TW201527577A - 半導體元件的製造方法 - Google Patents
半導體元件的製造方法 Download PDFInfo
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- TW201527577A TW201527577A TW103141124A TW103141124A TW201527577A TW 201527577 A TW201527577 A TW 201527577A TW 103141124 A TW103141124 A TW 103141124A TW 103141124 A TW103141124 A TW 103141124A TW 201527577 A TW201527577 A TW 201527577A
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- Prior art keywords
- ene
- group
- hept
- meth
- acrylate
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Classifications
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/06—Organic solvent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/14—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers obtained by ring-opening polymerisation of carbocyclic compounds having one or more carbon-to-carbon double bonds in the carbocyclic ring, i.e. polyalkeneamers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L33/04—Homopolymers or copolymers of esters
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- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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Abstract
提供一種半導體元件的製造方法,係具備以下步驟之半導體元件的製造方法:半導體層形成步驟,其係在基板上形成含有無機氧化物半導體之半導體層;鈍化膜形成步驟,其係將由有機材料所構成之鈍化膜成膜,以覆蓋前述半導體層;煅燒步驟,其係將前述鈍化膜進行煅燒;及冷卻步驟,其係煅燒後,進行冷卻;其特徵在於:在前述冷卻步驟進行冷卻時,將從前述煅燒步驟之煅燒時的煅燒溫度起至比煅燒時的煅燒溫度更低50℃的溫度為止之冷卻速度,實質地控制在0.5~5℃/分鐘的範圍。
Description
本發明係有關於一種半導體元件的製造方法,更詳言之,係有關於一種用以製造閥值電壓vth為接近零且移動度高的半導體元件之方法、及使用該製造方法而得到之半導體元件。
半導體元件係廣泛地被使用在電子製品。例如,作為半導體元件的一個例子之薄膜電晶體,係具有閘極電極、源極電極及汲極電極之開關元件,已被廣泛地應用在主動矩陣型液晶顯示器、有機電致發光等的顯示元件的主動矩陣基板之主動元件等。
在先前的薄膜電晶體,係藉由濺鍍法、氣相沉積法、CVD法在半導體層表面形成由矽氮化膜(SiNX膜)所構成之鈍化膜(保護膜)。但是,在形成由如矽氮化膜的無機材料所構成的鈍化膜之方法,鈍化膜的成膜係必須使材料在真空中電漿化、使其離子化等的狀態下形成膜,而有設備為大規模且操作麻煩之問題。又,將由無機材料所構成之鈍化膜除去、欲將材料和製法變更成為能夠使用較簡便製程的成膜法來成膜之方法等時,有可靠性變差之問題。
對此,例如專利文獻1係提案揭示一種使用有機
材料來形成薄膜電晶體的鈍化膜之方法。在此專利文獻1,係使用含有選自環狀烯烴聚合物、丙烯酸樹脂、卡多樹脂(cardo resin)、聚矽氧烷或聚醯亞胺之至少一種樹脂、及交聯劑之熱交聯性樹脂組成物,作為用以形成鈍化膜之有機材料。但是,此專利文獻1係使用由非晶矽層所構成的半導體層之技術,例如,將半導體層設作銦鎵鋅氧化物(IGZO)等的無機氧化物半導體時,有閥值電壓vth的絕對值變大、移動度低落等之課題。
[專利文獻1]國際公開第2011/108533號
本發明之目的,係提供一種用以製造閥值電壓vth為接近零且移動度高的半導體元件之方法、及使用此種製造方法而得到之半導體元件。
為了達成上述目的,本發明人們專心研討的結果,發現在製造使用含有無機氧化物半導體的半導體層之半導體元件時,形成由有機材料所構成之鈍化膜以覆蓋前述半導體層,且煅燒之後,藉由以預定的冷卻速度進行煅燒後的冷卻,能夠解決上述課題,而完成了本發明。
亦即,依照本發明,能夠提供一種半導體元件的製造方法,係具備以下步驟之半導體元件的製造方法:半導體層形成步驟,其係在基板上形成含有無機氧化物半導體之半導
體層;鈍化膜形成步驟,其係將由有機材料所構成之鈍化膜成膜,以覆蓋前述半導體層;煅燒步驟,其係將前述鈍化膜進行煅燒;及冷卻步驟,其係煅燒後,進行冷卻;其特徵在於:在前述冷卻步驟進行冷卻時,將從前述煅燒步驟之煅燒時的煅燒溫度起至比煅燒時的煅燒溫度更低50℃的溫度為止之冷卻速度,實質地控制在0.5~5℃/分鐘的範圍。
在本發明,前述煅燒步驟的煅燒溫度係以200~300℃為佳。
在本發明,在前述冷卻步驟進行冷卻時,係以將從前述煅燒步驟的煅燒溫度起至150℃為止之冷卻速度,實質地控制在0.5~5℃/分鐘的範圍為佳。
在本發明,係以在非氧化性環境下進行前述煅燒步驟的煅燒及在前述冷卻步驟之冷卻為佳。
在本發明,係以使用含有選自由環狀烯烴樹脂、丙烯酸樹脂、卡多樹脂、聚矽氧烷樹脂及聚醯亞胺樹脂所組成群組之至少1種樹脂之樹脂組成物來形成前述鈍化膜為佳。
在本發明,係以使用含有具有質子性極性基的環狀烯烴樹脂之樹脂組成物來形成前述鈍化膜為佳,前述樹脂組成物係以進一步含有含烷氧矽烷基的(甲基)丙烯酸酯化合物、4官能以上的(甲基)丙烯酸酯化合物、光聚合起始劑、及交聯劑為較佳。
又,依照本發明,能夠提供使用上述任一種方法而得到之半導體元件。
依照本發明,能夠提供一種閥值電壓vth為接近
零且移動度高之使用含有無機氧化物半導體的半導體層之半導體元件。特別是使用本發明的製造方法而得到之半導體元件,因為閥值電壓vth為接近零且移動度高,所以作為薄膜電晶體係有用的。
1‧‧‧半導體元件
2‧‧‧基板
3‧‧‧閘極電極
4‧‧‧半導體層
5‧‧‧源極電極
6‧‧‧汲極電極
7‧‧‧鈍化膜
10‧‧‧舉離用光阻
20‧‧‧由導電材料所構成之層
第1圖係作為使用本發明的製造方法而得到之半導體元件的一個例子之半導體元件1的剖面圖。
第2圖係顯示半導體元件1的製造步驟之圖(其1)。
第3圖係顯示半導體元件1的製造步驟之圖(其2)。
第4圖係顯示在實施例1及比較例2所得到的薄膜電晶體之在源極.汲極間流動電流的變化對閘極電壓的變化之圖表。
本發明之半導體元件的製造方法,係具備以下步驟之半導體元件的製造方法:半導體層形成步驟,其係在基板上形成含有無機氧化物半導體之半導體層;鈍化膜形成步驟,其係將由有機材料所構成之鈍化膜成膜,以覆蓋前述半導體層;煅燒步驟,其係將前述鈍化膜進行煅燒;及冷卻步驟,其係煅燒後,進行冷卻;其特徵在於:在前述冷卻步驟進行冷卻時,將從前述煅燒步驟之煅燒時的煅燒溫度起至比煅燒時的煅燒溫度更低50℃的溫度為止之冷卻速度,實質地控制在0.5~5℃/分鐘的範圍。
以下,參照圖式說明本發明的半導體元件之製造
方法。第1圖係作為使用本發明的製造方法而得到之半導體元件的一個例子之半導體元件1的剖面圖。如第1圖所示,作為使用本發明的製造方法得到之半導體元件的一個例子之半導體元件1,係在基板2的背面具有閘極電極3,且在基板2上具有半導體層4、源極電極5、汲極電極6、及鈍化膜7。
在第1圖所示的半導體元件1,係例如能夠使用以下的方法製造。在此,第2圖、第3圖係顯示半導體元件1的製造步驟之圖。
首先,如第2圖(A)所示,在基板2上形成半導體層4。作為基板2,係沒有特別限定,能夠舉出由聚碳酸酯、聚醯亞胺、聚對酞酸乙二酯、脂環式烯烴聚合物等具有柔軟性的塑膠所構成之軟性基板、石英、鈉鈣玻璃、無機鹼玻璃等的玻璃基板、矽晶圓等的矽基板等。又,使用矽基板作為作為基板2時,係以使用藉由預先使其熱氧化而在其表面形成有熱氧化膜者為佳。如此進行而形成的熱氧化膜,係通常使用作為閘極絕緣膜。
半導體層4係由無機氧化物半導體所構成之層,作為無機氧化物半導體,係含有In、Ga、及Zn之中至少1種元素者即可,例如可舉出氧化鋅(ZnO)、銦鋅氧化物(IZO)、鋅錫氧化物(ZTO)、鋁鋅氧化物(AZO)。鎵鋅氧化物(GZO)、銦鎵鋅氧化物(IGZO)等。半導體層4係可藉由使用濺鍍法在基板2上形成由無機氧化物半導體所構成之層,其次,圖案化成為預定的圖案來形成。
例如,使用銦鎵鋅氧化物(IGZO)來形成半導體層4
時,係首先使用將氧化銦(In2O3)、氧化鎵(Ga2O3)、及氧化鋅(ZnO)各自各等莫耳混合且燒結而成之靶材,藉由DC(直流電;Direct Current)濺鍍法來成膜且形成由無機氧化物半導體所構成之層。又,濺鍍係可將流量5~300sccm的氬(Ar)氣、及流量5~300sccm的氧(O2)氣導入反應室內而進行。又,將此時的基板溫度設為150~400℃。又,形成由無機氧化物半導體所構成層之後,亦可以在200~500℃的大氣環境中進行退火1~2小時左右。其次,在所形成之由無機氧化物半導體所構成之層的表面形成預定的光阻圖案,且使用光阻圖案作為遮罩且使用磷酸等的酸將由無機氧化物半導體所構成之層進行蝕刻,隨後,藉由將光阻圖案剝離而如第2圖(A)所示,可在基板2上形成半導體層4。
其次,各自如以下形成:在形成有半導體層4之基板2的背面,形成如第1圖所示之閘極電極3;及在形成有半導體層4之基板2上形成第1圖所示之源極電極5及汲極電極6。閘極電極3、源極電極4及汲極電極5係由導電性材料形成。作為導電性材料,例如可舉出鉑、金、銀、鎳、鉻、銅、鐵、錫、銻、鉛、鉭、銦、鈀、碲、錸、銥、鋁、釕、鍺、鉬、鎢、氧化錫.銻、氧化銦.錫(ITO)、摻雜氟的氧化鋅、鋅、碳、石墨、玻璃石墨(glassy carbon)、銀糊及碳糊、鋰、鈹、鎂、鉀、鈣、鈧、鈦、錳、鋯、鎵、鈮、鈉、鈉-鉀合金、鎂/銅混合物、鎂/銀混合物、鎂/鋁混合物、鎂/銦混合物、鋁/氧化鋁混合物、鋰/鋁混合物等。又,藉由摻雜等使導電率提升之習知的導電性聚合物,例如可舉出導電性聚苯胺、導電性聚吡
咯、導電性聚噻吩(聚伸乙基二氧噻吩與聚苯乙烯磺酸的錯合物等)。
