來純化。詳言之,含有1-6個碳原子之較短烷基鏈為較佳。含有1-4個碳原子之烷基鏈為最佳。 More specifically, the group R 1 may be selected from the group of organic substituents selected from C 1-12 alkyl groups which may be present in the alkoxy, cyano, amine, ester or carbonyl functional groups. The alkyl group may optionally be halogenated with at least one halogen atom (fluoro, chloro, bromo or iodo). The alkyl group may be a straight chain, a branched chain or a cyclic type. The precursor containing the above group is preferably purified by distillation. In particular, shorter alkyl chains containing from 1 to 6 carbon atoms are preferred. An alkyl chain having 1 to 4 carbon atoms is preferred.
基團R2可由羧酸、α-羥基羧酸、羧酸鹽、β-二酮、酯或β-酮酯的族群中選出,可存在鹵素、不飽和以及芳族官能基之C1-12烷基。含有上述基團之前驅物2較佳可藉由蒸餾來純化或經製備以致總金屬離子含量低於500ppb、較佳低於50ppb。詳言之,儘可能短的含有3-7個碳原子之烷基鏈為較佳。 The group R 2 may be selected from the group of carboxylic acids, α-hydroxycarboxylic acids, carboxylates, β-diketones, esters or β-ketoesters, and C 1-12 may be present in the halogen, unsaturated and aromatic functional groups. alkyl. The precursor 2 containing the above group may preferably be purified by distillation or prepared so that the total metal ion content is less than 500 ppb, preferably less than 50 ppb. In particular, an alkyl chain having 3 to 7 carbon atoms as short as possible is preferred.
含有4-6個碳原子之烷基鏈為最佳。更佳為含有有機 酸、β-二酮或β-二酮酯之實施例,其由亦含有可使用光微影技術聚合之官能基(諸如丙烯醯基、烷基丙烯醯基、丙烯酸酯基、烷基丙烯酸酯基以及環氧基官能基)的化合物組成。所述功能性化合物可含有5-12個碳原子。含有6-10個碳原子之烷基鏈為更佳。較佳實施例亦包含含有能夠吸收光微影加工中所用之波長的光之官能基之有機酸、β-二酮或β-二酮酯。尤其較佳光吸收實施例為芳族或聚芳族(含有2-6個芳環),其具有之取代基中至少一者為有機酸、β-二酮或β-二酮酯。 An alkyl chain having 4 to 6 carbon atoms is preferred. Better for organic Examples of acids, beta-diketones or beta-diketone esters which also contain functional groups which can be polymerized using photolithographic techniques (such as acrylonitrile, alkyl propylene sulfonyl, acrylate, alkyl acrylate) The composition of the compound of the group and the epoxy functional group). The functional compound may contain from 5 to 12 carbon atoms. An alkyl chain having 6 to 10 carbon atoms is more preferred. The preferred embodiment also includes an organic acid, a β-diketone or a β-diketonate containing a functional group capable of absorbing light of a wavelength used in photolithography. Particularly preferred light absorbing examples are aromatic or polyaromatic (containing 2-6 aromatic rings) having at least one of the substituents being an organic acid, a beta-diketone or a beta-diketonate.
基團R3可經選擇以使得可在加熱期間進行進一步反應,允許材料進一步密化(亦即交聯)。更佳為允許使用可在標準微影製程中活化以產生可圖案化之塗膜的潛伏催化劑之彼等官能基。所述取代基包含C1-12烯基、C1-12炔基、C1-12丙烯酸酯基、C1-12烷基丙烯酸酯基以及C1-12環氧基。較佳烯基以及炔基由1-6個碳原子組成,諸如乙烯基、烯丙基、丁烯基、戊烯基、己烯基、丁二烯基、戊二烯基、己二烯基、乙醯基、炔丙基、丁炔基、戊炔基以及己炔基。丙烯醯基、烷基丙烯醯基、丙烯酸酯基、烷基丙烯酸酯基取代基較佳由1-7個碳原子組成,其可雜有雜原子。更佳為允許使用可在標準微影製程中活化以產生可圖案化之塗膜的潛伏催化劑之彼等官能基。較佳丙烯酸酯基取代基含有丙烯酸甲酯以及丙烯酸乙酯。較佳烷基丙烯酸酯基取代基由甲基丙烯酸甲酯、乙基丙烯酸甲酯、甲基丙烯酸乙酯以及乙基丙烯酸乙酯組成。環氧基取代基較佳由1-8個碳 原子組成,其可雜有雜原子。較佳環氧基取代基為例如縮水甘油氧基丙基以及乙基-(3,4-環己基環氧基)。使用含有官能基烯基、炔基、環氧基、丙烯酸酯基以及烷基丙烯酸酯基之取代基可使得材料在與可藉由曝露於所需波長之光而活化的潛伏催化劑組合使用時成為光可圖案化材料。 The group R 3 can be selected such that further reaction can be carried out during heating, allowing the material to be further densified (ie, crosslinked). More preferably, it is allowed to use such functional groups of a latent catalyst which can be activated in a standard lithography process to produce a patternable coating film. The substituent includes a C 1-12 alkenyl group, a C 1-12 alkynyl group, a C 1-12 acrylate group, a C 1-12 alkyl acrylate group, and a C 1-12 epoxy group. Preferred alkenyl and alkynyl groups consist of from 1 to 6 carbon atoms, such as ethenyl, allyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl , ethenyl, propargyl, butynyl, pentynyl and hexynyl. The propylene fluorenyl group, the alkyl propylene sulfhydryl group, the acrylate group, and the alkyl acrylate group substituent are preferably composed of 1 to 7 carbon atoms, which may be hetero atom-containing. More preferably, it is allowed to use such functional groups of a latent catalyst which can be activated in a standard lithography process to produce a patternable coating film. Preferred acrylate-based substituents contain methyl acrylate and ethyl acrylate. Preferred alkyl acrylate substituents consist of methyl methacrylate, ethyl methacrylate, ethyl methacrylate and ethyl ethacrylate. The epoxy substituent preferably consists of from 1 to 8 carbon atoms which may be heteroatomized. Preferred epoxy substituents are, for example, glycidoxypropyl and ethyl-(3,4-cyclohexyl epoxy). The use of a substituent containing a functional alkenyl group, an alkynyl group, an epoxy group, an acrylate group, and an alkyl acrylate group allows the material to be used in combination with a latent catalyst that can be activated by exposure to light of a desired wavelength. Light can pattern the material.
基團R3亦可經選擇以致所得反應產物具有吸收光微影加工中所用之波長的光之能力。所述取代基包含C1-12烯基、C1-12炔基、C1-12丙烯酸酯基、C1-12烷基丙烯酸酯基、C6-C36芳族基以及C6-C36雜芳族基。更佳為可藉由蒸餾來純化之芳族化合物。較佳芳族基可含有諸如C1-6烷基、C1-6醯基、C1-6烷氧基、硝基、胺基以及鹵素官能基之取代基。尤其較佳為如下基團:可獨立地選擇且聯合使用以便在材料於半導體基板上固化後調節材料在所需波長下之光學性質(諸如折射率以及消光係數)。 The group R 3 can also be selected such that the resulting reaction product has the ability to absorb light of the wavelengths used in photolithographic processing. The substituent includes a C 1-12 alkenyl group, a C 1-12 alkynyl group, a C 1-12 acrylate group, a C 1-12 alkyl acrylate group, a C 6 -C 36 aromatic group, and a C 6 -C group. 36 heteroaromatic groups. More preferred is an aromatic compound which can be purified by distillation. Preferred aromatic groups may contain substituents such as C 1-6 alkyl, C 1-6 fluorenyl, C 1-6 alkoxy, nitro, amine and halogen functional groups. Particularly preferred are groups which can be independently selected and used in combination to adjust the optical properties (such as refractive index and extinction coefficient) of the material at a desired wavelength after the material is cured on the semiconductor substrate.
適合於前驅物1之化合物的明確實例包含氫氧化鋁、甲醇鋁、乙醇鋁、異丙醇鋁、第二丁醇鋁、氯化鋁(以及其他鹵化鋁酸鹽,包含其錯合物以及水合物)、硝酸鋁(包含其水合物)、硫酸鋁(包含其水合物)以及烷氧基與鹵化鋁前驅物之組合(諸如氯二異丙氧基鋁),以及任何其他由可在水解/縮聚期間輕易自鋁裂解之官能基組成的其他前驅物。 Clear examples of compounds suitable for precursor 1 include aluminum hydroxide, aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, aluminum second butoxide, aluminum chloride (and other aluminum halides, including complexes thereof and hydration) , aluminum nitrate (including hydrates thereof), aluminum sulfate (including hydrates thereof), and a combination of alkoxy groups and aluminum halide precursors (such as aluminum chlorodisisopropoxide), and any other Other precursors that are readily composed of functional groups that are cleaved from aluminum during polycondensation.
