CN1577912A - 包含多层栅绝缘体的有机薄膜晶体管 - Google Patents
包含多层栅绝缘体的有机薄膜晶体管 Download PDFInfo
- Publication number
- CN1577912A CN1577912A CNA2004100621484A CN200410062148A CN1577912A CN 1577912 A CN1577912 A CN 1577912A CN A2004100621484 A CNA2004100621484 A CN A2004100621484A CN 200410062148 A CN200410062148 A CN 200410062148A CN 1577912 A CN1577912 A CN 1577912A
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- Prior art keywords
- titanium
- otft
- zirconium
- active layer
- aluminium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
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Abstract
本发明公开了一种有机薄膜晶体管(OTFT),包括:顺序地形成在衬底上的栅电极、栅绝缘膜、有机有源层和源/漏电极,或者栅电极、栅绝缘膜、源/漏电极和有机有源层,其特征在于该栅绝缘膜是多层绝缘体,所述多层绝缘体包含高介电材料的第一层和能与该有机有源层相容的绝缘有机聚合物的第二层,所述第二层被直接放置在该有机有源层之下。本发明所述OTFT显示了低阈值和驱动电压、高电荷迁移率、高Ion/Ioff值,并且,还能通过湿法工艺制备。
Description
技术领域
本发明涉及有机薄膜晶体管(organic thin film transistor),具体而言,涉及包括以下的有机薄膜晶体管:顺序地形成在衬底(substrate)上的栅电极、栅绝缘膜、有机有源层(organic active layer)和源/漏电极,或者栅电极、栅绝缘膜、源/漏电极和有机有源层,其特征在于该栅绝缘膜是多层绝缘体(multi-layered insulator),包含高介电常数(k)材料的第一层和能与该有机有源层相容的绝缘有机聚合物的第二层,所述第二层被直接放置在该有机有源层之下。
背景技术
近年来,大部分用于显示器用途的薄膜晶体管(TFT)由作为半导体的非晶硅、作为绝缘体的氧化硅或氮化硅和金属电极组成。然而,随着近来各种导电有机材料的发展,开发使用有机材料作为半导体的有机薄膜晶体管(OTFT)的研究变得活跃起来。自从诞生于二十世纪80年代,OTFT的应用已经扩展到功能性的电子器件和光器件中。例如,在包括TFT作为控制电场的开关元件(switching element)的液晶显示器(LCD)领域,因为其柔性和制备工艺容易,有很多采用OTFT的尝试。作为新颖的电子材料,因为它具有很多合成途径并且能够形成从纤维到膜的各种形状,OTFT中的有机半导体优于它的无机对应物(即,非晶硅);而且,它显示高的柔性并且能够以低成本生产。因此,使用诸如导电聚合物作为有源层的有机半导体的OTFT被认为具有以下优越性:因为它的有源层可以在大气压下通过印刷工艺形成,而不需通过使用等离子体和需要高压和高温的化学气相沉积(CVD),所有的制造可以用塑料衬底通过滚筒对滚筒的工艺完成,这样可以实现低价格的TFT。
