TWI423341B - Organic thin film transistor and organic thin film emitting transistor - Google Patents
Organic thin film transistor and organic thin film emitting transistor Download PDFInfo
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- TWI423341B TWI423341B TW096144628A TW96144628A TWI423341B TW I423341 B TWI423341 B TW I423341B TW 096144628 A TW096144628 A TW 096144628A TW 96144628 A TW96144628 A TW 96144628A TW I423341 B TWI423341 B TW I423341B
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- thin film
- group
- organic thin
- film transistor
- carbon atoms
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- 239000010409 thin film Substances 0.000 title claims description 106
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Description
本發明係關於具有有機半導體層之有機薄膜電晶體及有機薄膜發光電晶體,特別,係關於含有具高移動度之化合物之可高速運作的有機薄膜電晶體,及使用其作為發光元件之有機薄膜發光電晶體。
薄膜電晶體(TFT)被廣泛使用作為液晶顯示裝置等之顯示用開關元件。代表性之TFT的剖面構造示於圖2。如同圖所示般,TFT為於基板上依序具有閘極及絕緣體層,並於絕緣體層上,具有以指定間隔所形成的源極及汲極。包含兩者電極的一部分表面,且於電極間露出的絕緣體層上,形成半導體層。此類構成的TFT中,半導體層變成通道區,藉由外加於閘極之電壓控制源極與汲極之間流動的電流而進行開/關動作。
以往,此TFT為使用非晶質和多結晶矽而製作,但使用此類矽製作TFT的CVD裝置為非常昂貴,使用TFT之顯示裝置等的大型化,具有伴隨製造費用大幅增加的問題點。又,非晶質和多結晶矽的成膜步驟為在非常高溫下進行,故可使用作為基板的材料種類受到限制,因此具有無法使用輕量樹脂基板等之問題。
為了解決此類問題,提案使用有機物代替非晶質和多結晶矽的TFT。以有機物形成TFT時所用的成膜方法已知有真空澱積法和塗佈法等,若根據此些成膜方法,則可抑制製造費用上升並且可實現元件的大型化,並令成膜時所必要的處理溫度較為低溫。因此,使用有機物的TFT,具有基板所使用之材料的選擇時限制少的優點,期望將其實用化,關於使用有機物的TFT已廣被報導,可列舉例如非專利文獻1~20等。
又,TFT之有機化合物層所使用的有機物,於p型為使用共軛系聚合物和噻吩等之多聚物(專利文獻1~5等)、金屬酞菁化合物(專利文獻6等)、戊烯等之縮合芳香族烴類(專利文獻7及8等)等,以單體或與其他化合物之混合物狀態供使用。又,n型FET之材料,例如,於專利文獻9中,揭示1,4,5,8-萘四羧基二非氫化物(NTCDA)、11,11,12,12-四氰基萘-2,6-喹啉并二甲烷(TCNNQD)、1,4,5,8-萘四羧基二醯亞胺(NTCDI)等,於專利文獻10中,揭示氟化酞菁。
另外,於非專利文獻19中記載伸苯基伸乙烯基聚合物(聚-對伸苯基伸乙烯基(PPV))的電子移動度為小至10-4
cm2
/Vs,並未達到實用性能。即,高分子化合物之PPV中,主鏈構造長而呈彎曲,因具有分子量分佈使得結晶構造紊亂而造成電場效果移動度變小。
另一方面,同樣使用電性傳導的裝置已有有機電致發光(EL)元件,有機EL元件,一般為對100nm以下之超薄膜的膜厚方向上外加106
V/cm以上之強電場令電荷強制性流動,相對地,於有機TFT之情形中必須以105
V/cm以下之電場令電荷高速流過數μm以上的距離,有機物本身必須具有更強的導電性。但是,先前的有機TFT中,上述化合物為電場效果移動度小,應答速度慢,且在作為電晶體的高速應答性上具有問題。又,開/關比亦小。此處所謂之開/關比,係指加以閘電壓(開)時之源-汲極間流動的電流,除以未加以閘電壓(關)時之源-汲極間流動的電流之數值,所謂開電流,通常係令閘電壓增加,且源-汲極間流動之電流為飽和時的電流值(飽和電流)。
專利文獻1:特開平8-228034號公報專利文獻2:特開平8-228035號公報專利文獻3:特開平9-232589號公報專利文獻4:特開平10-125924號公報專利文獻5:特開平10-190001號公報專利文獻6:特開2000-174277號公報專利文獻7:特開平5-55568號公報專利文獻8:特開2001-94107號公報專利文獻9:特開平10-135481號公報專利文獻10:特開平11-251601號公報專利文獻11:特開2005-142233號公報
非專利文獻1:F.Ebisawa等人,Journal of Applied Physics,54卷,3255頁,1983年非專利文獻2:A.Assadi等人,Applied PhysicsLetter,53卷,195頁,1988年非專利文獻3:G.Guillaud等人,Chemical Physics Letter,167卷,503頁,1990年非專利文獻4:X.Peng等人,Applied Physics Letter,57卷,2013頁,1990年非專利文獻5:G.Horowitz等人,Synthetic Metals,41-43卷,1127頁,1991年非專利文獻6:S.Miyauchi等人,Synthetic Metals,41-43卷,1991年非專利文獻7:H.Fuchigami等人,Applied Physics Letter,63卷,1372頁,1993年非專利文獻8:H.Koezuka等人,Applied Physics Letter,62卷,1794頁,1993年非專利文獻9:F.Garnier等人,Science,265卷,1684頁,1994年非專利文獻10:A.R.Brown等人,Synthetic Metals,68卷,65頁,1994年非專利文獻11:A.Dodabalapur等人,Science,268卷,270頁,1995年非專利文獻12:T.Sumimoto等人,Synthetic Metals,86卷,2259頁,1997年非專利文獻13:K.Kudo等人,Thin Solid Films,331卷,51頁,1998年非專利文獻14:K.Kudo等人,Synthetic Metals,102卷,900頁,1999年非專利文獻15:K.Kudo等人,Synthetic Metals,111-112卷,11頁,2000年非專利文獻16:Advanced Materials 13卷,16號,2001年,1273頁非專利文獻17:Advanced Materials 15卷,6號,2003年,478頁非專利文獻18:W.Geens等人,Synthetic Metals,122卷,191頁,2001年非專利文獻19:Lay-Lay Chua等人,Nature,434卷,2005年3月10日號,194頁非專利文獻20:Hong Meng等人,Journal of A merican Chemical Society,128卷,9304頁,2006年
