TWI611594B - Photoelectric conversion element, image capture element, optical sensor - Google Patents
Photoelectric conversion element, image capture element, optical sensor Download PDFInfo
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- TWI611594B TWI611594B TW102134566A TW102134566A TWI611594B TW I611594 B TWI611594 B TW I611594B TW 102134566 A TW102134566 A TW 102134566A TW 102134566 A TW102134566 A TW 102134566A TW I611594 B TWI611594 B TW I611594B
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- Prior art keywords
- photoelectric conversion
- group
- compound
- film
- conversion element
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- SIFIMQMTABTXMD-UHFFFAOYSA-N silylphosphonic acid Chemical compound OP(O)([SiH3])=O SIFIMQMTABTXMD-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000006836 terphenylene group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VELSFHQDWXAPNK-UHFFFAOYSA-N tetracontacyclo[25.6.5.516,28.44,32.35,11.321,34.28,10.212,15.222,35.229,31.113,20.124,38.02,6.014,19.017,25.018,23.030,37.033,36.547,54.446,53.448,58.126,51.150,52.03,45.07,42.09,61.039,40.041,43.044,63.049,76.055,78.056,62.057,68.059,64.060,67.065,69.066,71.070,73.072,75.074,77]octaheptaconta-1,3(45),4(48),5(61),6,8,10,12,14,16,18,20,22,24(39),25,27(38),28,30,32,34(42),35(40),36,41(43),44(63),46,49(76),50(77),51,53,55(78),56(62),57,59,64,66,68,70(73),71,74-nonatriacontaene Chemical compound c12c3c4c5c6c1c1c7c8c2c2c3c3c9c4c4c5c5c%10c%11c%12c%13c%14c%15c%12c%12c%16c%17c%18c%19c%20c%21c%17c%17c%22c%21c%21c%23c%20c%20c%19c%19c%24c%18c%16c%15c%15c%24c%16c(c7c%15c%14c1c6c5%13)c8c1c2c2c3c3c(c%21c5c%22c(c%11c%12%17)c%10c4c5c93)c%23c2c%20c1c%19%16 VELSFHQDWXAPNK-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical group C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical compound C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical group C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- YWBFPKPWMSWWEA-UHFFFAOYSA-O triazolopyrimidine Chemical compound BrC1=CC=CC(C=2N=C3N=CN[N+]3=C(NCC=3C=CN=CC=3)C=2)=C1 YWBFPKPWMSWWEA-UHFFFAOYSA-O 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- C09B3/78—Other dyes in which the anthracene nucleus is condensed with one or more carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
- H10K39/30—Devices controlled by radiation
- H10K39/32—Organic image sensors
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- Electromagnetism (AREA)
- Light Receiving Elements (AREA)
- Solid State Image Pick-Up Elements (AREA)
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Abstract
本發明的目的在於提供包含顯示出優異的耐熱性及響應性的光電轉換膜的光電轉換元件、及包含該光電轉換元件的攝影元件、光感測器。本發明的光電轉換元件是依序積層導電性膜、包含光電轉換材料的光電轉換膜、及透明導電性膜而成的光電轉換元件，光電轉換材料包含選自由通式(1)所表示的化合物、通式(2)所表示的化合物、及通式(3)所表示的化合物所構成的群組的至少一種化合物X。 An object of the present invention is to provide a photoelectric conversion element including a photoelectric conversion film exhibiting excellent heat resistance and responsiveness, and a photographing element and a light sensor including the photoelectric conversion element. The photoelectric conversion element of the present invention is a photoelectric conversion element in which a conductive film, a photoelectric conversion film including a photoelectric conversion material, and a transparent conductive film are sequentially laminated. The photoelectric conversion material includes a compound selected from the group consisting of a compound represented by the general formula (1) At least one compound X of the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3).
Description
本發明是有關於一種光電轉換元件、攝影元件、光感測器。 The invention relates to a photoelectric conversion element, a photographing element, and a light sensor.