但是,与非晶硅的TFT相比,OTFT表现出不占优势的较低电荷迁移率(charge mobility)和较高的驱动和阈电压(driving and threshold voltages)。在这点上,N.Jackson等人做出了改进并通过用并五苯有源层取得了0.6cm2·V-1·sec-1的电荷迁移率,提高了OTFT实际使用的可能性(54th Annualdevice Research Conference Digest,1996)。然而,N.Jackson取得的电荷迁移率仍然达不到所需要的值,而且,现有技术的0TFT需要的驱动电压高于100V并且亚阈值(sub-threshold)电压至少是非晶硅-TFT的50倍高。其间,美国专利5,981,970和Science(vol.283,p822-824)中,公开了通过使用高介电常数(即,高k)的栅绝缘体降低OTFT的驱动电压和阈电压的方法,其中栅绝缘体由无机金属氧化物制成诸如:BaxSr1-xTiO3(BST,钡锶钛酸盐)、Ta2O5、Y2O3、TiO2,或者铁电绝缘体(ferroelectric insulator)诸如:PbZrxTi1-xO3(PZT)、Bi4Ti3O12、BaMgF4、SrBi2(Ta1-xNbx)2O9、Ba(Zr1-xTix)O3(BZT)、BaTiO3、SrTiO3、Bi4Ti3O12。在用所述方法制备的OTFT中,栅绝缘体用化学气相沉积、物理气相沉积、溅射、或溶胶-凝胶涂布技术制备,并且其介电常数k为15或更高。通过使用该高k值绝缘体,驱动电压可以降低至-5V,但是电荷迁移率仍然不如人意,低于0.6cm2·V-1·sec-1。而且,因为该工艺需要200-400℃的高温,这也限制了对衬底类型的选择,采用普通的诸如简单涂布或印刷的湿法工艺(wet process)变得不可能。在美国专利6,232,157中公开的方法使用聚酰亚胺、苯并环丁烯或聚丙烯酰类(polyacryl)作为有机绝缘膜,但是,用该方法制备的OTFT没有表现出与无机绝缘体的TFT相等的器件特性。
为了改进现有技术中薄膜电子器件的性能,存在很多采用具有两层或以上的多层栅绝缘体(multi-layered gate insulator)的尝试。例如,美国专利6,563,174和美国专利6,558,987分别公开了由非晶氮化硅和氧化硅制成的多层栅绝缘膜,和由同种材料制成的双层绝缘膜,并且两个专利都报道绝缘体的电学性能和半导体层的结晶品质得到实质性的提高。然而,这些专利本质上涉及到使用诸如非晶硅或单晶硅的无机TFT,因此不能应用于有机半导体器件的制备。
近来,进行了很多努力来在各种驱动器件里使用OTFT。然而,为了实现在LCD或使用有机EL的柔性显示器(flexible display)中使用OTFT的实用性,不但应该将电荷迁移率提高到5cm2·V-1·sec-1或更高,而且也应该实现改进器件的驱动和阈电压。具体而言,为了使制备简化和降低成本,期望制备OTFT的整个工艺能够通过全印刷(all-printing)或全旋涂(all-spin)的方法在塑料衬底上进行。在这种环境下,有很多的研究用于开发一种方法,该方法用于简化有机栅绝缘膜的制备和提高在绝缘体和有机有源层之间界面处的电荷迁移率。然而,还没有获得满意的结果。
因此,在本领域中,有迫切的需求来开发新结构的有机TFT,它显示出高电荷迁移率、优越的绝缘性能、和低的驱动和阈电压、以及能够通过例如普通的湿法工艺容易地制备。
发明内容
本发明人投入了大量的努力来满足这些需求,并且发现当使用多层栅绝缘体,其包括有高k值材料的第一层和能与有机有源层相容的绝缘有机聚合物的第二层,该第二层被直接放置在该有机有源层之下,这样获得的OTFT表现出较高的电荷迁移率和较低的驱动和阈电压,以及其全部制备(wholepreparation)可以通过诸如印刷或旋涂的湿法工艺完成。
因而,本发明的实施方式的特征是提供一种有机薄膜晶体管,其包括:顺序地形成在衬底上的栅电极、栅绝缘膜、有机有源层和源/漏电极,或者栅电极、栅绝缘膜、源/漏电极和有机有源层,其中该栅绝缘膜是多层绝缘体,该多层绝缘体包含i)高介电性材料的第一层和ii)能与有机有源层相容的绝缘有机聚合物的第二层,并且该第二层被直接放置在该有机有源层之下。