適合於前驅物2之明確實例包含上述相關鋁前驅物,其中以共價鍵形式或經由配位包含有機基團R2。所述化合物為2,4-戊二酮、3-甲基-2,4-戊二酮、3-乙基-2,4-戊二酮、 3-丙基-2,4-戊二酮、3,3-二甲基-2,4-戊二酮、3,5-庚二酮、4-甲基-3,5-庚二酮、4-乙基-3,5-庚二酮、4-丙基-3,5-庚二酮、4,4-二甲基-3,5-庚二酮、6-甲基-2,4-庚二酮、1-苯基-1,3-丁二酮、1,1,1-三氟-2,4-戊二酮、3-氯-2,4-戊二酮、2-乙醯基環戊酮、2-乙醯基環己酮、乙醯乙酸甲酯、2-甲基乙醯乙酸乙酯、2-乙基乙醯乙酸甲酯、乙醯乙酸乙酯、丙醯乙酸乙酯、3-側氧基戊酸甲酯、乙醯乙酸異丙酯、2,4-二側氧基戊酸乙酯、3-側氧基己酸甲酯、4-甲基-3-側氧基戊酸甲酯、乙醯基乙醯乙酸烯丙酯、2-甲基-3-側氧基-戊-4-烯酸甲酯、4-甲氧基乙醯乙酸甲酯、2-羥基-2-甲基-3-側氧基丁酸甲酯、2-側氧基環戊烷甲酸甲酯、2-側氧基環己烷甲酸甲酯、2-側氧基環戊烷甲酸乙酯、2-側氧基環己烷甲酸乙酯、2-乙基乙醯乙酸乙酯、3-側氧基庚酸甲酯、乙醯乙酸異丁酯、4,4-二甲基-3-側氧基戊酸甲酯、異丁醯基乙酸乙酯、C1-12烷基羧酸、C1-12不飽和羧酸以及C1-12芳族羧酸。 A clear example of a suitable precursor 2 comprises the above-mentioned related aluminum precursor, wherein the organic group R 2 is contained in the form of a covalent bond or via coordination. The compound is 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-propyl-2,4-pentanedione , 3,3-dimethyl-2,4-pentanedione, 3,5-heptanedione, 4-methyl-3,5-heptanedione, 4-ethyl-3,5-heptanedione , 4-propyl-3,5-heptanedione, 4,4-dimethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione, 1-phenyl-1, 3-butanedione, 1,1,1-trifluoro-2,4-pentanedione, 3-chloro-2,4-pentanedione, 2-ethenylcyclopentanone, 2-ethenyl ring Hexanone, ethyl acetate, ethyl 2-methylacetate, ethyl 2-ethylacetate, ethyl acetate, ethyl acetate, methyl 3-oxovalerate , isopropyl acetate, isopropyl 2,4-dioxy valerate, methyl 3-oxohexanoate, methyl 4-methyl-3-oxo-pentanoate, ethyl ethane Allyl acetate, methyl 2-methyl-3-oxo-pent-4-enoate, methyl 4-methoxyacetate, 2-hydroxy-2-methyl-3-oxo Methyl butyrate, methyl 2-oxocyclopentanecarboxylate, methyl 2-oxocyclohexanecarboxylate, ethyl 2-oxocyclopentanecarboxylate, 2-oxocyclohexane Ethyl formate, ethyl 2-ethylacetate, 3-side Methyl heptyl group, acetyl isobutyl acetate, 4,4-dimethyl-3-oxo-pentanoate, ethyl isobutyl acyl, C 1-12 alkylcarboxylic acids, C 1-12 Unsaturated carboxylic acid and C 1-12 aromatic carboxylic acid.
可使用潛伏光活性催化劑活化之適合前驅物3的明確實例包含甲基丙烯醯氧基丙基三甲氧基矽烷、甲基丙烯醯氧基丙基三乙氧基矽烷、甲基丙烯醯氧基丙基三丙氧基矽烷、甲基丙烯醯氧基丙基參(異丙氧基)矽烷、甲基丙烯醯氧基丙基三氯矽烷、甲基丙烯醯氧基丙基甲基二甲氧基矽烷、甲基丙烯醯氧基丙基甲基二乙氧基矽烷、丙烯醯氧基丙基三甲氧基矽烷、丙烯醯氧基丙基三乙氧基矽烷、丙烯醯氧基丙基三丙氧基矽烷、丙烯醯氧基丙基參(異丙氧基)矽烷、丙烯醯氧基丙基三氯矽烷、丙烯醯氧基丙基甲基二 甲氧基矽烷、丙烯醯氧基丙基甲基二乙氧基矽烷、甲基甲基丙烯醯氧基丙基三甲氧基矽烷、甲基甲基丙烯醯氧基丙基三乙氧基矽烷、甲基甲基丙烯醯氧基丙基三丙氧基矽烷、甲基甲基丙烯醯氧基丙基參(異丙氧基)矽烷、甲基甲基丙烯醯氧基丙基三氯矽烷、甲基甲基丙烯醯氧基丙基甲基二甲氧基矽烷、甲基甲基丙烯醯氧基丙基甲基二乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷、甲基丙烯醯氧基丙基三乙氧基矽烷、甲基丙烯醯氧基丙基三丙氧基矽烷、甲基丙烯醯氧基丙基參(異丙氧基)矽烷、甲基丙烯醯氧基丙基三氯矽烷、甲基丙烯醯氧基丙基甲基二甲氧基矽烷、甲基丙烯醯氧基丙基甲基二乙氧基矽烷、縮水甘油氧基丙基三甲氧基矽烷、縮水甘油氧基丙基三乙氧基矽烷、縮水甘油氧基丙基三丙氧基矽烷、縮水甘油氧基丙基參(異丙氧基)矽烷、縮水甘油氧基丙基三氯矽烷、縮水甘油氧基丙基甲基二甲氧基矽烷、縮水甘油氧基丙基甲基二乙氧基矽烷、乙基-(3,4-環己基環氧基)三甲氧基矽烷、乙基-(3,4-環己基環氧基)三乙氧基矽烷、乙基-(3,4-環己基環氧基)三丙氧基矽烷、乙基-(3,4-環己基環氧基)三(異丙氧基)矽烷、乙基-(3,4-環己基環氧基)三氯矽烷、乙基-(3,4-環己基環氧基)甲基二甲氧基矽烷以及乙基-(3,4-環己基環氧基)甲基二乙氧基矽烷。 A clear example of a suitable precursor 3 that can be activated using a latent photoactive catalyst comprises methacryloxypropyltrimethoxydecane, methacryloxypropyltriethoxydecane, methacryloxypropane Tris-propoxydecane, methacryloxypropyl propylene (isopropoxy) decane, methacryloxypropyltrichlorodecane, methacryloxypropylmethyldimethoxy Decane, methacryloxypropylmethyldiethoxydecane, propyleneoxypropyltrimethoxydecane, propyleneoxypropyltriethoxydecane, propyleneoxypropyltripropoxide Base decane, propylene methoxy propyl stilbene (isopropoxy) decane, propylene methoxy propyl trichloro decane, propylene methoxy propyl methyl 2 Methoxydecane, propylene methoxy propyl methyl diethoxy decane, methyl methacryloxypropyl trimethoxy decane, methyl methacryloxypropyl triethoxy decane, Methyl methacryloxypropyltripropoxy decane, methyl methacryloxypropyl propylene (isopropoxy) decane, methyl methacryloxypropyl trichloro decane, A Methyl propylene methoxy propyl methyl dimethoxy decane, methyl methacryloxypropyl methyl diethoxy decane, methacryloxypropyl trimethoxy decane, methyl Propylene methoxypropyltriethoxy decane, methacryloxypropyltripropoxydecane, methacryloxypropyl propylene (isopropoxy)decane, methacryloxypropane Trichlorodecane, methacryloxypropylmethyldimethoxydecane, methacryloxypropylmethyldiethoxydecane, glycidoxypropyltrimethoxydecane, glycidol Oxypropyl triethoxy decane, glycidoxypropyl tripropoxy decane, glycidoxypropyl ginseng (isopropoxy) decane, glycidol Propyltrichlorodecane, glycidoxypropylmethyldimethoxydecane, glycidoxypropylmethyldiethoxydecane, ethyl-(3,4-cyclohexylcyclooxy)trimethyl Oxydecane, ethyl-(3,4-cyclohexyl epoxy)triethoxydecane, ethyl-(3,4-cyclohexyl epoxy)tripropoxydecane, ethyl-(3, 4-cyclohexyl epoxy) tris(isopropoxy)decane, ethyl-(3,4-cyclohexyl epoxy)trichlorodecane, ethyl-(3,4-cyclohexyl epoxy)-methyl Dimethoxy decane and ethyl-(3,4-cyclohexyl epoxy)methyldiethoxy decane.
