TWI411622B - Anti-reflective coating-forming composition containing nitrogen-containing aromatic ring structure for lithography - Google Patents
Anti-reflective coating-forming composition containing nitrogen-containing aromatic ring structure for lithography Download PDFInfo
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Abstract
Description
本發明有關製造半導體裝置的微影步驟(lithography process)中所使用之微影用形成防反射膜之組成物。詳言之,有關為形成用為減輕曝光照射光之來自半導體基板的反射之光阻(photo resist)下層的防反射膜之用的微影用形成防反射膜之組成物。又,本發明有關使用該微影用形成防反射膜之組成物之光阻圖型(photo resist pattern)的形成方法。The present invention relates to a composition for forming an antireflection film for use in lithography used in a lithography process for fabricating a semiconductor device. More specifically, a composition for forming an anti-reflection film for forming an anti-reflection film for lowering a photo resist lower layer of a reflection from a semiconductor substrate for reducing exposure light is used. Further, the present invention relates to a method of forming a photo resist pattern of a composition for forming an antireflection film using the lithography.
傳統上,於半導體裝置的製造中,在實施藉由光阻(photo resist)之使用之微影術之微細加工。前述微細加工,係一種於矽晶圓(silicon wafer)等半導體基板上形成光阻的薄膜,介由薄膜上所描繪之裝置(device)的圖型之遮罩圖型(mask pattern)而照射活性光線(active ray),並顯像後將所得光阻圖型作為保護膜以實施半導體基板之蝕刻(etching)處理之加工法。然而,近年來,由於裝置的高積體化之故,所使用的活性光線亦從i線(波長365nm)、KrF(氟化氪)準分子雷射(excimer laser)(波長248nm)進展至ArF(氟化氬)準分子雷射(波長193nm)之短波長化。隨著,照射光的來自基板的反射即成為問題。於是,開始廣泛研究在光阻與基板間設置防反射膜(bottom anti-reflective coating)之方法。Conventionally, in the manufacture of a semiconductor device, microfabrication by lithography using photoresic is performed. The microfabrication is a film in which a photoresist is formed on a semiconductor substrate such as a silicon wafer, and the activity is irradiated through a mask pattern of a device depicted on the film. An active ray is used, and the obtained photoresist pattern is used as a protective film to perform an etching process of a semiconductor substrate. However, in recent years, due to the high integration of the device, the active light used has also progressed from the i-line (wavelength 365 nm), KrF (fluorene fluoride) excimer laser (wavelength 248 nm) to ArF. Short-wavelength of (argon fluoride) excimer laser (wavelength 193 nm). As the illumination from the substrate is reflected, it becomes a problem. Thus, a method of providing a bottom anti-reflective coating between a photoresist and a substrate has been widely studied.
就防反射膜而言,周知有二氧化鈦及氮化鈦等無機系的防反射膜、及由吸光性物質和高分子化合物等所成有機系的防反射膜。前者係在膜形成時需要真空蒸鍍裝置、CVD(化學汽相沈積)裝置、濺鍍(sputtering)裝置等設備,而相對地,後者則因不需要特別的設備而有利之故有許多研究。可例舉:美國專利第5919599號說明書所記載之同一分子內具有本身為形成交聯之取代基之羥基與吸光基之丙烯酸樹脂型防反射膜、美國專利第5693691號說明書所記載之同一分子內具有本身為形成交聯之取代基之羥基與吸光基之酚醛清漆樹脂型防反射膜等。In the antireflection film, an inorganic antireflection film such as titanium oxide or titanium nitride, and an organic antireflection film made of a light absorbing material and a polymer compound are known. The former requires a vacuum vapor deposition apparatus, a CVD (Chemical Vapor Deposition) apparatus, a sputtering apparatus, and the like at the time of film formation, whereas the latter is advantageous because it does not require special equipment. In the same molecule as described in the specification of U.S. Patent No. 5,919,599, an acrylic resin-based antireflection film having a hydroxyl group and a light-absorbing group which form a crosslinking substituent in the same molecule, and the same intramolecular composition as described in the specification of U.S. Patent No. 5,693,691 A novolak resin type antireflection film or the like which has a hydroxyl group and a light absorbing group which form a crosslinking substituent.
作為有機性的防反射膜需要具備之物性而言,有:對用為曝光之光具有大吸光度、不會引起與光阻之間的混雜(intermix)(即不溶於光阻溶劑)、不會從防反射膜對上層的光阻的低分子化合物的擴散、以及具有較光阻為大的乾蝕刻(dry etching)速度等。As an organic anti-reflection film, it is necessary to have physical properties, such as having a large absorbance for light used for exposure, and not causing intermixing with the photoresist (that is, insoluble in a photoresist solvent), The diffusion of the low molecular compound from the antireflection film to the photoresist of the upper layer, and the dry etching speed which is larger than the photoresist.
近年來,在使用KrF準分子雷射、ArF準分子雷射之微影步驟中,進展有加工尺寸的微細化,亦即,所形成之光阻圖型尺寸(photoresist pattern size)的微細化。如進行光阻圖型尺寸的微細化時,則隨著而需要為防止光阻圖型的潰倒等之光阻的薄膜化。並且,如以薄膜使用為光阻的情形,則為抑制一起所使用之防反射膜因蝕刻所引起之去除步驟中之光阻層的膜厚減少起見,需要能以更短時間進行藉由蝕刻之去除之防反射膜的開發。亦即,為使蝕刻去除步驟短時間化起見,需要具有較傳統上者為快速的蝕刻速度的選擇比之防反射膜之出現。In recent years, in the lithography step using a KrF excimer laser or an ArF excimer laser, progress has been made in the miniaturization of the processing size, that is, the miniaturization of the formed photoresist pattern size. When the size of the photoresist pattern is miniaturized, it is necessary to prevent the photoresist from being thinned by a photoresist pattern or the like. Further, in the case where the film is used as a photoresist, it is necessary to suppress the film thickness of the photoresist layer in the removal step caused by etching in order to suppress the antireflection film used together. Development of an anti-reflection film for etching removal. That is, in order to make the etching removal step short-term, it is required to have a selection ratio of an anti-reflection film which is conventionally faster than the etching rate.
又,防反射膜,必須係能形成良好形狀的光阻圖型者。特別是,必須係能形成在其下部不會具有下擺形狀(footing)之光阻圖型者。如光阻圖型具有下擺形狀,則會對爾後的加工步驟有惡影響之故。又,隨著微影技術的進展而所使用之光阻種類亦在增加。因此,為因應多樣化的光阻的使用,而需要新的防反射膜的開發。Further, the antireflection film must be a photoresist pattern capable of forming a good shape. In particular, it is necessary to form a photoresist pattern which does not have a hem shape at its lower portion. If the photoresist pattern has a hem shape, it will have a bad effect on the subsequent processing steps. Moreover, the types of photoresists used with the advancement of lithography are also increasing. Therefore, in order to respond to the use of diverse photoresists, development of new anti-reflection films is required.
目前,周知有一種利用源自環氧化合物的反應生成物之防反射膜用的組成物(例如,參考專利文獻1、專利文獻2、專利文獻3)。又,周知有含有具有三三酮環構造之化合物之防反射膜用的組成物(例如,參考專利文獻4)。At present, a composition for an antireflection film using a reaction product derived from an epoxy compound is known (for example, refer to Patent Document 1, Patent Document 2, and Patent Document 3). Also, well known to have three A composition for an antireflection film of a compound of a triketone ring structure (for example, refer to Patent Document 4).
專利文獻1:美國專利第6670425號說明書專利文獻2:日本專利特開2004-212907號公報專利文獻3:國際公開第04/034435號小冊子專利文獻4:國際公開第04/034148號小冊子Patent Document 1: U.S. Patent No. 6,670,425, Patent Document 2: Japanese Patent Laid-Open No. 2004-212907, Patent Document 3: International Publication No. 04/034435, Patent Document 4: International Publication No. 04/034148
本發明之目的在於提供一種能用於使用KrF準分子雷射(波長248nm)、ArF準分子雷射(波長193nm)或F2 (氟氣)準分子雷射(波長157nm)所實施之製造半導體裝置的微影步驟之微影用形成防反射膜之組成物。It is an object of the present invention to provide a semiconductor which can be used for performing a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm) or a F 2 (fluorine gas) excimer laser (wavelength 157 nm). The lithography of the lithographic step of the device is used to form a composition of the antireflective film.