附图说明
图1是根据本发明的优选实施方式的有机薄膜晶体管(OTFT)的横截面示意图;
图2是显示随着施加在实施例1和3及对比实施例1中制备的OTFT上的电压的改变,漏电流(leakage current)的变化图;
图3通过作为栅电压的函数的漏极电流(drain current)图,分别显示了得到的实施例1和对比实施例1中制备的OTFT的操作特性;和
图4显示了作为实施例1和对比实施例1中制备的栅电压的函数的漏极电流的平方根图,从该图中可以得到OTFT的阈电压。
具体实施方式
如图1所示,根据本发明的OTFT包括(a)其上布置有一个或多个栅电极的衬底1,(b)一个或多个栅电极5,(c)布置在栅电极5之上的多层栅绝缘膜,包含:(i)高k值材料的第一绝缘层2和(ii)能与有机有源层4相容并且被直接放置在该层之下的有机聚合物的第二绝缘层3,(d)布置在栅绝缘膜上的作为有机有源层4的有机半导体层,(e)源/漏电极(6和7)。
如上所述,在有机有源层和源/漏电极之间的层的顺序可以互相交换。
图1示意性地示出本发明的一个优选实施方式,所以本发明的OTFT的栅绝缘膜(包含图1中的两层)可以根据需要具有两个或更多层。栅绝缘膜的总有效(total effective)介电常数可以通过控制第一绝缘层2和第二绝缘层3的厚度来调节。
本发明中,栅绝缘膜的第一层是由具有高介电常数(k)和优异的绝缘性能的高k值材料构成的,并且通过湿法工艺形成。具体地,第一绝缘层由以下混合物制成:(1)绝缘有机聚合物与介电常数为5或更高的有机金属化合物的混合物,或(2)绝缘有机聚合物与介电常数为5或更高的无机金属氧化物或铁电绝缘体的纳米颗粒(nanoparticle)的混合物。第一层的介电常数“k”可以通过控制有机聚合物与有机金属化合物或纳米颗粒的重量比调节。第一绝缘层的介电常数应控制在5或更高,在介电常数低于5的情形下,由于较低的有效介电常数,不能获得驱动性能的改善。为了形成第一层,该混合物通过湿法工艺涂布在包括栅电极的衬底上然后被烘焙。
可用于制备第一绝缘层的绝缘有机聚合物包括大部分表现出绝缘性能的聚合物。绝缘有机聚合物的实例包括,但不限于:聚酯、聚碳酸酯、聚乙烯醇、聚乙烯醇缩丁醛、聚缩醛、多芳基化合物、聚酰胺、聚(酰胺-酰亚胺)(polyamidimide)、聚醚酰亚胺、聚苯醚、聚苯硫醚、聚醚砜、聚醚酮、聚邻苯二酰胺、聚醚腈、聚醚砜、聚苯并咪唑、聚碳化二亚胺、聚硅氧烷、聚甲基丙烯酸甲酯、聚甲基丙烯酰胺、丁腈橡胶、丙烯酰类橡胶(acryl rubber)、聚四氟乙烯、环氧树脂、酚树脂、三聚氰胺树脂、尿素树脂、聚丁烯、聚戊烯、乙烯-丙烯共聚物、乙烯-丁烯-二烯共聚物(poly(ethylene-co-butenediene)、聚丁二烯、聚异戊二烯、乙烯-丙烯-二烯共聚物(poly(ethylene-co-propylenediene)、丁基橡胶、聚甲基戊烯、聚苯乙烯、苯乙烯-丁二烯共聚物、氢化苯乙烯-丁二烯共聚物、氢化聚异戊二烯、氢化聚丁二烯、及其混合物。
用于第一绝缘层的有机金属化合物是钛类、锆类、铪类和铝类的有机金属化合物。钛类化合物实例包括,但不限于:正丁醇钛(IV)、叔丁醇钛(IV)、乙醇钛(IV)、2-乙基己醇钛(IV)、异丙醇钛(IV)、(二异丙醇)双(乙酰丙酮酸)钛(IV)(titanium(di-isopropoxide)bis-(acetylacetonate))、双(乙酰丙酮酸)钛氧化物(IV)、三氯三(四氢呋喃)钛(III)、三(2,2,6,6-四甲基-3,5-庚二酮酸根合(heptanedionato))钛(III)、(三甲基)五甲基环戊二烯基钛(IV)、五甲基环戊二烯基钛三氯化物(IV)、五甲基环戊二烯基三甲醇钛(IV)、四氯双(环己基巯基)钛(IV)、四氯双(四氢呋喃)钛(IV)、四氯二氨合钛(IV)、四(二乙氨基)钛(IV