可用於調節所得材料之光學性質的適合前驅物3之明確實例為苯基三甲氧基矽烷、苯基三乙氧基矽烷、苯基三丙氧基矽烷、苯基參(異丙氧基)矽烷、苯基三氯矽烷、萘 基三甲氧基矽烷、萘基三乙氧基矽烷、萘基三丙氧基矽烷、萘基參(異丙氧基)矽烷、萘基三氯矽烷、蒽基三甲氧基矽烷、蒽基三乙氧基矽烷、蒽基三丙氧基矽烷、蒽基參(異丙氧基)矽烷、蒽基三氯矽烷、菲基三甲氧基矽烷、菲基三乙氧基矽烷、菲基三丙氧基矽烷、菲基參(異丙氧基)矽烷、菲基三氯矽烷、芘基三甲氧基矽烷、芘基三乙氧基矽烷、芘基三丙氧基矽烷、芘基參(異丙氧基)矽烷、芘基三氯矽烷、茀基三甲氧基矽烷、茀基三乙氧基矽烷、茀基三丙氧基矽烷、茀基參(異丙氧基)矽烷以及茀基三氯矽烷。芳族取代基之此等實例可與分子(例如1-萘基、2-萘基)任何部位上之矽連接且可另外在芳環上帶有諸如烷基、醯基、烷氧基、硝基、胺基或鹵素原子之官能基。 A clear example of a suitable precursor 3 that can be used to adjust the optical properties of the resulting material is phenyltrimethoxydecane, phenyltriethoxynonane, phenyltripropoxydecane, phenyl cis (isopropoxy)decane Phenyltrichloromethane, naphthalene Trimethoxy decane, naphthyltriethoxy decane, naphthyltripropoxydecane, naphthyl stilbene (isopropoxy)decane, naphthyltrichlorodecane, decyltrimethoxydecane, decyltriethyl Oxydecane, mercaptotripropoxydecane, decyl cis (isopropoxy) decane, decyl trichlorodecane, phenanthryl trimethoxy decane, phenanthryl triethoxy decane, phenanthryl tripropoxy Decane, phenanthryl (isopropoxy) decane, phenanthryl trichlorodecane, decyltrimethoxydecane, decyltriethoxydecane, decyltripropoxydecane, decyl hydrazine (isopropoxy) And decane, decyl trichloro decane, decyl trimethoxy decane, decyl triethoxy decane, decyl tripropoxy decane, decyl cis (isopropoxy) decane, and decyl trichloro decane. Such examples of aromatic substituents may be attached to the oxime at any position of the molecule (e.g., 1-naphthyl, 2-naphthyl) and may additionally carry, for example, an alkyl group, a decyl group, an alkoxy group, a nitrate on the aromatic ring. a functional group of a group, an amine group or a halogen atom.
由可相互水解以及共聚合且含有可在潛伏光活性催化劑活化後進一步反應之官能基的上述鋁以及矽烷前驅物獲得之聚合物產生可用作光微影製程中之硬質罩幕的塗膜。 The polymer obtained from the above-mentioned aluminum and decane precursor which are mutually hydrolyzable and copolymerizable and which contains a functional group which can be further reacted after activation of the latent photoactive catalyst produces a coating film which can be used as a hard mask in the photolithography process.
一般而言,以下為上述前驅物基團之功能:前驅物1-向硬質罩幕塗膜提供高鋁含量;前驅物2-賦予足夠存放期以及視情況由標準微影製程獲得的圖案化輪廓或提供材料光吸收功能;前驅物3-賦予由標準微影製程獲得之圖案化輪廓,光吸收功能。 In general, the following are the functions of the precursor groups described above: Precursor 1 - provides a high aluminum content to the hard mask coating; Precursor 2 - gives a sufficient shelf life and optionally patterned contours obtained from standard lithography processes Or provide material light absorption function; Precursor 3 - gives the patterned contour obtained by standard lithography process, light absorption function.
以所用前驅物之莫耳百分比計的較佳組合物為:前驅物1:50-99; 前驅物2:5-80;以及前驅物3:1-40。 A preferred composition based on the percentage of moles of the precursor used is: precursor 1:50-99; Precursor 2: 5-80; and precursor 3: 1-40.
尤其較佳莫耳百分比為:前驅物1:50-90;前驅物2:10-70;以及前驅物3:5-30。 Particularly preferred mole percentages are: precursor 1:50-90; precursor 2: 10-70; and precursor 3:5-30.
較佳實施例之製造藉由在溶劑或溶劑組合中執行視情況與矽烷前驅物共聚合之1-4種鋁前驅物、較佳1-2種鋁前驅物的酸或鹼催化之水解以及縮合反應來進行。適合於執行水解以及縮合步驟之溶劑為丙酮、四氫呋喃、2-甲基四氫呋喃、丁酮、環戊酮、環己酮、醇(甲醇、乙醇、丙醇)、丙二醇衍生物[尤其丙二醇單甲醚乙酸酯(propylene glycol monomethyl ether acetate;PGMEA)、丙二醇單甲醚(propylene glycol monomethyl ether;PGME)、丙二醇單***(propylene glycol monoethyl ether;PGEE)、丙二醇單丙醚(propylene glycol monopropyl ether;PNP)]、乙二醇衍生物以及甲基第三丁基醚。亦可使用由兩種或兩種以上此等溶劑組成之混合物。合成中溶劑與前驅物之重量比可為20:1至0.5:1。溶劑與前驅物之重量比較佳在10:1至1:1之範圍內。前驅物之酸或鹼催化的水解以及縮合反應中所用之水量可顯著不同。每一水解官能基使用1-3莫耳當量水,形成聚合材料,而按重量5-15倍過量產生聚陽離子性鋁物質之膠態懸浮液。為製備聚合材料,以水解官能基計1-2莫耳當量水為較佳,而當製備膠態聚陽離子性鋁物質時,以重量計5-10過量為較佳。在合成期間可在室溫下攪拌反應混合物或使其回流1-48小時,較佳1-24小時。 The preferred embodiment is produced by acid or base catalyzed hydrolysis and condensation of 1-4 aluminum precursors, preferably 1-2 aluminum precursors, optionally copolymerized with a decane precursor, in a solvent or solvent combination. The reaction proceeds. Suitable solvents for carrying out the hydrolysis and condensation steps are acetone, tetrahydrofuran, 2-methyltetrahydrofuran, butanone, cyclopentanone, cyclohexanone, alcohols (methanol, ethanol, propanol), propylene glycol derivatives [especially propylene glycol monomethyl ether) Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), propylene glycol monopropyl ether (PNP) ], ethylene glycol derivatives and methyl tert-butyl ether. A mixture of two or more of these solvents may also be used. The weight ratio of solvent to precursor in the synthesis can range from 20:1 to 0.5:1. The weight of the solvent and the precursor is preferably in the range of 10:1 to 1:1. The acid or base catalyzed hydrolysis of the precursor and the amount of water used in the condensation reaction can vary significantly. Each hydrolyzed functional group uses from 1 to 3 moles of water to form a polymeric material, and a colloidal suspension of polycationic aluminum species is produced in a 5-15 fold excess by weight. For the preparation of the polymeric material, 1-2 moles of water based on the hydrolyzable functional group is preferred, and when preparing the colloidal polycationic aluminum material, a 5-10 excess by weight is preferred. The reaction mixture may be stirred at room temperature during the synthesis or refluxed for 1-48 hours, preferably 1-24 hours.