又,本發明之目的在於提供一種在將KrF準分子雷射、ArF準分子雷射或F2 準分子雷射使用為微細加工時,能有效吸收來自基板之反射光,不會引起與光阻層之間的混雜,且具有較光阻為快速的乾蝕刻速度之防反射膜、以及為形成防反射膜之組成物。再者,提供使用該形成防反射膜之微影用防反射膜的形成方法、以及光阻圖型的形成方法。Moreover, an object of the present invention is to provide a KrF excimer laser, an ArF excimer laser or a F 2 excimer laser for micro-processing, which can effectively absorb reflected light from a substrate without causing a photoresist A mixture between layers, and an anti-reflection film having a faster dry etching speed than the photoresist, and a composition for forming an anti-reflection film. Further, a method of forming an antireflection film for lithography using the antireflection film and a method of forming a photoresist pattern are provided.
本發明人等,鑑於此種現狀下,經專心研究結果,發現如使用含有藉由具有2個縮水甘油基之環氧化合物與具有2個硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應(polgaddition reaction)而所得反應生成物之組成物,即可形成優異的防反射膜之事實,而完成本發明者。The inventors of the present invention have found that, as a result of intensive research, it has been found that the use of an epoxy compound having two glycidyl groups and a nitrogen-containing aromatic compound having two thiol groups or hydroxyl groups is used. The fact that the composition of the obtained reaction product is obtained by addition of a polgaddition reaction to form an excellent antireflection film is completed by the inventors.
亦即,本發明之第1要點係一種微影用形成防反射膜之組成物,其特徵為:含有;藉由具有2個縮水甘油基之環氧化合物與具有2個硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應而所得之反應生成物、交聯性化合物、交聯觸媒以及溶劑。That is, the first aspect of the present invention is a composition for forming an antireflection film for lithography, which comprises: comprising an epoxy compound having two glycidyl groups and having two thiol groups or hydroxyl groups; A reaction product obtained by an addition polymerization reaction between nitrogen-containing aromatic compounds, a crosslinkable compound, a crosslinking catalyst, and a solvent.
第2要點係如第1要點之微影用形成防反射膜之組成物,其中該環氧化合物,係二縮水甘油基醚化合物或二羧酸二縮水甘油酯化合物。The second point is a composition for forming an antireflection film for lithography according to the first aspect, wherein the epoxy compound is a diglycidyl ether compound or a dicarboxylic acid diglycidyl ester compound.
第3要點係如第1要點之微影用形成防反射膜之組成物,其中該環氧化合物,係可以式(1):
第4要點係如第1要點之微影用形成防反射膜之組成物,其中該含氮芳香族化合物,係具有2個羥基或硫醇基之三(triazine)化合物、噻二唑(thiadiazole)化合物或嘧啶(pyrimidine)化合物。The fourth point is a composition for forming an antireflection film for lithography according to the first aspect, wherein the nitrogen-containing aromatic compound has two hydroxyl groups or thiol groups. (triazine) a compound, a thiadiazole compound or a pyrimidine compound.
第5要點係如第1要點之微影用形成防反射膜之組成物,其中該交聯性化合物,係具有以羥甲基或烷氧甲基所取代之氮原子之含氮化合物。The fifth point is a composition for forming an antireflection film for lithography according to the first aspect, wherein the crosslinkable compound is a nitrogen-containing compound having a nitrogen atom substituted with a methylol group or an alkoxymethyl group.
第6要點係如第1要點之微影用形成防反射膜之組成物,其中該交聯觸媒,係芳香族磺酸化合物。The sixth point is a composition for forming an antireflection film for lithography according to the first aspect, wherein the crosslinking catalyst is an aromatic sulfonic acid compound.
第7要點係如第1要點之微影用形成防反射膜之組成物,其中再含有光引發酸產生劑。The seventh point is a composition for forming an antireflection film for lithography according to the first aspect, and further contains a photoinitiating acid generator.
第8要點係一種半導體裝置的製造所用之光阻圖型之形成方法,其特徵為:含有將第1要點至第7要點中之任一要點之微影用形成防反射膜之組成物塗佈於半導體基板上,並燒成以形成防反射膜之步驟,於該防反射膜上形成光阻層之步驟,將由該防反射膜與該光阻層所被覆之半導體基板進行曝光之步驟,於該曝光後進行光阻層之顯像之步驟。The eighth aspect is a method for forming a photoresist pattern for use in the manufacture of a semiconductor device, characterized in that the lithography containing any one of the first to seventh points is coated with a composition for forming an antireflection film. a step of forming a photoresist layer on the semiconductor substrate by firing to form an anti-reflection film, and exposing the semiconductor substrate covered by the anti-reflection film and the photoresist layer to a step of exposing the semiconductor substrate The step of developing the photoresist layer after the exposure.
本發明係為形成能對短波長的光,特別是KrF準分子雷射(波長248nm)、ArF準分子雷射(波長193nm)或F2 準分子雷射(波長157nm)顯示高度吸收之防反射膜之用的組成物。所得防反射膜,能有效吸收來自基板的反射光。The present invention is for forming an anti-reflection capable of exhibiting high absorption for short-wavelength light, particularly KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) or F 2 excimer laser (wavelength 157 nm). The composition for the film. The obtained anti-reflection film can effectively absorb reflected light from the substrate.
藉由本發明,可提供一種於使用KrF準分子雷射及ArF準分子雷射等之微細加工時,能有效吸收來自半導體基板的反射光,而不會引起與光阻層之間的混雜之防反射膜。According to the present invention, it is possible to provide an effective reflection of the reflected light from the semiconductor substrate without causing a mismatch with the photoresist layer when microfabrication using a KrF excimer laser and an ArF excimer laser or the like is performed. Reflective film.
藉由本發明,可提供一種具有較光阻為快的蝕刻速度之防反射膜。According to the present invention, an antireflection film having an etching speed faster than that of light can be provided.
又,藉由本發明之防反射膜之使用,而可於使用KrF準分子雷射及ArF準分子雷射等之微影步驟中,形成良好形狀的光阻圖型。Further, by using the antireflection film of the present invention, a photoresist pattern having a good shape can be formed in a lithography step using a KrF excimer laser or an ArF excimer laser.
本發明之微影用形成防反射膜之組成物,含有藉由具有2個縮水甘油基之環氧化合物與具有2個硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應而所得反應生成物、交聯性化合物、交聯觸媒以及溶劑。再者,本發明之微影用形成防反射膜之組成物,可含有光引發酸產生劑等。並且,於形成防反射膜之組成物中之固體成分的比例,只要是各成分能均勻溶解於溶劑中則並不特別限定,惟例如為0.5至50質量%、或1至30質量%、或3至25質量%、或5至15質量%。在此,固體成分,係指從形成防反射之組成物的全成分去除溶劑成分後者之意。The composition for forming an antireflection film for lithography of the present invention comprises an addition polymerization reaction between an epoxy compound having two glycidyl groups and a nitrogen-containing aromatic compound having two thiol groups or a hydroxyl group. The obtained reaction product, crosslinkable compound, crosslinking catalyst, and solvent. Further, the lithography of the present invention may contain a photo-initiated acid generator or the like for forming a composition of an anti-reflection film. Further, the ratio of the solid content in the composition for forming the antireflection film is not particularly limited as long as the components can be uniformly dissolved in the solvent, but is, for example, 0.5 to 50% by mass, or 1 to 30% by mass, or 3 to 25% by mass, or 5 to 15% by mass. Here, the solid content means the latter from which the solvent component is removed from the entire composition of the composition forming the antireflection.
本發明之微影用形成防反射膜之組成物,含有藉由具有2個縮水甘油基之環氧化合物與具有2個硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應而所製造之反應生成物。The composition for forming an antireflection film for lithography of the present invention comprises an addition polymerization reaction between an epoxy compound having two glycidyl groups and a nitrogen-containing aromatic compound having two thiol groups or a hydroxyl group. The reaction product produced.
環氧化合物而言,只要是具有2個縮水甘油基之化合物則並不特別限定而可使用。The epoxy compound is not particularly limited as long as it is a compound having two glycidyl groups.
具有2個縮水甘油基之環氧化合物而言,可使用二縮水甘油基醚化合物或者二羧酸二縮水甘油酯化合物。For the epoxy compound having two glycidyl groups, a diglycidyl ether compound or a dicarboxylic acid diglycidyl ester compound can be used.
二縮水甘油基醚化合物而言,可例舉:乙二醇二縮水甘油基醚、1,4-丁二醇二縮水甘油基醚、1,6-己二醇二縮水甘油基醚、1,2-雙(2,3-環氧丙氧基)苯、1,3-雙(2,3-環氧丙氧基)苯、1,4-雙(2,3-環氧丙氧基)苯、以及2,2-雙[4-(2,3-環氧丙氧)苯基]丙烷等。又,二縮水甘油基醚,係使具有2個羥基之化合物與環氧氯丙烷(epichlorohydrin)及縮水甘油對甲苯磺酸酯等化合物反應,即可製得。The diglycidyl ether compound may, for example, be ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether or 1,6-hexanediol diglycidyl ether; 2-bis(2,3-epoxypropoxy)benzene, 1,3-bis(2,3-epoxypropoxy)benzene, 1,4-bis(2,3-epoxypropoxy) Benzene, and 2,2-bis[4-(2,3-epoxypropoxy)phenyl]propane, and the like. Further, the diglycidyl ether can be obtained by reacting a compound having two hydroxyl groups with a compound such as epichlorohydrin or glycidyl p-toluenesulfonate.