)、四(二甲氨基)钛(IV)、双(叔丁基环戊二烯基)钛二氯化物、双(环戊二烯基)二羰基钛(II)、双(环戊二烯基)钛二氯化物、双(乙基环戊二烯基)钛二氯化物、双(五甲基环戊二烯基)钛二氯化物、双(异丙基环戊二烯基)钛二氯化物、三(2,2,6,6-四甲基-3,5-庚二酮酸根合)氧代钛(tris(2,2,6,6-tetramethyl-3,5-heptanedionato)oxotitanium)(IV)、三异丙醇氯钛、环戊二烯基钛三氯化物、二氯双(2,2,6,6-四甲基-3,5-庚二酮酸根合)钛(IV)、二甲基双(叔丁基环戊二烯基)钛(IV)和二异丙醇双(2,2,6,6-四甲基-3,5-庚二酮酸根合)钛(IV)。锆类化合物的实例包括,但不限于:正丁醇锆(IV)、叔丁醇锆(IV)、乙醇锆(IV)、异丙醇锆(IV)、正丙醇锆(IV)、乙酰丙酮酸锆(IV)、六氟代乙酰丙酮酸锆(IV)、三氟代乙酰丙酮酸锆(IV)、四(二乙氨基)锆、四(二甲氨基)锆、四(2,2,6,6-四甲基-3,5-庚二酮酸根合)锆(IV)和四水硫酸锆(IV)。铪类化合物的实例包括,但不限于:正丁醇铪(IV)、叔丁醇铪(IV)、乙醇铪(IV)、异丙醇铪(IV)、异丙醇铪(IV)单异丙醇盐(hafnium isopropoxidemonoisopropylate)、乙酰丙酮酸铪(IV)、四(二甲氨基)铪。铝类化合物的实例包括,但不限于:正丁醇铝、叔丁醇铝、仲丁醇铝(aluminium s-butoxide)、乙醇铝、异丙醇铝、乙酰丙酮酸铝、六氟代乙酰丙酮酸铝、三氟代乙酰丙酮酸铝、三(2,2,6,6-四甲基-3,5-庚二酮酸根合)铝。
用于制备第一绝缘层的金属氧化物纳米颗粒包括,但不限于:Ta2O5、Y2O3、TiO2、CeO2和ZrO2的纳米颗粒。优选该金属氧化物的纳米颗粒的介电常数为5或者更高。用于制备第一绝缘层的铁电绝缘体的纳米颗粒包括,但不限于:钡锶钛酸盐(BST)、PbZrxTi1-xO3(PZT)、Bi4Ti3O12、BaMgF4、SrBi2(Ta1-xNbx)2O9、Ba(Zr1-xTix)O3(BZT)、BaTiO3、SrTiO3或Bi4Ti3O12的纳米颗粒。纳米颗粒的直径没有具体的限制,但是优选为1到100nm。
在本发明的OTFT中,栅绝缘膜的第二绝缘层被直接布置在有机有源层之下,并且由能与该有机有源层相容的绝缘有机聚合物制成。如同第一层,第二层通过湿法工艺形成。适用于第二绝缘层的有机聚合物包括:聚乙烯基苯酚、聚甲基丙烯酸甲酯、多芳基化合物、聚乙烯醇或者下面式1所代表的聚合物:
式1
[其中,R由下面式2表示:
式2
(其中,R1选自以下基团,其中n是0到10的整数:
R2是选自以下(I)和(II)的光定向(photo-alignment)基团,其条件是当l为2或更高时,至少有一个R2选自(I):
R3是氢原子或选自以下基团,其中X是氢原子、1到13个碳原子的烷基或烷氧基、6到20个碳原子的芳基、在芳环上具有至少一个杂原子的4到14个碳原子的杂芳基、-(OCH2)pCH3(p是0到12的整数)、F或Cl,并且m是0到18的整数:
k是0到3的整数并且l是1到5的整数,其条件是当k或1为2或更高时,R1和R2能够各自不同);
m是0.3到0.7的实数,并且n是0.3到0.7的实数,其条件是m和n之和为1;x是0.3到0.7的实数,并且y是0.3到0.7的实数,其条件是x和y之和为1;i是0到1的实数并且j是0到1的实数,其条件是i和j之和为1]。
在将光定向基团引入到绝缘聚合物的情形下,如同式1的聚合物,有机有源层的取向增加,这样可以提供适于有机有源层形成的条件,因而有源层的晶核大小(grain size)可以更大;结果,晶体管的特性(包括在绝缘体和有源层之间的电荷迁移率)可以提高。式1表示的聚合物的优选实施例包括由下面式3到6所代表的聚合物:
式3
式4
式5
式6
