CN103003974A - 光电转换元件和固体摄像装置 - Google Patents
光电转换元件和固体摄像装置 Download PDFInfo
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- CN103003974A CN103003974A CN2011800337471A CN201180033747A CN103003974A CN 103003974 A CN103003974 A CN 103003974A CN 2011800337471 A CN2011800337471 A CN 2011800337471A CN 201180033747 A CN201180033747 A CN 201180033747A CN 103003974 A CN103003974 A CN 103003974A
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Abstract
本发明公开了具有出色灵敏度和响应性的光电转换元件,所述光电转换元件具有由有机材料组成的光电转换材料层。本发明公开的光电转换元件包括:(a-1)相互分开设置的第一电极(21)和第二电极(22);以及(a-2)设置在所述第一电极(21)和所述第二电极(22)间的光电转换材料层(30),其中,所述光电转换材料层(30)包含结构式(1)所示的具有偶氮部分的噻唑化合物。
Description
技术领域
本发明涉及光电转换元件和包含该光电转换元件的固体摄像装置。
背景技术
使用有机材料(有机光电二极管)的光电转换元件只能引起特定颜色(波长区)的光电转换。此外,由于该光电转换元件具有此类特性,在将其用作固体摄像装置中的光电转换元件时,所述光电转换元件可提供子像素层叠的结构,该结构不能由包含子像素的传统固体摄像装置得到,各子像素包含片上滤色器(OCCF)和光电转换元件的组合,其中,所述子像素以2维方式排列。因此,可高效地接收入射光,因而固体摄像装置的灵敏度增强是意料之中的。此外,该光电转换元件具有不需要去马赛克(mosaic processing)、因此不产生伪色(false color)的优点。
另一方面,用于固体摄像装置中的有机光电转换元件与各种有机薄膜太阳能电池具有相同或相似的结构(例如,参见特开2006-339424、特开2007-123707、特开2007-311647和特开2007-088033A),并旨在改善光电转换率。
引用列表
专利文献
专利文献1:特开2006-339424
专利文献2:特开2007-123707
专利文献3:特开2007-311647
专利文献4:特开2007-088033
发明内容
技术问题
然而,一般而言,相比于基于硅的半导体材料,有机材料具有更高的电阻、极低的迁移率和载流子密度。因此,在灵敏度和响应性方面,有机材料并未显示出与使用无机材料(如基于硅的半导体材料)的传统光电转换元件相当的特性。
因此,本发明的目的在于提供包含光电转换材料层的光电转换元件、以及包含该光电转换元件的固体摄像装置,所述光电转换材料层由比传统有机材料具有更出色的灵敏度和响应性的有机材料构成。
解决技术问题的手段
用于实现上述目的的本发明第一实施方式的光电转换元件包含:
(a-1)彼此分开设置的第一电极和第二电极;以及
(a-2)设置在所述第一电极和所述第二电极间的光电转换材料层;
其中,所述光电转换材料层由下述结构式(1)所示的含偶氮部分的噻唑化合物形成。
其中,X和Y各自表示氢原子或除氢原子以外的取代基,并且R1表示烷基基团、烯基基团、炔基基团或芳基基团。
用于实现上述目的的本发明第二实施方式的光电转换元件包含:
(a-1)彼此分开设置的第一电极和第二电极;以及
(a-2)设置在所述第一电极和所述第二电极间的光电转换材料层;
其中,所述光电转换材料层由下述结构式(2)所示的含偶氮部分的噻唑化合物形成。
其中,X和Y各自表示氢原子或除氢原子以外的取代基,并且R2至R6中的至少一个表示除氢原子以外的取代基。
用于实现上述目的的本发明第一实施方式的固体摄像装置包含光电转换元件,所述光电转换元件包含:
(a-1)彼此分开设置的第一电极和第二电极;以及
(a-2)设置在所述第一电极和所述第二电极间的光电转换材料层;
其中,所述光电转换材料层由上述结构式(1)所示的含偶氮部分的噻唑化合物形成。
用于实现上述目的的本发明第二实施方式的固体摄像装置包含光电转换元件,所述光电转换元件包含:
(a-1)彼此分开设置的第一电极和第二电极;以及
(a-2)设置在所述第一电极和所述第二电极间的光电转换材料层;
其中,所述光电转换材料层由上述结构式(2)所示的含偶氮部分的噻唑化合物形成。
本发明的效果
由结构式(1)或结构式(2)所示的、形成光电转换材料层的含偶氮部分的噻唑化合物具有比一般有机色素(例如喹吖啶酮)的吸收系数(约1.4×104dm3mol-1cm-1)更高的吸收系数(3×104dm3mol-1cm-1以上,通常为4.5×104dm3mol-1cm-1至5.0×104dm3mol-1cm-1),并能够实现光电流的增大。可向X、Y、R1和R2至R6处引入各种取代基,从而能够在400nm-800nm的范围内选择期望的吸收波长。另外,所述化合物具有深的HOMO能级,针对电极的能量势垒也高,这使得即使在施加了高偏置时也能抑制暗电流(电荷注入)。另外,由于所述化合物具有高的吸收系数,因此可将光电转换材料层制作得更薄。这使得能够提供各自具有高灵敏度、高响应速度的光电转换元件与固体摄像装置。并且在构成光电转换材料层的有机半导体材料的分子设计方面具有高的自由度,因此分子设计变得容易。另外,可改善方法适应性。即,不仅可基于PVD法,还可基于所谓的湿法方法(如涂布法和印刷法)形成光电转换材料层。因此,可容易地通过这一方式生产具有高性能的光电转换元件。此外,由于可容易地引入取代基并可通过选择适合的取代基来选择吸收波长,使得能够通过光电转换材料层来吸收特定波长的光。因此,当固体摄像装置通过本发明的光电转换元件构成时,不需要片上滤色器,因此使得能够构成包含多个层的光电转换元件。另外,无需使用经常需要的p-n接合、p-i-n接合、本体异质结构(bulk heterostructures)、多层化或其它传统技术,使用非常简单的结构即可提供光电转换元件和固体摄像装置。