現有的光感測器是在矽(Si)等半導體基板中形成有光電二極體(photodiode，PD)的元件，固態攝影元件廣泛使用平面型固態攝影元件，上述平面型固態攝影元件2維地排列PD，藉由電路讀出各PD所產生的訊號電荷。 The existing photo sensor is an element in which a photodiode (PD) is formed on a semiconductor substrate such as silicon (Si). The solid-state imaging element is widely used as a planar solid-state imaging element. The planar solid-state imaging element is two-dimensionally grounded. The PDs are arranged, and the signal charge generated by each PD is read out by the circuit.
為了實現彩色固態攝影元件，一般情況下是在平面型固態攝影元件的光入射面側配置透過特定波長光的彩色濾光片的結構。現在廣泛已知在數位相機等中所廣泛使用的單板式固態攝影元件，其在2維地排列的各PD上規則地配置透過藍色(B)光、綠色(G)光、紅色(R)光的彩色濾光片。 In order to realize a color solid-state imaging element, a color filter that transmits light of a specific wavelength is generally arranged on the light incident surface side of the flat-type solid-state imaging element. A single-plate solid-state imaging element widely used in digital cameras and the like is now widely known, and regularly arranges two PDs arranged in two dimensions to transmit blue (B) light, green (G) light, and red (R) Color filters for light.
在該單板式固態攝影元件中，並未利用未透過彩色濾光片的光，光利用效率差。近年來，在多畫素化的進展中，畫素尺寸變小，開口率(open area ratio)的降低、聚光效率的降低成為問題。 In this single-plate type solid-state imaging element, light that does not pass through a color filter is not used, and light utilization efficiency is poor. In recent years, in the progress of multi-pixelization, the pixel size has become smaller, a decrease in the open area ratio, and a decrease in the light collection efficiency have become problems.
為了解決該些缺點，已知在訊號讀出用基板上形成非晶矽的光電轉換膜或光電轉換膜的結構。 In order to solve these disadvantages, a structure is known in which a photoelectric conversion film or a photoelectric conversion film of amorphous silicon is formed on a signal readout substrate.
關於使用光電轉換膜的光電轉換元件、攝影元件、光感測器，已知有數種公知例。 There are several known examples of a photoelectric conversion element, a photographing element, and a light sensor using a photoelectric conversion film.
例如，在專利文獻1中，在其實施例欄中揭示了包含以下式所表示的化合物(3)等的光電轉換膜，主要記載了其為高光電轉換效率。而且，在專利文獻2及專利文獻3中亦揭示了包含二酮基吡咯并吡咯化合物的光電轉換元件。 For example, in Patent Document 1, a photoelectric conversion film containing a compound (3) and the like represented by the following formula is disclosed in the Example column, and it is mainly described that it has a high photoelectric conversion efficiency. In addition, Patent Documents 2 and 3 also disclose photoelectric conversion elements containing a diketopyrrolopyrrole compound.
[先前技術文獻] [Prior technical literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2006-339424號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2006-339424
[專利文獻2]日本專利特開2010-192782號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2010-192782
[專利文獻3]日本專利特開2003-346926號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2003-346926
近年來，隨著攝影元件或光感測器等的性能提高的要 求，關於該些中所使用的光電轉換膜所要求的耐熱性及響應速度等諸特性，亦要求其等提高。例如，在將光電轉換元件應用於攝影元件或光電池等各種用途中的情況下，自製程適合，性的方面考慮，要求光電轉換元件顯示出高的耐熱性。更具體而言，作為形成攝影元件的情況下的製程，存在許多實施加熱處理的步驟(設置彩色濾光片、設置保護膜、焊接元件等)，要求光電轉換元件即使經過該些步驟亦顯示出優異的特性(響應速度、低暗電流特性等)。 In recent years, as the performance of photographic elements, light sensors, etc. has improved, It is also required to improve various characteristics such as heat resistance and response speed required for the photoelectric conversion films used in these. For example, when the photoelectric conversion element is used in various applications such as a photographic element or a photovoltaic cell, the self-made process is suitable, and in terms of performance, the photoelectric conversion element is required to exhibit high heat resistance. More specifically, as a process for forming a photographic element, there are many steps for performing a heat treatment (setting a color filter, providing a protective film, a soldering element, and the like), and the photoelectric conversion element is required to show even after these steps. Excellent characteristics (response speed, low dark current characteristics, etc.).