在本发明的OTFT中,可以用于制备栅绝缘膜的第一或第二层的湿法工艺可以列举:浸涂、旋涂、印刷、喷涂、或辊涂(roll coating)技术,但不限于此。
根据本发明,不但多层栅绝缘膜具有优越的绝缘性能,而且与使用单层绝缘体的OTFT相比,由其所获得OTFT显示出高电荷迁移率、低驱动电压、低阈电压和优异的Ion/Ioff值。具体而言,栅绝缘膜的制备可以通过湿法工艺完成,诸如印刷或旋涂,同时因此在性能方面,所制成的OTFT可以与通过CVD工艺制备的无机绝缘膜的TFT相匹敌。
在本发明的OTFT中,有机有源层可以用任何已知为有机半导体的材料制成,包括导电聚合物。优选地,有机有源层从以下材料制备:并五苯、铜酞菁、聚噻吩、聚苯胺、聚乙炔、聚吡咯、聚亚苯基亚乙烯基、或其衍生物,但不限于此。
在本发明的OTFT中,用于衬底、栅电极和源/漏电极的材料可以为任何在薄膜晶体管领域中已知的材料。优选地,衬底由塑料、玻璃、石英或硅制成,栅电极和源/漏电极由金(Au)、银(Ag)、铝(Al)、镍(Ni)、铟锡氧化物(ITO)制成,但不限于此。
根据本发明的优选实施方式,OTFT可以通过包含如下步骤的工艺制备:顺序提供布置在衬底上的栅电极并形成高k值材料的第一层,与有机有源层相容的有机绝缘聚合物的第二层,有机有源层和源/漏电极,其中第一和第二层通过诸如旋涂的湿法工艺布置,第二层被直接放置在有机有源层下,并且在有机有源层和源/漏电极之间的层的顺序可以相反。
在下文中,将参照以下实施例更加详细地描述本发明。然而,这些实施例只是为了说明的目的而提供,并且不能解释为限制本发明的范围。
预备实施例1~4:高k值材料第一绝缘层的制备
聚乙烯醇缩丁醛(PVB)和钛酸四丁酯(Ti(OC4H9)4)按照如下表1所示的每个预备实施例的组分比例混合,所得混合物溶解在异丙醇中以制成10-20重量%的溶液。将该溶液通过旋涂法涂布在铝衬底上以形成2000厚的膜,接着在70℃热固化1小时然后150℃热固化30分钟,这样得到第一绝缘层。铝衬底放在第一绝缘层上以制造金属-绝缘膜-金属结构的电容器。借助于该电容器,在100kHz下测量绝缘性能,结果如下表1所示:
表1
预备实施例序号 | PVB(重量%) | Ti(OC4H9)4(重量%) | Ti(重量%) | k(介电常数) |
1 | 75 | 25 | 40 | 5.6 |
2 | 50 | 50 | 66 | 15 |
3 | 30 | 70 | 82 | 27 |
4 | 10 | 90 | 95 | 30 |
从上表可以看出,通过控制钛酸酯的量,介电常数可以提高到高达30。
实施例1
在具有由铝制成的栅电极的玻璃衬底上,按照与预备实施例2相同的方式形成第一绝缘层。制备式3所表示的聚合物(S1)的环己酮溶液(100重量%),接着旋涂在第一绝缘层上以形成5000厚的膜,接着在氮气下、100℃烘焙1小时以制备总厚度为700nm的两层的栅绝缘体。然后,通过使用OMBD(有机分子束沉积(Organic Molecular Beam Deposition))工艺,该工艺在2×10-6托下用0.3/秒的沉积速率进行,同时保持衬底温度为80℃,在该栅绝缘膜上形成700厚的并五苯有机有源层。在这样制成的有源层上,源/漏电极用顶接触(top contact)方法形成,该方法使用具有沟道长度为100μm、宽度为1mm的遮光板,从而制造出OTFT。对于这样获得的OTFT,按照以下程序测量出单位面积的介电常数(C0:nF/单位面积)、阈电压、Ion/Ioff值和电荷迁移率。结果如下表2所示。
(1)单位面积的介电常数,C0
显示介电性能的介电常数按照以下方程式确定:
C0=ε/ε0(A/d)
(其中,A表示器件面积;d表示电介质的厚度;ε和ε0分别表示电介质和真空的介电常数)。
(2)电荷迁移率和阈电压
电荷迁移率从以下饱和区域的电流方程式中测定。也就是说,在获得作为栅电压(VG)的函数的源-漏电流的平方根[(ISD)1/2]图后,电荷迁移率(μFET)从参照以下方程式的图的斜率中计算:
(其中,ISD表示源-漏电流;μ或μFET表示电荷迁移率;C0表示单位面积的电容;W表示沟道宽度;L表示沟道长度;VG和VT分别表示栅电压和阈电压)。
阈电压(VT)从(ISD)1/2和VG图中的线性部分的延长线与VG轴的截点确定。阈电压的绝对值与0越接近意味着电力损耗越小。
(3)Ion/Ioff值
Ion/Ioff值可以从开(on)-状态的最大电流与关(off)-状态的最小电流之比确定,并且满足如下方程式:
(其中,Ion是开(on)-状态的最大电流;Ioff是关(off)-状态的漏电流;μ是电荷迁移率;σ是薄膜的电导率;q是电荷量;NA是电荷密度;t是半导体膜的厚度;C0是氧化物膜的电容;VD是漏极电压)。
随介电膜的介电常数越高和其厚度越薄,Ion/Ioff变大,因此介电膜的种类和厚度是决定Ion/Ioff值的重要因素。关-状态的漏电流Ioff是在关-状态中流动的电流,可以作为关-状态的最小电流确定。
图2显示了随着施加在OTFT上电压的变化漏电流的变化。从显示ISD对VG变化的图3中,可以看出当使用本发明的栅绝缘膜时,曲线向靠近0的方向移动,这意味着较低的阈电压。而且,从图4中显示的(ISD)1/2和VG图中可以看出,本发明中OTFT的阈电压降低到50%或更多。
实施例2
按照与实施例1中相同的方式制备OTFT,但是在与预备实施例3相同的条件下使用组合物和溶剂形成第一绝缘层。对于该OTFT,按照与实施例1中相同的程序测量出单位面积的介电常数(C0:nF/单位面积)、阈电压、Ion/Ioff值和电荷迁移率。结果如下表2所示。
实施例3
按照与实施例1中相同的方式制备OTFT,但是采用了300nm厚的第一层和400nm厚的第二层。对于该OTFT,按照与实施例1中相同的程序测量出单位面积的介电常数(C0:nF/单位面积)、阈电压、Ion/Ioff值和电荷迁移率。结果如下表2所示。
对比实施例1
按照与实施例1中相同的方式制备OTFT,但是使用单层栅绝缘膜而不是多层栅绝缘膜,从S1的环己酮溶液(10重量%),将该溶液旋涂在第一绝缘层上以形成7000厚的膜,接着在氮气下、100℃烘焙1小时获得该单层栅绝缘膜。对于该OTFT,按照与实施例1中相同的程序测量出单位面积的介电常数(C0:nF/单位面积)、阈电压、Ion/Ioff值和电荷迁移率。结果如下表2所示。
实施例4
按照与实施例1中相同的方式制备OTFT,但是使用PVP(聚乙烯基苯酚)膜作为第二绝缘层,该膜通过在PGMEA(丙二醇甲基醚乙酸酯)中溶解PVP以获得15重量%的溶液,该溶液以5000的厚度旋涂,接着在氮气中、100℃烘焙1小时。对于该OTFT,按照与实施例1中相同的程序测量出单位面积的介电常数(C0:nF/单位面积)、阈电压、Ion/Ioff值和电荷迁移率。结果如下表2所示。
对比实施例2
按照与实施例1中相同的方式制备OTFT,但是使用单层栅绝缘膜而不是多层栅绝缘膜,该单层栅绝缘膜通过以下步骤获得:在PGMEA中溶解PVP以获得15重量%的溶液,该溶液以5000的厚度旋涂,接着在氮气中、100℃烘焙1小时。对于该OTFT,按照与实施例1中相同的程序测量出单位面积的介电常数(C0:nF/单位面积)、阈电压、Ion/Ioff值和电荷迁移率。结果如下表2所示。
表2
实施例序号 | 第一绝缘层 | 第二绝缘层 | C0(nF/单位面积) | 阈电压(V) | Ion/Ioff | 电荷迁移率 |
1 | PVB∶Ti(OC4H9)450∶50(200nm) | S1(500nm) | 7.0 | -11 | 1.02×104 | 3-5 |
2 | PVB∶Ti(OC4H9)430∶70(200nm) | S1(500nm) | 7.9 | -9 | 1.02×104 | 3-5 |