本發明係為了解決前述課題而完成者,以提供應答速度(驅動速度)為高速,且開/關比大之有機薄膜電晶體及利用其之有機薄膜發光電晶體為其目的。
本發明者等人為了達成前述目的而重複致力研究之結果,發現藉由對有機薄膜電晶體之有機半導體層,使用具有下述一般式(a)所示構造之有機化合物,則可令應答速度(驅動速度)高速化並且完成本發明。
即,本發明為提供至少在基板上設置閘極、源極及汲極之3個端子,絕緣體層以及有機半導體層,藉由使電壓外加於閘極來控制源-汲極間電流之有機薄膜電晶體中,該有機半導體層為含具有下述一般式(a)構造之有機化合物的有機薄膜電晶體。
又,本發明為提供於有機薄膜電晶體中,利用源-汲極間流動之電流而得發光,藉由使電壓外加於閘極而控制發光的有機薄膜發光電晶體。
本發明之有機薄膜電晶體為令應答速度(驅動速度)高速化,且開/關比大,作為電晶體的性能高,亦可利用作為可發光的有機薄膜發光電晶體。
本發明為至少在基板上設置閘極,源極及汲極之3個端子,絕緣體層以及有機半導體層,藉由使電壓外加於閘極來控制源-汲極間電流之有機薄膜電晶體中,該有機半導體層為含具有下述一般式(a)構造之有機化合物的有機薄膜電晶體。
於前述一般式(a)中,A為碳原子數6~60之2價芳香族烴基、或碳原子數1~60之2價芳香族雜環基,含苯環之基為佳,且含氮原子之芳香族雜環基亦佳。
前述A之芳香族烴基的具體例可列舉苯、萘、蒽、并四苯、并五苯、菲、、三鄰亞苯、Coranulene、暈苯、六苯并三伸苯基、六苯并暈苯、Sumanen等,且以為佳。又,芳香族雜環基之具體例可列舉吡啶、哌、喹啉、聯萘胺、喹喔啉、吩、二吖蒽、吡啶并喹啉、嘧啶并喹唑啉、吡并喹喔啉、菲繞啉、咔唑、6,12-二氫-6,12-二吖茚滿芴、二苯并噻吩、二噻苯并二茚、二噻茚滿茚、噻吩并噻吩、二噻吩并噻吩、二苯并呋喃、苯并二呋喃、二苯并硒吩、二硒苯并二茚、二硒茚滿茚、Dibenzosilol等,且以含有5員環芳香族雜環之芳香族雜環基為佳,且以含有5員環芳香族雜環和苯環者為更佳,並且以5員環芳香族雜環為具有一個以上氧原子或硫原子,並於前述苯環接續烯烴基之芳香族雜環基為特佳。又,二個伸丁二烯基為相對於A以對稱位置取代之構造為佳,且A與伸丁二烯基所構成的構造為呈平面般取代為更佳,A與伸丁二烯基所構成之π電子系為變長般取代為再佳。經由具有此類構造,則可令分子的平面性變高,又,分子間的相互作用變大,故認為可取得高性能。
又,於一般式(a)中,伸丁二烯基部分之立體構造亦可混合,但以共軛主鏈為具有反式配置之立體構造者為主成分為佳。
一般式(a)中,R1
~R10
各自獨立為氫原子、鹵原子、氰基、碳原子數1~30之烷基、碳原子數1~30之鹵烷基、碳原子數1~30之烷氧基、碳原子數1~30之鹵烷氧基、碳原子數1~30之烷硫基、碳原子數1~30之鹵烷硫基、碳原子數1~30之烷胺基、碳原子數2~60之二烷胺基(烷基係可互為鍵結而形成含氮原子之環構造)、碳原子數1~30之烷磺醯基、碳原子數1~30之鹵烷磺醯基、碳原子數6~60之芳香族烴基、或碳原子數1~60之芳香族雜環基,該等各基可具有取代基,又,可互為連接形成碳原子數6~60之芳香族烴基、或碳原子數1~60之芳香族雜環基。
一般式(a)中,R1
~R10
各自獨立為氫原子或碳原子數1~30之烷基為佳,以氫原子、鹵原子、氰基或碳原子數1~30之鹵烷基為佳。
一般式(a)中,R1
、R5
、R6
及R10
各自獨立為氫原子或氟原子為佳。
如此,若R2
~R4
及R7
~R9
為由上述選出之基,且碳原子數為30以下,則一般式(a)中所佔之規則性控制部位(R2
~R4
及R7
~R9
)的比率無過度變大,且參與電流控制之具有π電子的構造密度大,可控制膜的規則性,可取得高電場效果移動度和開/關比。
更且,前述一般式(a)中,R2
~R4
及R7
~R9
各自獨立為氫原子、鹵原子、氰基、碳原子數1~30之烷基或碳原子數1~30之鹵烷基為更佳。
又,本發明之有機薄膜電晶體所用之具有特定構造的有機化合物,基本上為顯示p型(空穴傳導)及n型(電子傳導)之兩極性,與後述源極、汲極組合則可以p型元件型式或者以n型元件型式驅動,於前述一般式(a)中,視需要適當選擇R1
~R10
、及、A之碳原子數6~60之2價芳香族烴基、或碳原子數1~60之2價芳香族雜環基上取代之基,則可更加增強作為p型及n型的性能。即,經由使用電子受容性之基作為R1
~R10
、及、A之碳原子數6~60之2價芳香族烴基、或碳原子數1~60之2價芳香族雜環基上取代之基,則可降低最低非佔有軌道(LUMO)程度並且作用為n型半導體。作為電子受容性之基之較佳者為氫原子、鹵原子、氰基、碳原子數1~30之鹵烷基、碳原子數1~30之鹵烷氧基、碳原子數1~30之鹵烷硫基、及碳原子數1~30之鹵烷磺醯基。又,經由使用電子供給性之基作為R1
~R10
、及、A之碳原子數6~60之2價芳香族烴基、或碳原子數1~60之2價芳香族雜環基上取代之基,則可提高最高佔有軌道(HOMO)程度並且作用為p型半導體。作為電子供給性之基之較佳者為氫原子、碳原子數1~30之烷基、碳原子數1~30之烷氧基、碳原子數1~30之烷硫基、碳原子數1~30之烷胺基、碳原子數2~60之二烷胺基(烷基係可互為鍵結而形成含氮原子之環構造)。
以下,說明一般式(a)之R1
~R10
所示各基的具體例。
前述鹵原子可列舉氟、氯、溴及碘原子。
前述烷基可列舉甲基、乙基、丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基等。
前述鹵烷基可列舉例如氯甲基、1-氯乙基、2-氯乙基、2-氯異丁基、1,2-二氯乙基、1,3-二氯異丙基、2,3-二氯-第三丁基、1,2,3-三氯丙基、溴甲基、1-溴乙基、2-溴乙基、2-溴異丁基、1,2-二溴乙基、1,3-二溴異丙基、2,3-二溴-第三丁基、1,2,3-三溴丙基、碘甲基、1-碘乙基、2-碘乙基、2-碘異丁基、1,2-二碘乙基、1,3-二碘異丙基、2,3-二碘-第三丁基、1,2,3-三碘丙基、氟甲基、1-氟甲基、2-氟甲基、2-氟異丁基、1,2-二氟乙基、二氟甲基、三氟甲基、五氟乙基、全氟異丙基、全氟丁基、全氟環己基等。