本發明者等人使用專利文獻1~專利文獻3中所具體地揭示的化合物(例如上述化合物3)而進行光電轉換膜的製作，結果發現在耐熱性及響應速度的方面未必達到最近所要求的水準，需要進一步的提高。 The inventors of the present invention used the compounds specifically disclosed in Patent Documents 1 to 3 (for example, the above-mentioned Compound 3) to produce a photoelectric conversion film. As a result, they found that the heat resistance and response speed did not necessarily reach the recently required The level needs to be further improved.
本發明的目的在於鑒於上述事實而提供一種光電轉換元件，該光電轉換元件包含顯示出優異的耐熱性及響應性的光電轉換膜。 An object of the present invention is to provide a photoelectric conversion element including a photoelectric conversion film exhibiting excellent heat resistance and responsiveness in view of the above-mentioned facts.
而且，本發明的目的亦在於提供包含光電轉換元件的攝影元件及光感測器。 It is another object of the present invention to provide a photographing element and a light sensor including a photoelectric conversion element.
本發明者等人對上述課題進行了努力研究，結果發現藉由如下方式可解決上述課題，從而完成本發明：在光電轉換膜中所含的二酮基吡咯并吡咯化合物、或在二酮基吡咯并吡咯的兩個吡咯環之間進一步縮環有芳香環而成的化合物的規定位置導入含有芳香族環的胺基。 The present inventors made diligent research on the above-mentioned problems, and as a result, they found that the above-mentioned problems can be solved by the following methods: the diketopyrrolopyrrole compound contained in the photoelectric conversion film, or the An aromatic ring-containing amine group is introduced into a predetermined position of a compound in which an aromatic ring is further condensed between two pyrrole rings of a pyrrolopyrrole.
亦即，藉由以下所示之手段可解決上述課題。 That is, the above-mentioned problems can be solved by the means shown below.
(1)一種光電轉換元件，其是依序積層導電性膜、包含光電轉換材料的光電轉換膜、及透明導電性膜而成的光電轉換元件，光電轉換材料包含選自由後述的通式(1)所表示的化合物、後述的通式(2)所表示的化合物、及後述的通式(3)所表示的化合物所構成的群組的至少一種化合物X。 (1) A photoelectric conversion element, which is a photoelectric conversion element in which a conductive film, a photoelectric conversion film including a photoelectric conversion material, and a transparent conductive film are sequentially laminated, and the photoelectric conversion material includes a component selected from a general formula (1) described later. At least one compound X of the group consisting of a compound represented by), a compound represented by general formula (2) described later, and a compound represented by general formula (3) described later.
(2)如(1)所述之光電轉換元件，其中，化合物X是後述的通式(4)所表示的化合物。 (2) The photoelectric conversion element according to (1), wherein the compound X is a compound represented by the general formula (4) described later.
(3)如(1)或(2)所述之光電轉換元件，其中，Ar1與R11、Ar1與R12、R11與R12、Ar2與R13、Ar2與R14、及R13與R14的至少一者分別相互鍵結而形成環。 (3) The photoelectric conversion element according to (1) or (2), wherein Ar 1 and R 11 , Ar 1 and R 12 , R 11 and R 12 , Ar 2 and R 13 , Ar 2 and R 14 , And at least one of R 13 and R 14 is bonded to each other to form a ring.