附图说明
图1为实施例1的光电转换元件的剖视示意图。
图2为示出在波长480nm的光线照射时和无光线照射时,分别得到的实施例1的光电转换元件的电流-电压曲线的图。
图3为实施例1的固体摄像装置的概念图。
图4(A)和图4(B)示出了实施例2和实施例3的光电转换元件的剖视示意图。
具体实施方式
下文中,将基于实施例并参考附图对本发明进行说明,但是并不能将本发明解释为限于实施例,实施例中的各数值和材料仅供示例。将按下文所示的顺序进行解释:
1.关于本发明第一实施方式和第二实施方式的光电转换元件和固体摄像装置的一般说明;
2.实施例1(本发明第一实施方式和第二实施方式的光电转换元件和固体摄像装置);以及其它内容。
[关于本发明第一实施方式和第二实施方式的光电转换元件和固体摄像装置的一般说明]
在本发明第二实施方式的光电转换元件、或本发明第二实施方式的固体摄像装置中的光电转换元件中(下文将其统一简称为“本发明第二实施方式的光电转换元件等”),R2至R6中的至少一个为:烷基基团、环烷基基团、烯基基团、炔基基团、芳基基团、芳基烷基基团、芳香族杂环、杂环基团、烷氧基基团、环烷氧基基团、芳基氧基基团、烷基硫基基团、环烷基硫基基团、芳基硫基基团、烷氧基羰基基团、芳基氧基羰基基团、氨磺酰基基团、酰基基团、硫代羰基基团、酰基氧基基团、酰胺基基团、氨甲酰基基团、脲基基团、亚硫酰基基团、烷基磺酰基基团、芳基磺酰基基团、氨基基团、卤素原子、氟代烃基团、氰基基团、异氰基基团、硝基基团、亚硝基基团、羧酸氰化物基团、氰酸根基团、异氰酸根基团、硫代氰酸根基团、异硫代氰酸根基团、甲酰基基团、硫 代甲酰基基团、酰肼基团、羟基基团、硫烷基基团、磺基基团或甲硅烷基基团。在具有这一特征的本发明第二实施方式的光电转换元件等之中,或者在本发明第一实施方式的光电转换元件、或本发明第一实施方式的固体摄像装置中的光电转换元件中(下文将其统一简称为“本发明第一实施方式的光电转换元件等”),X与Y可各自表示除氢原子以外的取代基。在这种情况下,所述取代基可选自于由如下基团所组成的组:烷基基团、环烷基基团、烯基基团、炔基基团、芳基基团、芳基烷基基团、芳香族杂环、杂环基团、烷氧基基团、环烷氧基基团、芳基氧基基团、烷基硫基基团、环烷基硫基基团、芳基硫基基团、烷氧基羰基基团、芳基氧基羰基基团、氨磺酰基基团、酰基基团、硫代羰基基团、酰基氧基基团、酰胺基基团、氨甲酰基基团、脲基基团、亚硫酰基基团、烷基磺酰基基团、芳基磺酰基基团、氨基基团、卤素原子、氟代烃基团、氰基基团、异氰基基团、硝基基团、亚硝基基团、羧酸氰化物基团、氰酸根基团、异氰酸根基团、硫代氰酸根基团、异硫代氰酸根基团、甲酰基基团、硫代甲酰基基团、酰肼基团、羟基基团、硫烷基基团、磺基基团和甲硅烷基基团。
具有上述优选特征的本发明第一实施方式或第二实施方式的光电转换元件、或在本发明第一实施方式或第二实施方式的固体摄像装置中的光电转换元件(下文将其统一简称为“本发明的光电转换元件等”),可形成如下构造,其中:
在透明基板上形成由透明导电材料所形成的第一电极,
在第一电极上形成光电转换材料层,以及
在光电转换材料层上形成第二电极。
或者,可形成如下构造,其中:
在基板上形成第一电极,
在第一电极上形成光电转换材料层,以及
在光电转换材料层上形成由透明导电材料形成的第二电极。
第一电极和第二电极彼此分开设置,并且作为该分开状态,可举出在第一电极之上设置第二电极的实施方式。
如上所述,在本发明的光电转换元件等中,优选位于光入射侧的电 极由透明导电材料形成。该电极被称为“透明电极”。作为构成透明电极的透明导电材料,可例举:铟锡氧化物(包括ITO、Sn掺杂的In2O3、结晶ITO和无定形ITO)、IFO(F掺杂的In2O3)、氧化锡(SnO2)、ATO(Sb掺杂的SnO2)、FTO(F掺杂的SnO2)、氧化锌(包括Al掺杂的ZnO和B掺杂的ZnO以及Ga掺杂的ZnO)、氧化铟-氧化锌(IZO)、氧化钛(TiO2)、尖晶石型氧化物以及具有YbFe2O4结构的氧化物。由此类材料形成的透明电极通常具有高的功函数并起到阳极电极的作用。形成透明电极的方法取决于构成透明电极的材料,并可例举:物理气相沉积(PVD法),如真空沉积法、反应沉积法、各种溅射法、电子束沉积法和离子电镀法;以及各种化学沉积法(CVD法),包括熔溶胶(pyrosol)法、通过将有机金属化合物热分解的方法、喷涂法、浸渍法和MOCVD法、无电镀法和电镀法。必要时,另一电极也可由透明导电材料构成。