二羧酸二縮水甘油酯化合物而言,可例舉:鄰苯二甲酸二縮水甘油酯、對苯二甲酸二縮水甘油酯、1,2-環己烷二羧酸二縮水甘油酯、1,4-丁烷二羧酸二縮水甘油酯、以及1,4-萘二羧酸二縮水甘油酯等。又,二羧酸二縮水甘油酯化合物,係使具有2個羧基之化合物與環氧氯丙烷及縮水甘油對甲苯磺酸酯之化合物反應,即可製得。The dicarboxylic acid diglycidyl ester compound may, for example, be diglycidyl phthalate, diglycidyl terephthalate or 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 1. 4-butanedicarboxylic acid diglycidyl ester, and 1,4-naphthalene dicarboxylic acid diglycidyl ester. Further, the dicarboxylic acid diglycidyl ester compound can be obtained by reacting a compound having two carboxyl groups with a compound of epichlorohydrin and glycidyl p-toluenesulfonate.
具有2個縮水甘油基之環氧化合物而言,又可例舉:可以式(1):
具有2個縮水甘油基之環氧化合物而言,又可例舉:雙[4-(2,3-環氧丙基硫)苯基]硫化物、雙(2,3-環氧丙基)硫化物、1,3-二縮水甘油基-5,5-二乙基巴比土酸(barbituric acid)、1,3-二縮水甘油基-5-苯基-5-乙基巴比土酸、以及1,3-二縮水甘油基-5,5-二甲基海因(hydantoin)等化合物。The epoxy compound having two glycidyl groups may, for example, be bis[4-(2,3-epoxypropylthio)phenyl]sulfide or bis(2,3-epoxypropyl). Sulfide, 1,3-diglycidyl-5,5-diethyl barbituric acid, 1,3-diglycidyl-5-phenyl-5-ethyl barbituric acid And compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin.
為製造本發明之微影用形成防反射膜之組成物中所含之藉由加成聚合反應之反應生成物之用的含氮芳香族化合物而言,只要是具有2個硫醇基或羥基之含氮芳香族化合物則並不特別限定而可使用。The nitrogen-containing aromatic compound for the reaction product of the addition polymerization reaction contained in the composition for forming the antireflection film of the present invention for producing the lithography of the present invention, as long as it has two thiol groups or hydroxyl groups. The nitrogen-containing aromatic compound is not particularly limited and can be used.
含氮芳香族化合物而言,可使用具有羥基或硫醇基之三化合物、噻二唑化合物或嘧啶化合物。For nitrogen-containing aromatic compounds, three having a hydroxyl group or a thiol group can be used. a compound, a thiadiazole compound or a pyrimidine compound.
三化合物而言,可例舉:2-二甲胺基-1,3,5-三-4,6-二硫醇、2-二乙胺基-1,3,5-三-4,6-二硫醇、2-二丁胺基-1,3,5-三-4,6-二硫醇、2-甲氧基-1,3,5-三-二硫醇、2-二丁胺基-1,3,5-三-4,6-二硫醇、2-甲硫基-1,3,5-三-4,6-二硫醇、2-N-苯胺基-1,3,5-三-4,6-二硫醇,以及二環己胺基-1,3,5-三-4,6-二硫醇等。three For the compound, it can be exemplified by 2-dimethylamino-1,3,5-three -4,6-dithiol, 2-diethylamino-1,3,5-three -4,6-dithiol, 2-dibutylamino-1,3,5-three -4,6-dithiol, 2-methoxy-1,3,5-three -dithiol, 2-dibutylamino-1,3,5-three -4,6-dithiol, 2-methylthio-1,3,5-three -4,6-dithiol, 2-N-anilino-1,3,5-three -4,6-dithiol, and dicyclohexylamino-1,3,5-three -4,6-dithiol and the like.
噻二唑化合物而言,可例舉:試鉍劑(bismuthiol:2,5-二巰基-1,3,4-噻二唑)、及5,5'-(伸乙二硫基)-雙(1,3,4-噻唑-2-硫醇)等。As the thiadiazole compound, a test agent (bismuthiol: 2,5-dimercapto-1,3,4-thiadiazole) and 5,5'-(ethylenedithio)-double can be exemplified. (1,3,4-thiazole-2-thiol) and the like.
嘧啶化合物而言,可例舉:2,6-二硫代嘌呤、2,8-二巰基-6-羥嘌呤、嘧啶-2,4-二硫醇、5,6,7,8-四氫喹唑啉-2,4-二硫醇、5-(4-氯代-苯基)嘧啶-4,6-二硫醇、5-苯基-嘧啶-4,6-二硫醇、5-甲氧-4,6-二硫醇、2,4-二巰基-5-甲基嘧啶以及2,6-二巰基-7-甲基嘧啶等。The pyrimidine compound may, for example, be 2,6-dithioindole, 2,8-dimercapto-6-hydroxyindole, pyrimidine-2,4-dithiol or 5,6,7,8-tetrahydrogen. Quinazoline-2,4-dithiol, 5-(4-chloro-phenyl)pyrimidine-4,6-dithiol, 5-phenyl-pyrimidine-4,6-dithiol, 5- Methoxy-4,6-dithiol, 2,4-dimercapto-5-methylpyrimidine, and 2,6-dimercapto-7-methylpyrimidine.
為製得本發明之微影用形成防反射膜之組成物中所含之反應生成物之用的具有2個縮水甘油基之環氧化合物與具有2個硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應,可從苯、甲苯、二甲苯、乳酸乙酯、乳酸丁酯、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、以及N-甲基吡咯烷酮等溶劑中,反應時間0.1至100小時,反應溫度20℃至200℃的範圍適當選擇條件以實施。例如,可從反應時間5至30小時,反應溫度80℃至150℃的範圍適當選擇條件以實施。並且,在此反應中,可作為觸媒而使用氯化苄基三乙基銨、氯化四丁基銨、以及溴化四乙基銨等四級銨鹽。如使用觸媒時,可對所使用之化合物的全質量,在例如0.001至30質量%、或者0.01至5質量%、或者0.1至3質量%的範圍使用。An epoxy compound having two glycidyl groups and a nitrogen-containing aromatic compound having two thiol groups or hydroxyl groups for use in producing the reaction product contained in the composition for forming an antireflection film for lithography of the present invention The addition polymerization reaction between the compounds may be carried out from solvents such as benzene, toluene, xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N-methylpyrrolidone. The reaction time is 0.1 to 100 hours, and the reaction temperature is suitably selected from the range of 20 ° C to 200 ° C to carry out. For example, conditions can be appropriately selected from the reaction time of 5 to 30 hours and the reaction temperature of 80 ° C to 150 ° C to carry out the conditions. Further, in this reaction, a quaternary ammonium salt such as benzyltriethylammonium chloride, tetrabutylammonium chloride or tetraethylammonium bromide may be used as a catalyst. When a catalyst is used, the total mass of the compound to be used can be used, for example, in the range of 0.001 to 30% by mass, or 0.01 to 5% by mass, or 0.1 to 3% by mass.
於加成聚合反應中,前述具有2個縮水甘油基之環氧化合物、及具有2個硫醇基或羥基之含氮芳香族化合物,可分別僅使用一種化合物、亦可組合二種以上的化合物使用。In the addition polymerization reaction, the epoxy compound having two glycidyl groups and the nitrogen-containing aromatic compound having two thiol groups or hydroxyl groups may be used alone or in combination of two or more compounds. use.
加成聚合反應中所使用之具有2個縮水甘油基之環氧化合物與具有2個硫醇基或羥基之含氮芳香族化合物的比例,係按環氧化合物:含氮芳香族化合物的莫耳比計,例如為3:1至1:3,或3:2至2:3,或者4:3至3:4,或者1:1。The ratio of the epoxy compound having two glycidyl groups used in the addition polymerization reaction to the nitrogen-containing aromatic compound having two thiol groups or hydroxyl groups is based on an epoxy compound: a molar of a nitrogen-containing aromatic compound The ratio is, for example, 3:1 to 1:3, or 3:2 to 2:3, or 4:3 to 3:4, or 1:1.