(4)如(1)~(3)中任一項所述之光電轉換元件，其中，X1及X2為O。 (4) The photoelectric conversion element according to any one of (1) to (3), wherein X 1 and X 2 are O.
(5)如(1)~(4)中任一項所述之光電轉換元件，其中，光電轉換膜進一步包含有機n型化合物。 (5) The photoelectric conversion element according to any one of (1) to (4), wherein the photoelectric conversion film further contains an organic n-type compound.
(6)如(5)所述之光電轉換元件，其中，有機n型化合物包含富勒烯類，上述富勒烯類包含富勒烯及其衍生物。 (6) The photoelectric conversion element according to (5), wherein the organic n-type compound includes fullerenes, and the fullerenes include fullerenes and derivatives thereof.
(7)如(6)所述之光電轉換元件，其中，化合物X與富勒烯類的莫耳比(富勒烯類的莫耳量/化合物X的莫耳量)為1.0以上。 (7) The photoelectric conversion element according to (6), wherein the molar ratio of the compound X to the fullerenes (the molar amount of the fullerenes / the molar amount of the compound X) is 1.0 or more.
(8)如(1)~(7)中任一項所述之光電轉換元件，其中， 在導電性膜與透明導電性膜之間配置電荷阻斷膜。 (8) The photoelectric conversion element according to any one of (1) to (7), wherein A charge blocking film is disposed between the conductive film and the transparent conductive film.
(9)一種攝影元件，其包含如(1)~(8)中任一項所述之光電轉換元件。 (9) A photographic element including the photoelectric conversion element according to any one of (1) to (8).
(10)一種光感測器，其包含如(1)~(8)中任一項所述之光電轉換元件。 (10) A light sensor including the photoelectric conversion element according to any one of (1) to (8).
藉由本發明可提供包含顯示出優異的耐熱性及響應性的光電轉換膜的光電轉換元件。 According to the present invention, a photoelectric conversion element including a photoelectric conversion film exhibiting excellent heat resistance and responsiveness can be provided.
而且，藉由本發明可提供包含光電轉換元件的攝影元件及光感測器。 Furthermore, the present invention can provide a photographing element and a light sensor including a photoelectric conversion element.
10a、10b‧‧‧光電轉換元件 10a, 10b ‧‧‧ photoelectric conversion element
11‧‧‧下部電極(導電性膜) 11‧‧‧Lower electrode (conductive film)
12‧‧‧光電轉換膜 12‧‧‧photoelectric conversion film
15‧‧‧上部電極(透明導電性膜) 15‧‧‧upper electrode (transparent conductive film)
16A‧‧‧電子阻斷膜 16A‧‧‧Electronic blocking film
16B‧‧‧電洞阻斷膜 16B‧‧‧hole blocking film
100‧‧‧攝影元件 100‧‧‧Photographic element
101‧‧‧基板 101‧‧‧ substrate
102‧‧‧絕緣層 102‧‧‧ Insulation
103‧‧‧連接電極 103‧‧‧ connecting electrode
104‧‧‧畫素電極(下部電極) 104‧‧‧pixel electrode (lower electrode)
105‧‧‧連接部 105‧‧‧Connection Department
106‧‧‧連接部 106‧‧‧Connection Department
107‧‧‧光電轉換膜 107‧‧‧photoelectric conversion film
108‧‧‧對向電極(上部電極) 108‧‧‧ Counter electrode (upper electrode)
109‧‧‧緩衝層 109‧‧‧Buffer layer
110‧‧‧密封層 110‧‧‧Sealing layer
111‧‧‧彩色濾光片(CF) 111‧‧‧ Color Filter (CF)
112‧‧‧隔板 112‧‧‧ partition
113‧‧‧遮光層 113‧‧‧Light-shielding layer
114‧‧‧保護層 114‧‧‧ protective layer
115‧‧‧對向電極電壓供給部 115‧‧‧ Counter electrode voltage supply unit
116‧‧‧讀出電路 116‧‧‧readout circuit
圖1(a)及圖1(b)是分別示意性表示光電轉換元件的一構成例的剖面圖。 1 (a) and 1 (b) are cross-sectional views each schematically showing a configuration example of a photoelectric conversion element.