在透明度并非必要的情况下,作为构成第一电极或第二电极的导电材料,当第一电极或第二电极起到阳极电极(阳极)的作用时(即,起到取出空穴的电极的作用),优选电极由具有高的功函数(例如,φ=4.5eV-5.5eV)的导电材料构成,并且可具体例举:金(Au)、银(Ag)、铬(Cr)、镍(Ni)、钯(Pd)、铂(Pt)、铁(Fe)、铱(Ir)、锗(Ge)、锇(Os)、铼(Re)和碲(Te)。另一方面,当第一电极或第二电极起到阴极电极(阴极)的作用时(即,起到取出电子的电极的作用),优选电极由具有低的功函数(例如,φ=3.5eV-4.5eV)的导电材料构成,并且可具体例举:碱金属(例如Li、Na和K等)及其氟化物或氧化物、碱土金属(例如Mg和Ca等)及其氟化物或氧化物、铝(Al)、锌(Zn)、锡(Sn)、铊(Tl)、钠-钾合金、铝-锂合金、镁-银合金、铟、稀土金属(如镱)或上述物质的合金。或者,作为构成第一电极或第二电极的材料,导电物质可例举:金属,如铂(Pt)、金(Au)、钯(Pd)、铬(Cr)、镍(Ni)、铝(Al)、银(Ag)、钽(Ta)、钨(W)、铜(Cu)、钛(Ti)、铟(In)、锡(Sn)、铁(Fe)、钴(Co)和钼(Mo);或者包含这些金属元素的合金、由这些金属形成的导电颗粒、包含这些金属的合金的导电颗粒、包含杂质的多晶硅、基于碳的材料、氧化物半导体、碳纳米管和石墨烯;而且还可形成包含这些元素的层的层叠结构。此外,作为构成第一电极和第二电极的材料,可例举有机材料(导电聚合物)、如聚(3,4-亚乙二氧 基噻吩)/聚苯乙烯磺酸[PEDOT/PSS]。或者,可将这些导电材料与粘结剂(聚合物)混合以形成糊状物或墨状物(ink),并可使糊状物或墨状物硬化并用作电极。形成第一电极和第二电极的方法取决于构成这些电极的材料,所述方法包括:各种PVD法;各种CVD法,包括MOCVD法;各种涂布法;剥离法;溶胶-凝胶法;电沉积法;掩模法(shadow maskmethods);施镀法,如电镀法和无电镀法或其组合;以及喷涂法;必要时,可将上述任意方法与图案化技术组合使用。
作为基板,可例举有机聚合物,如聚甲基丙烯酸甲酯(聚甲基丙烯酸甲酯,PMMA)和聚乙烯醇(PVA)、聚乙烯基苯酚(PVP)、聚醚砜(PES)、聚酰亚胺、聚碳酸酯(PC)、聚对苯二甲酸乙二醇酯(PET)以及聚萘二甲酸乙二醇酯(PEN)(这些聚合物具有聚合材料形态,如由聚合材料构成的、具有柔性的塑料膜、塑料片和塑料基板);或者还可例举云母。如果使用由此类柔性聚合材料构成的基板,例如可使电子装置的嵌入或一体化成为可能。或者,作为基板可例举:各种玻璃基板,包含在表面上形成的绝缘膜的各种玻璃基板;石英基板,包含在表面上形成的绝缘膜的石英基板;硅基板,包含在表面上形成的绝缘膜的硅基板;以及由各种合金或各种金属(如不锈钢)形成的金属基板。此外,作为绝缘膜,可例举:基于硅氧化物的材料(例如,SiOX和旋涂玻璃(SOG));硅氮化物(SiNY);氮氧化硅(SiON);氧化铝(Al2O3);金属氧化物;以及金属盐。或者,还可使用包含在表面上形成的绝缘膜的导电基板(由金属、如金和铝形成的基板和由高度定向石墨形成的基板)。期望基板的表面光滑,但该表面也可在具有对光电转换材料层的特性无有害影响的程度范围内具有粗糙度。第一电极或第二电极与基板间的粘着性可通过如下作用进行改善:通过硅烷偶联法在基板的表面上形成硅醇衍生物;或通过SAM法等形成薄膜,所述薄膜由硫醇衍生物、羧酸衍生物或磷酸衍生物等形成;或通过CVD法等形成薄膜,所述薄膜由绝缘金属盐或金属络合物形成。透明基板是指由以下材料构成的基板,所述材料不会过度吸收穿过基板进入光电转换材料层的光。
必要时,电极或光电转换材料层可涂覆有涂层。作为构成涂层的材料,可例举:基于无机物的绝缘材料,如基于硅氧化物的材料、硅氮化 物(SiNY)和金属氧化物高介电绝缘膜(如氧化铝(Al2O3));以及基于有机物的绝缘材料(有机聚合物),如聚甲基丙烯酸甲酯(PMMA)、聚乙烯基苯酚(PVP)、聚乙烯醇(PVA)、聚酰亚胺、聚碳酸酯(PC)、聚对苯二甲酸乙二醇酯(PET)、聚苯乙烯、硅醇衍生物(如N-2(氨基乙基)3-氨基丙基三甲氧基硅烷(AEAPTMS)、3-巯基丙基三甲氧基硅烷(MPTMS)和十八烷基三氯硅烷(OTS)(硅烷偶联剂))以及具有下述官能团的直链烃,所述官能团可在其一端结合至电极(如十八烷基硫醇和十二烷基异氰酸根);或者还可使用这些材料的组合。此外,作为基于硅氧化物的材料,可例举:硅氧化物(SiOX)、BPSG、PSG、BSG、AsSG、PbSG、氮氧化硅(SiON)、SOG(旋涂玻璃)以及低介电材料(例如,聚芳基醚、环全氟化碳聚合物和苯并环丁烯、环氟树脂、聚四氟乙烯、氟代芳基醚、氟代聚酰亚胺、无定形碳以及有机SOG)。
虽然在本发明光电转换元件等中并不对光电转换材料层的厚度加以限定,但可例举2.5×10-8m至3×10-7m、优选2.5×10-8m至2×10-7m、更优选1×10-7m至1.8×10-7m。由结构式(1)或结构式(2)所示的含偶氮部分的噻唑化合物具有高的吸收系数(α)。因此,使得能够降低光电转换材料层的厚度,并可以解决诸如高电阻、低迁移率和低载流子密度的问题(传统有机材料所具有的缺陷),因此可提供具有高灵敏度和高速响应性的光电转换元件或固体摄像装置。同时,在施加相同的电势时,施加至光电转换材料层的电场强度E可通过降低光电转换材料层的厚度而增加,并因此即使在迁移率或载流子密度低时也可得到高的光电流。作为形成光电转换材料层的方法,可例举涂布法、PVD法以及各种CVD法(包括MOCVD方法)。作为涂布法,可具体例举:旋涂法;浸渍法;铸造法;各种印刷法,如丝网印刷法、喷墨印刷法、胶版印刷法和凹版印刷法;压模法(stamping methods);喷涂法;各种涂覆法,如气刀涂布机法、刮刀涂布机法、棒式涂布机法、刀片涂布机法、挤压涂布机法、逆转辊式涂布机法、传输辊式涂布机法、凹版涂布机法、吻合式涂布机法、铸式涂布机法、喷涂涂布机法、狭缝式涂布机法和压延涂布机法。作为涂布法中的溶剂,可例举非极性或低极性有机溶剂,如甲苯、氯仿、己烷和乙醇。作为PVD方法,可例举:各种真空沉积方法,如电子束加热法、电阻加热法和快速沉积法(flash deposition);等离子沉积法;各 种溅射法,如双极溅射法、直流溅射法、直流磁控溅射法、高频波溅射法、磁控溅射法、离子束溅射法和偏置溅射法;以及各种离子镀法,如DC(直流)法、RF法、多阴极法、活化反应法、电场沉积法、高频波离子镀法和反应离子镀法。或者,当将构成固体摄像装置的光电转换元件进行集成时,可采用基于PLD法(脉冲激光沉积法)形成图案的方法。