在具有2個縮水甘油基與具有2個硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應中,硫醇基或羥基與環氧基之間的反應,會在化合物間連續發生。而其結果,會獲得高分子量的反應生成物。因具有2個縮水甘油基之環氧化合物與具有2個硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應所生成之反應生成物,係作為重複單元構造而具有可以式(2)表示之構造之高分子量的化合物。In the addition polymerization reaction between two glycidyl groups and a nitrogen-containing aromatic compound having two thiol groups or hydroxyl groups, the reaction between the thiol group or the hydroxyl group and the epoxy group is continuous between the compounds. occur. As a result, a high molecular weight reaction product is obtained. A reaction product formed by an addition polymerization reaction between an epoxy compound having two glycidyl groups and a nitrogen-containing aromatic compound having two thiol groups or a hydroxyl group is a repeating unit structure and has a formula ( 2) A high molecular weight compound of the structure indicated.
式(2)中,R係在具有2個縮水甘油基之環氧化合物中,去除2個縮水甘油基之部分。例如,具有2個縮水甘油基之環氧化合物為乙二醇二縮水甘油基醚時,則R即成為-OCH2 CH2 O-。又,式(2)中,X表示氧原子或硫原子。Ar係對應於具有2個硫醇基或羥基之含氮芳香族化合物的芳香環構造之部分。例如,具有2個硫醇基或羥基之含氮芳香族化合物為2-二甲胺基-1,3,5-三-4,6-二硫醇時,X均表示硫原子、Ar則表示2-二甲胺基-1,3,5-三構造。In the formula (2), R is a portion in which two glycidyl groups are removed in an epoxy compound having two glycidyl groups. For example, when the epoxy compound having two glycidyl groups is ethylene glycol diglycidyl ether, R becomes -OCH 2 CH 2 O-. Further, in the formula (2), X represents an oxygen atom or a sulfur atom. The Ar system corresponds to a portion of an aromatic ring structure having a nitrogen-containing aromatic compound having two thiol groups or a hydroxyl group. For example, a nitrogen-containing aromatic compound having two thiol groups or a hydroxyl group is 2-dimethylamino-1,3,5-three In the case of -4,6-dithiol, X represents a sulfur atom, and Ar represents 2-dimethylamino-1,3,5-three. structure.
因本發明之微影用形成防反射膜之組成物中所含之具有2個縮水甘油基之化合物與具有硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應所生成之反應生成物的分子量而言,按重量平均分子量計,例如,為1000至100000、或者2000至50000、或者3000至20000。The reaction formed by the addition polymerization reaction between the compound having two glycidyl groups contained in the composition for forming the antireflection film and the nitrogen-containing aromatic compound having a thiol group or a hydroxyl group by the lithography of the present invention The molecular weight of the product is, for example, from 1,000 to 100,000, or from 2,000 to 50,000, or from 3,000 to 20,000, based on the weight average molecular weight.
本發明之微影用形成防反射膜之組成物的固體成分所佔反應生成物的比例,係例如為50至99質量%、或者60至95質量%、或者70至90質量%。如反應生成物的比例少於前述質量%的範圍之下限值時,則所形成之防反射膜的吸光性能不足夠。The ratio of the solid content of the composition forming the antireflection film to the reaction product of the lithography of the present invention is, for example, 50 to 99% by mass, or 60 to 95% by mass, or 70 to 90% by mass. When the ratio of the reaction product is less than the lower limit of the range of the aforementioned mass%, the light absorption performance of the formed antireflection film is insufficient.
於本發明之微影用形成防反射膜之組成物中,右單離(isolation)反應生成物後使用。又,亦可不單離反應生成物之下,將含有反應生成物之反應溶液直接用為本發明之微影用形成防反射膜之組成物。In the composition for forming an antireflection film of the lithography of the present invention, the right is isolated from the reaction product and used. Further, the reaction solution containing the reaction product may be directly used as a composition for forming an antireflection film for the lithography of the present invention, not separately from the reaction product.
本發明之微影用形成防反射膜之組成物中含有交聯性化合物。The lithography of the present invention contains a crosslinkable compound in the composition for forming an antireflection film.
交聯性化合物而言,可使用:具有能與因具有2個縮水甘油基之環氧化合物與具有2個硫醇基或羥基之含氮芳香族化合物之間的加成聚合反應所生成之反應生成物中所含羥基進行反應之取代基2個以上,例如2個至6個、或者2個至4個之化合物。For the crosslinkable compound, a reaction which can be formed by an addition polymerization reaction with an epoxy compound having two glycidyl groups and a nitrogen-containing aromatic compound having two thiol groups or a hydroxyl group can be used. The substituent contained in the product contains two or more substituents, for example, two to six or two to four compounds.
如使用此種交聯性化合物,即可於為形成防反射膜時的燒成時,於反應生成物與交聯性化合物之間進行反應,而所形成之防反射膜即具有交聯構造。其結果,防反射膜即變成堅固者,並成為對使用為將於其上層塗佈之光阻的溶液之有機溶劑之溶解性低者。能與反應生成物所含羥基進行反應之取代基而言,可例舉:三聚異氰酸酯基、環氧基、羥基甲胺基、以及烷氧基甲胺基等。因而,具有此等取代基2個以上,例如2個至6個,或者2個至4個之化合物即可作為交聯性化合物使用。When such a crosslinkable compound is used, it is possible to react between the reaction product and the crosslinkable compound at the time of firing in forming the antireflection film, and the formed antireflection film has a crosslinked structure. As a result, the antireflection film becomes solid and becomes low in solubility in an organic solvent using a solution which is a photoresist which is applied to the upper layer. The substituent which can react with the hydroxyl group contained in the reaction product may, for example, be a trimeric isocyanate group, an epoxy group, a hydroxymethylamino group or an alkoxymethylamino group. Therefore, a compound having two or more such substituents, for example, two to six, or two to four, can be used as the crosslinkable compound.
本發明之微影用形成防反射膜之組成物中所含交聯性化合物而言,可例舉:具有以羥甲基或烷氧甲基取代之氮原子之含氮化合物。亦即,具有以羥甲基、甲氧甲基、乙氧甲基、丁氧甲基、以及己氧甲基等基取代之氮原子之含氮化合物。In the lithographic composition of the present invention, the crosslinkable compound contained in the composition for forming the antireflection film may, for example, be a nitrogen-containing compound having a nitrogen atom substituted with a methylol group or an alkoxymethyl group. That is, a nitrogen-containing compound having a nitrogen atom substituted with a group such as a methylol group, a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group, and a hexyloxymethyl group.
具體而言,六甲氧甲基三聚氰胺、四甲氧甲基苯并鳥糞胺(guanamine)、1,3,4,6-四(丁氧甲基)甘脲、1,3,4,6-四(羥甲基)甘脲、1,3-雙(羥甲基)脲、1,1,3,3-四(丁氧甲基)脲、1,1,3,3-四(甲氧甲基)脲、1,3-雙(羥甲基)-4,5-二羥基-2-咪唑啉酮、以及1,3-雙(甲氧甲基)-4,5-二甲氧基-2-咪唑啉酮等含氮化合物。Specifically, hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, guanamine, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6- Tetrakis (hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetra(methoxy) Methyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy A nitrogen-containing compound such as 2-imidazolidinone.
交聯性化合物而言,又可例舉:三井塞特克(股)製甲氧甲基型三聚氰胺化合物(商品名塞美爾300、塞美爾301、塞美爾303、塞美爾350)、丁氧甲基型三聚氰胺化合物(商品名麥科特506、麥科特508)、甘脲化合物(商品名塞美爾1170、包達啉克1174)等化合物、甲基化脲樹脂(商品名UFR65)、丁基化脲樹脂(商品名UFR300、U-VAN10S60、U-VAN10R、U-VAN11HV)、大日本油墨化學工業(股)製脲/甲醛系樹脂(高縮合型、商品名別卡敏J-300S、別卡敏P-955、別卡敏N)等市售之化合物。又,可為使此種胺基的氫原子經以羥甲基或烷氧甲基取代之三聚氰胺化合物、脲化合物、甘脲化合物以及苯并鳥糞胺化合物縮合後所得化合物,亦可例舉:美國專利6323310號所記載之由三聚氰胺化合物(商品名塞美爾303)及苯并鳥糞胺化合物(商品名塞美爾1123)所製造之高分子量的化合物。As the crosslinkable compound, a methoxymethyl type melamine compound manufactured by Mitsui Setek (trade name: Semel 300, Semel 301, Semel 303, Semel 350) can be exemplified. , butanoxymethyl melamine compound (trade name Mecote 506, McCort 508), glycoluril compound (trade name Semel 1170, budalinker 1174) and other compounds, methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin manufactured by Dainippon Ink Chemical Industry Co., Ltd. (high condensation type, product name Kamin Commercially available compounds such as J-300S, Bikamin P-955, and Bikamin N). Further, a compound obtained by condensing a hydrogen atom of such an amine group with a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound substituted with a methylol group or an alkoxymethyl group may also be exemplified: A high molecular weight compound produced from a melamine compound (trade name Semel 303) and a benzoguanamine compound (trade name Semel 1123) as described in U.S. Patent No. 6,323,310.