圖2是攝影元件的1畫素份的示意性剖面圖。 FIG. 2 is a schematic cross-sectional view of one pixel of a photographing element.
以下，對本發明的光電轉換元件的適宜的實施方式加以說明。 Hereinafter, preferred embodiments of the photoelectric conversion element of the present invention will be described.
首先，對本發明的與現有技術相比較而具有的特徵點加以詳述。 First, the features of the present invention which are compared with the prior art will be described in detail.
如上所述，發現在本發明中，藉由在光電轉換膜中所含的二酮基吡咯并吡咯化合物、或在二酮基吡咯并吡咯的兩個吡咯環之 間進一步縮環有芳香環而成的化合物中的規定位置導入含有芳香族環的胺基，可獲得所期望的效果。推測藉由導入此種含有芳香族環的胺基，所使用的化合物的分子量變大且化合物間的相互作用適度地變大，且藉由導入大量的環結構而使分子的自由度降低，其結果耐熱性提高。而且，推測藉由導入含有芳香族環的胺基，可穩定地保持電洞的骨架突出至分子的外側，分子間的電洞的交換變容易，其結果響應速度提高。 As described above, in the present invention, it has been found that by using a diketopyrrolopyrrole compound contained in a photoelectric conversion film or two pyrrole rings of a diketopyrrolopyrrole A desired effect can be obtained by introducing an amine group containing an aromatic ring at a predetermined position in a compound having an aromatic ring that is further condensed in between. It is speculated that by introducing such an aromatic ring-containing amine group, the molecular weight of the compound used is increased and the interaction between the compounds is moderately increased, and the degree of freedom of the molecule is reduced by the introduction of a large number of ring structures. As a result, heat resistance is improved. Furthermore, it is estimated that by introducing an amine group containing an aromatic ring, the skeleton of the hole can be stably held to protrude to the outside of the molecule, the exchange of holes between the molecules is facilitated, and as a result, the response speed is improved.
以下，參照圖式對本發明的光電轉換元件的適宜的實施方式加以說明。在圖1(a)及圖1(b)中示意性表示本發明的光電轉換元件的一實施方式的剖面圖。 Hereinafter, preferred embodiments of the photoelectric conversion element of the present invention will be described with reference to the drawings. 1 (a) and 1 (b) are cross-sectional views schematically showing an embodiment of a photoelectric conversion element according to the present invention.
圖1(a)中所示的光電轉換元件10a具有依序積層有如下者的構成：作為下部電極而發揮功能的導電性膜(以下亦記為下部電極)11、形成在下部電極11上的電子阻斷膜16A、形成在電子阻斷膜16A上的光電轉換膜12、作為上部電極而發揮功能的透明導電性膜(以下亦記為上部電極)15。 The photoelectric conversion element 10 a shown in FIG. 1 (a) has a structure in which a conductive film (hereinafter also referred to as a lower electrode) 11 that functions as a lower electrode is sequentially laminated, and a layer formed on the lower electrode 11 is formed. The electron blocking film 16A, the photoelectric conversion film 12 formed on the electron blocking film 16A, and a transparent conductive film (hereinafter also referred to as an upper electrode) 15 functioning as an upper electrode.