作為各自在形成有半導體層4之基板2的背面形成如第1圖所示之閘極電極3,及在形成有半導體層4之基板2上形成如第1圖所示之源極電極5及汲極電極6之方法,例如可舉出以下說明之方法。亦即,首先如第2圖(B)所示,以預定圖案形成用以藉由舉離法形成源極電極5及汲極電極6之舉離用光阻10,而且如第2圖(C)所示,在形成有形半導體層4及舉離用光阻10之基板2上面的全面範圍,藉由濺鍍法形成用以形成源極電極5及汲極電極6之由導電性材料所構成之層20。
其次,除此以外,如第3圖(A)所示,另外藉由濺鍍法等在基板2的背面之全面範圍形成閘極電極3。然後,接著使用丙酮等將舉離用光阻10、及由導電性材料所構成之層20之中位於舉離用光阻10上之部分除去,而形成如第3圖(B)所示之源極電極5及汲極電極6。
又,在上述,係例示了藉由舉離法來形成源極電極5及汲極電極6之方法,但是不特別地被限定於此種方法,例如,亦可藉由使用濺鍍法形成用以形成源極電極5及汲極電極6之由導電性材料所構成之層,其次,以光阻圖案作為遮罩而將由導電性材料所構成之層進行蝕刻,隨後,將光阻圖案剝離之方法,來形成源極電極5及汲極電極6。又,在上述,係例示了從形成閘極電極3之後,形成源極電極5及汲極電極6之方法,但是其形成順序係沒有特別限定。
其次,如第3圖(C)所示,形成鈍化膜(保護層)7以覆蓋基板2、半導體層4、源極電極5及汲極電極的上面(露出面)的全體。具體而言,係使用用以形成鈍化膜7之樹脂組成物且將其成膜,而且在必要時進行加熱乾燥(預烘烤)之後,進行煅燒。煅燒係主要是為了使在樹脂組成物所含有的交聯劑交聯而進行,其條件係依照所使用的樹脂組成物的組成和交聯劑的種類而不同,通常是氮環境等的非氧化性環境下,煅燒溫度係150~350℃為佳,較佳為200~300℃,煅燒時間係以30~90分鐘為佳,較佳是設為45~75分鐘。又,針對用以形成鈍化膜7所使用的樹脂組成物,係後述。
其次,煅燒後,對形成有閘極電極3、半導體層4、源極電極5、汲極電極6及鈍化膜7之基板2進行冷卻。在本實施形態,在前述冷卻步驟進行冷卻時,將從煅燒時的煅燒溫度起至比煅燒時的煅燒溫度更低50℃的溫度為止之冷卻速度(亦即,將煅燒溫度設作TF[℃]時,於TF[℃]進行煅燒之後,從TF[℃]起至TF-50[℃]為止的冷卻速度),實質地控制在0.5~5℃/分鐘的範圍。在本發明,藉由如此地將煅燒後,如上述控制進行冷卻時的冷卻速度,可使所得到的半導體元件1成為閥值電壓Vth為接近零且具有高移動度者。另一方面,在上述溫度範圍之冷卻速度太快時,在冷卻的過程,半導體層4中的缺陷増加且產生源自缺陷之載體上升,致使閥值電壓Vth從零大幅地產生偏離。又,在上述溫度範圍之冷卻速度太慢時,有造成產能低落的不良之情形。在本發明,作為將冷卻速度實質地控制在0.5~5℃/分鐘的範圍而進行冷卻之方法,係沒有特
別限定,例如可舉出以0.5~5℃/分鐘的冷卻速度將煅燒時所使用的烘箱內之溫度冷卻之方法等。又,所謂「實質地」,係例如雖然認為冷卻速度有瞬間從上述範圍脫離之情況,但是即便此種情況亦是本發明的範圍所包含的宗旨,只要全冷卻時間的50%以上(較佳為90%以上)的時間係被控制在上述冷卻速度的範圍內即可。
又,將冷卻速度實質地控制在0.5~5℃/分鐘的範圍而進行冷卻時,冷卻時的環境係沒有特別限定,但是從可使所得到的半導體元件1之閥值電壓Vth較接近零且具有較高的移動度者之觀點而言,係與煅燒時同樣地,以設為氮環境等的非氧化性環境為佳。
而且,煅燒後,在對形成有閘極電極3、半導體層4、源極電極5、汲極電極6及鈍化膜7之基板2進行冷卻時,作為將冷卻速度控制在0.5~5℃/分鐘的範圍之溫度範圍,係從煅燒時的煅燒溫度起至比煅燒時的煅燒溫度更低50℃的溫度為止即可,但是從能夠使所得到的半導體元件1之閥值電壓Vth較接近零且具有較高的移動度者之觀點而言,係以設為從煅燒時的煅燒溫度起至150℃為佳。將冷卻速度控制在0.5~5℃/分鐘的範圍時,係可以在一定的溫度進行冷卻,或者亦可以是隨著冷卻而在0.5~5℃/分鐘的範圍內使溫度變化之態樣。例如,使溫度變化時,冷卻開始後,在比較高的溫度區域係使冷卻速度為較低。隨著冷卻的進行,能夠設為如冷卻速度變高的態樣。
又,上述冷卻速度係設為0.5~5℃/分鐘的範圍即
可,以0.6~3℃/分鐘為佳,較佳為0.8~1.5℃/分鐘。
而且,在本發明,將冷卻速度控制在0.5~5℃/分鐘的範圍之冷卻,係至少進行至上述預定溫度(比煅燒溫度更低50℃的溫度,較佳為150℃)為止即可,即便低於上述預定溫度之後,係可將冷卻速度控制在0.5~5℃/分鐘的範圍,或者在低於上述預定溫度之後,亦可設為在預定時序,將冷卻後之形成有閘極電極3、半導體層4、源極電極5、汲極電極6及鈍化膜7之基板2,在常溫、大氣環境下取出之態樣。
其次,說明用以形成鈍化膜7所使用的樹脂組成物。
作為用以形成鈍化膜7所使用的樹脂組成物,係沒有特別限定,但是從使所得到的半導體元件1成為即便在嚴酷的環境下亦能夠具有高可靠性者而言,以含有選自由環狀烯烴樹脂、丙烯酸樹脂、卡多樹脂、聚矽氧烷樹脂及聚醯亞胺樹脂所組成群組之至少1種樹脂(A)為佳,從可靠性的提升效果較高而言,以環狀烯烴樹脂為較佳,以具有質子性極性基的環狀烯烴樹脂為特佳。該等樹脂係各自可以單獨使用或併用2種以上。
在此,所謂質子性極性基,係指含有氫原子係直接鍵結在屬於週期表第15族或第16族的原子之原子之基。屬於週期表第15族或第16族的原子之中,以屬於週期表第15族或第16族的第1或第2週期的原子為佳,較佳為氧原子、氮原子或硫原子,特佳為氧原子。
作為此種質子性極性基的具體例,可舉出羥基、羧基(羥羰基)、磺酸基、磷酸基等的具有氧原子之極性基;第
一級胺基、第二級胺基、第一級醯胺基、第二級醯胺基(醯亞胺基)等具有氮原子之極性基;硫醇基等具有硫原子之極性基等。這些之中,以具有氧原子者為佳,較佳為羧基。在本發明,鍵結在具有質子性極性基的環狀烯烴樹脂之質子性極性基的數目係沒有特別限定,又,亦可含有不同種類的質子性極性基。
作為用以構成具有質子性極性基的環狀烯烴樹脂之單體,可舉出具有質子性極性基的環狀烯烴單體(a)、具有質子性極性基以外的極性基之環狀烯烴單體(b)、未具有極性基之環狀烯烴單體(c)、及環狀烯烴以外的單體(d)(以下將這些單體簡稱為單體(a)~(d))。在此,單體(d)係可以具有質子性極性基或其以外的極性基,亦可以完全未具有極性基。在本發明,具有質子性極性基的環狀烯烴樹脂係以由單體(a)、單體(b)及/或單體(c)所構成為佳,以由單體(a)及單體(b)所構成為更佳。
作為具有質子性極性基的環狀烯烴單體(a)的具體例,可舉出2-羥羰基雙環[2.2.1]庚-5-烯、2-甲基-2-羥羰基雙環[2.2.1]庚-5-烯、2-羧甲基-2-羥羰基雙環[2.2.1]庚-5-烯、2-羥羰基-2-甲氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-乙氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-丙氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-丁氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-戊氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-己戊氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-環己氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-苯氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-萘氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-聯苯氧基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-苄氧
基羰甲基雙環[2.2.1]庚-5-烯、2-羥羰基-2-羥乙氧基羰甲基雙環[2.2.1]庚-5-烯、2,3-二羥羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-甲氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-乙氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-丙氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-丁氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-戊氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-己氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-環己氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-苯氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-萘氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-聯苯氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-苄氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-羥乙氧基羰基雙環[2.2.1]庚-5-烯、2-羥羰基-3-羥羰基甲基雙環[2.2.1]庚-5-烯、3-甲基-2-羥羰基雙環[2.2.1]庚-5-烯、3-羥甲基-2-羥羰基雙環[2.2.1]庚-5-烯、2-羥羰基三環[5.2.1.02,6]癸-3,8-二烯、4-羥羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-羥羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4,5-二羥羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-羧甲基-4-羥羰基四環[6.2.1.13,6.02,7]十二基-9-烯、N-(羥羰基甲基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(羥羰基乙基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(羥羰基戊基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(二羥羰基乙基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(二羥羰基丙基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(羥羰基苯乙基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-(4-羥苯基)-1-(羥羰基)乙基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(羥羰基苯基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺等含羧基的環狀