又,交聯化合物而言,可採用使用N-羥甲基丙烯醯胺、N-甲氧甲基甲基丙烯醯胺、N-乙氧甲基丙烯醯胺、N-丁氧甲基甲基丙烯醯胺等經以羥甲基或烷氧甲基取代之丙烯醯胺化合物或甲基丙烯醯胺化合物所製之聚合物。此種聚合物而言,可例舉:聚(N-丁氧甲基丙烯醯胺)、N-丁氧甲基丙烯醯胺與苯乙烯的共聚物、N-羥甲基甲基丙烯醯胺與甲基甲基丙烯酸酯的共聚物、N-乙氧甲基甲基丙烯醯胺與苄基甲基丙烯酸酯的共聚物、以及N-丁氧甲基丙烯醯胺與苄基甲基丙烯酸酯與2-羥丙基甲基丙烯酸酯的共聚物等。Further, as the crosslinking compound, N-methylol acrylamide, N-methoxymethylmethacrylamide, N-ethoxymethyl decylamine, N-butoxymethylmethyl group can be used. A polymer prepared from a acrylamide compound or a methacrylamide compound substituted with a methylol group or an alkoxymethyl group, such as acrylamide. Such a polymer may, for example, be a poly(N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, or N-methylol methacrylamide. Copolymer with methyl methacrylate, copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, and N-butoxymethyl acrylamide and benzyl methacrylate Copolymer with 2-hydroxypropyl methacrylate, etc.
交聯性化合物,可僅使用一種化合物,亦可組合二種以上的化合物使用。The crosslinkable compound may be used alone or in combination of two or more.
本發明之微影用形成防反射膜之組成物之固體成分中所佔交聯性化合物的比例而言,例如為0.1至40質量%、或者3至35質量%、或者5至25質量%。The ratio of the crosslinkable compound in the solid content of the composition for forming the antireflection film of the present invention is, for example, 0.1 to 40% by mass, or 3 to 35% by mass, or 5 to 25% by mass.
本發明之微影用形成防反射膜之組成物中,含有交聯觸媒。如使用交聯觸媒,即可促進交聯性化合物的反應。The composition for forming an antireflection film for lithography of the present invention contains a crosslinking catalyst. If a cross-linking catalyst is used, the reaction of the crosslinkable compound can be promoted.
交聯觸媒而言,可使用:對甲苯磺酸、三氟甲烷磺酸、吡啶鎓對甲苯磺酸、水楊酸、樟腦磺酸、磺基水楊酸、檸檬酸、安息酸、以及羥基安息酸等酸化合物。For the cross-linking catalyst, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxyl group can be used. An acid compound such as benzoic acid.
交聯觸媒而言,可使用芳香族磺酸化合物。芳香族磺酸化合物的具體例而言,可例舉:對甲苯磺酸、吡啶鎓對甲苯磺酸、磺基水楊酸、4-氯苯磺酸、4-羥苯磺酸、苯二磺酸、1-萘磺酸、以及吡啶鎓-1-萘磺酸等。For the cross-linking catalyst, an aromatic sulfonic acid compound can be used. Specific examples of the aromatic sulfonic acid compound include p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, and benzene disulfonate. Acid, 1-naphthalenesulfonic acid, pyridinium-1-naphthalenesulfonic acid, and the like.
交聯觸媒,可僅使用一種,亦可組合二種以上使用。The cross-linking catalyst may be used alone or in combination of two or more.
本發明之微影用形成防反射膜之組成物之固體成分中所佔交聯觸媒的比例而言,例如為0.1至10質量%,或者0.2至5質量%、或者0.5至5質量%。The ratio of the cross-linking catalyst to the solid content of the composition for forming the anti-reflection film of the present invention is, for example, 0.1 to 10% by mass, or 0.2 to 5% by mass, or 0.5 to 5% by mass.
本發明之微影用形成防反射膜之組成物中,可含有光引發酸產生劑。光引發酸產生劑,會有光阻的曝光時產生酸。因而,可實施防反射膜的酸度(acidity)的調整。此乃係一種為將防反射膜的酸度配合上層的光阻的酸度之方法。又,因防反射膜的酸度的調整,亦可實施上層所形成之光阻的圖型形狀的調整。The composition for forming an antireflection film for lithography of the present invention may contain a photoinitiating acid generator. The photoinitiator generates an acid which generates an acid upon exposure to a photoresist. Thus, the adjustment of the acidity of the antireflection film can be performed. This is a method for matching the acidity of the antireflection film to the acidity of the photoresist of the upper layer. Moreover, the adjustment of the acidity of the antireflection film can also adjust the pattern shape of the photoresist formed by the upper layer.
光引發酸產生劑而言,可例舉:鎓鹽化合物、磺醯亞胺化合物、以及二磺醯基重氮甲烷化合物等。The photo-initiating acid generator may, for example, be an onium salt compound, a sulfonium imine compound, or a disulfonyldiazomethane compound.
鎓鹽化合物而言,可例舉:二苯基碘鎓六氟磷酸酯、二苯基碘鎓三氟甲烷磺酸酯、二苯基碘鎓九氟正丁烷磺酸酯、二苯基碘鎓全氟正辛烷磺酸酯、二苯基碘鎓樟腦磺酸酯、雙(4-第三丁苯基)碘鎓樟腦磺酸酯以及雙(4-第三丁苯基)碘鎓三氟甲烷磺酸酯等碘鎓鹽化合物、以及三苯基鋶(sulfonium)六氟銻酸酯、三苯基鋶九氟正丁烷磺酸酯、三氟鋶樟腦磺酸酯以及三苯基鋶三氟甲烷磺酸酯等鋶鹽化合物等。The onium salt compound may, for example, be diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate or diphenyliodine.鎓Perfluoro-n-octane sulfonate, diphenyl iodonium sulfonate, bis(4-tert-butylphenyl) iodonium sulfonate, and bis(4-tert-butylphenyl) iodonium Iodine salt compound such as fluoromethanesulfonate, and sulfonium hexafluoroantimonate, triphenylsulfonium nonafluorobutane sulfonate, trifluoro camphorsulfonate, and triphenylsulfonium An onium salt compound such as trifluoromethanesulfonate or the like.
磺醯亞胺化合物而言,可例舉:N-(三氟甲烷磺醯氧)琥珀醯亞胺、N-(九氟正丁烷磺醯氧)琥珀醯亞胺、N-(樟腦磺醯氧)琥珀醯亞胺以及N-(三氟甲烷磺醯氧)萘二甲醯亞胺等。The sulfonimide compound may, for example, be N-(trifluoromethanesulfonyloxy)arene, N-(nonafluoro-n-butanesulfonyloxy)arene, N-( camphorsulfonate) Oxygen) amber imine and N-(trifluoromethanesulfonyloxy)naphthylimine.
二磺醯基重氮甲烷化合物而言,可例舉:雙(三氟甲基磺醯基)重氮甲烷、雙(環己基磺醯基)重氮甲烷、雙(苯基磺醯基)重氮甲烷、雙(對甲苯磺醯基)重氮甲烷、雙(2,4-二甲基苯磺醯基)重氮甲烷、以及甲基磺醯基對甲苯磺醯基重氮甲烷等。The disulfonyldiazomethane compound may, for example, be bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane or bis(phenylsulfonyl) Nitrogen methane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and methylsulfonyl p-toluenesulfonyldiazomethane.
光引發酸產生劑,可僅使用一種,亦可組合二種以上使用。The photoinitiator may be used alone or in combination of two or more.
如本發明之微影用形成防反射膜之組成物中含有光引發酸產生劑時,其含量而言,在固體成分中例如為0.01至5質量%、或者0.1至3質量%、或者0.5至2質量%。When the photo-initiated acid generator is contained in the composition for forming an anti-reflection film according to the present invention, the content thereof is, for example, 0.01 to 5% by mass, or 0.1 to 3% by mass, or 0.5 to 5% in the solid content. 2% by mass.
本發明之微影用形成防反射膜之組成物中,需要時可添加表面活性劑、流變學(rheology)調整劑以及黏接補助劑等。表面活性劑係為抑制針孔(pin hole)或條紋(striation)等發生方面有效者。流變學調整劑,係改善形成防反射膜之組成物的流動性,特別是在燒成步驟中,為提高對孔(hole)內部的形成防反射膜之組成物的塡充性方面有效者。黏接補助劑,係改善半導體基板或光阻與防反射膜間的密接性,特別是在顯像時為抑制光阻的剝離方面有效者。In the composition for forming an antireflection film for lithography of the present invention, a surfactant, a rheology modifier, an adhesion aid, and the like may be added as needed. The surfactant is effective for suppressing occurrence of pin holes or striations. The rheology modifier is for improving the fluidity of the composition forming the antireflection film, particularly in the step of firing, in order to improve the adhesion of the composition forming the antireflection film inside the hole. . The adhesion aid is used to improve the adhesion between the semiconductor substrate or the photoresist and the antireflection film, and is particularly effective for suppressing peeling of the photoresist during development.