在圖1(b)中表示其他光電轉換元件的構成例。圖1(b)中所示的光電轉換元件10b具有在下部電極11上依序積層有電子阻斷膜16A、光電轉換膜12、電洞阻斷膜16B、上部電極15的構成。 另外，圖1(a)、圖1(b)中的電子阻斷膜16A、光電轉換膜12、電洞阻斷膜16B的積層順序亦可根據用途、特性而相反。例如，亦可使電子阻斷膜16A與光電轉換膜12的位置相反。 FIG. 1 (b) shows a configuration example of another photoelectric conversion element. The photoelectric conversion element 10 b shown in FIG. 1 (b) has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are sequentially laminated on the lower electrode 11. In addition, the lamination order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 (a) and 1 (b) may be reversed depending on the application and characteristics. For example, the positions of the electron blocking film 16A and the photoelectric conversion film 12 may be reversed.
在光電轉換元件10a(10b)的構成中，較佳的是經由透 明導電性膜15而使光入射至光電轉換膜12中。 In the configuration of the photoelectric conversion element 10a (10b), it is preferable that The conductive film 15 is illuminated so that light is incident on the photoelectric conversion film 12.
而且，在使用光電轉換元件10a(10b)的情況下，可施加電場。在這種情況下，使導電性膜11與透明導電性膜15成為一對電極，較佳的是在該一對電極間施加1×10-5V/cm~1×107V/cm的電場。自性能及消耗電力的觀點考慮，較佳的是1×10-4V/cm~1×106V/cm的電場，特佳的是1×10-3V/cm~5×105V/cm的電場。 Furthermore, when the photoelectric conversion element 10a (10b) is used, an electric field can be applied. In this case, the conductive film 11 and the transparent conductive film 15 are used as a pair of electrodes. It is preferable to apply a voltage of 1 × 10 -5 V / cm to 1 × 10 7 V / cm between the pair of electrodes. electric field. From the viewpoint of performance and power consumption, an electric field of 1 × 10 -4 V / cm to 1 × 10 6 V / cm is preferable, and 1 × 10 -3 V / cm to 5 × 10 5 V is particularly preferable. / cm of electric field.
另外，關於電壓施加方法，在圖1(a)及圖1(b)中，以電子阻斷膜16A側成為陰極，光電轉換膜12側成為陽極的方式進行施加。在使用光電轉換元件10a(10b)作為光感測器的情況下，而且在內裝至攝影元件中的情況下亦可藉由同樣的方法施加電壓。 The voltage application method is applied so that the electron blocking film 16A side becomes a cathode and the photoelectric conversion film 12 side becomes an anode in FIGS. 1 (a) and 1 (b). In the case where the photoelectric conversion element 10a (10b) is used as a light sensor, and when it is incorporated in a photographing element, a voltage can be applied by the same method.
以下，對構成光電轉換元件10a(10b)的各層(光電轉換膜12、電子阻斷膜16A、下部電極11、上部電極15、電洞阻斷膜16B等)的形態加以詳述。 Hereinafter, the form of each layer (the photoelectric conversion film 12, the electron blocking film 16A, the lower electrode 11, the upper electrode 15, the hole blocking film 16B, etc.) constituting the photoelectric conversion element 10a (10b) will be described in detail.
首先，對光電轉換膜12加以詳述。 First, the photoelectric conversion film 12 will be described in detail.
[光電轉換膜] [Photoelectric conversion film]
光電轉換膜12是包含選自由後述的通式(1)所表示的化合物、後述的通式(2)所表示的化合物、及後述的通式(3)所表示的化合物所構成的群組的至少1種化合物X來作為光電轉換材料的膜。藉由使用該化合物X而獲得顯示出優異的耐熱性及高速響應性的光電轉換膜。 The photoelectric conversion film 12 is selected from the group consisting of a compound represented by the general formula (1) described later, a compound represented by the general formula (2) described later, and a compound represented by the general formula (3) described later. At least one compound X is used as a film of a photoelectric conversion material. By using this compound X, a photoelectric conversion film exhibiting excellent heat resistance and high-speed response is obtained.
首先，對光電轉換膜12中所使用的通式(1)~通式(3)所 表示的化合物加以詳述。 First, the general formula (1) to the general formula (3) used in the photoelectric conversion film 12 The compounds represented are detailed.