烯烴;2-(4-羥苯基)雙環[2.2.1]庚-5-烯、2-甲基-2-(4-羥苯基)雙環[2.2.1]庚-5-烯、4-(4-羥苯基)四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-(4-羥苯基)四環[6.2.1.13,6.02,7]十二基-9-烯、2-羥基雙環[2.2.1]庚-5-烯、2-羥甲基雙環[2.2.1]庚-5-烯、2-羥乙基雙環[2.2.1]庚-5-烯、2-甲基-2-羥甲基雙環[2.2.1]庚-5-烯、2,3-二羥甲基雙環[2.2.1]庚-5-烯、2-(羥乙氧基羰基)雙環[2.2.1]庚-5-烯、2-甲基-2-(羥乙氧基羰基)雙環[2.2.1]庚-5-烯、2-(1-羥基-1-三氟甲基-2,2,2-三氟乙基)雙環[2.2.1]庚-5-烯、2-(2-羥基-2-三氟甲基-3,3,3-三氟丙基)雙環[2.2.1]庚-5-烯、3-羥基三環[5.2.1.02,6]癸-4,8-二烯、3-羥甲基三環[5.2.1.02,6]癸-4,8-二烯、4-羥基四環[6.2.1.13,6.02,7]十二基-9-烯、4-羥甲基四環[6.2.1.13,6.02,7]十二基-9-烯、4,5-二羥甲基四環[6.2.1.13,6.02,7]十二基-9-烯、4-(羥乙氧基羰基)四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-(羥乙氧基羰基)四環[6.2.1.13,6.02,7]十二基-9-烯、N-(羥乙基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(羥苯基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺等含羥基的環狀烯烴等。這些之中,以含羧基的環狀烯烴為佳,以4-羥羰基四環[6.2.1.13,6.02,7]十二基-9-烯為特佳。這些單體(a)係各自可以單獨使用,亦可組合2種以上而使用。
作為具有質子性極性基以外的極性基之環狀烯烴單體(b),例如,可舉出N-取代醯亞胺基、酯基、氰基、酸酐基或具有鹵素原子之環狀烯烴。
作為具有N-取代醯亞胺基之環狀烯烴,例如,可舉出以下述式(1)表示之單體、或以下述式(2)表示之單體。
(上述式(1)中,R1係表示氫原子或碳數1~16的烷基或芳基。n係表示1或2的整數)。
(上述式(2)中,R2係表示碳數1~3的二價伸烷基,R3係表示碳數1~10的一價烷基、或碳數1~10的一價鹵化烷基)。
在上述式(1)中,R1係碳數1~1的烷基或芳基,作為烷基的具體例,可舉出甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一基、正十二基、正十三基、正十四基、正十五基、正十六基等的直鏈烷基;環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一基、環十二基、降莰基、莰基、異莰
基、十氫萘基、三環癸烷基、金剛烷基等的環狀烷基;2-丙基、2-丁基、2-甲基-1-丙基、2-甲基-2-丙基、1-甲基丁基、2-甲基丁基、1-甲基戊基、1-乙基丁基、2-甲基己基、2-乙基己基、4-甲基庚基、1-甲基壬基、1-甲基十三基、1-甲基十四基等的分枝狀烷基等。又,作為芳基的具體例,可舉出苄基等。這些之中,因為耐熱性及對極性溶劑的溶解性較優異,以碳數6~14的烷基及芳基為佳,以碳數6~10的烷基及芳基為較佳。碳數為4以下時,對極性溶劑的溶解性差,碳數為17以上時,耐熱性差且在將樹脂膜圖案化後之情況,有因熱而熔融致使圖案消失掉之問題。
作為以上述式(1)表示之單體的具體例,可舉出雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-苯基-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-甲基雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-乙基雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-丙基雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-丁基雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-環己基雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-金剛烷基雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基丁基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-甲基丁基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基戊基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-甲基戊基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-乙基丁基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-乙基丁基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基己基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-甲基己基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(3-甲基己基)-雙環
[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-丁基戊基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-丁基戊基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基庚基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-甲基庚基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(3-甲基庚基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-甲基庚基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-乙基己基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-乙基己基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(3-乙基己基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-丙基戊基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-丙基戊基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基辛基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-甲基辛基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(3-甲基辛基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-甲基辛基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-乙基庚基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-乙基庚基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(3-乙基庚基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-乙基庚基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-丙基己基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-丙基己基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(3-丙基己基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基壬基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-甲基壬基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(3-甲基壬基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-甲基壬基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(5-甲基壬基)-雙環[2.2.1]庚-5-烯-2,3-二羧
醯亞胺、N-(1-乙基辛基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-乙基辛基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(3-乙基辛基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-乙基辛基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基癸基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基十二基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基十一基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基十二基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基十三基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基十四基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(1-甲基十五基)-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-苯基-四環[6.2.1.13,6.02,7]十二基-9-烯-4,5-二羧醯亞胺、N-(2,4-二甲氧基苯基)-四環[6.2.1.13,6.02,7]十二基-9-烯-4,5-二羧醯亞胺等。又,這些係各自可以單獨使用,亦可組合2種以上而使用。