表面活性劑而言,可例舉:聚氧化乙烯月桂基醚、聚氧化乙烯硬脂基醚、聚氧化乙烯鯨蠟基醚、聚氧化乙烯油烯基醚等聚氧化乙烯烷基醚類;聚氧化乙烯辛基苯酚醚、聚氧化乙烯壬基苯酚醚等聚氧化乙烯烷基芳基醚類;聚氧化乙烯.聚氧化丙烯成塊共聚物(block copolymer)類;山梨糖醇酐單月桂酸酯、山梨糖醇酐單棕櫚酸酯、山梨糖醇酐單硬脂酸酯、山梨糖醇酐單油酸酯、山梨糖醇酐三油酸酯、山梨糖醇酐三硬脂酸酯等山梨糖醇酐脂肪酸酯類;聚氧化乙烯山梨糖醇酐單月桂酸酯、聚氧化乙烯山梨糖醇酐單棕櫚酸酯、聚氧化乙烯山梨糖醇酐單硬脂酸酯、聚氧化乙烯山梨糖醇酐三油酸酯、聚氧化乙烯山梨糖醇酐三硬脂酸酯等聚氧化乙烯山梨糖脂肪酸酯類等非離子系表面活性劑;商品名埃富特補EF301、EF303、EF352(東化學產品(股)製)、商品名美加法克F171、F173、R-08、R-30(大日本油墨化學工業(股)製)、富樂拉特FC430、FC431(住友3M(股)製)、商品名旭蓋特AG710、沙弗隆S-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子(股)製)等氟系表面活性劑,以及有機矽氧烷聚合物KP341(信越化學工業(股)製)等。此等表面活性劑可以單獨使用,亦可以組合二種以上之方式使用。如本發明之形成防反射膜之組成物中含有表面活性劑時,則其含量係在固體成分中為0.0001至5質量%、或者0.001至2質量%。The surfactant may, for example, be a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether or polyoxyethylene oleyl ether; Polyoxyethylene alkyl aryl ethers such as oxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyethylene oxide. Polypropylene oxide block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitol fatty acid esters such as sorbitan trioleate, sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate Non-ionic such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactant; trade name Effort EF301, EF303, EF352 (made by Dong Chemical Products Co., Ltd.), trade name Mecca F171, F173, R-08, R-30 (Daily Ink Chemical Industry Co., Ltd. )), Fullerate FC430, FC431 (Sumitomo 3M (share) system), trade name Xugete AG710, Schaffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) A fluorine-based surfactant, and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used singly or in combination of two or more. When a surfactant is contained in the composition for forming an antireflection film of the present invention, the content thereof is 0.0001 to 5% by mass, or 0.001 to 2% by mass in the solid content.
可使用於本發明微影用形成防反射膜之組成物之溶劑而言,只要是能溶解前述固體成分之溶劑者,均可使用。此種溶劑而言,可例舉:乙二醇單甲基醚、乙二醇單乙基醚、甲基溶纖素乙酸酯、乙基溶纖素乙酸酯、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、丙二醇丙基醚、甲苯、二甲苯、甲基乙基甲酮、環戊酮、環己酮、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧丙酸甲酯、3-甲氧丙酸乙酯、3-乙氧丙酸乙酯、3-乙氧丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、以及乳酸丁酯等。此等溶劑可以單獨,或組合二種以上之方式使用。再者,可混合丙二醇單丁基醚、丙二醇單丁基醚乙酸酯等高沸點溶劑使用。The solvent used for the composition for forming the antireflection film for lithography of the present invention can be used as long as it is a solvent capable of dissolving the solid component. Such a solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl fibrin acetate, ethyl fibrin acetate, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, Cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3 -methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, acetic acid Butyl ester, ethyl lactate, and butyl lactate. These solvents may be used singly or in combination of two or more. Further, a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate may be used.
以下,就本發明之微影用形成防反射膜之組成物的使用加以說明。Hereinafter, the use of the composition for forming an antireflection film for lithography of the present invention will be described.
於半導體基板(例如,矽晶圓基板,矽/二氧化矽被覆基板、矽氮化物基板、以及ITO(銦錫氧化物)基板等)之上,使用旋塗器、塗佈器等適當塗佈方法塗佈本發明之形成防反射膜之組成物,然後燒成即可形成防反射膜。燒成之條件而言,可適當選自燒成溫度80℃至250℃、燒成時間0.3至60分鐘之中。較佳為燒成溫度150℃至250℃、燒成時間0.5至5分鐘。在此,所形成之防反射膜之膜厚而言,例如為0.01至3.0μm、較佳為例如0.03至1.0μm、或者0.05至0.5μm、或者0.05至0.2μm。Applying on a semiconductor substrate (for example, a tantalum wafer substrate, a tantalum/yttria-coated substrate, a tantalum nitride substrate, and an ITO (indium tin oxide) substrate), using a spin coater, an applicator, or the like Method The composition for forming an antireflection film of the present invention is applied and then fired to form an antireflection film. The firing conditions may be appropriately selected from the range of firing temperature of 80 ° C to 250 ° C and firing time of 0.3 to 60 minutes. The firing temperature is preferably from 150 ° C to 250 ° C and the firing time is from 0.5 to 5 minutes. Here, the film thickness of the antireflection film formed is, for example, 0.01 to 3.0 μm, preferably 0.03 to 1.0 μm, or 0.05 to 0.5 μm, or 0.05 to 0.2 μm, for example.
其次,於防反射膜上,形成光阻之層。光阻層之形成,則可依周知之方法,亦即,將光阻組成物溶液塗佈於防反射膜上並實施燒成。Next, on the antireflection film, a layer of photoresist is formed. In the formation of the photoresist layer, the photoresist composition solution can be applied to the antireflection film by a known method and fired.
將塗佈形成於本發明之防反射膜上之光阻而言,只要是能對使用為曝光之光感光者則並不特別限定。負型光阻及正型光阻之任一種均可使用。有:酚醛清漆樹脂與1,2-萘醌二疊氮基磺酸酯所成正型光阻,由因酸而分解並具有使鹼溶解速度加速之基之黏合劑(binder)與光引發酸產生劑所成化學放大型光阻、由因酸而分解並使光阻的鹼溶解速度加速之低分子化合物與鹼可溶性黏合劑與光引發酸產生劑所成化學放大型光阻、以及由因酸而分解並使鹼溶解速度加速之基之黏合劑與因酸而分解並使鹼溶解速度加速之低分子化合物與光引發酸產生劑所成化學放大型光阻等。又可例舉;如攝影儀器工程師學會會誌(Proc.SPIE),第3999卷,第330至334頁,(2000年出版)、攝影儀器工程師學會會誌,第3999卷,第357至364頁(2000年出版),或攝影儀器工程師學會會誌,第3999卷,第365至374頁(2000年出版)所記載之含氟原子聚合物系光阻。The photoresist which is applied to the antireflection film of the present invention is not particularly limited as long as it can be used for light exposure to be used for exposure. Any of a negative photoresist and a positive photoresist can be used. There are: a photoresist of a novolac resin and a 1,2-naphthoquinonediazide sulfonate, which is formed by a binder and a photo-initiated acid which are decomposed by an acid and have a base for accelerating the dissolution rate of the alkali. The chemically amplified photoresist, the chemically amplified photoresist formed by the low molecular compound which is decomposed by acid and accelerates the alkali dissolution rate of the photoresist, and the alkali-inducing binder and the photoinitiated acid generator, and the acid The binder which decomposes and accelerates the alkali dissolution rate and the low-molecular compound which decomposes by the acid and accelerates the alkali dissolution rate, and the photo-initiated acid generator form a chemically amplified photoresist. Also exemplified; such as the Society of Photographic Instrumentation Engineers (Proc. SPIE), Vol. 3999, pp. 330-334 (published in 2000), Society of Photographic Instrumentation Engineers, Vol. 3999, pp. 357-364 (published in 2000), or the fluorine atomic polymer system photoresist described in Journal of the Society of Photographic Instrumentation Engineers, Vol. 3999, pp. 365-374 (published in 2000).