一旦完成水解以及縮合反應,可在減壓下移除過量試劑(水)、反應副產物(諸如甲醇、乙醇、異丙醇、2-丁醇)以及溶劑。在移除揮發性物質期間,根據在聚合物溶液之進一步製造步驟中的用途,可引入另一種具有較高沸點且性質更合乎需要的溶劑。一旦移除揮發性物質,接著可將所獲得之材料調配成其最終組合物或經受分子量調節步驟。此分子量增加步驟在50℃至180℃之高溫範圍下進行。在分子量調節步驟期間更佳使用60-120℃。分子量增加步驟後,可將材料調配成其最終組合物。 Once the hydrolysis and condensation reactions are completed, excess reagent (water), reaction by-products (such as methanol, ethanol, isopropanol, 2-butanol) and solvent can be removed under reduced pressure. During the removal of the volatile material, another solvent having a higher boiling point and a more desirable nature may be introduced depending on the use in the further manufacturing step of the polymer solution. Once the volatiles are removed, the resulting material can then be formulated into its final composition or subjected to a molecular weight adjustment step. This molecular weight increasing step is carried out at a high temperature range of 50 ° C to 180 ° C. More preferably, 60-120 ° C is used during the molecular weight adjustment step. After the molecular weight increase step, the material can be formulated into its final composition.
所述調配由使用溶劑或此等溶劑之組合稀釋材料組成。選擇用於最終調配物中之溶劑以使塗膜均勻性以及儲存穩定性最大。對於良好旋塗性質,較高沸點以及黏度之溶劑可為較佳(例如PGMEA)。可將穩定溶劑添加至產物中以改良儲存穩定性。所述溶劑最通常具有羥基,因為此等溶劑與聚合OH配位或與此等聚合OH明顯反應而不會不利地影響固化膜之性質。可添加諸如界面活性劑(來自例如BYK-Chemie、3M以及Air Products)之添加劑、光潛伏催化劑或熱潛伏催化劑(例如Rhodorsil 2074以及Irgacure 819)以及其他膠溶劑。界面活性劑可改良待塗佈之基板的濕潤且因此改良所得膜之均勻性。通常,非離子性界面活性劑為較佳。膠溶劑提供給產物改良之存放期。膠溶劑可由無機酸或有機酸或β二酮衍生物組成。 The formulation consists of using a solvent or a combination of such solvents to dilute the material. The solvent used in the final formulation is selected to maximize film uniformity and storage stability. For good spin-on properties, higher boiling and viscosity solvents may be preferred (e.g., PGMEA). A stabilizing solvent can be added to the product to improve storage stability. The solvent most typically has a hydroxyl group because these solvents coordinate with the polymeric OH or react with such polymeric OH without adversely affecting the properties of the cured film. Additives such as surfactants (from, for example, BYK-Chemie, 3M and Air Products), photolatent catalysts or thermal latent catalysts (such as Rhodorsil 2074 and Irgacure 819), as well as other peptizers, may be added. The surfactant can improve the wetting of the substrate to be coated and thus improve the uniformity of the resulting film. Generally, a nonionic surfactant is preferred. The peptizer provides a modified shelf life for the product. The peptizer may consist of an inorganic or organic acid or a beta diketone derivative.
塗佈、乾燥以及固化後,形成由具有碳基官能基之氧化鋁或鋁矽氧烷核心組成之膜。固化溫度較佳為至多 400℃,但更佳為250℃。單個固化步驟為較佳。所得固化膜厚度視聚合物溶液之稀釋度而定且通常在10-1000奈米之間的範圍內。當在632奈米之波長下使用工具量測時,膜之折射率介於1.4-1.7之間。膜較佳具有高達400℃之熱穩定性以及揮發性組份之最小釋氣作用以減少對隨後用於半導體製造中之塗膜或製程的不利影響。 After coating, drying, and curing, a film composed of an alumina or aluminoxane core having a carbon-based functional group is formed. The curing temperature is preferably at most 400 ° C, but more preferably 250 ° C. A single curing step is preferred. The resulting cured film thickness depends on the dilution of the polymer solution and is typically in the range of from 10 to 1000 nm. When measured using a tool at a wavelength of 632 nm, the refractive index of the film is between 1.4 and 1.7. The film preferably has a thermal stability of up to 400 ° C and a minimum outgassing of the volatile components to reduce the adverse effects on subsequent coating or processing in semiconductor fabrication.
圖1展示微影製程:使硬質罩幕沈積於待圖案化之基板上,使光阻劑沈積,使光阻劑曝光,使所述光阻劑顯影,蝕刻所述硬質罩幕,移除光阻劑,對所需材料蝕刻圖案以及移除硬質罩幕。根據所述圖中所示之實施例,藉助於旋塗將所述材料塗覆於基板10上。若使用所述材料之應用有需要,則其他塗佈方法亦可適用。塗佈後,接著使所述材料固化以產生硬質罩幕20。接著將光阻劑30塗覆於所述硬質罩幕上且進行加工(曝光並顯影)以產生曝光硬質罩幕之圖案。接著藉由乾式或濕式蝕刻將所述圖案轉移至硬質罩幕。在經由硬質罩幕上所產生之開放圖案蝕刻基板之前,可按照熟習此項技術者所熟知之慣例移除光阻劑。最後,在基板上蝕刻深的高縱橫比通孔後,使用乾式或濕式清潔程序移除硬質罩幕。然而,若藉由此技術足以轉移圖案,則在光阻劑顯影期間可同時圖案化硬質罩幕材料為較佳。當硬質罩幕層與光阻劑一起顯影時,此舉可進行,且當硬質罩幕不需要藉由濕式或乾式蝕刻進行之獨立圖案轉移步驟時,此舉可使得大大節約時間以及成本。 1 shows a lithography process: depositing a hard mask on a substrate to be patterned, depositing a photoresist, exposing the photoresist, developing the photoresist, etching the hard mask, and removing the light A resist that etches the pattern of the desired material and removes the hard mask. According to the embodiment shown in the figures, the material is applied to the substrate 10 by means of spin coating. Other coating methods may also be suitable if the application of the material is required. After coating, the material is then cured to create a hard mask 20. A photoresist 30 is then applied to the hard mask and processed (exposed and developed) to produce a pattern of exposed hard masks. The pattern is then transferred to a hard mask by dry or wet etching. The photoresist can be removed prior to etching the substrate through an open pattern created on the hard mask, as is well known to those skilled in the art. Finally, after etching a deep high aspect ratio via on the substrate, the hard mask is removed using a dry or wet cleaning procedure. However, if the technique is sufficient to transfer the pattern, it may be preferable to simultaneously pattern the hard mask material during development of the photoresist. This can be done when the hard mask layer is developed with the photoresist, and this can result in significant time and cost savings when the hard mask does not require a separate pattern transfer step by wet or dry etching.
圖2展示基板10以及光可成像硬質罩幕20。使用圖 2所示光可成像硬質罩幕包含使硬質罩幕沈積於待圖案化之基板上,使可圖案化之硬質罩幕曝光,使經曝光之硬質罩幕的可溶性部分顯影,對所需材料蝕刻圖案以及移除硬質罩幕。 2 shows a substrate 10 and a photoimageable hard mask 20. Use map The photoimageable hard mask shown in Fig. 2 comprises depositing a hard mask on the substrate to be patterned, exposing the patternable hard mask, developing the soluble portion of the exposed hard mask, and etching the desired material. Pattern and remove the hard cover.
實例1至3描述以此方式製備以及固化之材料。使此等材料經受常見深反應離子蝕刻(DRIE)蝕刻條件(表1)。其對Si之蝕刻選擇性展示於表2中。 Examples 1 to 3 describe materials prepared and cured in this manner. These materials were subjected to common deep reactive ion etching (DRIE) etching conditions (Table 1). Its etch selectivity to Si is shown in Table 2.
使用常見圖案轉移,利用光阻劑形成氧化鋁塗膜之標準圖案。使用相同DRIE條件形成深通孔而受氧化鋁硬質罩幕保護之Si無降解(圖3-5)。 A standard pattern of alumina coating film is formed using a photoresist using a common pattern transfer. The deep D-holes were formed using the same DRIE conditions and the Si protected by the alumina hard mask was not degraded (Figures 3-5).