前述烷氧基為以-OX1
表示之基,X1
之例可列舉前述烷基所說明者同樣之例,且前述鹵烷氧基為以-OX2
表示之基,X2
之例可列舉與前述鹵烷基所說明者同樣之例。
前述烷硫基為以-SX1
表示之基,X1
之例可列舉與前述烷基所說明者同樣之例,且前述鹵烷硫基為以-SX2
表示之基,X2
之例可列舉與前述鹵烷基所說明者同樣之例。
前述烷胺基為以-NHX1
表示之基,二烷胺基為以-NX1
X3
表示之基,X1
及X3
分別可列舉與前述烷基所說明者同樣之例。另外,二烷胺基之烷基為互相鍵結而形成含氮原子之環構造,且環構造可列舉例如吡咯烷、哌啶等。
前述烷磺醯基為以-SO2
X1
表示之基,X1
之例可列舉與前述烷基所說明者同樣之例,前述鹵烷磺醯基為以-SO2
X2
表示之基,X2
之例可列舉與前述鹵烷基所說明者同樣之例。
前述芳香族烴基可列舉例如苯基、萘基、蒽基、菲基、芴基、苝基、并五苯基等。
前述芳香族雜環基可列舉例如呋喃基、噻吩基、吡咯基、吡唑基、咪唑基、三唑基、四唑基、唑基、異唑基、噻唑基、噻二唑基、吡啶基、嘧啶基、苯并呋喃基、苯并噻吩基、吲哚基、喹啉基、咔唑基、二苯并呋喃基、二苯并噻吩基等。
將前述一般式(a)所示之各基進一步取代之取代基可列舉芳香族烴基、芳香族雜環基、烷基、烷氧基、芳烷基、芳氧基、芳硫基、烷氧羰基、胺基、鹵原子、氰基、硝基、羥基、羧基等。
以下,列舉本發明之有機薄膜電晶體之有機半導體層中所用之具有特定構造之有機化合物的具體例,但並非限定於此。
本發明之有機薄膜電晶體之有機半導體層所用的化合物,可依各種方法合成,例如,根據Organic ReactionsVolume 14.3(John Wiley & Sons,Inc.)、Organic Reactions Volume 25.2(John Wiley & Sons,Inc.)、Organic Reactions Volume 27.2(John Wiley & Sons,Inc.)、Organic Reactions Volume 50.1(John Wiley & Sons,Inc.)之文獻中記載之方法則可合成。又,視需要,將烯烴部分之立體利用熱反應、光反應、加成反應等整理成單一的位置異構物。
於電晶體般之電子裝置中經由使用高純度的材料,則可取得電場效果移動度和開/關比高的裝置。因此,視需要,期望根據柱層析、再結晶、蒸餾、昇華等之手法加以精製。較佳為重複使用此些精製方法,並且組合複數之手法則可提高純度。更且期望至少重複2次以上之昇華精製作為精製的最終步驟。使用經由此等手法以HPLC測定之純度90%以上的材料為佳,且更佳為使用95%以上,特佳為使用99%以上之材料,則可提高有機薄膜電晶體之電場效果移動度和開/關比,並且可引出材料本來具有的性能。
以下,說明關於本發明之有機薄膜電晶體的元件構成。
本發明之有機薄膜電晶體的元件構成若為至少在基板上設置閘極、源極及汲極之3個端子,絕緣體層及有機半導體層,藉由使電壓外加於閘極來控制源-汲極間電流之薄膜電晶體,則無限定,且亦可具有公知的元件構成。
其中,作為代表性之有機薄膜電晶體的元件構成之元件A~D示於圖1~4。如此,根據電極的位置、層的層合順序等而知有數種構成,本發明之有機薄膜電晶體為具有電場效果電晶體(FET:Field Effect Transistor)構造。有機薄膜電晶體為具有有機半導體層(有機化合物層)、和相互以指定間隔對向形成之源極及汲極、和由源極、汲極分別以指定距離所形成之閘極,且藉由使電壓外加於閘極來控制源-汲極間流動之電流。此處,源極與汲極之間隔為根據使用本發明之有機薄膜電晶體之用途而決定,通常為0.1 μm~1mm,較佳為1 μm~100 μm,更佳為5 μm~100 μm。
元件A~D中,若以圖2之元件B為例進一步詳細說明,則元件B之有機薄膜電晶體為於基板上,依序具有閘極及絕緣體層,並於絕緣體層上,具有以指定間隔所形成之一對源極及汲極,並於其上形成有機半導體層。有機半導體層成為通道區,藉由使電壓外加於閘極來控制源-汲極間流動之電流而進行開/關動作。
本發明之有機薄膜電晶體於前述元件A~D以外之元件構成,亦已提案作為有機薄膜電晶體的各種構成,若為藉由使電壓外加於閘極來控制源-汲極間流動之電流而表現開/關動作和放大等效果之組裝,則不限定於此些元件構成,例如,亦可具有產業技術綜合研究所之吉田等人於第49回應用物理學關係連合講演會講演預稿集27a-M-3(2002年3月)中所提案之Top & Bottom接觸型有機薄膜電晶體(參照圖5)、和千葉大學之工藤等人於電氣學會論文誌118-A(1998)1440頁中所提案之縱形有機薄膜電晶體(參照圖6)般之元件構成。
本發明之有機薄膜電晶體中的基板為擔任支撐有機薄膜電晶體構造的職務、材料除了玻璃以外,亦可使用金屬氧化物和氮化物等之無機化合物、塑膠薄膜(PET、PES、PC)和金屬基板或其複合體和層合體等。又,藉由基板以外之構成要素可充分支撐有機薄膜電晶體之構造時,亦可不使用基板。又,基板材料多使用矽(Si)晶圓。在此情形,可使Si本身做為閘電極兼基板使用。又,將Si表面氧化,形成SiO2
活用作為絕緣層亦可。此時,亦有如圖8所示般,將兼作基板之閘極的Si基板作為導線接續用之電極成膜Au等之金屬層。
本發明之有機薄膜電晶體中之閘極、源極及汲極之材料若為導電性材料則無特別限定,可使用鉑、金、銀、鎳、鉻、銅、鐵、錫、銻、鉛、鉭、銦、鈀、硒、錸、銥、鋁、釕、鍺、鉬、鎢、氧化錫.銻、氧化銦錫(ITO)、摻雜氟之氧化鋅、鋅、碳、石墨、玻璃碳、銀漿料及碳漿料、鋰、鈹、鈉、鎂、鉀、鈣、鈧、鈦、錳、鋯、鎘、鈮、鈉、鈉-鉀合金、鎂、鋰、鋁、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。
於本發明之有機薄膜電晶體中,源極、汲極為使用含有上述導電性材料之溶液、漿料、油墨、分散液等之流動性電極材料所形成者,特別,以含有導電性聚合物、或鉑、金、銀、銅之金屬微粒子的流動性電極材料為佳。又,溶劑和分散介質為了抑制對於有機半導體的損傷,乃以含有60質量%以上,較佳為90質量%以上水之溶劑或分散介質為佳。含有金屬微粒子之分散物例如可使用公知的導電性漿料等,通常含有粒徑為0.5nm~50nm、1nm~10nm之金屬微粒子的分散物為佳。此金屬微粒子材料可使用例如鉑、金、銀、鎳、鉻、銅、鐵、錫、銻、鉛、鉭、銦、鈀、硒、錸、銥、鋁、釕、鍺、鉬、鎢、鋅等。
將此些金屬微粒子,使用主要由有機材料所構成的分散安定劑,並且使用於水和任意之有機溶劑分散介質中分散的分散物形成電極為佳。此類金屬微粒子之分散物的製造方法可列舉氣體中蒸發法、濺鍍法、金屬蒸氣合成法等之物理性生成法、和膠體法、共沈法等之以液相還原金屬離子並且生成金屬微粒子的化學性生成法,較佳為特開平11-76800號公報、同11-80647號公報、同11-319538號公報、特開2000-239853號公報等所示之膠體法、特開2001-254185號公報、同2001-53o28號公報、同2001-35255號公報、同2000-124157號公報、同2000-123634號公報等所記載之氣體中蒸發法所製造的金屬微粒子分散物。