其次,透過既定的遮光罩(mask)而進行曝光。曝光時,可使用KrF準分子雷射(波長248nm)、ArF準分子雷射(波長193nm)、以及F2 準分子雷射(波長157nm)等。曝光後,需要時,亦可實施曝光後加熱(post exposure bake曝光後之烘烤處理)。曝光後加熱,可從溫度70℃至150℃、時間0.3至10分鐘的範圍適當選擇實施。Next, exposure is performed through a predetermined mask. At the time of exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and an F 2 excimer laser (wavelength 157 nm) can be used. After exposure, if necessary, post-exposure heating (bake treatment after post exposure bake exposure) can also be performed. The post-exposure heating can be appropriately selected from the range of a temperature of 70 ° C to 150 ° C and a time of 0.3 to 10 minutes.
其次,使用顯像液以進行顯像。由此,例如使用正型光阻時,被曝光的部分的光阻去除,而將形成光阻的圖型。Next, a developing solution is used for development. Thus, for example, when a positive photoresist is used, the photoresist of the exposed portion is removed, and a pattern of photoresist is formed.
顯像液而言,可例舉:氫氧化鉀、氫氧化鈉等鹼金屬氫氧化物的水溶液、氫氧化四甲銨、氫氧化四乙銨、膽鹼(choline)等氫氧化四級銨的水溶液、乙醇胺、丙胺、伸乙二胺等胺水溶液等鹼性水溶液。顯像液而言,可使用泛用之2.38質量%的氫氧化四甲銨水溶液。再者,亦可於此等顯像液中添加表面活性劑。顯像條件而言,可從溫度5至50℃、時間10至300秒中適當選擇。The developing solution may, for example, be an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, or a tetraammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline. An aqueous alkaline solution such as an aqueous solution, an amine solution such as ethanolamine, propylamine or ethylenediamine. For the developing liquid, a general-purpose 2.38 mass% aqueous solution of tetramethylammonium hydroxide can be used. Further, a surfactant may be added to the developing solution. The development conditions can be appropriately selected from a temperature of 5 to 50 ° C and a time of 10 to 300 seconds.
然後,將如此所形成之光阻圖型作為保護膜,進行防反射膜之去除及半導體基板之加工。防反射膜之去除,可使用四氟甲烷、全氟環丁烷(C4 F8 )、全氟丙烷(C3 F8 )、三氟甲烷、一氧化碳、氬氣、氧氣、氮氣、六氟化硫、二氟甲烷、三氟化氮以及三氟化氯等氣體實施。Then, the photoresist pattern thus formed is used as a protective film to remove the antireflection film and process the semiconductor substrate. For the removal of the antireflection film, tetrafluoromethane, perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, hexafluoride can be used. Gases such as sulfur, difluoromethane, nitrogen trifluoride, and chlorine trifluoride are used.
在半導體基板上,使用本發明之微影用形成防反射膜之組成物以形成防反射膜之前,亦可形成平坦化膜或間隙塡充(gap filling)材料層。如使用具有孔或較大高低差之半導體基板之半導體基板時,則在形成防反射之前,較佳為形成有平坦化膜或間隙塡充材料層。A planarization film or a gap filling material layer may be formed on the semiconductor substrate before the composition for forming the antireflection film is formed by using the lithography of the present invention to form the antireflection film. When a semiconductor substrate having a hole or a semiconductor substrate having a large height difference is used, it is preferable to form a planarizing film or a gap-filling material layer before forming anti-reflection.
又,將塗佈本發明之形成防反射膜之組成物之半導體基板,可為具有依CVD法所形成之無機系的防反射膜者,亦可於其上面形成本發明之防反射膜。Moreover, the semiconductor substrate to which the composition for forming an antireflection film of the present invention is applied may be an inorganic antireflection film formed by a CVD method, or an antireflection film of the present invention may be formed thereon.
再者,由本發明之微影用形成防反射膜之組成物所形成之防反射膜,亦能作為:為防止基板與光阻之間的相互作用之層,為防止光阻所用材料或對光阻的曝光時所生成物質對基板的惡作用之層,為防止燒成時從基板所生成物質對上層光阻的擴散之層,以及為減少半導體基板介電體層所引起的光阻層的中毒效果(poisoning effect)之阻障層(barrier layer)等使用。Further, the anti-reflection film formed by the composition for forming an anti-reflection film of the lithography of the present invention can also be used as a layer for preventing interaction between the substrate and the photoresist, and a material for preventing photoresist or for light-proofing. The layer of the substance generated on the substrate during the exposure is resistant to the diffusion of the substance generated from the substrate during the firing to the upper layer resist, and the poisoning of the photoresist layer caused by the dielectric layer of the semiconductor substrate is reduced. It is used for a barrier layer or the like of a poisoning effect.
又,由本發明之形成防反射膜之組成物所形成之防反射膜,如適用於雙道金屬鑲嵌步驟(dual damascene process)中所使用之形成有介層洞(via hole)之基板時,亦可使用為作為能按無間隙之方式塡充介層洞之塡埋材料。又亦可使用為作為使具有凹凸之半導體基板表面平坦化的平坦化材料。Further, when the antireflection film formed of the composition for forming an antireflection film of the present invention is applied to a substrate on which a via hole is formed for use in a dual damascene process, It can be used as a buried material that can fill a via hole in a gap-free manner. Further, it is also possible to use a planarizing material as a surface for flattening the surface of the semiconductor substrate having irregularities.
以下,藉由實施例以更具體說明本發明內容,惟本發明並不因此等實施例而有所限定。In the following, the present invention will be more specifically described by the examples, but the invention is not limited thereto.
於丙二醇單甲基醚21.5g中添加2-二甲胺基-4,6-二硫醇-1,3,5-三2.25g、乙二醇二縮水甘油醚2.00g、以及作為觸媒之氯化苄基三乙基銨0.14g後,在回流下反應24小時,製得含有反應生成物之溶液。實施所得反應生成物的GPC(凝膠滲透色譜)分析結果,按標準聚苯乙烯換算計,重量平均分子量為5800。所得反應生成物,可推測為具有可以式(3)表示之重複單元之構造者。Add 2-dimethylamino-4,6-dithiol-1,3,5-three to 21.5 g of propylene glycol monomethyl ether 2.25 g, ethylene glycol diglycidyl ether 2.00 g, and 0.14 g of benzyltriethylammonium chloride as a catalyst were reacted under reflux for 24 hours to obtain a solution containing a reaction product. The GPC (gel permeation chromatography) analysis of the obtained reaction product was carried out, and the weight average molecular weight was 5,800 in terms of standard polystyrene. The obtained reaction product can be estimated to have a structure in which a repeating unit represented by the formula (3) is present.
於丙二醇單乙基醚30.71g中添加2-二丁胺基-4,6-二硫醇-1,3,5-三(三協化成(股)製,商品名吉時耐得BD)3.53g、對苯二甲酸二縮水甘油醚4.00g、以及作為觸媒之氯化苄基三乙基銨0.15g後,在回流下反應24小時,製得含有反應生成物之溶液。實施所得反應生成物的GPC分析結果,按標準聚苯乙烯換算計,重量平均分子量為7000。所得反應生成物,可推測為具有可以式(4)表示之重複單元之構造者。Add 2-dibutylamino-4,6-dithiol-1,3,5-three to propylene glycol monoethyl ether 30.71g (Sanxie Chemical Co., Ltd., product name: Kyrgyzstan BD) 3.53g, terephthalic acid diglycidyl ether 4.00g, and 0.15g of benzyltriethylammonium chloride as a catalyst, after reflow The reaction was carried out for 24 hours to obtain a solution containing the reaction product. The GPC analysis result of the obtained reaction product was carried out, and the weight average molecular weight was 7,000 in terms of standard polystyrene. The obtained reaction product can be estimated to have a structure in which a repeating unit represented by the formula (4) can be used.
於丙二醇單甲基醚24.45g中添加2-二丁胺基-4,6-二硫醇-1,3,5-三(三協化成(股)製、商品名吉時耐得BD)2.99g、單芳基二縮水甘油三聚異氰酸3.00g、以及作為觸媒之氯化苄基三乙基胺0.12g後,在回流下反應24小時,製得含有反應生成物之溶液。實施所得反應生成物的GPC分析結果,按標準聚苯乙烯換算計,重量平均分子量為15400。所得反應生成物,可推測為具有可以式(5)表示之重複單元之構造者。Add 2-dibutylamino-4,6-dithiol-1,3,5-three to propylene glycol monomethyl ether 24.45g (Sanxiehuacheng (share) system, the product name JI shi BD) 2.99g, monoaryl diglycidyl trimeric isocyanate 3.00g, and 0.14g of benzyl triethylamine chloride as a catalyst The reaction was carried out under reflux for 24 hours to obtain a solution containing the reaction product. The GPC analysis result of the obtained reaction product was carried out, and the weight average molecular weight was 15,400 in terms of standard polystyrene. The obtained reaction product is presumed to have a structure in which a repeating unit represented by the formula (5) is present.