在硬質罩幕上產生圖案之更佳方法在於製備自身可藉由光微影技術進行圖案化之硬質罩幕。在所述情況下,可大大節約製造時間以及成本。可經由用於負型色調光阻劑之技術獲得經圖案化之硬質罩幕(圖2),所述技術包含塗佈基板(10),乾燥,經由罩幕曝光硬質罩幕(20),曝光後烘烤,使非曝光區顯影以及最終固化。蝕刻後,使用乾式或濕式清潔程序移除硬質罩幕。類似地,亦可經由用於正型色調光阻劑之技術獲得經圖案化之硬質罩幕。使用潛伏輻射敏感性催化劑可提供交聯氧化鋁基硬質罩幕之所述可能性。所述潛伏催化劑在曝光於輻射後分解產生引起官能基進行反應之酸或自由基。由於經由曝光釋放之強酸所催化的縮合反應,經曝光部分發生固化。所述固化亦可藉由其他方法達成,其限制條件為聚合物之組成中存在的官能基可進行由酸或自由基引發之聚合反應。如先前所 述,使用含有反應性R2或R3取代基(諸如烯基、炔基、環氧基、丙烯酸酯基以及烷基丙烯酸酯基)之前驅物2或3可使材料在與可藉由曝露於所需波長之光而活化的催化劑組合使用時經由後一機制固化。在負型色調製程中,當照射通過經圖案化之罩幕時,光穿過至膜之區域將固化。接著可將非曝光區溶解於水性顯影劑中,使得罩幕上之圖案轉移至膜。在使膜曝露於輻射之前,進行加熱步驟以移除調配物中之揮發性組份。此溫度介於50-170℃之間,較佳介於70-150℃之間,此不會引起可能導致非曝光區對於顯影劑而言不可溶之樹脂的過早交聯。類似地,曝光後,進行曝光後烘烤以加速由潛伏催化劑引發之反應。對於正型色調製程而言,與負型色調製程相比,圖像實際上是顛倒的。因此,正型色調材料之曝光區溶解於顯影劑中。 A better method of creating a pattern on a hard mask is to prepare a hard mask that can be patterned by photolithography. In this case, manufacturing time and cost can be greatly saved. A patterned hard mask (Fig. 2) can be obtained via a technique for a negative tone photoresist, the technique comprising coating a substrate (10), drying, exposing the hard mask (20) via a mask, exposing Post-baking, developing the non-exposed areas and final curing. After etching, the hard mask is removed using a dry or wet cleaning procedure. Similarly, a patterned hard mask can also be obtained via techniques for positive tone photoresists. The use of latent radiation-sensitive catalysts provides the possibility of cross-linking alumina-based hard masks. The latent catalyst decomposes upon exposure to radiation to produce an acid or free radical that causes the functional group to react. The exposed portion is cured due to the condensation reaction catalyzed by the strong acid released by exposure. The curing can also be achieved by other methods, with the proviso that the functional groups present in the composition of the polymer can undergo polymerization initiated by acid or free radicals. As described previously, the use of a precursor 2 or 3 containing a reactive R 2 or R 3 substituent such as an alkenyl group, an alkynyl group, an epoxy group, an acrylate group, and an alkyl acrylate group allows the material to be The catalyst activated by exposure to light of the desired wavelength is used in combination to cure via the latter mechanism. In the negative color modulation process, when the illumination passes through the patterned mask, the area through which the light passes to the film will solidify. The non-exposed areas can then be dissolved in the aqueous developer such that the pattern on the mask is transferred to the film. Prior to exposing the film to radiation, a heating step is performed to remove volatile components from the formulation. This temperature is between 50 and 170 ° C, preferably between 70 and 150 ° C, which does not cause premature crosslinking of the resin which may cause the non-exposed areas to be insoluble to the developer. Similarly, after exposure, post-exposure bake is performed to accelerate the reaction initiated by the latent catalyst. For a positive color modulation process, the image is actually reversed compared to the negative color modulation process. Therefore, the exposed region of the positive-tone material is dissolved in the developer.
當前驅物2帶有可由輻射敏感性潛伏催化劑引發聚合之反應性官能基時,亦可獲得可圖案化材料。對於熟習此項技術者,此舉以及上文提供當引導光穿過罩幕以及步進機(stepper)時形成經圖案化之結構的可能性。 A patternable material can also be obtained when the precursor 2 carries a reactive functional group that can be initiated by a radiation-sensitive latent catalyst. For those skilled in the art, this and the above provide the possibility of forming a patterned structure when guiding light through the mask and stepper.
為獲得可圖案化材料,含有反應性R2或R3取代基之前驅物2或3的量很重要。已發現10%之反應性前驅物3不足以產生可圖案化材料(實例4)。類似地,發現過量或不足量之前驅物2導致不會形成有利圖案或極少形成有利圖案(實例9)。 To obtain a patternable material, the amount of precursor 2 or 3 containing the reactive R 2 or R 3 substituent is important. It has been found that 10% of the reactive precursor 3 is insufficient to produce a patternable material (Example 4). Similarly, it was found that excess or insufficient amount of precursor 2 resulted in no favorable pattern formation or minimal formation of a favorable pattern (Example 9).
在形成深的高縱橫比通孔之加工流程中,移除氧化鋁硬質罩幕亦可省去。因此,預期氧化鋁基材料之CTE值接 近矽之CTE值。所述CTE值之相似性在材料之非犧牲應用中對於使在各種製造步驟(涉及高溫)期間以及之後所產生之機械應力或裝置中所經歷之熱錯配最小而言很重要。 In the process of forming deep high aspect ratio through holes, the removal of the alumina hard mask can also be omitted. Therefore, it is expected that the CTE value of the alumina-based material will be connected. The CTE value of the near sputum. The similarity of the CTE values is important in non-sacrificial applications of materials to minimize the mechanical stresses experienced during and after various manufacturing steps (involving high temperatures) or the thermal mismatch experienced in the device.
含有能夠吸收光之基團之氧化鋁基硬質罩幕塗膜可用於形成窄線寬之先進微影應用中。可引入吸光基團作為矽之取代基(前驅物3中之R3)或作為與鋁配位之配位體(前驅物2中之R2)。在所述微影應用中,控制膜之光學性質(諸如折射率以及消光係數)之能力很重要。實例6-8描述材料之合成,其中光學常數可藉由控制氧化鋁基硬質罩幕中之取代基以及其含量來調節。微影應用中所用之各種波長的光學常數值展示於圖7-9中。對於熟習此項技術者,折射率以及消光係數可藉由選擇既定硬質罩幕組合物中的吸光化合物以及其含量來調節。因此,吸光部分並不限於實例中所給出之基團且其他已知吸收所需波長之部分可用於調節適合於特定應用之光學常數。 Alumina-based hard mask films containing groups capable of absorbing light can be used in advanced lithography applications that form narrow line widths. A light absorbing group may be introduced as a substituent of hydrazine (R 3 in the precursor 3 ) or as a ligand coordinated to aluminum (R 2 in the precursor 2 ). In the lithography application, the ability to control the optical properties of the film, such as refractive index and extinction coefficient, is important. Examples 6-8 describe the synthesis of materials in which the optical constants can be adjusted by controlling the substituents in the alumina-based hard mask and their contents. The optical constant values for the various wavelengths used in lithography applications are shown in Figures 7-9. For those skilled in the art, the refractive index and extinction coefficient can be adjusted by selecting the light absorbing compound and its amount in a given hard mask composition. Thus, the light absorbing portion is not limited to the groups given in the examples and other portions of the wavelengths known to absorb can be used to adjust the optical constants suitable for a particular application.
基於上文,在一實施例中,本發明方法包括使用微影以及蝕刻使硬質罩幕圖案化之步驟。此實施例包括以下步驟之組合:- 藉助於旋轉、縫塗、噴塗、或其他適合於在溶液狀態下塗覆材料之方法使硬質罩幕材料沈積;在所需溫度下使所述硬質罩幕材料固化;- 使光阻劑在所述硬質罩幕上沈積、圖案化以及顯影以曝光硬質罩幕之所需區域; - 藉助於選擇性蝕刻將圖案自所提及之光阻劑轉移至既定硬質罩幕的指定曝光區域;- 視情況使用習知蝕刻技術移除所述經圖案化之光阻劑;以及- 使用蝕刻製程將圖案自所提及之硬質罩幕以及光阻劑轉移至既定基板。 Based on the above, in one embodiment, the method of the present invention includes the step of patterning the hard mask using lithography and etching. This embodiment comprises a combination of the following steps: - depositing a hard mask material by means of spin, slit coating, spraying, or other suitable method of coating the material in solution; making the hard mask material at the desired temperature Curing; - depositing, patterning, and developing a photoresist on the hard mask to expose a desired area of the hard mask; - transferring the pattern from the mentioned photoresist to a specified exposed area of a given hard mask by means of selective etching; - removing the patterned photoresist using conventional etching techniques as appropriate; and - using The etching process transfers the pattern from the hard mask and photoresist mentioned to a given substrate.