3 | PVB∶Ti(OC4H9)450∶50(300nm) | S1(400nm) | 8.6 | -7 | 7.76×103 | 3-5 |
4 | PVB∶Ti(OC4H9)450∶50(200nm) | PVP(500nm) | 7.3 | -13 | 1.24×105 | 6 |
对比例1 | - | S1(700nm) | 5.9 | -15 | 6.67×103 | 3-5 |
对比例2 | - | PVP(700nm) | 5.5 | -17 | 0.71×105 | 6 |
从上表可以看出,本发明的OTFT具有高电荷迁移率、高Ion/Ioff值、低驱动电压和低阈电压、和优越的电绝缘性能。因此,本发明的OTFT可以作为晶体管有效地应用在各种电子器件中。
如上所述,根据本发明,提供了包含多层栅绝缘膜的有机薄膜晶体管,其有利地显示了低驱动电压和阈电压,高电荷迁移率、高Ion/Ioff值。而且,本发明的绝缘膜可以有助于形成有机有源层,还能通过湿法工艺制备,这样简化了制备工艺并降低了制备成本。本发明的OTFT可以应用于柔性显示器领域。
本发明只是以说明的方式描述,应该理解所用的术语是为了说明而不是限制的目的。根据以上技术,本发明的很多改进和变化是可能的。因此,应当理解在附属权力要求的范围内,本发明可以用除了具体描述之外的其它方式实施。
Claims (11)
1.一种有机薄膜晶体管,包含:顺序地形成在衬底上的栅电极、栅绝缘膜、有机有源层和源/漏电极,或者栅电极、栅绝缘膜、源/漏电极和有机有源层,
其中所述栅绝缘膜是多层绝缘体,其包含第一层高k值材料和能与有机有源层相容的第二层绝缘有机聚合物,所述第二层被直接放置在该有机有源层之下。
2.权利要求1的有机薄膜晶体管,其中所述栅绝缘膜的第一和第二层是通过湿法工艺制备的。
3.权利要求1的有机薄膜晶体管,其中所述第一层的高k值材料是绝缘有机聚合物和介电常数(k)为5或更高的有机金属化合物的混合物,或者是绝缘有机聚合物和介电常数(k)为5或更高的无机金属氧化物或铁电绝缘体的纳米颗粒的混合物。
4.权利要求1的有机薄膜晶体管,其中所述第二绝缘层的绝缘有机聚合物选自:聚乙烯基苯酚、聚丙烯酸酯、聚乙烯醇或者下面式1所代表的聚合物:
式1
[其中,R由下面式2表示:
式2
(其中,R1选自以下基团,其中n是0到10的整数:
R2是选自以下(I)和(II)的光定向基团,其条件是当l为2或更高时,至少有一个R2选自(I):
R3是氢原子或选自以下基团,其中X是氢原子、1到13个碳原子的烷基或烷氧基、6到20个碳原子的芳基、在芳环上具有至少一个杂原子的4到14个碳原子的杂芳基、-(OCH2)pCH3(p是0到12的整数)、F或Cl,并且m是0到18的整数:
k是0到3的整数并且l是1到5的整数,条件是当k或l为2或更高时,R1和R2能够各自不同);
m是0.3到0.7的实数,并且n是0.3到0.7的实数,条件是m与n之和为1;x是0.3到0.7的实数,并且y是0.3到0.7的实数,条件是x与y之和为1;i是0到1的实数并且j是0到1的实数,条件是i与j之和为1]。
6.权利要求1的有机薄膜晶体管,其中所述衬底是塑料、玻璃、石英、或硅衬底。
7.权利要求2的有机薄膜晶体管,其中所述湿法工艺是通过旋涂、浸涂、印刷、或辊涂方法进行的。
8.权利要求3的有机薄膜晶体管,其中所述用于第一层的绝缘有机聚合物选自:聚酯、聚碳酸酯、聚乙烯醇、聚乙烯醇缩丁醛、聚缩醛、多芳基化合物、聚酰胺、聚(酰胺-酰亚胺)、聚醚酰亚胺、聚苯醚、聚苯硫醚、聚醚砜、聚醚酮、聚邻苯二酰胺、聚醚腈、聚醚砜、聚苯并咪唑、聚碳化二亚胺、聚硅氧烷、聚甲基丙烯酸甲酯、聚甲基丙烯酰胺、丁腈橡胶、丙烯酰类橡胶、聚四氟乙烯、环氧树脂、酚树脂、三聚氰胺树脂、尿素树脂、聚丁烯、聚戊烯、乙烯-丙烯共聚物、乙烯-丁烯-二烯共聚物、聚丁二烯、聚异戊二烯、乙烯-丙烯-二烯共聚物、丁基橡胶、聚甲基戊烯、聚苯乙烯、苯乙烯-丁二烯共聚物、氢化苯乙烯-丁二烯共聚物、氢化聚异戊二烯、氢化聚丁二烯、及其混合物。