於丙二醇單甲基醚63.77g中添加2-硫甲基-4,6-二硫醇-1,3,5-三5.54g、單芳基二縮水甘油三聚異氰酸10.00g、以及作為觸媒之氯化苄基三乙基銨0.40g後,在回流下反應24小時,製得含有反應生成物之溶液。實施所得反應生成物的GPC分析之結果,按標準聚苯乙烯換算計,重量平均分子量為15500。所得反應生成物,可推測為具有可以(6)表示之重複單元之構造者。Add 2-thiomethyl-4,6-dithiol-1,3,5-three to 63.77g of propylene glycol monomethyl ether 5.54 g, 10.00 g of monoaryl diglycidyl tripolyisocyanate, and 0.40 g of benzyltriethylammonium chloride as a catalyst were reacted under reflux for 24 hours to obtain a solution containing a reaction product. The GPC analysis of the obtained reaction product was carried out, and the weight average molecular weight was 15,500 in terms of standard polystyrene. The obtained reaction product can be estimated to have a structure of a repeating unit which can be represented by (6).
於丙二醇單甲基醚43.80g中添加試鉍劑(bismuthiol)4.00g、乙二醇二縮水甘油醚6.68g、以及作為觸媒之氯化苄基三乙基銨0.18g後,在回流下反應24小時,製得含有反應生成物之溶液。實施所得反應生成物的GPC分析結果,按標準聚苯乙烯換算計,重量平均分子量為4500。所得反應生成物,可推測為具有可以(7)表示之重複單元之構造者。Adding 4.50 g of bismuthiol, 6.68 g of ethylene glycol diglycidyl ether, and 0.18 g of benzyltriethylammonium chloride as a catalyst to 43.80 g of propylene glycol monomethyl ether, and reacting under reflux A solution containing the reaction product was obtained for 24 hours. The GPC analysis result of the obtained reaction product was carried out, and the weight average molecular weight was 4,500 in terms of standard polystyrene. The obtained reaction product is presumed to have a structure of a repeating unit which can be represented by (7).
於前述合成例1所得溶液3.92g中混合丙二醇單甲基醚2.50g、乳酸乙酯13.3g、四甲氧甲基甘脲(三井塞特克(股)製、商品名包達啉克1174)0.20g、以及吡啶鎓對甲苯磺酸0.02g,並作成5質量%溶液。然後,使用篩孔徑0.05μm的聚乙烯製微過濾器(micro filter)過濾,以調製微影用形成防反射膜之組成物的溶液。To 3.92 g of the solution obtained in the above Synthesis Example 1, 2.50 g of propylene glycol monomethyl ether, 13.3 g of ethyl lactate, and tetramethoxymethyl glycoluril (manufactured by Mitsui Setek Co., Ltd., trade name: budadolin 1174) were mixed. 0.20 g and 0.02 g of pyridinium p-toluenesulfonic acid were prepared as a 5 mass% solution. Then, it was filtered using a polyethylene microfilter having a sieve opening of 0.05 μm to prepare a solution for forming a composition of the antireflection film by lithography.
按與實施例1同樣方式,於合成例2至5所得溶液3.92g中,分別混合丙二醇單乙基醚2.56g、乳酸乙酯13.3g、四甲氧甲基甘脲(三並塞特克(股)製、商品名包達啉克1174)0.20g、以及吡啶鎓對甲苯磺酸0.02g,並作成5質量%溶液。然後,使用篩孔徑0.05μm的聚乙烯製微過濾器過濾,以調製微影用形成防反射膜之組成物的溶液。In the same manner as in Example 1, in the 3.92 g of the solutions obtained in Synthesis Examples 2 to 5, 2.66 g of propylene glycol monoethyl ether, 13.3 g of ethyl lactate, and tetramethoxymethyl glycoluril (triple dextran ( The product was made into a 5% by mass solution of 0.20 g of palladium ketone 1174) and 0.02 g of pyridinium p-toluenesulfonic acid. Then, it was filtered using a polyethylene microfilter having a sieve opening of 0.05 μm to prepare a solution for forming a composition of the antireflection film by lithography.
使用旋塗器,分別將實施例1至5所得溶液塗佈於矽晶圓基板上。然後,在熱板上,205℃下燒成1分鐘,以形成防反射膜(膜厚0.078μm)。將此防反射膜浸漬於使用為光阻之溶劑之乳酸乙酯及丙二醇單甲基醚中,以確認不溶於該溶劑之事實。又,浸漬於光阻顯現用的鹼性顯像液中,以確認不溶之事實。The solutions obtained in Examples 1 to 5 were each applied onto a tantalum wafer substrate using a spin coater. Then, it was baked at 205 ° C for 1 minute on a hot plate to form an antireflection film (film thickness: 0.078 μm). This antireflection film was immersed in ethyl lactate and propylene glycol monomethyl ether using a solvent which is a photoresist to confirm the fact that it was insoluble in the solvent. Further, it was immersed in an alkaline developing solution for developing a photoresist to confirm the fact that it was insoluble.
使用旋塗器,分別將實施例1至5所得溶液塗佈於矽晶圓基板上。然後,在熱板上,205℃燒成1分鐘,以形成防反射膜(膜厚0.078μm)。然後,使用分光橢圓對稱計(ellipsometer)(J.A.Woollan社製、VUV-VASE VU-302),測定此等防反射膜在波長248nm及波長193nm下的折射率(n)值及消光係數(extinction coefficient)(k值)。結果如表1及表2所示。The solutions obtained in Examples 1 to 5 were each applied onto a tantalum wafer substrate using a spin coater. Then, it was baked at 205 ° C for 1 minute on a hot plate to form an antireflection film (film thickness: 0.078 μm). Then, using a ellipsometer (manufactured by JAWoollan Co., Ltd., VUV-VASE VU-302), the refractive index (n) value and the extinction coefficient of the antireflection film at a wavelength of 248 nm and a wavelength of 193 nm were measured. ) (k value). The results are shown in Tables 1 and 2.
按與上述同樣方法,使用實施例1至5的溶液,於矽晶圓基板上形成防反射膜。然後,在使用日本科學(股)製RIE(reactive ion etching system,反應性離子蝕刻系統)ES401,作為乾蝕刻氣體而使用CF4 之條件下,測定此等防反射膜的乾蝕刻速度。An antireflection film was formed on the tantalum wafer substrate by using the solutions of Examples 1 to 5 in the same manner as above. Then, in the case of using Japan Science (shares) manufactured by RIE (reactive ion etching system, a reactive ion etching systems) ES401, was used as dry etching gas CF 4 conditions, the measurement of these anti-reflection film dry etching rate.
又,使用旋塗器,將光阻溶液(住友化學工業(股)製,商品名PAR710)塗佈於矽晶圓基板上,並在加熱板上90℃下燒成1分間,以形成光阻層。然後,在使用日本科學(股)製RIE系統ES401,作為乾蝕刻氣體而使用CF4 之條件下,測定光阻PAR710的乾蝕刻速度。實施由實施例1至5所得防反射膜與光阻的乾蝕刻速度的比較。結果如表1及表2所示。Further, a photoresist solution (manufactured by Sumitomo Chemical Co., Ltd., trade name PAR710) was applied onto a tantalum wafer substrate by a spin coater, and fired at a temperature of 90 ° C for 1 minute on a hot plate to form a photoresist. Floor. Then, the dry etching rate of the photoresist PAR710 was measured under the condition that CF 4 was used as a dry etching gas using the RIE system ES401 manufactured by Nippon Scientific Co., Ltd. A comparison of the dry etching rates of the antireflection films obtained in Examples 1 to 5 and the photoresist was carried out. The results are shown in Tables 1 and 2.
表1,表示在波長248nm下的折射率(n值)及消光係數(k值),表2則表示在波長193nm下的折射率(n值)及消光係數(k值)。Table 1 shows the refractive index (n value) and the extinction coefficient (k value) at a wavelength of 248 nm, and Table 2 shows the refractive index (n value) and the extinction coefficient (k value) at a wavelength of 193 nm.
又,表1及表2中,選擇比表示當光阻PAR710的乾蝕刻速度作為1.00時之由各實施例所形成之防反射膜的乾蝕刻速度。Further, in Tables 1 and 2, the selection ratio indicates the dry etching rate of the antireflection film formed by each of the examples when the dry etching rate of the photoresist PAR710 is 1.00.
從表1及表2可知,由本發明之形成防反射膜之組成物所得防反射膜,對波長248nm及193nm的光具有有效的折射率及消光係數之事實。又,可知對光阻具有較快速蝕刻速度之事實。As is apparent from Tables 1 and 2, the antireflection film obtained from the composition for forming an antireflection film of the present invention has an effective refractive index and extinction coefficient for light having wavelengths of 248 nm and 193 nm. Moreover, the fact that the photoresist has a relatively fast etching speed is known.
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