在最後一步中,較佳使用具有高選擇性且不會由於硬質罩幕層之不當反應而對基板之非曝光區造成損傷的蝕刻製程。 In the final step, an etching process which is highly selective and does not cause damage to the non-exposed areas of the substrate due to improper reaction of the hard mask layer is preferably used.
在一實施例中,硬質罩幕組合物至少含有雜有有機取代基之-Al-O-以及-Si-O-樹脂核心。在另一實施例中,硬質罩幕組合物至少含有雜有有機取代基之-Al-O-樹脂核心。 In one embodiment, the hard mask composition contains at least an Al-O- and -Si-O-resin core with an organic substituent. In another embodiment, the hard mask composition contains at least an Al-O-resin core with an organic substituent.
在一實施例中,所產生之結構可展現的硬質罩幕與基板之間的蝕刻選擇性為至少500:1。然而,其亦可在約10,000:1之較寬範圍內變化。 In one embodiment, the resulting structure can exhibit an etch selectivity between the hard mask and the substrate of at least 500:1. However, it can also vary over a wide range of about 10,000:1.
在一實施例中,塗膜之固化是在200-400℃之溫度下、較佳在200-300℃下在加熱板上進行。在另一實施例中,塗膜之固化是在400-1000℃之溫度下、較佳在400-650℃下在爐中進行。 In one embodiment, the curing of the coating film is carried out on a hot plate at a temperature of from 200 to 400 ° C, preferably from 200 to 300 ° C. In another embodiment, the curing of the coating film is carried out in an oven at a temperature of from 400 to 1000 ° C, preferably from 400 to 650 ° C.
在任一上述實施例中,可使用包括稀氫氧化四甲銨(TMAH)溶液或由稀TMAH溶液組成之顯影劑。 In any of the above embodiments, a developer comprising a dilute tetramethylammonium hydroxide (TMAH) solution or a dilute TMAH solution may be used.
本發明之製程可用於目的是具有高縱橫比之通孔結構的實施例中。因此,在一實施例中,所述製程在半導體基板上產生高縱橫比通孔結構,其中縱橫比為至少5:1或 更佳為較高50:1。在另一實施例中,製程在半導體基板上產生高縱橫比通孔結構,其中通孔深度為100微米、較佳超過200微米。 The process of the present invention can be used in embodiments where the purpose is a via structure having a high aspect ratio. Thus, in one embodiment, the process produces a high aspect ratio via structure on a semiconductor substrate, wherein the aspect ratio is at least 5:1 or More preferably 50:1 higher. In another embodiment, the process produces a high aspect ratio via structure on the semiconductor substrate, wherein the via depth is 100 microns, preferably more than 200 microns.
顯而易見,本發明可用於使用能夠吸收微影加工中所用之光的保護性氧化鋁基硬質罩幕層執行半導體微影、蝕刻以及通孔形成製程之各種方法中。 It will be apparent that the present invention can be used in various methods of performing semiconductor lithography, etching, and via formation processes using a protective alumina-based hard mask layer capable of absorbing light used in lithographic processing.
在另一實施例中,本發明包括在基板上形成薄膜硬質罩幕之方法,其包括以下步驟:- 使基板表面與藉由在膠溶劑以及溶劑存在下利用水解催化劑水解第一金屬氧化物前驅物所獲得之化學組合物反應;- 視情況進一步使所述第一金屬氧化物前驅物與第二金屬或類金屬(metalloid)氧化物前驅物共反應;- 以產生中間物寡聚或聚合材料之溶液;- 視情況對所述中間物化學溶液執行溶劑交換製程;- 在高溫下加熱薄膜硬質罩幕以進行部分或完全移除溶劑之交聯反應;以及- 藉由半導體光微影方法加工薄膜硬質罩幕。 In another embodiment, the invention includes a method of forming a thin film hard mask on a substrate, comprising the steps of: - hydrolyzing the surface of the substrate with a precursor of the first metal oxide by using a hydrolysis catalyst in the presence of a peptizing agent and a solvent The chemical composition obtained by the reaction; - optionally reacting the first metal oxide precursor with a second metal or metalloid oxide precursor; to produce an intermediate oligomer or polymeric material Solution; - performing a solvent exchange process on the intermediate chemical solution as appropriate; - heating the film hard mask at a high temperature to partially or completely remove the solvent crosslinking reaction; and - processing by semiconductor photolithography Film hard cover.
在所述方法中,自上文顯而易見,第一金屬氧化物前驅物可由氯化鋁、烷醇鋁、硝酸鋁、乙酸鋁、乙醯乙酸鋁前驅物以及其組合的族群中選出。 In the method, it will be apparent from the above that the first metal oxide precursor may be selected from the group consisting of aluminum chloride, aluminum alkoxide, aluminum nitrate, aluminum acetate, aluminum acetacetate precursor, and combinations thereof.
在一實施例中,中間物寡聚或聚合薄膜硬質罩幕可在高溫下固化,可藉由使用負型微影製程以微影法進行圖案化。 In one embodiment, the intermediate oligomer or polymeric film hard mask can be cured at elevated temperatures and can be patterned by lithography using a negative lithography process.
在任一上述實施例中,R3基團較佳為苯基與聚芳族化合物之混合物。此實施例藉由微影圖案化獲得預定光學性質。 In any of the above embodiments, the R 3 group is preferably a mixture of a phenyl group and a polyaromatic compound. This embodiment achieves predetermined optical properties by lithographic patterning.
更特定言之,材料充當硬質罩幕之應用實例包含: More specifically, examples of applications in which materials act as hard masks include:
A.與再分佈、晶圓凸塊介電質或鈍化層相容之硬質罩幕。詳言之,可將硬質罩幕塗佈於介電質(有機、混合或無機)材料上,通常在微影製程中進行圖案化且隨後利用適度化學剝離化學物質移除而不移除或損傷介電質膜。剝離選擇性可在聚合期間利用諸如乙醯丙酮酸酯(acac)之有機添加劑進行調節。 A. Hard mask compatible with redistribution, wafer bump dielectric or passivation layer. In particular, a hard mask can be applied to a dielectric (organic, hybrid or inorganic) material, typically patterned in a lithography process and subsequently removed using a moderate chemical stripping chemistry without removal or damage. Dielectric film. The stripping selectivity can be adjusted during the polymerization using an organic additive such as acetoacetate (acac).
B.含有吸收微影製程波長(通常為193奈米-460奈米)之有機基團的硬質罩幕。此光衰減組份使得材料在與光阻劑微影圖案化結合使用時同時用於抗反射塗膜功能中。 B. A hard mask containing organic groups that absorb the lithography process wavelength (typically 193 nm to 460 nm). This light attenuating component allows the material to be used in the antireflective coating function simultaneously in combination with photoresist lithographic patterning.
C.與諸如旋塗碳(spin-on-carbon;SOC)聚合物之第二轉移層材料相容的硬質罩幕。可將硬質罩幕塗佈於SOC聚合物上以增強總堆疊選擇性。通孔圖案化後,可利用適度濕式化學移除來移除堆疊。 C. A hard mask compatible with a second transfer layer material such as a spin-on-carbon (SOC) polymer. A hard mask can be applied to the SOC polymer to enhance overall stack selectivity. After the vias are patterned, moderate wet chemical removal can be used to remove the stack.
D.雙金屬鑲嵌互連製造中之硬質罩幕以及蝕刻終止劑。在雙金屬鑲嵌製程中,使用SiCxNy或SiOxNy作為分離Cu含量之蝕刻終止劑。藉由用所述材料置換習知蝕刻終止劑,可降低通孔高度,由此降低總Cu線長。 D. Hard masks and etch stopers in the manufacture of dual damascene interconnects. In the dual damascene process, SiCxNy or SiOxNy is used as an etch stop for separating the Cu content. By replacing the conventional etch stop agent with the material, the via height can be reduced, thereby reducing the total Cu line length.