9.权利要求3的薄膜晶体管,其中所述用于第一层的有机金属化合物选自钛类化合物,包括:正丁醇钛(IV)、叔丁醇钛(IV)、乙醇钛(IV)、2-乙基己醇钛(IV)、异丙醇钛(IV)、(二异丙醇)双(乙酰丙酮酸)钛(IV)、双(乙酰丙酮酸)钛氧化物(IV)、三氯三(四氢呋喃)钛(III)、三(2,2,6,6-四甲基-3,5-庚二酮酸根合)钛(III)、(三甲基)五甲基环戊二烯基钛(IV)、五甲基环戊二烯基钛三氯化物(IV)、五甲基环戊二烯基三甲醇钛(IV)、四氯双(环己基巯基)钛(IV)、四氯双(四氢呋喃)钛(IV)、四氯二氨合钛(IV)、四(二乙氨基)钛(IV)、四(二甲氨基)钛(IV)、双(叔丁基环戊二烯基)钛二氯化物、双(环戊二烯基)二羰基钛(II)、双(环戊二烯基)钛二氯化物、双(乙基环戊二烯基)钛二氯化物、双(五甲基环戊二烯基)钛二氯化物、双(异丙基环戊二烯基)钛二氯化物、三(2,2,6,6-四甲基-3,5-庚二酮酸根合)氧代钛(IV)、三异丙醇氯钛、环戊二烯基钛三氯化物、二氯双(2,2,6,6-四甲基-3,5-庚二酮酸根合)钛(IV)、二甲基双(叔丁基环戊二烯基)钛(IV)或二异丙醇双(2,2,6,6-四甲基-3,5-庚二酮酸根合)钛(IV);锆类化合物或铪类化合物,包括:正丁醇锆(IV)、叔丁醇锆(IV)、乙醇锆(IV)、异丙醇锆(IV)、正丙醇锆(IV)、乙酰丙酮酸锆(IV)、六氟代乙酰丙酮酸锆(IV)、三氟代乙酰丙酮酸锆(IV)、四(二乙氨基)锆、四(二甲氨基)锆、四(2,2,6,6-四甲基-3,5-庚二酮酸根合)锆(IV)和四水硫酸锆(IV),正丁醇铪(IV)、叔丁醇铪(IV)、乙醇铪(IV)、异丙醇铪(IV)、异丙醇铪(IV)单异丙醇盐、乙酰丙酮酸铪(IV)或四(二甲氨基)铪;铝类化合物,包括:正丁醇铝、叔丁醇铝、仲丁醇铝、乙醇铝、异丙醇铝、乙酰丙酮酸铝、六氟代乙酰丙酮酸铝、三氟代乙酰丙酮酸铝、或三(2,2,6,6-四甲基-3,5-庚二酮酸根合)铝;及其混合物。
10.权利要求3的薄膜晶体管,其中所述无机金属氧化物的纳米颗粒包括:Ta2O5、Y2O3、TiO2、CeO2或ZrO2的纳米颗粒,所述铁电绝缘体的纳米颗粒包括:钡锶钛酸盐(BST)、PbZrxTi1-xO3(PZT)、Bi4Ti3O12、BaMgF4、SrBi2(Ta1-xNbx)2O9、Ba(Zr1-xTix)O3(BZT)、BaTiO3、SrTiO3或Bi4Ti3O12的纳米颗粒,其中纳米颗粒的直径为1到100nm。
11.权利要求1的薄膜晶体管,其中所述有机有源层由任一种选自以下的材料制成:并五苯、铜酞菁、聚噻吩、聚苯胺、聚乙炔、聚吡咯、聚亚苯基亚乙烯基、及其衍生物。
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Also Published As
Publication number | Publication date |
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US20050001210A1 (en) | 2005-01-06 |
JP2005026698A (ja) | 2005-01-27 |
KR100995451B1 (ko) | 2010-11-18 |
KR20050004565A (ko) | 2005-01-12 |
EP1494298A3 (en) | 2006-06-14 |
US7005674B2 (en) | 2006-02-28 |
JP5054885B2 (ja) | 2012-10-24 |
EP1494298A2 (en) | 2005-01-05 |
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