另一方面,在上述式(2),R2係碳數1~3的二價伸烷基,作為碳數1~3的二價伸烷基,可舉出亞甲基、伸乙基、伸丙基及異伸丙基。這些之中,因為聚合活性良好,以亞甲基及伸乙基為佳。
又,在上述式(2),R3係碳數1~10的一價烷基、或碳數1~10的一價鹵化烷基。作為碳數1~10的一價烷基,例如,可舉出甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、己基及環己基等。作為碳數1~10的一價鹵化烷基,例如可舉出氟甲基、氯甲基、溴甲基、二氟甲基、二氯甲基、二氟甲基、三氟甲基、三氯甲基、2,2,2-三氟乙基、五氟乙基、七氟丙基、全氟丁基及全氟戊基等。這些之中,因為對極性溶
劑的溶解性優異,作為R3,係以甲基或乙基為佳。
又,以上述式(1)、(2)表示之單體,係例如能夠藉由對應之胺、與5-降莰烯-2,3-二羧酸酐之醯亞胺化反應來得到。又,所得到的單體,係能夠藉由習知的方法將醯亞胺化反應的反應液.純化而效率良好地離析。
作為具有酯基之環狀烯烴,例如,可舉出2-乙醯氧基雙環[2.2.1]庚-5-烯、2-乙醯氧基甲基雙環[2.2.1]庚-5-烯、2-甲氧基羰基雙環[2.2.1]庚-5-烯、2-乙氧基羰基雙環[2.2.1]庚-5-烯、2-丙氧基羰基雙環[2.2.1]庚-5-烯、2-丁氧基羰基雙環[2.2.1]庚-5-烯、2-環己氧基羰基雙環[2.2.1]庚-5-烯、2-甲基-2-甲氧基羰基雙環[2.2.1]庚-5-烯、2-甲基-2-乙氧基羰基雙環[2.2.1]庚-5-烯、2-甲基-2-丙氧基羰基雙環[2.2.1]庚-5-烯、2-甲基-2-丁氧基羰基雙環[2.2.1]庚-5-烯、2-甲基-2-環己氧基羰基雙環[2.2.1]庚-5-烯、2-(2,2,2-三氟乙氧基羰基)雙環[2.2.1]庚-5-烯、2-甲基-2-(2,2,2-三氟乙氧基羰基)雙環[2.2.1]庚-5-烯、2-甲氧基羰基三環[5.2.1.02,6]癸-8-烯、2-乙氧基羰基三環[5.2.1.02,6]癸-8-烯、2-丙氧基羰基三環[5.2.1.02,6]癸-8-烯、4-乙醯氧基四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲氧基羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-乙氧基羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-丙氧基羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-丁氧基羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-甲氧基羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-乙氧基羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-丙氧基羰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-丁氧基羰基四環
[6.2.1.13,6.02,7]十二基-9-烯、4-(2,2,2-三氟乙氧基羰基)四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-(2,2,2-三氟乙氧基羰基)四環[6.2.1.13,6.02,7]十二基-9-烯等。
作為具有氰基之環狀烯烴,例如,可舉出4-氰基四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-氰基四環[6.2.1.13,6.02,7]十二基-9-烯、4,5-二氰基四環[6.2.1.13,6.02,7]十二基-9-烯、2-氰基雙環[2.2.1]庚-5-烯、2-甲基-2-氰基雙環[2.2.1]庚-5-烯、2,3-二氰基雙環[2.2.1]庚-5-烯等。
作為具有酸酐基之環狀烯烴,例如,可舉出四環[6.2.1.13,6.02,7]十二基-9-烯-4,5-二羧酸酐、雙環[2.2.1]庚-5-烯-2,3-二羧酸酐、2-羧甲基-2-羥羰基雙環[2.2.1]庚-5-烯酐等。
作為具有鹵素原子之環狀烯烴,例如,可舉出2-氯雙環[2.2.1]庚-5-烯、2-氯甲基雙環[2.2.1]庚-5-烯、2-(氯苯基)雙環[2.2.1]庚-5-烯、4-氯四環[6.2.1.13,6.02,7]十二基-9-烯、4-甲基-4-氯四環[6.2.1.13,6.02,7]十二基-9-烯等。
這些單體(b)係各自可以單獨使用,亦可組合2種以上而使用。
作為未具有極性基之環狀烯烴單體(c),可舉出雙環[2.2.1]庚-2-烯(亦稱為「降莰烯」)、5-乙基-雙環[2.2.1]庚-2-烯、5-丁基-雙環[2.2.1]庚-2-烯、5-亞乙基-雙環[2.2.1]庚-2-烯、5-亞甲基-雙環[2.2.1]庚-2-烯、5-乙烯基-雙環[2.2.1]庚-2-烯、三環[5.2.1.02,6]癸-3,8-二烯(慣用名:二環戊二烯)、四環[10.2.1.02,11.04,9]十五基-4,6,8,13-四烯、四環[6.2.1.13,6.02,7]十二基-4-烯(亦稱為「四環十二烯」)、9-甲基-四環[6.2.1.13,6.02,7]
十二基-4-烯、9-乙基-四環[6.2.1.13,6.02,7]十二基-4-烯、9-亞甲基-四環[6.2.1.13,6.02,7]十二基-4-烯、9-亞乙基-四環[6.2.1.13,6.02,7]十二基-4-烯、9-乙烯基-四環[6.2.1.13,6.02,7]十二基-4-烯、9-丙烯基-四環[6.2.1.13,6.02,7]十二基-4-烯、五環[9.2.1.13,9.02,10.04,8]十五基-5,12-二烯、環丁烯、環戊烯、環戊二烯、環己烯、環庚烯、環辛烯、環辛二烯、茚、3a,5,6,7a-四氫-4,7-亞甲基-1H-茚、9-苯基-四環[6.2.1.13,6.02,7]十二基-4-烯、四環[[9.2.1.02,10.03,8]十四基-3,5,7,12-四烯、五環[9.2.1.13,9.02,10.04,8]十五基-12-烯等。單體(C)係各自可以單獨使用,亦可組合2種以上而使用。
作為環狀烯烴以外的單體(d)之具體例,可舉出乙烯;丙烯、1-丁烯、1-戊烯、1-己烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙烯-1-己烯、3-乙基-1-己烯、1-辛烯、1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、1-二十烯等碳數2~20的α-烯烴;1,4-己二烯、1,5-己二烯、4-甲基-1,4-己二烯、5-甲基-1,4-己二烯、1,7-辛二烯等的非共軛二烯、及該等的衍生物等。這些之中,以α-烯烴為佳。這些單體(d)係各自可以單獨使用,亦可組合2種以上而使用。
又,在本發明所使用之具有質子性極性基的環狀烯烴樹脂,亦能夠藉由利用習知的改性劑而將質子性極性基導入至不具有質子性極性基之環狀烯烴樹脂,且依照需要而進行氫化之方法來得到。氫化亦可以對導入質子性極性基前的聚合
物而進行。又,亦可進一步改性而將質子性極性基導入至具有質子性極性基的環狀烯烴樹脂。不具有質子性極性基之聚合物係能夠藉由將前述單體(b)~(d)任意地組合且聚合而得到。
而且,在本發明所使用之具有質子性極性基的環狀烯烴樹脂,亦可以是使上述單體開環聚合而成之開環聚合物,或者亦可以是使上述單體加成聚合而成之加成聚合物,從本發明的效果係變為更顯著而言,以開環聚合物為佳。
開環聚合物,係可藉由將具有質子性極性基的環狀烯烴單體(a)及必要時使用之能夠共聚合的單體(b),在複分解(metathesis)反應觸媒的存在下進行開環複分解聚合來製造。作為製造方法,例如,可使用在國際公開第2010/110323號的[0039]~[0079]所記載之方法等。另一方面,加成聚合物係可藉由將具有質子性極性基的環狀烯烴單體(a)及必要時使用之可共聚合的單體(b),使用習知的加成聚合觸媒、例如由鈦、鋯或釩化合物及有機鋁化合物所構成之觸媒使其聚合而得到。
又,在本發明所使用之具有質子性極性基的環狀烯烴樹脂係開環聚合物時,係以進一步進行氫化反應,而成為將在主鏈所含有的碳-碳雙鍵氫化而成之氫化物為佳。
又,在本發明所使用之丙烯酸樹脂係沒有特別限定,以選自具有丙烯醯基之羧酸、具有丙烯醯基之羧酸酐、或含環氧基的丙烯酸酯化合物及含氧雜環丁烷基的丙烯酸酯化合物之至少一種作為必要成分之同元聚合物或共聚物為佳。
作為具有丙烯醯基之羧酸的具體例,可舉出(甲基)丙烯酸[丙烯酸及/或甲基丙烯酸的意思。以下,(甲基)丙烯酸
甲酯等亦同樣]、巴豆酸、順丁烯二酸、反丁烯二酸、檸康酸、中康酸、戊烯二酸、酞酸單-(2-((甲基)丙烯醯氧基)乙基)、N-(羧苯基)順丁烯二醯亞胺、N-(羧苯基)(甲基)丙烯醯胺等。作為具有丙烯醯基之羧酸酐的具體例,可舉出順丁烯二酸酐、檸康酸酐等。
作為含環氧基的丙烯酸酯化合物的具體例,可舉出丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯、α-乙基丙烯酸環氧丙酯、α-正丙基丙烯酸環氧丙酯、α-正丁基丙烯酸環氧丙酯、丙烯酸-3,4-環氧丁酯、甲基丙烯酸-3,4-環氧丁酯、丙烯酸-6,7-環氧庚酯、甲基丙烯酸-6,7-環氧庚酯、α-乙基丙烯酸-6,7-環氧庚酯、丙烯酸-3,4-環氧環己基甲酯、甲基丙烯酸-3,4-環氧環己基甲酯等。
作為含氧雜環丁烷基的丙烯酸酯化合物的具體例,可舉出(甲基)丙烯酸(3-甲基氧雜環丁烷-3-基)甲酯、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、(甲基)丙烯酸(3-甲基氧雜環丁烷-3-基)乙酯、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)乙酯、(甲基)丙烯酸(3-環甲基氧雜環丁烷-3-基)甲酯、(甲基)丙烯酸(氧雜環丁烷-2-基)甲酯、(甲基)丙烯酸(2-甲基氧雜環丁烷-2-基)甲酯、(甲基)丙烯酸(2-乙基氧雜環丁烷-2-基)甲酯、(1-甲基氧雜環丁烷-2-苯基)-3-(甲基)丙烯酸酯、(1-甲基氧雜環丁烷)-2-三氟甲基-3-(甲基)丙烯酸酯、及(1-甲基氧雜環丁烷)-4-三氟甲基-2-(甲基)丙烯酸酯等。這些之中,以(甲基)丙烯酸、順丁烯二酸酐、(甲基)丙烯酸環氧丙酯、甲基丙烯酸-6,7-環氧基庚酯等為佳。
丙烯酸樹脂係可以是選自不飽和羧酸、不飽和羧酸酐及含環氧基的不飽和化合物之至少一種、與其他的丙烯酸酯系單體或丙烯酸酯以外之能夠共聚合的單體之共聚物。