在其上将形成光电转换材料层的底层(base)的Ra、具体来说例如第一电极和基板的表面粗糙度Ra优选为1.0nm以下。通过使底层平坦化,构成光电转换材料层的分子可在平坦的底层上以水平方向或垂直方向按照有序的方式进行排列,从而形成了在光电转换材料层和第一电极的界面处难以发生显著电势下降的结构。同时,众所周知的是,此类电势下降起因于光电转换材料层和第一电极界面处的晶格失配,并导致缺陷水平的形成和界面电阻的增大,从而抑制第一电极和光电转换材料层之间的载流子传输。在光电转换材料层和基板间可形成平坦化的层。该平坦化的层可具有防止穿过基板的光发生反射的功能。该平坦化的层可具有由聚甲基丙烯酸甲酯、聚乙烯醇、聚乙烯基苯酚、聚醚砜、聚酰亚胺、聚碳酸酯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、基于硅氧化物的材料、硅氮化物、氮氧化硅或氧化铝形成的构造。
第一电极的表面作为底层(在其上将形成光电转换材料层)可进行等离子灰化处理。作为用于等离子灰化的气体种类,可例举选自Ar、N2和O2的至少一种或多种气体种类。通过对第一电极的表面进行等离子灰化处理,在光电转换中的不均衡和噪音水平降低,并且暗电流水平可降低至1nA/cm2同时保持光电流值。此外,由于暗电流水平可如上所述地降低,因而可提供动态范围宽并能以高灵敏度提供对比度(contrast)的有机光电转换元件。
在结构式(1)或结构式(2)中,取代基X或取代基Y可为烷基基团,如,甲基、乙基、丙基、异丙基、叔丁基、戊基、己基、辛基或十二烷基等。所述基团可为直链或支链。此外,环烷基基团可包括环戊基基团和环己基基团等;烯基基团可包括乙烯基基团等;炔基基团可包括乙炔基基团等;芳基基团可包括苯基基团、萘基基团和联苯基基团等;芳基烷基基团可包括甲基芳基基团、乙基芳基基团、异丙基芳基基团、 正丁基芳基基团、对甲苯基基团、对乙基苯基基团、对异丙基苯基基团、4-丙基苯基基团、4-丁基苯基基团和4-壬基苯基基团等;芳香族杂环可包括吡啶基基团、噻吩基基团、呋喃基基团、哒嗪基基团、嘧啶基基团、吡嗪基基团、三嗪基基团、咪唑基基团、吡唑基基团、噻唑基基团、喹唑啉基基团和酞嗪基基团等;杂环基团可包括吡咯烷基基团、咪唑烷基基团、吗啉基基团和噁唑烷基基团等;烷氧基基团可包括甲氧基基团、乙氧基基团、丙氧基基团、戊氧基基团和己氧基基团等;环烷氧基基团可包括环戊基氧基基团和环己基氧基基团等;芳基氧基基团可包括苯氧基基团和萘基氧基基团等;烷基硫基基团可包括甲基硫基基团、乙基硫基基团、丙基硫基基团、戊基硫基基团和己基硫基基团等;环烷基硫基基团可包括环戊基硫基基团和环己基硫基基团等;芳基硫基基团可包括苯基硫基基团和萘基硫基基团等;烷氧基羰基基团可包括甲基氧基羰基基团、乙基氧基羰基基团、丁基氧基羰基基团和辛基氧基羰基基团等;芳基氧基羰基基团可包括苯基氧基羰基基团和萘基氧基羰基基团等;氨磺酰基基团可包括氨基磺酰基基团、甲基氨基磺酰基基团、二甲基氨基磺酰基基团、环己基氨基磺酰基基团、苯基氨基磺酰基团、萘基氨基磺酰基基团和2-吡啶基氨基磺酰基基团等;酰基基团可包括乙酰基基团、乙基羰基基团、丙基羰基基团、环己基羰基基团、辛基羰基基团、2-乙基己基羰基基团、十二烷基羰基基团、苯基羰基基团、萘基羰基基团和吡啶基羰基基团等;硫代羰基基团可包括硫代乙酰基基团、乙基硫代羰基基团、丙基硫代羰基基团、环己基硫代羰基基团、辛基硫代羰基基团、2-乙基己基硫代羰基基团、十二烷基硫代羰基基团、苯基硫代羰基基团、萘基硫代羰基基团和吡啶基硫代羰基基团等;酰基氧基基团可包括乙酰基氧基基团、乙基羰基氧基基团、辛基羰基氧基基团和苯基羰基氧基基团等;酰胺基基团可包括甲基羰基氨基基团、乙基羰基氨基基团、二甲基羰基氨基基团、戊基羰基氨基基团、环己基羰基氨基基团、2-乙基己基羰基氨基基团、苯基羰基氨基基团和萘基羰基氨基基团等;氨甲酰基基团可包括氨基羰基基团、甲基氨基羰基基团、二甲基氨基羰基基团、环己基氨基羰基基团、2-乙基己基氨基羰基基团、苯基氨基羰基基团、萘基氨基羰基基团和2-吡啶基氨基羰基基团等;脲基基团可包括甲基脲基基团、乙基脲基基团、环己基脲基基团、十二烷基脲基基团、苯基脲 基基团、萘基脲基基团和2-吡啶基氨基脲基基团等;亚硫酰基基团可包括甲基亚硫酰基基团、乙基亚亚硫酰基基团、丁基亚硫酰基基团、环己基亚硫酰基基团、2-乙基己基亚硫酰基基团、苯基亚硫酰基基团、萘基亚硫酰基基团和2-吡啶基亚硫酰基基团等;烷基磺酰基基团可包括甲基磺酰基基团、乙基磺酰基基团、丁基磺酰基基团、环己基磺酰基基团、2-乙基己基磺酰基基团和十二烷基磺酰基基团等;芳基磺酰基基团可包括苯基磺酰基基团、萘基磺酰基基团和2-吡啶基磺酰基基团等;氨基基团可包括氨基基团、乙基氨基基团、二甲基氨基基团、丁基氨基基团、2-乙基己基氨基基团、苯胺基基团、萘基氨基基团和2-吡啶基氨基基团等;卤素原子可包括氟原子、氯原子、溴原子和碘原子;氟代烃基团可包括氟代甲基基团、三氟代甲基基团、五氟代乙基基团和五氟代苯基基团等。此外,可例举:氰基基团、异氰基基团、硝基基团、亚硝基基团、羧酸氰化物基团、氰酸根基团、异氰酸根基团、硫代氰酸根基团、异硫代氰酸根基团、甲酰基基团、硫代甲酰基基团、酰肼基团、羟基基团、硫烷基基团和磺基基团,并且甲硅烷基基团可包括三甲基甲硅烷基基团、三异丙基甲硅烷基基团、三苯基甲硅烷基基团和苯基二乙基甲硅烷基基团等。上述示例的取代基可进一步用上述取代基进行取代。此外,多个这些取代基可彼此结合形成环。