使用此些金屬微粒子分散物成形出前述電極,令溶劑乾燥後,視需要以100℃~300℃,較佳為150℃~200℃之範圍加熱成類似形狀,則可令金屬微粒子熱熔黏,形成具有目的形狀的電極圖型。
更且,閘極、源極及汲極之材料使用摻混劑等令導電率提高的公知導電性聚合物亦佳,例如,導電性聚苯胺、導電性聚吡咯、導電性聚噻吩(聚乙二氧基噻吩與聚苯乙烯磺酸的錯合物等)、聚乙二氧基噻吩(PEDOT)與聚苯乙烯磺酸的錯合物等亦適合使用。經由此些材料可減低源極與汲極之有機半導體層的接觸電阻。
形成源極及汲極之材料,於前述例中亦以與有機半導體層之接觸面中之電阻少者為佳。此時之電阻,即對應於製作電流控制裝置時之電場效果移動度,為了取得大的移動度乃必須儘可能令電阻小。其一般係以電極材料之工作函數與有機半導體層之能量準位的大小關係決定。
若將電極材料之工作函數(W)視為a、有機半導體層之離子化電勢(Ip)視為b、有機半導體層之電子親和力(Af)視為c,則以滿足下列關係式為佳。此處,a、b及c均為以真空準位為基準的正值。
於p型有機薄膜電晶體之情形中,以b-a<1.5eV(式(I))為佳,,且更佳為b-a<1.0eV。於與有機半導體層之關係中若可維持上述關係,則可取得高性能裝置,特別選擇電極材料之工作函數儘可能大者為佳,且以工作函數4.0eV以上為佳,更佳為工作函數4.2eV以上。
金屬之工作函數值若由例如化學便覽基礎編II-493頁(改訂3版日本化學會編丸善股份有限公司發行1983年)記載之具有4.0eV或以上工作函數之前述有效金屬表中選出即可,高工作函數金屬主要為Ag(4.26、4.52、4.64、4.74eV)、Al(4.06、4.24、4.41eV)、Au(5.1、5.37、5.47eV)、Be(4.98eV)、Bi(4.34eV)、Cd(4.08eV)、Co(5.0eV)、Cu(4.65eV)、Fe(4.5、4.67、4.81eV)、Ga(4.3eV)、Hg(4.4eV)、Ir(5.42、5.76eV)、Mn(4.1eV)、Mo(4.53、4.55、4.95eV)、Nb(4.02、4.36、4.87eV)、Ni(5.04、5.22、5.35eV)、Os(5.93eV)、Pd(4.25eV)、Pt(5.64eV)、Pd(5.55eV)、Re(4.72eV)、Ru(4.71eV)、Sb(4.55、4.7eV)、Sn(4.42eV)、Ta(4.0、4.15、4.8eV)、Ti(4.33eV)、V(4.3eV)、W(4.47、4.63、5.25eV)、Zr(4.05eV)。其中,以貴金屬(Ag、Au、Cu、Pt)、Ni、Co、Os、Fe、Ga、Ir、Mn、Mo、Pd、Re、Ru、V、W為佳。金屬以外,以ITO、聚苯胺和PEDOT:PSS般之導電性聚合物及碳為佳。電極材料可含有一種或數種此些高工作函數的物質,若工作函數為滿足前述式(I)則無特別限制。
於n型有機薄膜電晶體之情形中,以a-c<1.5eV(式(II))為佳,且更佳為a-c<1.0eV。於與有機半導體層之關係中若可維持上述關係,則可取得高性能裝置,特別選擇電極材料之工作函數儘可能小者為佳,且以工作函數4.3eV以下為佳,更佳為工作函數3.7eV以下。
低工作函數金屬之具體例若由例如化學便覽基礎編II-493頁(改訂3版日本化學會編丸善股份有限公司發行1983年)記載之具有4.3eV或以下工作函數之前述有效金屬表中選出即可,可列舉Ag(4.26eV)、Al(4.06、4.28eV)、Ba(2.52eV)、Ca(2.9eV)、Ce(2.9eV)、Cs(1.95eV)、Er(2.97eV)、Eu(2.5eV)、Gd(3.1eV)、Hf(3.9eV)、In(4.09eV)、K(2.28eV)、La(3.5eV)、Li(2.93eV)、Mg(3.66eV)、Na(2.36eV)、Nd(3.2eV)、Rb(4.25eV)、Sc(3.5eV)、Sm(2.7eV)、Ta(4.0、4.15eV)、Y(3.1eV)、Yb(2.6eV)、Zn(3.63eV)等。其中亦以Ba、Ca、Cs、Er、Eu、Gd、Hf、K、La、Li、Mg、Na、Nd、Rb、Y、Yb、Zn為佳。電極材料可含有一種或數種此些低工作函數的物質,若工作函數為滿足前述式(II)則無特別限制。但,低工作函數金屬若與大氣中之水分和氧氣接觸則容易惡化,故視需要期望以Ag和Au般之空氣中安定的金屬予以被覆。被覆所必要之膜厚為必須以10nm以上,膜厚愈厚則愈可保護其免受到氧和水分,但在實用上,由提高生產性等理由而言則期望為1 μm以下。
前述電極之形成方法例如以澱積、電子束澱積、濺鍍、大氣壓電漿法、離子電鍍、化學氣相澱積、電極沈積、無電解鍍層、旋塗、印刷或噴墨等之手段形成。又,視需要予以圖型化之方法,可將使用上述方法所形成的導電性薄膜,使用公知的光微影法和Lift-off法形成電極之方法,於鋁和銅等之金屬箔上經由熱轉印、噴墨等,形成光阻並且蝕刻之方法。又,將導電性聚合物之溶液或分散液,含有金屬微粒子之分散液等以直接噴墨法予以圖型化亦可,且由塗佈膜以微影術和雷射切除等形成亦可。更且將含有導電性聚合物和金屬微粒子之導電性油墨、導電性漿料等以凸版、凹版、平版、網版印刷等之印刷法予以圖型化之方法亦可使用。
如此處理所形成之電極膜厚若可令電流導通即可,並無特別限制,較佳為0.2nm~10 μm,更佳為4nm~300nm之範圍。若為此較佳之範圍內,則因膜厚薄不會產生電阻變高且電壓降低。又,因為不會過厚,故形成膜上不會耗費時間,於層合保護層和有機半導體層等其他層之情形中,不會產生段差且層合膜可為圓滑。
又,本實施之有機薄膜電晶體中,例如,於提高注入效率之目的下,於有機半導體層與源極及汲極之間,亦可設置緩衝層。緩衝層對於n型有機薄膜電晶體,期望具有有機EL陰極所用之LiF、Li2
O、CsF、NaCO3
、KCl、MgF2
、CaCO3
等之鹼金屬、鹼土類金屬離子鍵之化合物。又,亦可將Alq等之有機EL插入使用作為電子注入層、電子輸送層之化合物。
對於p型有機薄膜電晶體期望以FeCl3
、TCNQ、F4
-TCNQ、HAT等之氰基化合物、CFx和GeO2
、SiO2
、MoO3
、V2
O5
、VO2
、V2
O3
、MnO、Mn3
O4
、ZrO2
、WO3
、TiO2
、In2
O3
、ZnO、NiO、HfO2
、Ta2
O5
、ReO3
、PbO2
等之鹼金屬、鹼土金屬以外之金屬氧化物、ZnS、ZnSe等之無機化合物。此些氧化物多時,引起氧缺損,且適於空穴注入。更且於TPD和NPD等之胺系化合物和CuPc等有機EL元件中使用作為空穴注入層、空穴輸送層之化合物亦可。又,期望由上述化合物之二種以上所構成。