作為其他的丙烯酸酯系單體,可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酸酯、(甲基)丙烯酸異硬脂酸酯等的(甲基)丙烯酸烷酯;(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等的(甲基)丙烯酸羥基烷酯;(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯等的(甲基)丙烯酸苯氧基烷酯;(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-甲氧基丁酯等的(甲基)丙烯酸烷氧基烷酯;聚乙二醇一(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、聚丙二醇一(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、乙氧基聚丙二醇(甲基)丙烯酸酯、壬基苯氧基聚丙二
醇(甲基)丙烯酸酯等的聚伸烷基二醇(甲基)丙烯酸酯;(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸4-丁基環己酯、(甲基)丙烯酸1-金剛烷酯、(甲基)丙烯酸2-甲基-2-金剛烷酯、(甲基)丙烯酸2-乙基-2-金剛烷酯、(甲基)丙烯酸三環[5.2.1.02,6]癸-8-基酯、(甲基)丙烯酸三環[5.2.1.02,6]-3-癸-8-基酯、(甲基)丙烯酸三環[5.2.1.02,6]-3-癸烯-9-基酯、(甲基)丙烯酸莰酯、(甲基)丙烯酸異莰酯等的(甲基)丙烯酸環烷酯;(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸聯苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸5-四氫糠氧基羰基戊酯、(甲基)丙烯酸乙烯酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸2-(2-乙烯氧基乙氧基)乙酯、(甲基)丙烯酸2-[三環[5.2.1.02,6]癸-8-基氧基]乙酯、(甲基)丙烯酸2-[三環[5.2.1.02,6]-3-癸烯-8-基氧基]乙酯、(甲基)丙烯酸2-[三環[5.2.1.02,6]-3-癸烯-9-基氧基]乙酯、(甲基)丙烯酸γ-丁內酯、順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-丁基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-(2,6-二乙基苯基)順丁烯二醯亞胺、N-(4-乙醯基苯基)順丁烯二醯亞胺、N-(4-羥苯基)順丁烯二醯亞胺、N-(4-乙醯氧基苯基)順丁烯二醯亞胺、N-(4-二甲胺基-3,5-二硝基苯基)順丁烯二醯亞胺、N-(1-苯胺基萘基-4)順丁烯二醯亞胺、N-[4-(2-苯并唑基)苯基]順丁烯二醯亞胺、N-(9-吖啶基)順丁烯二醯亞胺等。這些之中,係以(甲基)丙烯酸甲酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸苄酯、(甲
基)丙烯酸三環[5.2.1.02,6]癸-8-基酯、N-苯基順丁烯二醯亞胺及N-環己基順丁烯二醯亞胺等為佳。
作為丙烯酸酯以外之能夠共聚合的單體,只要能夠與上述具有丙烯醯基之羧酸、具有丙烯醯基之羧酸酐或含環氧基的丙烯酸酯化合物共聚合的化合物,就沒有特別限制,例如可舉出乙烯基苄基甲醚、乙烯基環氧丙基醚、苯乙烯、α-甲基苯乙烯、乙烯基甲苯、茚、乙烯基萘、乙烯基聯苯、氯苯乙烯、溴苯乙烯、氯甲基苯乙烯、對第三丁氧基苯乙烯、對羥基苯乙烯、對羥基-α-甲基苯乙烯、對乙醯氧基苯乙烯、對羧基苯乙烯、4-羥苯基乙烯基酮、丙烯腈、甲基丙烯腈、(甲基)丙烯醯胺、1,2-環氧基-4-乙烯基環已烷、異丁烯、降莰烯、丁二烯、異戊二烯等的自由基聚合性化合物。這些化合物係各自可以單獨使用,亦可組合2種以上而使用。上述單體的聚合方法係依照常用的方法即可,例如能夠採用懸浮聚合法、乳化聚合法、溶液聚合法等。
在本發明所使用之卡多樹脂,係具有卡多構造、亦即二個環狀構造鍵結在構成環狀構造之4級碳原子而成的骨架構造之樹脂。通常的卡多構造係苯環鍵結在茀環而成者。
作為二個環狀構造鍵結在構成環狀構造之4級碳原子而成之骨架構造的具體例,可舉出具有茀骨架、雙酚茀骨架、雙胺苯基茀骨架、具有環氧基之茀骨架、具有丙烯醯基之茀骨架等。
在本發明所使用之卡多樹脂,係能夠藉由該具有卡多構造之骨架與在其所鍵結的官能基之間的反應等進行聚合而形成。卡多樹脂係具有大體積的側鏈以一個元素與主鏈連接而成
之構造(卡多構造),且在對主鏈為大約垂直方向具有環狀構造。
在下述式(3)顯示具有環氧環氧丙基醚構造之卡多構造的例子,作為卡多構造的一個例子。
(上述式(3)中,n係0~10的整數)。
具有卡多構造之單體,係例如可舉出雙(環氧丙氧基苯基)茀型環氧樹脂;雙酚茀型環氧樹脂與丙烯酸之縮合物;9,9-雙(4-羥苯基)茀、9,9-雙(4-羥基-3-甲基苯基)茀等含卡多構造的雙酚類;9,9-雙(氰甲基)茀等的9,9-雙(氰烷基)茀類;9,9-雙(3-胺丙基)茀等的9,9-雙(胺烷基)茀類等。
卡多樹脂係將具有卡多構造的單體進行聚合而得到之聚合物,但是亦可以是與其他能夠共聚合的單體之共聚物。
上述單體的聚合方法係可依照常用的方法。例如,能夠採用開環聚合法、加成聚合法等。
作為在本發明所使用之聚矽氧烷樹脂,係沒有特別限定,較佳能夠舉出藉由將下述式(4)表示之有機矽烷的1種或2種以上混合且使其反應而得到之聚合物。
(R4)m-Si-(OR5)4-m (4)
上述式(4)中,R4係氫原子、碳數1~10的烷基、
碳數2~10的烯基、或碳數6~15的芳基,複數個R4係各自可以相同亦可以不同。又,這些烷基、烯基、芳基係任一者均可以具有取代基,又,亦可以是未具有取代基之未取代物,可按照組成物的特性而選擇。作為烷基的具體例,可舉出甲基、乙基、正丙基、異丙基、正丁基、第三丁基、正己基、正癸基、三氟甲基、2,2,2-三氟乙基、3,3,3-三氟丙基、3-環氧丙氧基丙基、2-(3,4-環氧環己基)乙基、3-胺丙基、3-氫硫基丙基、3-異氰酸酯丙基。作為烯基的具體例,可舉出乙烯基、3-丙烯醯氧基丙基、3-甲基丙烯醯氧基丙基。作為芳基的具體例,可舉出苯基、甲苯基、對羥苯基、1-(對羥基苯基)乙基、2-(對羥苯基)乙基、4-羥基-5-(對羥苯基羰基氧基)戊基、萘基。
又,上述式(4)中,R5係氫原子、碳數1~6的烷基、碳數1~6的醯基、或碳數6~15的芳基,複數個R5係各自可以相同亦可以不同。又,這些烷基、醯基係任一者均可以具有取代基、又,亦可以是未具有取代基之未取代物,可按照組成物的特性而選擇。作為烷基的具體例,可舉出甲基、乙基、正丙基、異丙基、正丁基。作為醯基的具體例,可舉出乙醯基。作為芳基的具體例,可舉出苯基。
而且,上述式(4)中,m係0~3的整數,m=0時係4官能性矽烷,m=1時係3官能性矽烷,m=2時係2官能性矽烷,m=3時係1官能性矽烷。
作為以上述式(4)表示之有機矽烷的具體例,可舉出四甲氧基矽烷、四乙氧基矽烷、四乙醯氧基矽烷、四苯氧基矽烷等的4官能性矽烷;甲基三甲氧基矽烷、甲基三乙氧基矽
烷、甲基三異丙氧基矽烷、甲基三正丁氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙基三異丙氧基矽烷、乙基三正丁氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、正丁基三甲矽烷、正丁基三乙氧基矽烷、正己基三甲氧基矽烷、正己基三乙氧基矽烷、癸基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、對羥苯基三甲氧基矽烷、1-(對羥苯基)乙基三甲氧基矽烷、2-(對羥苯基)乙基三甲氧基矽烷、4-羥基-5-(對羥苯基羰氧基)戊基三甲氧基矽烷、三氟甲基三甲氧基矽烷、三氟甲基三乙氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷等的3官能性矽烷;二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二乙醯氧基矽烷、二正丁基二甲氧基矽烷、二苯基二甲氧基矽烷等的2官能性矽烷;三甲基甲氧基矽烷、三正丁基乙氧基矽烷等的1官能性矽烷。
在本發明所使用之聚矽氧烷樹脂,係可藉由使上述的有機矽烷水解及部分縮合而得到。水解及部分縮合係可使用通常的方法。例如在混合物添加溶劑、水、及必要時之觸媒且進行加熱攪拌。攪拌中亦可在必要時藉由蒸餾將水解副產物(甲醇等的醇類)和縮合副產物(水)餾去。
在本發明所使用之聚醯亞胺樹脂,係可藉由將使
四羧酸酐與二胺反應而得到之聚醯亞胺前驅物進行熱處理而得到。作為用以得到聚醯亞胺樹脂之前驅物,可舉出聚醯胺酸、聚醯胺酸酯、聚異醯亞胺、聚醯胺酸磺醯胺等。
在本發明所使用之聚醯亞胺樹脂,係藉由習知的方法而合成。亦即,藉由將四羧酸二酐及二胺選擇性地組合,且使其在N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、二甲基甲醯胺、二甲基亞碸、六甲基磷醯三胺、γ-丁內酯、環戊酮等的極性溶劑中反應等習知的方法而合成。
過剩地使用二胺而聚合時,可使所生成的聚醯亞胺樹脂之末端胺基與羧酸酐反應,來保護末端胺基。又,過剩地使用四羧酸酐而聚合時,亦可使所生成的聚醯亞胺樹脂之末端酸酐基與胺化合物反應,來保護末端酸酐基。
作為此種羧酸酐的例子,可舉出酞酸酐、1,2,4-苯三甲酸酐、順丁烯二酸酐、萘二甲酸酐、氫化酞酸酐、甲基-5-降莰烯-2,3-二羧酸酐、伊康酸酐、四氫酞酸酐等;作為胺化合物的例子,苯胺,可舉出2-羥基苯胺、3-羥基苯胺、4-羥基苯胺、2-乙炔基苯胺、3-乙炔基苯胺、4-乙炔基苯胺等。
本發明所使用之樹脂(A)的重量平均分子量(Mw),係通常為1,000~1,000,000,以1,500~100,000為佳,較佳為2.000~10,000的範圍。樹脂(A)的分子量分布係以重量平均分子量/數量平均分子量(Mw/Mn)比計,通常為4以下,以3以下為佳,較佳為2.5以下。樹脂(A)的重量平均分子量(Mw)和分子量分布,係能夠使用凝膠滲透層析法而測定。例如將四氫呋喃等的溶劑作為洗提液且以聚苯乙烯換算分子量的方式
求取。
又,在本發明所使用之樹脂組成物,係以進一步含有含烷氧矽烷基的(甲基)丙烯酸酯化合物(B)、4官能以上的(甲基)丙烯酸酯化合物(C)、光聚合起始劑(D)、及交聯劑(E)之中至少1種為佳。
含烷氧矽烷基的(甲基)丙烯酸酯化合物(B),係(甲基)丙烯酸的酯而且含有烷氧矽烷基之化合物。
作為含烷氧矽烷基的(甲基)丙烯酸酯化合物(B)之具體例,可舉出2-丙烯醯氧基乙基三甲氧基矽烷、2-丙烯醯氧基乙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基甲基二甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、4-丙烯醯氧基丁基三甲氧基矽烷、4-丙烯醯氧基丁基三乙氧基矽烷、2-甲基丙烯醯氧基乙基三甲氧基矽烷、2-甲基丙烯醯氧基乙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基甲基二乙氧基矽烷、4-甲基丙烯醯氧基丁基三甲氧基矽烷、4-甲基丙烯醯氧基丁基三乙氧基矽烷等。這些係可以單獨1種或是組合2種以上而使用。