E.用於微機電系統(micro-electro-mechanical system;MEMS)製造之硬質罩幕。可使用光微影技術將所述材料圖案化成所需形狀。藉由蝕刻基板來調節垂直尺寸。 E. Hard mask for micro-electro-mechanical system (MEMS) manufacturing. The material can be patterned into the desired shape using photolithography. The vertical dimension is adjusted by etching the substrate.
除了形成深的高縱橫比結構,亦可包含材料之潛在應用。所述特定實例包含: In addition to forming deep high aspect ratio structures, potential applications of materials can also be included. The specific example includes:
A.鈍化塗覆(Passivation application),其中需要高機械性質。 A. Passivation application in which high mechanical properties are required.
B.用於邏輯裝置與記憶體裝置之淺溝槽隔離。所述材料亦可用作經隔離之淺溝槽的填充材料。 B. Shallow trench isolation for logic devices and memory devices. The material can also be used as a fill material for isolated shallow trenches.
以下非限制性實例說明本發明。 The following non-limiting examples illustrate the invention.
實例1Example 1
將異丙醇鋁(15公克)以及THF(52.5公克)置於裝備有磁力攪拌棒以及回流冷凝器之圓底燒瓶中。一旦異丙醇鋁溶解,則逐滴添加乙醯丙酮酸酯(acac,7.35公克)。在室溫下攪拌混合物1小時且接著緩慢添加甲醇(52.5公克),隨後添加0.01M HNO3(5.29公克)與異丙醇(5.29公克)之混合物。完成添加後,藉由將燒瓶置於100℃油浴中來使反應混合物回流16小時。當反應混合物冷卻至室溫時,在減壓下移除揮發性物質直至殘餘35.4公克混合物。添加2-丁酮(95公克)且重複蒸發步驟直至殘餘33.7 公克材料。接著用2-丁酮以及甲醇調配所得溶液,產生溶液,將其旋塗於基板上。200℃固化後,獲得折射率為1.50且厚度為81奈米之塗膜。 Aluminum isopropoxide (15 grams) and THF (52.5 grams) were placed in a round bottom flask equipped with a magnetic stir bar and a reflux condenser. Once the aluminum isopropoxide was dissolved, acetamyl pyruvate (acac, 7.35 grams) was added dropwise. The mixture was stirred at room temperature for 1 hour and then methanol (52.5 g) was slowly added, followed by a mixture of 0.01 M HNO 3 (5.29 g) and isopropanol (5.29 g). After the addition was completed, the reaction mixture was refluxed for 16 hours by placing the flask in a 100 ° C oil bath. When the reaction mixture was cooled to room temperature, the volatile material was removed under reduced pressure until 35.4 g of mixture remained. 2-butanone (95 grams) was added and the evaporation step was repeated until 33.7 grams of material remained. The resulting solution was then formulated with 2-butanone and methanol to produce a solution which was spin coated onto the substrate. After curing at 200 ° C, a coating film having a refractive index of 1.50 and a thickness of 81 nm was obtained.
實例2Example 2
使用acac(3.68公克)重複上文。接著用2-丁酮以及甲醇調配所得溶液,產生溶液,將其旋塗於基板上。200℃固化後,獲得折射率為1.44且厚度為108奈米之塗膜。 Repeat above using acac (3.68 grams). The resulting solution was then formulated with 2-butanone and methanol to produce a solution which was spin coated onto the substrate. After curing at 200 ° C, a coating film having a refractive index of 1.44 and a thickness of 108 nm was obtained.
實例3Example 3
將異丙醇鋁(3公克)以及乙醇(11.25公克)置於裝備有頂置式攪拌器以及回流冷凝器之三頸圓底燒瓶中。將所述燒瓶浸沒於100℃油浴中。5分鐘後,緩慢添加去離子水(22.5公克)與60% HNO3(0.14公克)之混合物且使其回流24小時。進一步使用去離子水以及乙醇調配反應混合物。將溶液旋塗於基板上且在200℃下固化,得到折射率為1.50且厚度為93奈米之塗膜。 Aluminum isopropoxide (3 grams) and ethanol (11.25 grams) were placed in a three-necked round bottom flask equipped with an overhead stirrer and a reflux condenser. The flask was immersed in a 100 ° C oil bath. After 5 minutes, slowly adding deionized water (22.5 g) and 60% HNO 3 (0.14 g) and the mixture was refluxed for 24 hours. The reaction mixture was further formulated using deionized water and ethanol. The solution was spin-coated on a substrate and cured at 200 ° C to obtain a coating film having a refractive index of 1.50 and a thickness of 93 nm.
實例4Example 4
重複實例2之製備。移除揮發性物質後,獲得42.5公克固體含量為18.1%之材料。在另一反應中,在室溫下攪拌縮水甘油氧基丙基-三甲氧基矽烷(5公克)、丙酮(10公克)以及0.01M HNO3(1.14公克)24小時,得到基於縮水甘油氧基丙基矽烷之水解物。將含鋁溶液(3公克)與0.44公克基於縮水甘油氧基丙基矽烷之水解物混合,得到Al:Si莫耳比等於9:1之共聚物。在60℃下加熱均質混合物30分鐘。用光酸催化劑調配材料,塗佈且經由罩幕曝 光。顯影後,未獲得圖案。 The preparation of Example 2 was repeated. After removal of the volatiles, 42.5 grams of material having a solids content of 18.1% was obtained. In another reaction, glycidoxypropyl-trimethoxydecane (5 g), acetone (10 g), and 0.01 M HNO 3 (1.14 g) were stirred at room temperature for 24 hours to give a glycidyloxy group. Hydrolyzate of propyl decane. The aluminum-containing solution (3 g) was mixed with 0.44 g of the glycidoxypropyl decane-based hydrolyzate to obtain a copolymer having an Al:Si molar ratio of 9:1. The homogenous mixture was heated at 60 ° C for 30 minutes. The material was formulated with a photoacid catalyst, coated and exposed via a mask. After development, no pattern was obtained.
實例5Example 5
重複實例4之程序。Al:Si之莫耳比設定為7.5:2.5。將含鋁溶液(16.6公克)與7.3公克基於縮水甘油氧基丙基矽烷之水解物混合。在75℃下加熱均質混合物45分鐘且用環己酮以及光酸產生劑調配所得溶液。將溶液旋塗於基板上且在200℃下固化,產生折射率為1.51且厚度為152奈米之塗膜。可使用光微影技術使材料圖案化(圖5)。 Repeat the procedure of Example 4. The molar ratio of Al:Si is set to 7.5:2.5. The aluminum containing solution (16.6 grams) was mixed with 7.3 grams of glycidoxypropyl decane based hydrolyzate. The homogenous mixture was heated at 75 ° C for 45 minutes and the resulting solution was formulated with cyclohexanone and a photoacid generator. The solution was spin-coated on a substrate and cured at 200 ° C to produce a coating film having a refractive index of 1.51 and a thickness of 152 nm. The material can be patterned using photolithography (Figure 5).
表2展示與標準光阻劑相比,藉由以下實例製備之材料的性質以及蝕刻速率結果。基於包希(Bosch)型之蝕刻速率1以及基於低溫DRIE製程之蝕刻速率2。 Table 2 shows the properties of the materials prepared by the following examples and the etch rate results compared to standard photoresists. The etch rate 1 based on the Bosch type and the etch rate 2 based on the low temperature DRIE process.