緩衝層已知為經由降低載體的注入障壁,而具有降低閾值電壓,令電晶體低電壓驅動之效果,但發現對於本發明之化合物不僅具有低電壓效果並且具有提高移動度之效果。其係因在有機半導體與絕緣體層之界面存在載體陷阱,若外加閘電壓引起載體注入,則最初注入之載體為用以埋住陷阱,經由插入緩衝層,則可在低電壓下提高掩埋陷阱的移動度。緩衝層若於電極與有機半導體層之間薄膜存在即可,其厚度為0.1nm~30nm,較佳為0.3nm~20nm。
本發明之有機薄膜電晶體中之絕緣體層的材料,若可形成具有電絕緣性之薄膜者,則無特別限定,可使用金屬氧化物(包含矽之氧化物)、金屬氮化物(包含矽之氮化物)、高分子、有機低分子等之室溫下的電阻率為10 Ω cm以上的材料,特別,以比介電率高之無機氧化物皮膜為佳。
無機氧化物可列舉氧化矽、氧化鋁、氧化鉭、氧化鈦、氧化錫、氧化釩、鈦酸鋇鍶、鋯酸鈦酸鋇、鋯酸鈦酸鉛、鈦酸鉛鑭、鈦酸鍶、鈦酸鋇、氟化鋇鎂、鑭氧化物、氟氧化物、鎂氧化物、鉍氧化物、鈦酸鉍、鈮氧化物、鈦酸鍶鉍、鉭酸鍶鉍、五氧化鉭、鉭酸鈮酸鉍、三氧化銥及其組合,且以氧化矽、氧化鋁、氧化鉭、氧化鈦為佳。
又,氮化矽(Si3
N4
、SixNy(x、y>0)、氮化鋁等之無機氮化物亦適合使用。
更且,絕緣體層亦可由含有醇鹽金屬之前驅物質所形成,將此前驅物質之溶液,例如覆被至基板,並且進行包含熱處理的化學溶液處理則可形成絕緣體層。
前述醇鹽金屬中之金屬例如由過渡金屬、鑭系元素、或主族元素中選取,具體而言,可列舉鋇(Ba)、鍶(Sr)、鈦(Ti)、鉍(Bi)、鉭(Ta)、鋯(Zr)、鐵(Fe)、鎳(Ni)、錳(Mn)、鉛(Pb)、鑭(La)、鋰(Li)、鈉(Na)、鉀(K)、銣(Rb)、銫(Cs)、鈁(Fr)、鈹(Be)、鎂(Mg)、鈣(Ca)、鈮(Nb)、鉈(Tl)、汞(Hg)、銅(Cu)、鋯(Co)、銠(Rh)、鈧(Sc)及銥(Y)等。又,前述醇鹽金屬中之醇鹽可列舉例如包含甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇等之醇類,包含甲氧基乙醇、乙氧基乙醇、丙氧基乙醇、丁氧基乙醇、戊氧基乙醇、庚氧基乙醇、甲氧基丙醇、乙氧基丙醇、丙氧基丙醇、丁氧基丙醇、戊氧基丙醇、庚氧基丙醇之烷氧基醇類等所衍生之物質。
於本發明中,若以如上述之材料構成絕緣體層,則於絕緣體層中易發生空乏層,且可減低電晶體動作的閾值電壓。又,上述材料中,特別,若以Si3
N4
、SixNy、SiONx(x、y>0)等之氮化矽形成絕緣體層,則易進一步發生空乏層,且可更加減低電晶體動作的閾值電壓。
使用有機化合物的絕緣體層亦可使用聚醯亞胺、聚醯胺、聚酯、聚丙烯酸酯、光自由基聚合系、光陽離子聚合系之光硬化性樹脂、含有丙烯腈成分之共聚物、聚乙烯苯酚、聚乙烯醇、酚醛清漆樹脂、及氰乙基支鏈澱粉等。
此外,亦可使用蠟、聚乙烯、聚氯丁烯、聚對苯二甲酸乙二酯、聚甲醛、聚氯乙烯、聚偏氟乙烯、聚甲基丙烯酸甲酯、聚碸、聚碳酸酯、聚醯亞胺氰乙基支鏈澱粉、聚(乙烯苯酚)(PVP)、聚(甲基丙烯酸甲酯)(PMMA)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚烯烴、聚丙烯醯胺、聚(丙烯酸)、酚醛清漆樹脂、甲鄰酚醛樹脂、聚醯亞胺、聚二甲苯、環氧樹脂,加上亦可使用支鏈澱粉等之具有高介電率的高分子化合物。
絕緣體層之材料特佳為具有拒水性的有機化合物,經由具有拒水性而抑制絕緣體層與有機半導體層的相互作用,且利用有機半導體本來所保有之凝集性,提高有機半導體層的結晶性並且提高裝置性能。其例可列舉Yasuda等人Jpn.J.Appl.Phys.Vol.42(2003)pp.6614-6618記載之聚對二甲苯衍生物和Janos Veres等人Chem.Mater.,Vol.16(2004)pp.4543-4555記載之物質。
又,使用如圖1及圖4所示之頂部閘極構造時,若將此類有機化合物使用作為絕緣體層的材料,則可減小對於有機半導體層所造成之損傷並且成膜,故為有效之方法。
前述絕緣體層可為使用數種前述無機或有機化合物材料的混合層,且亦可為其層合構造體。此時,視需要將介電率高之材料與具有拒水性的材料混合、層合則亦可控制裝置的性能。
又,前述絕緣體層亦可為陽極氧化膜、或者含有該陽極氧化膜作為其構成。陽極氧化膜經封孔處理為佳。陽極氧化膜可將能陽極氧化的金屬經由公知方法予以陽極氧化而形成。能陽極氧化處理的金屬,可列舉鋁或鉭,陽極氧化處理之方法並無特別限制,可使用公知之方法。經由進行陽極氧化處理,則可形成氧化被膜。陽極氧化處理所用之電解液若可形成多孔質氧化皮膜,則均可使用,一般而言,可使用硫酸、磷酸、草酸、鉻酸、硼酸、胺基磺酸、苯磺酸等或將其組合二種以上之混合酸或其鹽。陽極氧化之處理條件因為根據所使用之電解液而有各種變化,故無法一概特定,但一般而言,電解液之濃度為1~80質量%、電解液之溫度5~70℃、電流密度0.5~60A/cm2
、電壓1~100伏特、電解時間10秒~5分鐘之範圍為適當。較佳之陽極氧化處理為使用硫酸、磷酸或硼酸之水溶液作為電解液,並以直流電流進行處理之方法,但亦可使用交流電流。此些酸之濃度為5~45質量%為佳,電解液之溫度20~50℃、電流密度0.5~20A/cm2
電解處理20~250秒鐘為佳。
絕緣體層之厚度,若層厚度薄,則外加至有機半導體的實效電壓變大,故可降低裝置本身的驅動電壓、閾值電壓,但相反地,因為源閘極間的漏電電流變大,故必須選取適切的膜厚,通常為10nm~5 μm,較佳為50nm~2 μm,更佳為100nm~1 μm。
又,於前述絕緣體層與有機半導體層之間,亦可施加任意之配向處理。其較佳例為對絕緣體層表面施以拒水化處理等且減低絕緣體層與有機半導體層的相互作用,並且提高有機半導體層之結晶性的方法,具體而言,可列舉將矽烷偶合劑,例如,十八烷基三氯矽烷、三氯甲基矽氮烷、和鏈烷磷酸、鏈烷磺酸、鏈烷羧酸等之自我組織化配向膜材料,以液相或氣相狀態,接觸至絕緣膜表面形成自我組織化膜之後,適度施以乾燥處理的方法。又,以使用於液晶之配向般,於絕緣膜表面設置聚醯亞胺等所構成的膜,並且將其表面予以磨擦處理的方法亦為佳。
前述絕緣體層的形成方法可列舉真空澱積法、分子射線外延成長法、離子簇束法、低能量離子束法、離子電鍍法、CVD法、濺鍍法、特開平11-61406號公報、同11-133205號公報、特開2000-121804號公報、同2000-147209號公報、同2000-185362號公報記載之大氣電漿法等之乾式步驟、和噴霧塗層法、旋塗法、刮刀塗層法、浸塗法、澆鑄法、輥塗法、棒塗法、型板塗層法等之塗佈方法、印刷和噴墨等之圖型化方法等之濕式步驟,且可根據材料使用。濕式步驟為將無機氧化物之微粒子於任意之有機溶劑或水中,視需要使用界面活性劑等之分散輔助劑予以分散的液體進行塗佈、乾燥之方法、和使用將氧化物前體,例如,醇鹽體之溶液予以塗佈、乾燥,所謂之溶膠凝膠法。
本發明之有機薄膜電晶體中之有機半導體層的膜厚並無特別限制,通常,以0.5nm~1 μm,且以2nm~250nm為佳。