在本發明所使用之樹脂組成物中,相對於黏結樹脂(A)100重量份,含烷氧矽烷基的(甲基)丙烯酸酯化合物(B)的含量係以0.5~4重量份為佳,較佳為0.5~2.5重量份,更佳為0.8~2重量份。
4官能以上的(甲基)丙烯酸酯化合物(C),係(甲基)
丙烯酸的酯而且具有4個以上的(甲基)丙烯醯基之化合物。
作為4官能以上的(甲基)丙烯酸酯化合物(C)之具體例,可舉出二新戊四醇六丙烯酸酯(例如,製品名「DPHA」、DAICEL-CYTEC公司製,或是製品名「LIGHT-ACRYLATE DPE-6A」、共榮化學公司製,製品名「A-DPH」、新中村化學工業公司製)、新戊四醇乙氧基四丙烯酸酯(例如,製品名「EBECRYL40」、DAICEL-CYTEC公司製)、雙三羥甲基丙烷四丙烯酸酯(例如,製品名「AD-TMP」、新中村化學工業公司製)、乙氧基新戊四醇四丙烯酸酯(例如,製品名「ATM-35E」、新中村化學工業公司製)、新戊四醇四丙烯酸酯(例如,製品名「A-TMMT」、新中村化學工業公司製)、二新戊四醇聚丙烯酸酯(例如,製品名「A-9550」、新中村化學工業公司製)、新戊四醇三/四丙烯酸酯(例如,製品名「ARONIX M-303 Tri 40-60%」,或是製品名「ARONIX M-305 Tri 55-63%」、製品名「ARONIX M-306 Tri 65-70%」,任一者均是東亞合成公司製)、二新戊四醇五/六丙烯酸酯(例如,製品名「ARONIX M-402 Penta 30-40%」,或是製品名「ARONIX M-406 Penta 25-35%」,任一者均是東亞合成公司製)、雙三羥甲基丙烷四丙烯酸酯(例如,製品名「ARONIX M-408」、東亞合成公司製)、多元酸改性丙烯酸寡聚物(例如,製品名「ARONIX M-510」、東亞合成公司製)等。這些係可以單獨1種或是組合2種以上而使用。
在本發明所使用之樹脂組成物中,相對於黏結樹脂(A)100重量份,4官能以上的(甲基)丙烯酸酯化合物(C)之含量係以0.5~7重量份為佳,較佳為0.5~5重量份,更佳為1~4
重量份,最佳為2~4重量份。
作為光聚合起始劑(D),係藉由光線引起化學反應之化合物即可,而沒有特別限定,較佳是以藉由光線產生自由基且藉此引起化學反應之自由基產生型光聚合起始劑為佳,自由基產生型光聚合起始劑之中,特別是以對400nm以下的波長之光線具有敏感度且照射400nm以下的波長之光線、具體而言為紫外線、電子射線等的放射線時,能夠產生自由基且引起化學反應之化合物為佳。
作為此種自由基產生型光聚合起始劑的具體例,可舉出二苯基酮、鄰苯甲醯基苯甲酸甲酯、4,4-雙(二甲胺)二苯基酮、4,4-雙(二乙胺)二苯基酮、α-胺基-苯乙酮、4,4-二氯二苯基酮、4-苯甲醯基-4-甲基二苯基酮、二苄基酮、茀酮、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2-羥基-2-甲基苯丙酮、對第三丁基二氯苯乙酮、塞吨酮(thioxanthone)、2-甲基塞吨酮、2-氯塞吨酮、2-異丙基9-氧硫塞吨酮、二乙基塞吨酮、苄基二甲基縮酮、苄基甲氧基乙基縮醛、苯偶姻甲醚、苯偶姻丁醚、蒽醌、2-第三丁基蒽醌、2-戊基蒽醌、β-氯蒽醌、蒽酮、苯并蒽酮、二苯并環庚酮、亞甲基蒽酮、4-疊氮苄基苯乙酮、2,6-雙(對疊氮亞苄基)環己烷、2,6-雙(對疊氮亞苄基)-4-甲基環己酮、2-苯基-1,2-丁二酮-2-(鄰甲氧基羰基)肟、1-苯基-丙二酮-2-(鄰乙氧基羰基)肟、1,3-二苯基-丙三酮-2-(鄰乙氧基羰基)肟、1-苯基-3-乙氧基-丙三酮-2-(鄰苯甲醯基)肟、米其勒酮、2-甲基-1[4-(甲硫基)苯基]-2-嗎啉丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉苯基)-丁酮、萘磺醯氯、喹啉磺醯氯、n-苯基
硫代吖酮、4,4-偶氮雙異丁腈、二苯基二硫醚、苯并噻唑二硫醚、三苯基膦、樟腦醌、N,N-八亞甲基雙吖啶、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮(製品名「Irgacure379EG」、BASF公司製)、1-羥基-環己基-苯基-酮(製品名「IRGACURE184」、BASF公司製)、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮(製品名「IRGACURE127」、BASF公司製)、2-甲基-1-(4-甲硫基苯基)-2-嗎啉丙烷-1-酮(製品名「IRGACURE907」、BASF公司製)、1,7-雙(9-吖啶基)-庚烷(ADEKA公司製、N1717)、1,2-辛二酮,1-[4-(苯硫基)-,2-(鄰苯甲醯基肟)](BASF公司製、OXE-01)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(BASF公司製、OXE-02)、四氯化碳、三溴苯基碸、過氧化苯偶姻、曙紅、亞甲藍等的光還原性色素與如抗壞血酸和三乙醇胺的還原劑之組合等。這些係可以單獨1種或是組合2種以上而使用。
在本發明所使用之樹脂組成物中,相對於黏結樹脂(A)100重量份,光聚合起始劑(D)的含量係以0.3~8重量份為佳,較佳為0.5~6重量份,更佳為0.7~4重量份。
作為交聯劑(E),係藉由加熱而在交聯劑分子之間形成交聯結構者;樹脂(A)反應而在樹脂分子之間形成交聯結構者等;具體而言係可舉出具有2個以上的反應性基之化合物。作為此種反應性基,例如可舉出胺基、羧基、羥基、環氧基、異氰酸酯基,較佳為胺基、環氧基及異氰酸酯基,以胺基及環氧基為特佳。
作為交聯劑(E)的具體例,可舉出六亞甲二胺等的脂肪族多元胺類;4,4’-二胺基二苯基醚、二胺基二苯基碸等的芳香族多元胺類;2,6-雙(4’-疊氮亞苄基)環己酮、4,4’-二疊氮二苯基碸等的疊氮類;耐綸、聚六亞甲二胺對酞醯胺、聚六亞甲基異酞醯胺等的聚醯胺類;N,N,N’,N’,N”,N”-(六烷氧基烷基)三聚氰胺等亦可具有羥甲基、亞胺基等的三聚氰胺類(製品名「CYMEL303、CYMEL325、CYMEL370、CYMEL232、CYMEL235、CYMEL272、CYMEL212、Mycoat506」{以上、CYTEC Industries公司製}等的CYMEL Series、Mycoat Series);N,N’,N”,N'''-(四烷氧基烷基)甘脲等亦可具有羥甲基、亞胺基等的甘脲類(製品名「CYMEL1170」{以上、CYTEC Industries公司製}等的CYMELSeries);乙二醇二(甲基)丙烯酸酯等的丙烯酸酯化合物;六亞甲基二異氰酸酯系聚異氰酸酯、異佛爾酮二異氰酸酯系聚異氰酸酯、甲苯二異氰酸酯系聚異氰酸酯、氫化二苯基甲烷二異氰酸酯等的異氰酸酯系化合物;1,4-二-(羥甲基)環己烷、1,4-二-(羥甲基)降莰烷;1,3,4-三羥基環己烷;雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、多酚型環氧樹脂、環狀脂肪族環氧樹脂、脂肪族環氧丙基醚、環氧丙烯酸酯聚合物等的環氧化合物。
又,作為環氧化合物的具體例,可舉出以二環戊二烯作為骨架之3官能性的環氧化合物(製品名「XD-1000」、日本化藥公司製)、2,2-雙(羥甲基)1-丁醇的1,2-環氧基-4-(2-環氧乙基)環己烷加成物(具有環己烷骨架及末端環氧基之15
官能性的脂環式環氧樹脂、製品名「EHPE3150」、Daicel化學工業公司製)、環氧化3-環己烯-1,2-二羧酸雙(3-環己烯基甲基)改性ε-己內酯(脂肪族環狀3官能性的環氧樹脂、製品名「EPOLEAD GT301」、Daicel化學工業公司製)、環氧化丁烷四羧酸肆(3-環己烯基甲基)改性ε-己內酯(脂肪族環狀4官能性的環氧樹脂、製品名「EPOLEAD GT401」、Daicel化學工業公司製)等具有脂環構造之環氧化合物;芳香族胺型多官能環氧化合物(製品名「H-434」、東都化成工業公司製)、甲酚酚醛清漆型多官能環氧化合物(製品名「EOCN-1020」、日本化藥公司製)、苯酚酚醛清漆型多官能環氧化合物(EPICOAT 152、154、JAPAN EPOXY RESINS公司製)、具有萘骨架之多官能環氧化合物(製品名EXA-4700、DIC股份公司製)、鏈狀烷基多官能環氧化合物(製品名「SR-TMP」、阪本藥品工業股份公司製)、多官能環氧聚丁二烯(製品名「EPOLEAD PB3600」、Daicel化學工業公司製)、甘油的環氧丙基聚醚化合物(製品名「SR-GLG」、阪本藥品工業股份公司製)、二甘油聚環氧丙基醚化合物(製品名「SR-DGE」、阪本藥品工業股份公司製、聚甘油聚環氧丙基醚化合物(製品名「SR-4GL」、阪本藥品工業股份公司製)等未具有脂環構造的環氧化合物。
在本發明所使用之樹脂組成物中,交聯劑(E)的含量係沒有特別限定,相對於樹脂(A)100重量份,以3~70重量份為佳,較佳為4~45重量份,更佳為5~25重量份。交聯劑(E)為太多或太少,耐熱性均有低落之傾向。
又,在本發明所使用之樹脂組成物,亦可進一步含有溶劑。作為溶劑,係沒有特別限定,習知作為樹脂組成物的溶劑,係例如可舉出丙酮、甲基乙基酮、環戊酮、2-己酮、3-己酮、2-庚酮、3-庚酮、4-庚酮、2-辛酮、3-辛酮、4-辛酮等直鏈的酮類;正丙醇、異丙醇、正丁醇、環己醇等的醇類;乙二醇二甲醚、乙二醇二乙基醚、二烷等的醚類;乙二醇一甲醚、乙二醇一乙醚等的醇醚類;甲酸丙酯、甲酸丁酯、乙酸丙酯、乙酸丁酯、丙酸甲酯、丙酸乙酯、酪酸甲酯、酪酸乙酯、乳酸甲酯、乳酸乙酯等的酯類;乙酸賽路蘇、乙酸甲基賽路蘇、乙酸乙基賽路蘇、乙酸丙基賽路蘇、乙酸丁基賽路蘇等的賽路蘇酯類;丙二醇、丙二醇一甲醚、丙二醇一甲醚乙酸酯、丙二醇一乙醚乙酸酯、丙二醇一丁基醚等的丙二醇類;二乙二醇一甲醚、二乙二醇一乙醚、二乙二醇二甲醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚等的二乙二醇類;γ-丁內酯、γ-戊內酯、γ-己內酯、γ-辛內酯等的飽和γ-內酯類;三氯乙烯等的鹵化烴類;甲苯、二甲苯等的芳香族烴類;二甲基乙醯胺、二甲基甲醯胺、N-甲基乙醯胺等的極性溶劑等。這些溶劑係可單獨亦可組合2種以上而使用。相對於樹脂(A)100重量份,溶劑的含量係以10~10000重量份為佳,較佳為50~5000重量份,更佳為100~1000重量份的範圍。
又,在本發明所使用之樹脂組成物,亦可進一步含有放射線感應性化合物。放射線感應性化合物係藉由照射紫外線、電子射線等的放射線,能夠引起化學反應之化合物。作為放射線感應性化合物,係以能夠控制從樹脂組成物形成而成
之鈍化膜7的鹼溶解性者為佳,特別是以使用光酸產生劑為佳
作為此種放射線感應性化合物,例如,可舉出苯乙酮化合物、三芳基鋶鹽、苯醌二疊氮化合物等的疊氮化合物等,較佳為疊氮化合物,特佳為苯醌二疊氮化合物。