结构式(1)中的取代基R1或结构式(2)中的取代基R2至R6可各自为烷基基团,如,甲基、乙基、丙基、异丙基、叔丁基、戊基、己基、辛基或十二烷基等。所述基团可为直链或支链。此外,环烷基基团可包括环戊基基团和环己基基团等;烯基基团可包括乙烯基基团等;炔基基团可包括乙炔基基团等;芳基基团可包括苯基基团、萘基基团和联苯基基团等;芳基烷基基团可包括甲基芳基基团、乙基芳基基团、异丙基芳基基团、正丁基芳基基团、对甲苯基基团、对乙基苯基基团、对异丙基苯基基团、4-丙基苯基基团、4-丁基苯基基团和4-壬基苯基基团等;芳香族杂环可包括吡啶基基团、噻吩基基团、呋喃基基团、哒嗪基基团、嘧啶基基团、吡嗪基基团、三嗪基基团、咪唑基基团、吡唑基基团、噻唑基基团、喹唑啉基基团和酞嗪基基团等;杂环基团可包括吡咯烷基基团、咪唑烷基基团、吗啉基基团和噁唑烷基基团等;烷氧基基团可包括甲氧基基团、乙氧基基团、丙氧基基团、戊氧基基团和己氧基基团等; 环烷氧基基团可包括环戊基氧基基团和环己基氧基基团等;芳基氧基基团可包括苯氧基基团和萘基氧基基团等;烷基硫基基团可包括甲基硫基基团、乙基硫基基团、丙基硫基基团、戊基硫基基团和己基硫基基团等;环烷基硫基基团可包括环戊基硫基基团和环己基硫基基团等;芳基硫基基团可包括苯基硫基基团和萘基硫基基团等;烷氧基羰基基团可包括甲基氧基羰基基团、乙基氧基羰基基团、丁基氧基羰基基团和辛基氧基羰基基团等;芳基氧基羰基基团可包括苯基氧基羰基基团和萘基氧基羰基基团等;氨磺酰基基团可包括氨基磺酰基基团、甲基氨基磺酰基基团、二甲基氨基磺酰基基团、环己基氨基磺酰基基团、苯基氨基磺酰基团、萘基氨基磺酰基基团和2-吡啶基氨基磺酰基基团等;酰基基团可包括乙酰基基团、乙基羰基基团、丙基羰基基团、环己基羰基基团、辛基羰基基团、2-乙基己基羰基基团、十二烷基羰基基团、苯基羰基基团、萘基羰基基团和吡啶基羰基基团等;硫代羰基基团可包括硫代乙酰基基团、乙基硫代羰基基团、丙基硫代羰基基团、环己基硫代羰基基团、辛基硫代羰基基团、2-乙基己基硫代羰基基团、十二烷基硫代羰基基团、苯基硫代羰基基团、萘基硫代羰基基团和吡啶基硫代羰基基团等;酰基氧基基团可包括乙酰基氧基基团、乙基羰基氧基基团、辛基羰基氧基基团和苯基羰基氧基基团等;酰胺基基团可包括甲基羰基氨基基团、乙基羰基氨基基团、二甲基羰基氨基基团、戊基羰基氨基基团、环己基羰基氨基基团、2-乙基己基羰基氨基基团、苯基羰基氨基基团和萘基羰基氨基基团等;氨甲酰基基团可包括氨基羰基基团、甲基氨基羰基基团、二甲基氨基羰基基团、环己基氨基羰基基团、2-乙基己基氨基羰基基团、苯基氨基羰基基团、萘基氨基羰基基团和2-吡啶基氨基羰基基团等;脲基基团可包括甲基脲基基团、乙基脲基基团、环己基脲基基团、十二烷基脲基基团、苯基脲基基团、萘基脲基基团和2-吡啶基氨基脲基基团等;亚硫酰基基团可包括甲基亚硫酰基基团、乙基亚亚硫酰基基团、丁基亚硫酰基基团、环己基亚硫酰基基团、2-乙基己基亚硫酰基基团、苯基亚硫酰基基团、萘基亚硫酰基基团和2-吡啶基亚硫酰基基团等;烷基磺酰基基团可包括甲基磺酰基基团、乙基磺酰基基团、丁基磺酰基基团、环己基磺酰基基团、2-乙基己基磺酰基基团和十二烷基磺酰基基团等;芳基磺酰基基团可包括苯基磺酰基基团、萘基磺酰基基团和2-吡啶基磺酰基 基团等;氨基基团可包括氨基基团、乙基氨基基团、二甲基氨基基团、丁基氨基基团、2-乙基己基氨基基团、苯胺基基团、萘基氨基基团和2-吡啶基氨基基团等;卤素原子可包括氟原子、氯原子、溴原子和碘原子;氟代烃基团可包括氟代甲基基团、三氟代甲基基团、五氟代乙基基团和五氟代苯基基团等。此外,可例举:磺基基团、氰基基团、异氰基基团、硝基基团、亚硝基基团、羧酸氰化物基团、氰酸根基团、异氰酸根基团、硫代氰酸根基团、异硫代氰酸根基团、甲酰基基团、硫代甲酰基基团、酰肼基团、羟基基团、硫烷基基团和磺基基团,并且甲硅烷基基团可包括三甲基甲硅烷基基团、三异丙基甲硅烷基基团、三苯基甲硅烷基基团和苯基二乙基甲硅烷基基团等。上述示例的取代基可进一步用上述取代基进行取代。此外,多个这些取代基可彼此结合形成环。
本发明的固体摄像装置可为表面照射型或背面照射型,并可构成单板式彩色固体摄像装置。此外,在必要时,可将片上微透镜和遮光层设置在构成本发明固体摄像装置的固体摄像元件上,并设置用于驱动光电转换元件(固体摄像元件)的驱动电路和电线。必要时,可设置用于控制光向光电转换元件(固体摄像元件)中入射的快门(shutter),并且本发明的固体摄像装置根据其目的可包含光学截止滤镜。此外,当固体摄像装置中的固体摄像元件通过本发明光电转换元件的单层构成时,光电转换元件的阵列的实例可包括:Bayer阵列、行间阵列、G条带-RB网格阵列(G stripe-RB checker arrangement)、G条带-RB全网格阵列、网格补色阵列(complementary color checker arrangement)、条带阵列、对角条带阵列(oblique stripe array)、原色色差阵列、场色差顺序阵列、帧色差顺序阵列、MOS型阵列、改良MOS型阵列、帧交错阵列和场交错阵列。同时,根据本发明的光电转换元件,可构成摄像装置(固体摄像装置)(如电视照相机)以及光学传感器、图像传感器和太阳能电池。
实施例
[实施例1]
实施例1涉及本发明的第一实施方式和第二实施方式的光电转换元件和固体摄像装置。如图1中的局部剖面示意图所示,实施例1中的光电转换元件11包含:
(a-1)彼此分开设置的第一电极21和第二电极22,以及
(a-2)设置在所述第一电极21和所述第二电极22间的光电转换材料层30。更具体而言,在透明基板20上形成由透明导电材料所形成的第一电极21,在该第一电极21上形成光电转换材料层30,在该光电转换材料层30上形成第二电极22。