又,有機半導體層之形成方法並無特別限定且可應用公知之方法,例如,經由分子射線澱積法(MBE法)、真空澱積法、化學澱積,將材料溶解於溶劑之溶液浸漬法、旋塗法、澆鑄法、棒塗法、輥塗法等之印刷、塗佈法及烘烤、電聚合化法、分子束澱積,由溶液之自我裝配、及其組合手段,以前述之有機半導體層材料形成。
若提高有機半導體層的結晶性則提高電場效果移動度,故使用由氣相成膜(澱積、濺鍍等)時,期望將成膜中的基板溫度保持高溫。其溫度為50~250℃為佳,且以70~150℃為更佳。又,無關於成膜方法,若於成膜後實施退火,則可取得高性能裝置,故為佳。退火的溫度為50~200℃為佳,且以70~200℃為更佳,時間為10分鐘~12小時為佳,且以1~10小時為更佳。
於本發明中,有機半導體層可使用由一般式(a)中選出之一種材料,且亦可組合數種,使用并五苯和噻吩低聚物等公知的半導體層合複數的混合薄膜供使用亦可。
本發明之有機薄膜電晶體的形成方法並無特別限定,若根據公知的方法即可,但若根據所欲之元件構成,令基板投入、閘極形成、絕緣體層形成、有機半導體層形成、源極形成、汲極形成為止之一連串的元件製作步驟全部未接觸大氣進行形成,則可防止與大氣接觸所造成之大氣中水分和氧氣等阻礙元件性能,故為佳。當然,若不得不暫時接觸大氣時,令有機半導體層成膜以後之步驟為完全不接觸大氣之步驟,且在有機半導體層成膜前,立即將層合有機半導體層之面(例如元件B之情況為於絕緣層層合一部分源極、汲極的表面)以紫外線照射、紫外線/臭氧照射、氧電漿、氬電漿等予以清淨化.活化後,層合有機半導體層為佳。
更且,例如考慮大氣中所含之氧、水等對於有機半導體層的影響,並且於有機電晶體元件之外周面的全面或一部分形成阻氣層亦可。形成阻氣層之材料可使用此領域所常用者,可列舉例如聚乙烯醇、乙烯-乙烯醇共聚物、聚氯乙烯、聚偏氯乙烯、聚氯三氟乙烯等。更且,前述絕緣體層所例示之具有絕緣性的無機物亦可使用。
本發明中,有機薄膜電晶體亦可使用由源、汲極所注入之電荷作為發光元件。即,有機薄膜電晶體可使用作為兼具發光元件(有機EL)機能之有機薄膜發光電晶體。其係藉由以閘極控制源-汲極間流動之電流而控制發光強度。因為可統合控制發光之電晶體與發光元件,故取得提高顯示器開口率和製作步驟簡易化而降低費用之實用上的大優點。使用作為有機發光電晶體時,以上述詳細說明所描述之內容即已充分,但將本發明之有機薄膜電晶體以有機發光電晶體型式運作上,必須由源極、汲極之一者注入空穴,由另一者注入電子,故為了提高發光性能乃以滿足下列條件為佳。
本發明之有機薄膜發光電晶體為了提高空穴的注入性,令至少一者為空穴注入性電極為佳。所謂空穴注入電極係指含有上述工作函數4.2eV以上之物質的電極。
又,為了提高電子的注入性,令至少一者為電子注入性電極為佳。所謂電子注入性電極係指含有工作函數4.3eV以下之物質的電極。更佳為其一者為空穴注入性,且,另一者為電子注入性之具備電極的有機薄膜發光電晶體。
本發明之有機薄膜發光元件為了提高空穴的注入性,令至少一者電極與有機半導體層之間插入空穴注入層為佳。空穴注入層可列舉於有機EL元件中,使用作為空穴注入材料、空穴輸送材料的胺系材料等。
又,為了提高電子的注入性,令至少一者電極與有機半導體層之間插入電子注入性層為佳。與空穴相同於電子注入層中可使用於有機EL元件中所用的電子注入材料等。
更佳為於一者電極下具備空穴注入層,且,於另一電極下具備電子注入層的有機薄膜發光電晶體。
又,本實施之有機薄膜發光電晶體中,例如,於提高注入效率之目的下,於有機半導體層與源極及汲極之間,亦可設置緩衝層。
其次,使用實施例進一步詳細說明本發明。
如下處理合成上述化合物(A-1)。以下示出合成途徑。
於肉桂醛2.64克(20毫莫耳)、亞磷酸酯化合物3.78克(10毫莫耳)之四氫呋喃溶液(100毫升)中,加入第三丁氧基鉀3.36克(30毫莫耳),並於氬氛圍氣下,以室溫攪拌。反應終了後,加入水、甲醇並且過濾。再以甲苯進行再結晶,取得化合物(A-1)2.01克(產率60%)。根據FD-MS(場解析質量分析)之測定確認為目的物。以下示出測定所用之裝置,測定條件、及、所得之結果。
裝置:HX110(日本電子公司製)條件:加速電壓8kV掃描範圍m/z=50~1500結果:FD-MS,calcd for C26
H22
=334,實測,m/z=334(M+
,100)
以下列手續製作有機薄膜電晶體。首先,將玻璃基板,以中性洗劑、純水、丙酮及乙醇各超音波洗淨30分鐘後,以濺鍍法將金(Au)成膜出40nm之膜厚,製作閘極。其次,將此基板安裝至熱CVD裝置的成膜部。另一方面,於原料之蒸發部,將絕緣體層原料之聚對二甲苯衍生物[聚對氯化二甲苯(Parylene)](商品名;diX-C,第三化成股份有限公司製)250毫克放入玻璃皿並設置。將熱CVD裝置以真空泵抽成真空,減壓至5Pa為止之後,將蒸發部加熱至180℃,聚合部加熱至680℃並放置2小時,於閘極上形成厚度1μm之絕緣體層。
其次,設置於真空澱積裝置(ULVAC公司製,EX-400)於絕緣體層上將前述化合物(A-2)以0.05nm/s之澱積速度成膜出50nm膜厚之有機半導體層。其次,透過金屬罩將金成膜出50nm之膜厚,令相互未連接之源極及汲極,形成間隔(通道長L)為75μm。此時以源極與汲極之寬度(通道寬W)為5mm般成膜製作有機薄膜電晶體(參照圖7)。
所得之有機薄膜電晶體為使用KEITHLEY公司製(4200-SCS)於室溫下如下進行評價。對有機薄膜電晶體之閘極外加-40V之閘電壓,並於源-汲極間外加電壓且流過電流。此時,空穴為在有機半導體層之通道區(源-汲極間)被激起,且以p型電晶體型式運作。電流飽和區域之源-汲極間之電流的開/關比為1×106
。又,空穴之電場效果移動度μ由下式式(A)算出時為2×10-1
cm2
/Vs。
ID
=(W/2L).C μ.(VG
-VT
)2
(A)
式中,ID
為源-汲極間電流、W為通道寬、L為通道長、C為閘極絕緣體層之每單位面積的電容量、VT
為閘極閾值電壓、VG
為閘電壓。
於實施例1中,除了將有機半導體層之材料使用化合物(A-11)代替化合物(A-2)以外,同樣處理成膜至有機半導體層。其次透過金屬罩將Ca代替Au以0.05nm/s之澱積速度真空澱積20nm作為源-汲極,其後將Ag以0.05nm/s之澱積速度澱積50nm且覆被Ca,製作有機薄膜電晶體。對於所得之有機薄膜電晶體,以+40V之閘電壓VG
令n型驅動以外同實施例1處理,測定源-汲極間之電流的開/關比,算出電子之電場效果移動度μ之結果示於表1。
於實施例1中,除了分別使用表1記載之化合物代替化合物(A-2)作為有機半導體層之材料以外,同樣處理製作有機薄膜電晶體。對於所得之有機薄膜電晶體,同實施例1處理,以-40V之閘電壓VG
令p型驅動。又,同實施例1處理,測定源-汲極間之電流的開/關比,算出空穴之電場效果移動度μ之結果示於表1。