作為苯醌二疊氮化合物,例如,能夠使用苯醌二疊氮磺醯鹵與具有酚性羥基的化合物之酯化合物。作為苯醌二疊氮磺醯鹵的具體例,可舉出1,2-萘醌二疊氮-5-磺醯氯、1,2-萘醌二疊氮-4-磺醯氯、1,2-苯醌二疊氮-5-磺醯氯等。作為具有酚性羥基的化合物之代表例,可舉出1,1,3-參(2,5-二甲基-4-羥苯基)-3-苯基丙烷、4,4’-[1-[4-[1-[4-羥苯基]-1-甲基乙基]苯基]亞乙基]雙酚等。作為該等以外之具有酚性羥基之化合物,可舉出2,3,4-三羥基二苯基酮、2,3,4,4’-四氫二苯基酮、2-雙(4-羥苯基)丙烷、參(4-羥苯基)甲烷、1,1,1-參(4-羥基-3-甲基苯基)乙烷、1,1,2,2-肆(4-羥苯基)乙烷、酚醛清漆樹脂的寡聚物、將具有1個以上的酚性羥基之化合物與二環戊二烯共聚合而得到的寡聚物等。
這些之中,係以1,2-萘醌二疊氮-5-磺醯氯與具有酚性羥基之化合物之縮合物為佳,以1,1,3-參(2,5-二甲基-4-羥苯基)-3-苯基丙烷(1莫耳)與1,2-萘醌二疊氮-5-磺醯氯(1.9莫耳)之縮合物為較佳。
而且,作為光酸產生劑,係可使用苯醌二疊氮化合物、以及鎓鹽、鹵化有機化合物、α-α’-雙(磺醯基)重氮甲烷系化合物、α-羰基-α’-磺醯基重氮甲烷系化合物、碸化合物、有機酸酯化合物、有機酸醯胺化合物、有機酸醯亞胺化合物等
習知物。這些放射線感應性化合物係能夠單獨1種或組合2種以上而使用。
又,在本發明所使用之樹脂組成物,亦可依照需要而含有界面活性劑、酸性化合物、偶合劑或其衍生物、増感劑、潛在性酸產生劑、抗氧化劑、光安定劑、消泡劑、顏料、染料、填料等其他的調配劑等。
界面活性劑係為了防止條紋(塗布線條痕跡)、提升顯像性等之目的而使用。作為界面活性劑的具體例,可舉出聚氧乙烯月桂基醚、聚氧乙烯硬脂醯基醚、聚氧乙烯油醯基醚等的聚氧乙烯烷基醚類;聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等的聚氧乙烯芳基醚類;聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等的聚氧乙烯二烷酯類等的非離子系界面活性劑;氟系界面活性劑;聚矽氧系界面活性劑;甲基丙烯酸共聚物系界面活性劑;丙烯酸共聚物系界面活性劑等。
偶合劑或其衍生物,係具有進一步提高由樹脂組成物所構成之樹脂膜與包含構成半導體元件基板的半導體層之各層的密著性之效果。作為偶合劑或其衍生物,係可使用具有選自矽原子、鈦原子、鋁原子、鋯原子之一種原子且具有鍵結於該原子的烴氧基或羥基之化合物等。
作為偶合劑或其衍生物,例如,可舉出四甲氧基矽烷、四乙氧基矽烷、四正丙氧基矽烷、四異丙氧基矽烷、四正丁氧基矽烷等的四烷氧基矽烷類、
甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧
基矽烷、異丙基三甲氧基矽烷、異丙基三乙氧基矽烷、正丁基三甲氧基矽烷、正丁基三乙氧基矽烷、正戊基三甲氧基矽烷、正己基三甲氧基矽烷、正庚基甲氧基矽烷、正辛基三甲氧基矽烷、正癸基三甲氧基矽烷、對苯乙烯基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、環己基三甲氧基矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、3-氯丙基三乙氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷、3,3,3-三三氟丙基三乙氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、N-2-(胺乙基)-3-胺丙基三甲氧基矽烷、N-苯基-3-胺丙基三甲氧基矽烷、2-羥乙基三甲氧基矽烷、2-羥乙基三乙氧基矽烷、2-羥丙基三甲氧基矽烷、2-羥丙基三乙氧基矽烷、3-羥丙基三甲氧基矽烷、3-羥丙基三乙氧基矽烷、3-氫硫基丙基三甲氧基矽烷、3-氫硫基丙基三乙氧基矽烷、3-異氰酸酯丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-脲丙基三甲氧基矽烷、3-脲丙基三乙氧基矽烷、3-乙基(三甲氧基矽烷基丙氧基甲基)氧雜環丁烷、3-乙基(三乙氧基矽烷基丙氧基甲基)氧雜環丁烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙胺、雙(三乙氧基矽烷基丙基)四硫醚等的三烷氧基矽烷類、
二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙基二甲
氧基矽烷、二乙基二乙氧基矽烷、二-正丙基二甲氧基矽烷、二-正丙基二乙氧基矽烷、二-異丙基二甲氧基矽烷、二-異丙基二乙氧基矽烷、二-正丁基二甲氧基矽烷、二-正戊基二甲氧基矽烷、二-正戊基二乙氧基矽烷、二-正己基二甲氧基矽烷、二-正己基二乙氧基矽烷、二-正庚基二甲氧基矽烷、二-正庚基二乙氧基矽烷、二-正辛基二甲氧基矽烷、二-正辛基二乙氧基矽烷、二-正環己基二甲氧基矽烷、二-正環己基二乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-丙烯醯氧基丙基甲基二乙氧基矽烷、N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷等的二烷氧基矽烷類、
以及甲基三乙醯氧基矽烷、二甲基二乙醯氧基矽烷等含矽原子的化合物;四異丙氧基鈦、四正丁氧基鈦、四(2-乙基己氧基)鈦、異丙氧基辛二醇鈦、二異丙氧基.雙(乙醯丙酮)鈦、丙烷二氧鈦雙(乙基乙醯乙酸鹽)、三正丁氧基鈦單硬脂酸鹽、二異丙氧基二硬脂酸鈦、硬脂酸鈦、二異丙氧基鈦二異硬脂酸鹽、(2-正丁氧羰基苯甲醯氧基)三丁氧基鈦、二正丁氧基.雙(三乙醇胺)鈦、以及PLENACT Series(Ajinomoto Fine-Techno股份公司製)等含鈦原子的化合物;乙醯烷氧基鋁二異丙酸鹽等含鋁原子的化合物;四正丙氧基鋯、四正丁氧基鋯、四乙醯丙酮酸鋯、三丁氧
基乙醯丙酮酸鋯、一丁氧基乙醯丙酮酸鋯雙(乙醯乙酸乙酯)、二丁氧基雙(乙醯乙酸乙基)鋯、四乙醯丙酮酸鋯、三丁氧基硬脂酸鋯等含鋯原子的化合物。
作為増感劑的具體例,可舉出2H-吡啶并-(3,2-b)-1,4-嗪-3(4H)-酮類、10H-吡啶并-(3,2-b)-7,4-苯并噻嗪類、脲唑(urazole)類、海因(hydantoin)類、巴比妥酸(barbituric acid)類、甘胺酸酐類、1-羥基苯并三唑類、阿尿素(alloxan)類、順丁烯二醯亞胺類等。
作為抗氧化劑,能夠使用在通常的聚合物所使用之酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、內酯系抗氧化劑等。例如,作為酚類,能夠舉出2,6-二-第三丁基-4-甲基苯酚、對甲氧基苯酚、苯乙烯化苯酚、N-十八基-3-(3’,5’-二-第三丁基-4’-羥苯基)丙酸酯、2,2’-亞甲基-雙(4-甲基-6-第三丁基苯酚)、2-第三丁基-6-(3’-第三丁基-5’-甲基-2’-羥苄基)-4-甲基苯基丙烯酸酯、4,4’-亞丁基-雙-(3-甲基-6-第三丁基苯酚)、4,4’-硫-雙(3-甲基-6-第三丁基苯酚)、新戊四醇肆[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]、烷基化雙酚等。作為磷系抗氧化劑,可舉出亞磷酸三苯酯、亞磷酸參(壬基苯基)酯,作為硫系,可舉出硫二丙酸二月桂酸酯等。
作為光安定劑,可以是二苯基酮系、柳酸酯系、苯并三唑系、氰基丙烯酸酯系、金屬錯鹽系等的紫外線吸收劑、受阻胺系(HALS)等捕捉因光線而產生的自由基者等的任一種。該等之中,因為HALS係具有哌啶構造之化合物,對樹脂組成物之著色較少且安定性良好,乃是較佳。作為具體的化合
物,可舉出雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、1,2,2,6,6-五甲基-4-哌啶基/十三基1,2,3,4-丁烷四羧酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯等。
在本發明所使用之樹脂組成物,係藉由使用習知的方法將構成樹脂組成物之各成分混合來調製。混合方法係沒有特別限定,以將構成樹脂組成物之各成分溶解或分散在溶劑而得到的溶液或分散液混合為佳。藉此,樹脂組成物係以溶液或分散液的形態獲得。
在本發明的製造方法,係使用如以上的樹脂組成物而形成鈍化膜7。
本發明的製造方法,係以形成鈍化膜7來將基板2、半導體層4、源極電極5及汲極電極6的上面(露出面)的全體覆蓋之後,亦可在進行煅燒之前進行圖案化。鈍化膜7的圖案化,係可藉由例如以光阻作為遮罩而進行乾式蝕刻之方法;使樹脂組成物含有上述的放射線感應性性化合物,而且使用活性放射線在使用此樹脂組成物而形成的樹脂膜形成潛像圖案且使用顯像液使潛像圖案顯在化之方法等來進行。
作為活性放射線,係只要能夠放射線感應性化合物活性化且使鈍化膜7的鹼可溶性變化者,就沒有特別限定。具體而言,係能夠使用紫外線、g射線、i射線等單一波長的紫外線、KrF準分子雷射光、ArF準分子雷射光等的光線;如電子射線的粒子射線等。作為選擇性且圖案狀地照射該等活性放射線而形成潛像圖案之方法,係依照常用的方法即可,例如能夠使用藉由縮小投影曝光裝置等透過所需要的遮罩圖案而
照射紫外線、g射線、i射線、KrF準分子雷射光、ArF準分子雷射光等的光線之方法;或是藉由電子射線等的粒子射線進行描繪之等。使用光線作為活性放射線時,可為單一波長光線,亦可為混合波長光線。照射條件係按照所使用的活性放射線而適當地選擇,例如使用波長200~450nm的光線時,照射量係通常為10~1,000mJ/cm2,較佳為50~500mJ/cm2的範圍,且按照照射時間及照度而決定。如此進行而照射活性放射線之後,係必要時在60~130℃左右的溫度將鈍化膜7加熱處理1~2分鐘左右。
其次,將在鈍化膜7所形成的潛像圖案顯像而使其顯在化,藉此使其圖案化。作為顯像液,通常係使用鹼性化合物的水性溶液。作為鹼性化合物,例如能夠使用鹼金屬鹽、胺、銨鹽。鹼性化合物係可為無機化合物亦可為有機化合物。作為該等化合物的具體例,可舉出氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉等的鹼金屬鹽;氨水;乙胺、正丙胺等的第一級胺;二乙胺、二正丙胺等的第二級胺;三乙胺、甲基二乙胺等的第三級胺;氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丁基銨、膽鹼等的第四級銨鹽;二甲基乙醇胺、三乙醇胺等的醇胺;吡咯、哌啶、1,8-二氮雜雙環[5.4.0]十一基-7-烯、1,5-二氮雜雙環[4.3.0]壬-5-烯、N-甲基吡咯啶酮等的環狀胺類等。這些鹼性化合物係可各自單獨或組合2種以上而使用。
作為鹼水性溶液的水性媒體,能夠使用水;甲醇、乙醇等的水溶性有機溶劑。鹼水性溶液亦可添加適當量的界面活性劑等。
作為使具有潛像圖案之鈍化膜7接觸顯像液之方法,例如,可使用浸置法、噴霧法、浸漬法等的方法。顯像係在通常為0~100℃,以5~55℃為佳,較佳為10~30℃的範圍,且通常係設為30~180秒鐘的範圍。