第一电极21为处于光入射侧的电极,由透明导电材料、特别是厚度为120nm的氧化铟锡(ITO)形成。第二电极22由厚度为100nm的铝(Al)形成。在透明基板20上形成由透明导电材料所形成的第一电极21,在该第一电极21上形成光电转换材料层30,并在该光电转换材料层30上形成第二电极22。光穿过基板20和第一电极21进入光电转换材料层30。基板20由厚度为0.7mm的石英基板形成。处于光电转换材料层一侧的第一电极21的表面粗糙度Ra为0.28nm且Rmax为3.3nm。通常,期望第一电极21的表面粗糙度Ra为1.0nm以下、优选0.3nm以下。
此外,光电转换材料层30由上述结构式(1)(本发明第一实施方式)或结构式(2)(本发明第二实施方式)所示的含偶氮部分的噻唑化合物形成。更具体而言,在实施例1中,光电转换材料层30由以下结构式(3)所示的4-(2-噻唑基偶氮)间苯二酚形成,并吸收蓝色光。4-(2-噻唑基偶氮)间苯二酚的吸收系数是3.45×104dm3mol-1cm-1。
通过下述方法制备实施例1的光电转换元件11。即,首先基于光刻(photolithographic)技术使用光掩模在基板20上形成第一电极21,所述第一电极21由厚度为100nm的ITO形成。接下来,在所述基板20和第一电极21上形成由绝缘材料所形成的凸部31,此后,基于真空沉积方法,使用金属掩模由真空沉积方法自所述第一电极21到所述凸部31在各处形成(成膜)光电转换材料层30(厚度107nm),所述光电转换材料层30由上述结构式(1)、结构式(2)或结构式(3)的含偶氮部分的噻唑化合物形成。真空沉积期间的基板温度为室温(25℃),光电转换 材料层30的膜形成速度为0.1nm/sec。接下来,通过PVD方法,使用金属掩模自光电转换材料层30到基板20在各处形成第二电极22,所述第二电极22由厚度为100nm的铝形成。作为形成第二电极22的条件,基板温度为室温(25℃),并且第二电极22的膜形成速度为0.5nm/sec。形成凸部31,以使其环绕基板20上将形成光电转换材料层30的区域。此外,在光电转换材料层30的膜形成之前,对第一电极21(作为底层)和凸部31进行UV臭氧处理。同时可在下文所述的实施例2和实施例3中,以类似方式制备光电转换元件。
图2示出了实施例1所得到的光电转换元件11的电流-电压曲线,其中,当以波长480nm的光照射时得到曲线A,而当无光照射时得到曲线B。在图2中,纵轴表示所流经的电流的值,横轴表示施加至第二电极的电压。第一电极接地。图2显示出,流经光电转换元件11的电流随是否照射波长480nm的光而变化,并且当照射波长480nm的光时,产生光电流的打开-关闭(on-off)响应。
图3示出了实施例1的固体摄像装置(固体摄像元件)的概念图。在下述实施例2和实施例3中,所述固体摄像装置(固体摄像元件)与实施例1的固体摄像装置(固体摄像元件)具有类似的构造和结构。实施例1的固体摄像装置40由如下构成:摄像区域41,其中以二维阵列在半导体基板(例如,Si基板)上设置上述光电转换元件11;以及垂直驱动电路42、列信号处理电路43、水平驱动电路44、输出电路45和控制电路46等作为其外围电路。不必赘述的是,这些电路可由公知的电路构成,或者可通过使用其它电路构造(例如,在传统CCD摄像装置和CMOS摄像装置中使用的各种电路)来构成。
基于垂直同步信号、水平同步信号和主时钟,控制电路46产生时钟信号或控制信号,所述时钟信号和控制信号形成了垂直驱动电路42、列信号处理电路43和水平驱动电路44的运行基础。此外,将所产生的时钟信号或控制信号输入至垂直驱动电路42、列信号处理电路43和水平驱动电路44中。
垂直驱动电路42通过例如移位寄存器构成,并在垂直方向上,顺序地对摄像区域41上的各光电转换元件11的各行选择性地进行扫描。此 外,像素信号以根据各光电转换元件11中所接收的光的量而产生的电流(信号)为基础,该像素信号通过垂直信号线47被发送至列信号处理电路43。
将列信号处理电路43设置于例如光电转换元件11的每列上,并通过来自黑基准像素(black reference pixels)的信号(未对其示出,但是在有效像素区域周围形成),用于在各光电转换元件上对从一行上的光电转换元件11所输出的信号进行噪音消除或信号放大的信号处理。将水平选择开关(未示出)通过与水平信号线48相连接而设置在列信号处理电路43的输出级上。
水平驱动电路44通过例如移位寄存器构成,并通过顺序输出水平扫描脉冲来顺序选择各个列信号处理电路43,然后从各个列信号处理电路43向水平信号线48输出信号。
输出电路45对来自各个列信号处理电路43的、经由水平信号线48顺序供给的信号进行信号处理,然后输出信号。
[实施例2]
实施例2为实施例1的光电转换元件的变形。在实施例2的光电转换元件12中,如图4(A)中的局部剖面示意图所示,在基板20A上形成第一电极21A,在所述第一电极21A上形成光电转换材料层30,在所述光电转换材料层30上形成由透明导电材料所形成的第二电极22A。光穿过第二电极22A进入光电转换材料层30。具体而言,基板20A由例如硅半导体基板形成,第一电极21A由铝形成,第二电极22A由ITO形成。除这一点外,实施例2的光电转换元件12的构造和结构可与实施例1的光电转换元件11的构造和结构相同,因此略去详细的解释。
[实施例3]
实施例3也是实施例1的光电转换元件的变形。在实施例3的光电转换元件13中,如图4(B)中的局部剖面示意图所示,在基板上形成第一电极21B和第二电极22B,在自所述第一电极21B至所述第二电极22B的基板20B上全部形成光电转换材料层30。光穿过第二电极22B进入光电转换材料层30。或者,光穿过基板20B和第一电极21B进入光电 转换材料层30。具体而言,基板20B由例如硅半导体基板形成,并且第一电极21B和第二电极22B由金属材料或透明导电材料形成。除这一点外,实施例3的光电转换元件13的构造和结构可与实施例1的光电转换元件11的构造和结构相似,并因此略去详细的解释。