同實施例1實施基板之洗淨,閘極成膜、絕緣體層。其次令聚對伸苯基伸乙烯基(PPV)[分子量(Mn)86000,分子量分佈(Mw/Mn=5.1)]以3質量%溶解於甲苯,並於前述成膜至絕緣體層的基板上以旋塗法成膜,並於氮氛圍氣下以120℃乾燥成膜作為有機半導體層。其次,以真空澱積裝置透過金屬罩將金(Au)以50nm之膜厚成膜,形成相互不連接的源極及汲極,製作有機薄膜電晶體。
對於所得之有機薄膜電晶體,同實施例1處理,以-40V之閘電壓VG
令p型驅動。測定源-汲極間之電流的開/關比,算出空穴之電場效果移動度μ之結果示於表1。
使用聚對伸苯基伸乙烯基(PPV)作為有機半導體層之材料,且至有機半導體層為止為與比較例1完全同樣成膜。其次透過金屬罩將Ca代替Au以0.05nm/s之澱積速度真空澱積20nm作為源-汲極,其後將Ag以0.05nm/s之澱積速度澱積50nm且覆被Ca,製作有機薄膜電晶體。
對於所得之有機薄膜電晶體,同實施例1處理,以+40V之閘電壓VG
令n型驅動。測定源-汲極間之電流的開/關比,算出電子之電場效果移動度μ之結果示於表1。
以下列手續製作有機薄膜發光電晶體。首先,將Si基板(P型比電阻1 Ω cm閘極兼用)以熱氧化法令表面氧化,於基板上製作300nm之熱氧化膜作為絕緣體層。再將基板一者成膜之SiO2
膜以乾式蝕刻完全除去後,以濺鍍法將鉻成膜出20nm之膜厚,再於其上將金(Au)濺鍍100nm成膜並且取出作為電極。將此基板,以中性洗劑、純水、丙酮及乙醇各超音波洗淨30分鐘。
其次,設置於真空澱積裝置(ULVAC公司製,EX-900),於絕緣體層(SiO2
)上將前述化合物(A-2)以0.05nm/s之澱積速度成膜出100nm膜厚之有機半導體發光層。其次,同上述設置通道長75 μm,通道寬5mm之金屬罩,將基板相對於蒸發源以傾斜45度之狀態透過罩將金以50nm之膜厚成膜。其次將基板於逆方向上以傾斜45度之狀態將Mg澱積100nm,製作相互不連接之源極及汲極,但實質上具備空穴注入性電極(Au)與電子注入性電極(Mg)的有機薄膜發光電晶體(參照圖9)。
於源-汲極間外加-100V,若對閘極外加-100V則取得藍色發光。
同實施例1處理成膜至有機半導體層。其次透過金屬罩在澱積Au作為源-汲極前,將緩衝層MoO3
以0.05nm/s之澱積速度真空澱積10nm,接著澱積Au。對於所得之有機薄膜電晶體,同實施例1處理,以-40V之閘電壓VG
令p型驅動。測定源-汲極間之電流的開/關比,算出空穴之電場效果移動度μ之結果,電場效果移動度3×10-1
cm2
/Vs,開關比1×106
。
如以上所詳細說明般,本發明之有機薄膜電晶體為經由使用具有高電子移動度之特定構造的化合物作為有機半導體層之材料,使得應答速度(驅動速度)為高速,且開/關比大,作為電晶體之性能高,亦可利用作為可發光的有機薄膜發光電晶體。
圖1為示出本發明之有機薄膜電晶體之元件構成的一例圖。
圖2為示出本發明之有機薄膜電晶體之元件構成的一例圖。
圖3為示出本發明之有機薄膜電晶體之元件構成的一例圖。
圖4為示出本發明之有機薄膜電晶體之元件構成的一例圖。
圖5為示出本發明之有機薄膜電晶體之元件構成的一例圖。
圖6為示出本發明之有機薄膜電晶體之元件構成的一例圖。
圖7為示出本發明之實施例中之有機薄膜電晶體之元件構成的一例圖。
圖8為示出本發明之實施例中之有機薄膜電晶體之元件構成的一例圖。
圖9為示出本發明之實施例中之有機薄膜電晶體之元件構成的一例圖。
Claims (15)
- 一種有機薄膜電晶體,其為至少在基板上設置閘極、源極及汲極之3個端子,絕緣體層以及有機半導體層,藉由使電壓外加於閘極來控制源-汲極間電流之有機薄膜電晶體,其特徵為,該有機半導體層係含具有下述一般式(a)構造之有機化合物,
- 如申請專利範圍第1項之有機薄膜電晶體,其中該一般式(a)中,A為含苯環之基。
- 如申請專利範圍第1項之有機薄膜電晶體,其中該一般式(a)中,A為含氮原子之芳香族雜環基。
- 如申請專利範圍第1項之有機薄膜電晶體,其中該一般式(a)中,A為之2價殘基。
- 如申請專利範圍第1項之有機薄膜電晶體,其中該一般式(a)中A為含5員環之芳香族雜環的芳香族雜環基。
- 如申請專利範圍第4項之有機薄膜電晶體,其中該一般式(a)中A為含5員環之芳香族雜環與苯環的芳香族雜環基。
- 如申請專利範圍第5項之有機薄膜電晶體,其中該5員環之芳香族雜環係具有氧原子或硫原子1個以上,且於該苯環上連接有烯烴基。
- 如申請專利範圍第1項之有機薄膜電晶體,其中該一般式(a)中,相對於A有2個伸丁二烯基在對稱位置取代之構造。
- 如申請專利範圍第1項之有機薄膜電晶體,其中該一般式(a)中,R1 、R5 、R6 及R10 係各自獨立表示氫原子或氟原子。
- 如申請專利範圍第1項之有機薄膜電晶體,其中該一般式(a)中,R1 ~R10 係各自獨立表示氫原子或碳原 子數1~30之烷基。
- 如申請專利範圍第1項之有機薄膜電晶體,其中該一般式(a)中,R1 ~R10 係各自獨立表示氫原子、鹵原子、氰基或碳原子數1~30之鹵烷基。
- 如申請專利範圍第1項之有機薄膜電晶體,其中在源極與有機半導體層之間及汲極與有機半導體層之間具有緩衝層。
- 一種有機薄膜發光電晶體,其特徵為,在如申請專利範圍第1項之有機薄膜電晶體中,利用源-汲極間流動之電流而得發光,藉由使電壓外加於閘極而控制發光者。
- 如申請專利範圍第13項之有機薄膜發光電晶體,其中源極及汲極之至少一者係由工作函數4.2eV以上之物質所成,且/或至少一者為工作函數4.3eV以下之物質所成者。
- 如申請專利範圍第13項之有機薄膜發光電晶體,其中在源極與有機半導體層之間及汲極與有機半導體層之間具有緩衝層者。
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US5100985A (en) * | 1991-03-25 | 1992-03-31 | Hoechst Celanese Corp. | 1,4-bis(4-arylbutadienyl) benzenes exhibiting nonlinear optical response |
US5468519A (en) * | 1992-12-11 | 1995-11-21 | Sharp Kabushiki Kaisha | Method for forming an orientation film including coupling an organic compound to a silane coupling agent in a magnetic or electrical field |
US5500537A (en) * | 1989-08-17 | 1996-03-19 | Mitsubishi Denki Kabushiki Kaisha | Field-effect transistor with at least two different semiconductive organic channel compounds |