如此進行而形成具有所需要的圖案之鈍化膜7之後,能夠在必要時使用沖洗液進行沖洗,用以將顯像殘渣除去。沖洗處理之後,係藉由壓縮空氣和壓縮氮而將殘留的沖洗液除去。而且,亦能夠在必要時對形成有鈍化膜7之元件全面照射活性放射線,用以使放射線感應性化合物去活。活性放射線的照射係可利用在上述潛像圖案的形成已例示的方法。然後,如此進行而形成具有所需要的圖案之鈍化膜7之後,係如上述進行煅燒,其次,藉由以預定的冷卻速度進行冷卻,而能夠得到具有己圖案化的鈍化膜7之半導體元件1。
又,在上述,係例示在第1圖所示的半導體元件1而進行說明,但是作為本發明的製造方法之半導體元件,係未特別地被限定於第1圖所示的態樣,只要在基板上具有含有無機氧化物半導體之半導體層,而且以將此半導體層覆蓋的方式所形成之具有由有機材料所構成的鈍化膜之半導體元件,係可為任何態樣。
而且,因為使用本發明的製造方法得到之半導體元件,其閥值電壓Vth為接近零且具有高移動度者,所以能夠活用其特性而使用作為被納入各種半導體裝置之半導體元件。特別是使用本發明的製造方法得到的半導體元件,係能夠適合使用作為在主動矩陣型液晶顯示器、主動矩陣型有機EL
等的顯示裝置等所使用的薄膜電晶體。
以下,舉出實施例及比較例而更具體地說明本發明。各例中的「份」及「%」係只要未特別預先告知,就是重量基準。又,各特性的定義及評價方法係如以下。
<閥值電壓V th>
針對所得的薄膜電晶體,藉由在大氣下.暗室中使用半導體參數分析器(Agilent公司製、4156C)且使閘極電壓從-60V至+20V為止進行變化,且測定在源極.汲極間流動電流的變化對閘極電壓的變化。然後,將測定結果之在源極.汲極間流動電流之值係成為Id=100nA×(W/L)(其中,W係通道寬度,L係通道長度,Id係汲極電流)時的電壓設作閥值電壓Vth。在第4圖,係顯示在實施例1及比較例2所得到的薄膜電晶體之在源極.汲極間流動電流的變化對閘極電壓的變化。
<移動度>
針對所得的薄膜電晶體,藉由在大氣下.暗室中使用半導體參數分析器(Agilent公司製、4156C)且使閘極電壓從-60V至+20V為止進行變化,且測定在源極.汲極間流動電流的變化對閘極電壓的變化,而且依照下述式從薄膜電晶體的飽和區域求取電場效果移動度。
Id=μ Cin.W.(Vg-Vth)2/2L
(其中,Cin係閘極絕緣膜之平均單位面積的靜電容量,W係通道寬度、L係通道長度、Vg係閘極電壓,Id係汲極電流,μ係移動度,Vth係閘極的閥值電壓)
《合成例》
<環狀烯烴聚合物(A-1)的調製>
將由N-苯基-雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺(NBPI)40莫耳%、及4-羥羰基四環[6.2.1.13,6.02,7]十二基-9-烯(TCDC)60莫耳%所構成之單體混合物100份、1,5-己二烯2.0份、(1,3-二-2,4,6-三甲苯基咪唑啉-2-亞基)(三環己基膦)亞苄基二氯化釕(使用在「Org.Lett(有機通訊).,第1卷,第953頁,1999年」所記載的方法合成而成)0.02份、及二乙二醇乙基甲醚200份,添加至已氮置換的玻璃製耐壓反應器,邊攪拌邊在80℃使其反應4小時而得到聚合反應液。
然後,將所得到的聚合反應液放入高壓釜,在150℃、氫壓4MPa攪拌5小時而進行氫化反應,來得到含有環狀烯烴聚合物(A-1)之聚合物溶液。所得到的環狀烯烴聚合物(A-1)的聚合轉化率為99.7%,聚苯乙烯換算重量平均分子量為7,150、數量平均分子量為4,690,分子量分布為1.52,氫化率為99.7%,所得到的環狀烯烴聚合物(A-1)的聚合物溶液之固體成分濃度為34.4重量%。
《實施例1》
<樹脂組成物的調製>
將作為樹脂(A)之在合成例1所得到之環狀烯烴聚合物(A-1)的聚合物溶液291份(就環狀烯烴聚合物(A-1)而言為100份)、作為含烷氧矽烷基的(甲基)丙烯酸酯化合物(B)之3-丙烯醯氧基丙基三甲氧基矽烷(製品名「KBM-5103」、信越化學工業公司製)1份、作為4官能以上的(甲基)丙烯酸酯化合物(C)
之二新戊四醇五/六丙烯酸酯(製品名「ARONIX M-406 Penta 25-35%」、東亞合成公司製)3份,作為光聚合起始劑(D)之2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮(製品名「Irgacure127」、BASF公司製)1份,作為交聯劑(E)之環氧化丁烷四羧酸肆(3-環己烯基甲基)改性ε-己內酯(脂肪族環狀4官能性的環氧樹脂、製品名「EPOLEAD GT401」、Daicel化學工業公司製)15份、聚矽氧系界面活性劑(製品名「KP-341」、信越化學工業公司製)0.03份、作為及溶劑之乙二醇乙基甲醚270份混合且使該等溶之後,使用孔徑0.45μm的聚四氟乙烯製過濾器過濾而調製樹脂組成物。
<薄膜電晶體的製造>
其次,使用以下的方法,來製造具有在第1圖所示的構成之薄膜電晶體。亦即,首先準備p型矽基板作為基板2,藉由在氧及氫的環境下且在1000℃、13分鐘的條件下對p型矽基板進行熱處理,而在p型矽基板上形成當作閘極絕緣膜之100nm的熱氧化膜。其次,藉由將成膜時的Ar/O2的流量比設為50%之濺鍍法,在其上形成50nm的In-Ga-Zn-O系非單結晶膜。其次,為了將In-Ga-Zn-O系非單結晶膜圖案化,係藉由使用旋轉塗布法在半導體層上塗布蝕刻遮罩用的正型光阻,且使用加熱板而將溶劑除去而形成光阻膜,接著經由曝光步驟、顯像步驟而將光阻膜圖案化。其次,使用所形成的遮罩,藉由使用磷酸之濕式蝕刻,將In-Ga-Zn-O系非單結晶膜圖化圖案化成島狀,接著藉由使用剝離液將光阻膜而形成半導體層4(參照第2圖(A))。其次,在水蒸氣環境下(H2O/O2:10H2O)且在
220℃、1小時的條件下進行加熱處理。
其次,為了形成源極電極5及汲極電極6,係藉由使用旋轉塗布法塗布正型光阻,且藉由使用加熱板將溶劑除去而形成光阻膜,接著藉由經由曝光步驟、顯像步驟而將光阻膜圖案化而形成舉離用光阻10(參照第2圖(B))。其次,在形成有半導體層4及舉離用光阻10之p型矽基板(基板2)上,藉由濺鍍法濺鍍Ti而形成Ti膜作為用以形成源極電極5及汲極電極6之由導電性材料所構成之層20(參照第2圖(C))。其次,將基板2的背面(與形成有半導體層4之面相反面)暴露在HF的蒸氣而將基板2背面上的SiO2膜除去之後,藉由濺鍍法將Al濺鍍在基板2的背面,來形成作為閘極電極3之Al膜(參照第3圖(A))。
其次,藉由將形成有閘極電極3、半導體層4、舉離用光阻10、及由導電性材料所構成的層20之基板2放入丙酮中且使用超音波處理將舉離光阻10除去,而形成源極電極5及汲極電極6(參照第3圖(B))。其次,藉由旋轉塗布法在其上塗布在上述所得到的樹脂組成物,且藉由使用加熱板在115℃、2分鐘的條件下進行加熱乾燥(預烘烤)而形成厚度1.5μm的樹脂膜,來得到形成有閘極電極3、半導體層4、源極電極5、汲極電極6及樹脂膜之基板(以下,稱為「樹脂膜形成基板」)。然後,將所得到的樹脂膜形成基板放入烘箱,在烘箱內,於N2環境下、230℃且60分鐘的條件下進行樹脂膜的煅燒。然後,煅燒後在烘箱放入有樹脂膜形成基板的狀態下,在N2環境下且1℃/分鐘的冷卻速度下開始冷卻,在已被冷卻至150℃
為止的時點,藉由將樹脂膜形成基板取出至大氣環境、室溫的條件下,而得到如第1圖所示之由基板2、閘極電極3、半導體層4、源極電極5、汲極電極6及鈍化膜7所構成之薄膜電晶體。然後,使用所得到的薄膜電晶體且依照上述的方法而進行測定閥值電壓Vth及移動度。將結果顯示在表1。
《實施例2》
除了將在進行樹脂膜煅燒之後的冷卻,在N2環境下且以0.5℃/分鐘的冷卻速度進行冷卻至150℃為止以外,係與實施例1同樣地進行而得到薄膜電晶體且同樣地進行評價。將結果顯示在表1。
《實施例3》
除了將在進行樹脂膜煅燒之後的冷卻,在N2環境下且以5℃/分鐘的冷卻速度進行冷卻至150℃為止以外,係與實施例1同樣地進行而得到薄膜電晶體且同樣地進行評價。將結果顯示在表1。
《比較例1》
除了進行樹脂膜的煅燒之後,立即將煅燒後的樹脂膜形成基板取出至大氣環境、室溫的條件下以外,係與實施例1同樣地進行而得到薄膜電晶體且同樣地進行評價。將結果顯示在表1。
《比較例2》
除了不形成鈍化膜7以外,係與實施例1同樣地進行而得到薄膜電晶體且同樣地進評價。亦即,在比較例2,係不進行使用樹脂組成物來形成樹脂膜且藉由在與實施例1同樣的條件
下進行煅燒及冷卻而得到薄膜電晶體。亦即,在比較例2,不是顯示鈍化膜的形成條件,而是顯示無鈍化膜之加熱冷卻的條件。將結果顯示在表1。
又,在表1中,所謂「冷卻結束溫度」,係指煅燒後,以預定的冷卻速度進行冷卻之後,取出至大氣環境、室溫的條件下時點的溫度。因此,在比較例1,因為煅燒後,係不以預定的冷卻速度進行冷卻而取出至大氣環境、室溫的條件下,所以煅燒溫度係成為與冷卻結束溫度相同。
如表1所示,將進行樹脂膜的煅燒之後進行冷卻時的冷卻速度設為0.5~5℃/分鐘的範圍時,所得到的薄膜電晶體係任一者均是閥值電壓Vth為接近零且具有高移動度者(實施例1~3)。
另一方面,進行樹脂膜的煅燒之後,未以0.5~5℃/分鐘的冷卻速度進行冷卻時,及未形成鈍化膜時,所得到的薄膜電晶
體係任一者均是閥值電壓Vth的絕對值變大且移動度亦低者(比較例1、2)。
1‧‧‧半導體元件
2‧‧‧基板
3‧‧‧閘極電極
4‧‧‧半導體層
5‧‧‧源極電極
6‧‧‧汲極電極
7‧‧‧鈍化膜
Claims (8)
- 一種半導體元件的製造方法,係具備以下步驟之半導體元件的製造方法:半導體層形成步驟,其係在基板上形成含有無機氧化物半導體之半導體層;鈍化膜形成步驟,其係將由有機材料所構成之鈍化膜成膜,以覆蓋前述半導體層;煅燒步驟,其係將前述鈍化膜進行煅燒;及冷卻步驟,其係煅燒後,進行冷卻;其特徵在於:在前述冷卻步驟進行冷卻時,將從前述煅燒步驟之煅燒時的煅燒溫度起至比煅燒時的煅燒溫度更低50℃的溫度為止之冷卻速度,實質地控制在0.5~5℃/分鐘的範圍。
- 如申請專利範圍第1項所述之半導體元件的製造方法,其中前述煅燒步驟的煅燒溫度係200~300℃。
- 如申請專利範圍第1項所述之半導體元件的製造方法,其中在前述冷卻步驟進行冷卻時,係將從前述煅燒步驟的煅燒溫度起至150℃為止之冷卻速度,實質地控制在0.5~5℃/分鐘的範圍。
- 如申請專利範圍第1項所述之半導體元件的製造方法,其中在非氧化性環境下進行前述煅燒步驟的煅燒及在前述冷卻步驟之冷卻。
- 如申請專利範圍第1項所述之半導體元件的製造方法,其中使用含有選自由環狀烯烴樹脂、丙烯酸樹脂、卡多樹脂、聚矽氧烷樹脂及聚醯亞胺樹脂所組成群組之至少1種樹脂 之樹脂組成物來形成前述鈍化膜。
- 如申請專利範圍第5項所述之半導體元件的製造方法,其中使用含有具有質子性極性基的環狀烯烴樹脂之樹脂組成物來形成前述鈍化膜。
- 如申請專利範圍第6項所述之半導體元件的製造方法,其中前述樹脂組成物係進一步含有含烷氧矽烷基的(甲基)丙烯酸酯化合物、4官能以上的(甲基)丙烯酸酯化合物、光聚合起始劑、及交聯劑。
- 一種半導體元件,係使用如申請專利範圍第1至7項中任一項所述之方法而得到。
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