實例6Example 6
重複實例2之製備。移除揮發性物質後,獲得263.97公克固體含量為19.76%之含有氧化鋁的材料。在另一反應中,將丙酮(49.76公克)以及苯基三甲氧基矽烷(51.76公克)置於裝備有經鐵氟龍(Teflon)覆蓋之磁力攪拌棒以及回流冷凝器之圓底燒瓶中。將硝酸(0.01M,14.10 公克)逐滴添加至所述燒瓶中且接著在室溫下攪拌反應混合物至少一小時。將10.0公克氧化鋁溶液置於裝備有經鐵氟龍覆蓋之磁力攪拌棒以及回流冷凝器之50毫升圓底燒瓶中。藉由逐滴添加0.92公克苯基矽烷氧基水解物而獲得含有10莫耳%苯基矽烷氧基之氧化鋁混合物。在室溫下攪拌混合物5分鐘且接著置於75℃油浴中10分鐘。獲得高黏性膠狀材料且儲存於室溫下隔夜。接著添加正丙氧基丙醇(PNP,15公克)且添加6滴濃硝酸,同時劇烈攪拌混合物。接著過濾材料且在2000轉/分鐘(rpm)下旋塗並在200℃下固化5分鐘,獲得折射率為1.5171且厚度為134奈米之膜。 The preparation of Example 2 was repeated. After removal of the volatiles, 263.97 grams of a material containing alumina having a solids content of 19.76% was obtained. In another reaction, acetone (49.76 grams) and phenyltrimethoxydecane (51.76 grams) were placed in a round bottom flask equipped with a Teflon-coated magnetic stir bar and a reflux condenser. Nitric acid (0.01M, 14.10 The gram was added dropwise to the flask and then the reaction mixture was stirred at room temperature for at least one hour. A 10.0 gram alumina solution was placed in a 50 ml round bottom flask equipped with a Teflon-covered magnetic stir bar and a reflux condenser. An alumina mixture containing 10 mol% of a phenyl alkoxy group was obtained by dropwise addition of 0.92 g of a phenyl decyloxy hydrolyzate. The mixture was stirred at room temperature for 5 minutes and then placed in a 75 ° C oil bath for 10 minutes. Obtain a highly viscous gelatinous material and store at room temperature overnight. Next, n-propoxypropanol (PNP, 15 g) was added and 6 drops of concentrated nitric acid were added while vigorously stirring the mixture. The material was then filtered and spin-coated at 2000 revolutions per minute (rpm) and cured at 200 ° C for 5 minutes to obtain a film having a refractive index of 1.5171 and a thickness of 134 nm.
實例7Example 7
重複實例6之製備。藉由逐滴添加0.43公克苯基矽烷氧基水解物而獲得含有5莫耳%苯基矽烷氧基之氧化鋁混合物。在室溫下攪拌混合物5分鐘且接著置於75℃油浴中30分鐘。獲得高黏性膠狀材料且儲存於室溫下隔夜。接著添加環己酮,過濾材料且在2000rpm下旋塗並在200℃下固化5分鐘,獲得折射率為1.4555且厚度為427奈米之膜。 The preparation of Example 6 was repeated. An alumina mixture containing 5 mol% of phenyl alkoxy group was obtained by dropwise addition of 0.43 g of a phenyl alkoxy hydrolyzate. The mixture was stirred at room temperature for 5 minutes and then placed in a 75 ° C oil bath for 30 minutes. Obtain a highly viscous gelatinous material and store at room temperature overnight. Next, cyclohexanone was added, the material was filtered and spin-coated at 2000 rpm and cured at 200 ° C for 5 minutes to obtain a film having a refractive index of 1.4555 and a thickness of 427 nm.
實例8Example 8
重複實例6之製備。藉由逐滴添加0.20公克苯基矽烷氧基水解物以及0.79公克以類似於苯基矽烷氧基水解物之方式製備的菲基矽烷氧基水解物而獲得含有5莫耳%苯基矽烷氧基以及5莫耳%菲基矽烷氧基之氧化鋁混合物。將兩種水解物同時逐滴添加至含有氧化鋁之溶液中。在室 溫下攪拌混合物5分鐘且接著置於75℃油浴中20分鐘。獲得高黏性半透明膠狀材料且儲存於室溫下隔夜。接著添加正丙氧基丙醇(PNP,15公克)且添加6滴濃硝酸,同時劇烈攪拌混合物。接著過濾材料且在2000rpm下旋塗並在200℃下固化5分鐘,獲得折射率為1.5456且厚度為194奈米之膜。 The preparation of Example 6 was repeated. A 5 mol% phenyl decyloxy group was obtained by dropwise addition of 0.20 g of a phenyl decyloxy hydrolyzate and 0.79 g of a phenanthryloxy hydrolyzate prepared in a manner similar to a phenyl decyloxy hydrolyzate. And a mixture of 5 mole % phenanthryloxy alkoxide. The two hydrolyzates were simultaneously added dropwise to the solution containing alumina. In the room The mixture was stirred at room temperature for 5 minutes and then placed in a 75 ° C oil bath for 20 minutes. Obtain a highly viscous translucent gelatinous material and store at room temperature overnight. Next, n-propoxypropanol (PNP, 15 g) was added and 6 drops of concentrated nitric acid were added while vigorously stirring the mixture. The material was then filtered and spin-coated at 2000 rpm and cured at 200 ° C for 5 minutes to obtain a film having a refractive index of 1.5456 and a thickness of 194 nm.
實例9Example 9
將異丙醇鋁(5公克)以及異丙醇(IPA)(15公克)置於裝備有磁力攪拌棒且經氬氣覆蓋之圓底燒瓶中。一旦異丙醇鋁溶解,則逐滴添加苯甲醯乙酸乙酯(1.95公克)。在室溫下攪拌混合物5分鐘,隨後添加鹽酸(10M,0.01公克)以及水(0.38公克)。完成添加後,在室溫下攪拌反應混合物16小時。接著用Irgacure 819(5重量%)調配固體含量為31%之溶液且過濾(0.1微米),隨後旋塗。經塗佈之材料可藉由光微影技術進行圖案化以產生正型色調圖像。 Aluminum isopropoxide (5 grams) and isopropyl alcohol (IPA) (15 grams) were placed in a round bottom flask equipped with a magnetic stir bar and covered with argon. Once the aluminum isopropoxide was dissolved, ethyl benzamidineacetate (1.95 g) was added dropwise. The mixture was stirred at room temperature for 5 minutes, followed by the addition of hydrochloric acid (10M, 0.01 g) and water (0.38 g). After the addition was completed, the reaction mixture was stirred at room temperature for 16 hours. A solution having a solids content of 31% was then formulated with Irgacure 819 (5 wt%) and filtered (0.1 micron), followed by spin coating. The coated material can be patterned by photolithography to produce a positive tone image.
10‧‧‧基板 10‧‧‧Substrate
20‧‧‧硬質罩幕 20‧‧‧hard cover
30‧‧‧光阻劑 30‧‧‧ photoresist
圖1以簡化方式展示在微影應用中塗覆硬質罩幕之製程。 Figure 1 shows in a simplified manner a process for applying a hard mask in a lithography application.
圖2展示在微影應用中塗覆光可成像氧化鋁基硬質罩幕材料之類似描述。 Figure 2 shows a similar depiction of coating a photoimageable alumina-based hard mask material in a lithography application.
圖3展示在包希型DRIE蝕刻中使用實例1之聚合物作為硬質罩幕而形成於矽上之深通孔的側視圖。 3 shows a side view of a deep via formed on a crucible using the polymer of Example 1 as a hard mask in a packaged DRIE etch.
圖4展示在低溫DRIE蝕刻(AR=7)中使用實例1之聚合物作為硬質罩幕而形成於矽上之深通孔的側視圖。 4 shows a side view of a deep via hole formed on a crucible using the polymer of Example 1 as a hard mask in a low temperature DRIE etch (AR=7).
圖5展示使用實例3之聚合物而形成於矽上之深通孔。 Figure 5 shows a deep via formed on the crucible using the polymer of Example 3.
圖6展示藉由光微影加工實例5中所製備之材料所獲得之圖案;圖案之解析度:5微米、4微米、3微米、2微米以及1微米。 Figure 6 shows the pattern obtained by photolithographic processing of the material prepared in Example 5; the resolution of the pattern: 5 microns, 4 microns, 3 microns, 2 microns and 1 micron.
圖7展示與10%苯基矽烷共聚合之基於AlxOy之塗膜的光學常數(折射率以及消光係數)與波長之函數關係曲線。 Figure 7 shows the optical constants (refractive index and extinction coefficient) of a coating film based on Al x O y copolymerized with 10% phenyl decane as a function of wavelength.
圖8展示與5%苯基矽烷共聚合之基於AlxOy之塗膜的光學常數(折射率以及消光係數)與波長之函數關係曲線。 Figure 8 is a graph showing the optical constants (refractive index and extinction coefficient) of a coating film based on Al x O y copolymerized with 5% phenyl decane as a function of wavelength.
圖9展示與5%苯基矽烷以及5%菲基矽烷共聚合之基於AlxOy之塗膜的光學常數(折射率以及消光係數)與波長之函數關係曲線。 Figure 9 shows the optical constants (refractive index and extinction coefficient) of a coating film based on Al x O y copolymerized with 5% phenyl decane and 5% phenanthrene, as a function of wavelength.
10‧‧‧基板 10‧‧‧Substrate
20‧‧‧硬質罩幕 20‧‧‧hard cover
30‧‧‧光阻劑 30‧‧‧ photoresist
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