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JPH0555568A (ja) | 1991-08-28 | 1993-03-05 | Asahi Chem Ind Co Ltd | 有機薄膜トランジスタ |
US5574291A (en) | 1994-12-09 | 1996-11-12 | Lucent Technologies Inc. | Article comprising a thin film transistor with low conductivity organic layer |
US6278127B1 (en) | 1994-12-09 | 2001-08-21 | Agere Systems Guardian Corp. | Article comprising an organic thin film transistor adapted for biasing to form a N-type or a P-type transistor |
JPH10135481A (ja) | 1996-10-15 | 1998-05-22 | Lucent Technol Inc | 薄膜トランジスタからなるデバイス |
JP4085438B2 (ja) | 1996-10-17 | 2008-05-14 | 松下電器産業株式会社 | 有機薄膜トランジスタ及び液晶素子と有機発光素子 |
US6107117A (en) | 1996-12-20 | 2000-08-22 | Lucent Technologies Inc. | Method of making an organic thin film transistor |
TW399338B (en) | 1997-11-24 | 2000-07-21 | Lucent Technologies Inc | Method of making an organic thin film transistor and article made by the method |
JP2000174277A (ja) | 1998-12-01 | 2000-06-23 | Hitachi Ltd | 薄膜トランジスタおよびその製造方法 |
JP2001094107A (ja) | 1999-09-20 | 2001-04-06 | Hitachi Ltd | 有機半導体装置及び液晶表示装置 |
JP2001176666A (ja) | 1999-12-17 | 2001-06-29 | Matsushita Electric Ind Co Ltd | 有機電界発光素子 |
JP2005142233A (ja) | 2003-11-04 | 2005-06-02 | Yamanashi Tlo:Kk | 液晶化合物薄膜の配向制御方法及びこれを用いて形成された液晶化合物薄膜の膜構造、薄膜トランジスタ並びに有機エレクトロルミネッセンス素子 |
CN101553929B (zh) * | 2005-04-15 | 2012-12-05 | E.I.内穆尔杜邦公司 | 芳基-乙烯取代的芳族化合物及其作为有机半导体的应用 |
JP2007258253A (ja) * | 2006-03-20 | 2007-10-04 | Kyoto Univ | トランジスタ材料及びこれを用いた発光トランジスタ素子 |
-
2007
- 2007-11-21 US US12/516,085 patent/US8203139B2/en not_active Expired - Fee Related
- 2007-11-21 JP JP2008545437A patent/JPWO2008062841A1/ja active Pending
- 2007-11-21 WO PCT/JP2007/072578 patent/WO2008062841A1/ja active Application Filing
- 2007-11-23 TW TW096144628A patent/TWI423341B/zh not_active IP Right Cessation
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US4855376A (en) * | 1986-11-21 | 1989-08-08 | Hoechst Celanese Corp. | Side chain liquid crystalline polymers exhibiting nonlinear optical properties |
US5500537A (en) * | 1989-08-17 | 1996-03-19 | Mitsubishi Denki Kabushiki Kaisha | Field-effect transistor with at least two different semiconductive organic channel compounds |
US5100985A (en) * | 1991-03-25 | 1992-03-31 | Hoechst Celanese Corp. | 1,4-bis(4-arylbutadienyl) benzenes exhibiting nonlinear optical response |
US5468519A (en) * | 1992-12-11 | 1995-11-21 | Sharp Kabushiki Kaisha | Method for forming an orientation film including coupling an organic compound to a silane coupling agent in a magnetic or electrical field |
US6326640B1 (en) * | 1996-01-29 | 2001-12-04 | Motorola, Inc. | Organic thin film transistor with enhanced carrier mobility |
Also Published As
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TW200901326A (en) | 2009-01-01 |
US8203139B2 (en) | 2012-06-19 |
US20100051919A1 (en) | 2010-03-04 |
JPWO2008062841A1 (ja) | 2010-03-04 |
WO2008062841A1 (fr) | 2008-05-29 |
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