已基于优选的实施例在上文中对本发明进行了解释,但是本发明并不应视为限于这些实施例。实施例中所解释的光电转换元件、固体摄像装置的结构和构造、生产条件、生产方法和使用的材料是用于示例并可进行适当变化。光电转换材料层可由一种含偶氮部分的噻唑化合物构成,或者可由多种含偶氮部分的噻唑化合物的混合产物构成。或者,光电转换材料层可由多个层形成,并且各光电转换材料层可由不同的含偶氮部分的噻唑化合物构成。或者,具有层叠光电转换元件(光接收区域)的结构(即,其中的子像素层叠的结构)的固体摄像装置可通过如下步骤得到:将实施例1所述的光电转换元件设置在例如硅半导体基板上,然后将一层或多层(例如2层)的光电转换区域设置在硅半导体基板内,所述硅半导体基板位于光电转换元件之下。在此类固体摄像装置中,例如通过实施例1所述的光电转换元件可接收蓝光,通过将一层或多层的光电转换区域设置在硅半导体基板内可接收其它颜色的光。此外,除了将光电转换区域设置在硅半导体基板内,光电转换区域可通过外延生长法(epitaxial growth)在半导体基板上形成,或者可在所谓的SOI结构中的硅层上形成。当本发明的光电转换元件将作为太阳能电池起作用时,仅需要在电压未被施加至第一电极和第二电极的间隙的状态下用光照射光电转换材料。
符号说明
11…光电转换元件;20…基板;21…第一电极;22…第二电极;30…光电转换材料层;31…凸部;40…固体摄像装置;41…摄像区域;42…垂直驱动电路;43…列信号处理电路;44…水平驱动电路;45…输出电路;46…控制电路;47…垂直信号线;48…水平信号线 。
Claims (8)
2.如权利要求1所述的光电转换元件,其中,X和Y各自表示除氢原子以外的取代基时,所述取代基选自于由如下基团所组成的组:烷基基团、环烷基基团、烯基基团、炔基基团、芳基基团、芳基烷基基团、芳香族杂环、杂环基团、烷氧基基团、环烷氧基基团、芳基氧基基团、烷基硫基基团、环烷基硫基基团、芳基硫基基团、烷氧基羰基基团、芳基氧基羰基基团、氨磺酰基基团、酰基基团、硫代羰基基团、酰基氧基基团、酰胺基基团、氨甲酰基基团、脲基基团、亚硫酰基基团、烷基磺酰基基团、芳基磺酰基基团、氨基基团、卤素原子、氟代烃基团、氰基基团、异氰基基团、硝基基团、亚硝基基团、羧酸氰化物基团、氰酸根基团、异氰酸根基团、硫代氰酸根基团、异硫代氰酸根基团、甲酰基基团、硫代甲酰基基团、酰肼基团、羟基基团、硫烷基基团、磺基基团和甲硅烷基基团。
3.一种光电转换元件,所述光电转换元件包含:
(a-1)彼此分开设置的第一电极和第二电极;以及
(a-2)设置在所述第一电极和所述第二电极间的光电转换材料层,
其中,所述光电转换材料层由下述结构式(2)所示的含偶氮部分的噻唑化合物形成:
其中,X和Y各自表示氢原子或除氢原子以外的取代基,并且R2至R6中的至少一个表示除氢原子以外的取代基。
4.如权利要求3所述的光电转换元件,其中,R2至R6中的至少一个表示如下基团:烷基基团、环烷基基团、烯基基团、炔基基团、芳基基团、芳基烷基基团、芳香族杂环、杂环基团、烷氧基基团、环烷氧基基团、芳基氧基基团、烷基硫基基团、环烷基硫基基团、芳基硫基基团、烷氧基羰基基团、芳基氧基羰基基团、氨磺酰基基团、酰基基团、硫代羰基基团、酰基氧基基团、酰胺基基团、氨甲酰基基团、脲基基团、亚硫酰基基团、烷基磺酰基基团、芳基磺酰基基团、氨基基团、卤素原子、氟代烃基团、氰基基团、异氰基基团、硝基基团、亚硝基基团、羧酸氰化物基团、氰酸根基团、异氰酸根基团、硫代氰酸根基团、异硫代氰酸根基团、甲酰基基团、硫代甲酰基基团、酰肼基团、羟基基团、硫烷基基团、磺基基团或甲硅烷基基团。
5.如权利要求3或4所述的光电转换元件,其中,X和Y各自表示除氢原子以外的取代基时,所述取代基选自于由如下基团所组成的组:烷基基团、环烷基基团、烯基基团、炔基基团、芳基基团、芳基烷基基团、芳香族杂环、杂环基团、烷氧基基团、环烷氧基基团、芳基氧基基团、烷基硫基基团、环烷基硫基基团、芳基硫基基团、烷氧基羰基基团、芳基氧基羰基基团、氨磺酰基基团、酰基基团、硫代羰基基团、酰基氧基基团、酰胺基基团、氨甲酰基基团、脲基基团、亚硫酰基基团、烷基磺酰基基团、芳基磺酰基基团、氨基基团、卤素原子、氟代烃基团、氰基基团、异氰基基团、硝基基团、亚硝基基团、羧酸氰化物基团、氰酸根基团、异氰酸根基团、硫代氰酸根基团、异硫代氰酸根基团、甲酰基基团、硫代甲酰基基团、酰肼基团、羟基基团、硫烷基基团、磺基基团和甲硅烷基基团。
6.如权利要求1-5中任一项所述的光电转换元件,其中,光入射侧的电极由透明导电材料形成。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007311647A (ja) * | 2006-05-19 | 2007-11-29 | Fujifilm Corp | 固体撮像素子 |
CN101645454A (zh) * | 2008-08-05 | 2010-02-10 | 索尼株式会社 | 光电转换器和光电转换元件 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2417502C (en) * | 2000-07-27 | 2012-01-10 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
JP2003092417A (ja) * | 2001-09-18 | 2003-03-28 | Seiko Epson Corp | 光電変換素子 |
JP5022573B2 (ja) | 2005-06-02 | 2012-09-12 | 富士フイルム株式会社 | 光電変換素子、及び撮像素子、並びに、これらに電場を印加する方法 |
JP4677314B2 (ja) | 2005-09-20 | 2011-04-27 | 富士フイルム株式会社 | センサーおよび有機光電変換素子の駆動方法 |
JP4914597B2 (ja) | 2005-10-31 | 2012-04-11 | 富士フイルム株式会社 | 光電変換素子及び撮像素子、並びに、これらに電場を印加する方法 |
JP2007305875A (ja) * | 2006-05-12 | 2007-11-22 | Matsushita Electric Ind Co Ltd | 基板及びこれを用いた太陽電池 |
JP2007327834A (ja) * | 2006-06-07 | 2007-12-20 | Aloka Co Ltd | ラック認識装置 |
DE102006035035A1 (de) | 2006-07-28 | 2008-01-31 | Merck Patent Gmbh | Neue Materialien für organische Elektrolumineszenzvorrichtungen |
DE102006059369A1 (de) * | 2006-12-15 | 2008-06-26 | Industrial Technology Research Institute, Chutung | Fotoelement |
JP2009029746A (ja) | 2007-07-27 | 2009-02-12 | Sony Corp | 有機材料および半導体装置 |
JP5470935B2 (ja) | 2008-05-26 | 2014-04-16 | ソニー株式会社 | ジオキサアンタントレン系化合物及び半導体装置 |
JP5640310B2 (ja) * | 2008-09-12 | 2014-12-17 | 三菱化学株式会社 | 組成物、反射防止膜基板、並びに、太陽電池システム |
FR2939239B1 (fr) * | 2008-12-03 | 2010-12-31 | Ecole Polytech | Module photovoltaique comprenant une electrode transparente conductrice d'epaisseur variable et procedes de fabrication d'un tel module |
JP5454394B2 (ja) | 2010-07-09 | 2014-03-26 | ソニー株式会社 | 光電変換素子及び固体撮像装置 |
-
2010
- 2010-07-09 JP JP2010156642A patent/JP2012019131A/ja active Pending
-
2011
- 2011-04-25 US US13/808,014 patent/US8963142B2/en active Active
- 2011-04-25 WO PCT/JP2011/060566 patent/WO2012005048A1/ja active Application Filing
- 2011-04-25 KR KR1020137000020A patent/KR20130020824A/ko not_active Application Discontinuation
- 2011-04-25 EP EP11803384.4A patent/EP2592669A4/en not_active Withdrawn
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007311647A (ja) * | 2006-05-19 | 2007-11-29 | Fujifilm Corp | 固体撮像素子 |
CN101645454A (zh) * | 2008-08-05 | 2010-02-10 | 索尼株式会社 | 光电转换器和光电转换元件 |
Non-Patent Citations (1)
Title |
---|
KATSUJI HIGASHINO ET AL.: "Photovoltaic properties of azo compounds containing the thiazole group", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A:CHEMISTRY》, vol. 79, no. 12, 1 April 1994 (1994-04-01), pages 81 - 88, XP055070471, DOI: doi:10.1016/1010-6030(94)87017-9 * |
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CN103003974B (zh) | 2016-06-22 |
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US8963142B2 (en) | 2015-02-24 |
EP2592669A1 (en) | 2013-05-15 |
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