通式(1)~通式(3)中，R1及R2分別獨立地表示烷基、芳基、或雜芳基。其中，自合成容易、光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，較佳的是烷基。 In the general formulae (1) to (3), R 1 and R 2 each independently represent an alkyl group, an aryl group, or a heteroaryl group. Among them, an alkyl group is preferred in terms of ease of synthesis and more excellent properties (heat resistance and responsiveness) of the photoelectric conversion film.
烷基中的碳數並無特別限制，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，較佳的是1~10，更佳的是1~6，進一步更佳的是1~3。烷基可為直鏈狀、分支狀、環狀中的任一結構。 The number of carbons in the alkyl group is not particularly limited, and from the viewpoint of more excellent characteristics (heat resistance and responsiveness) of the photoelectric conversion film, it is preferably 1 to 10, more preferably 1 to 6, and even more preferably It's 1 ~ 3. The alkyl group may have any of a linear structure, a branched structure, and a cyclic structure.
作為烷基而較佳之基例如可列舉甲基、乙基、正丙基、正丁基、正己基等。 Preferred examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, and n-hexyl.
芳基中的碳數並無特別限制，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，較佳的是6~30，更佳的是6~18。芳基可為單環結構，亦可為2個環以上的環縮環而成的縮合環結構，亦可具有後述的取代基W。 The number of carbon atoms in the aryl group is not particularly limited, and from the viewpoint of better characteristics (heat resistance and responsiveness) of the photoelectric conversion film, it is preferably 6 to 30, and more preferably 6 to 18. The aryl group may have a single ring structure, or a condensed ring structure formed by condensing two or more rings, and may have a substituent W described later.
芳基例如可列舉苯基、萘基、蒽基、芘基、菲基、甲基苯基、二甲基苯基、聯苯基、茀基等，較佳的是苯基、萘基、或蒽基。 Examples of the aryl group include phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, methylphenyl, dimethylphenyl, biphenyl, and fluorenyl. Phenyl, naphthyl, or Anthracenyl.
雜芳基(1價芳香族雜環基)中的碳數並無特別限制，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，較佳的是3~30，更佳的是3~18。雜芳基亦可具有後述的取代基W。 The number of carbon atoms in the heteroaryl group (monovalent aromatic heterocyclic group) is not particularly limited, and from the viewpoint of better characteristics (heat resistance and responsiveness) of the photoelectric conversion film, it is preferably 3 to 30, more The best is 3 ~ 18. The heteroaryl group may have a substituent W described later.
在雜芳基中除了碳原子及氫原子以外亦包含雜原子，雜原子例如可列舉氮原子、硫原子、氧原子、硒原子、碲原子、磷原子、矽原子、或硼原子，較佳的是氮原子、硫原子、或氧原子。雜芳基中所含的雜原子數並無特別限制，通常為1個~10個左右，較佳的是1個~4個。 Heteroaryl groups also include heteroatoms in addition to carbon and hydrogen atoms. Examples of the heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, or boron. It is a nitrogen atom, a sulfur atom, or an oxygen atom. The number of heteroatoms contained in the heteroaryl group is not particularly limited, but is usually about 1 to 10, and preferably 1 to 4.
雜芳基的環員數並無特別限制，較佳的是3員環~8員環，進一步更佳的是5員環~7員環，特佳的是5員環~6員環。 The number of ring members of a heteroaryl group is not particularly limited. A 3-membered ring to a 8-membered ring is preferred, a 5-membered ring to a 7-membered ring is even more preferred, and a 5-membered to 6-membered ring is particularly preferred.
雜芳基例如可列舉吡啶基、喹啉基、異喹啉基、吖啶基、啡啶基(phenanthridinyl)、喋啶基(pteridinyl)、吡嗪基、喹噁啉基(quinoxalinyl)、嘧啶基、喹唑啉基、噠嗪基、噌啉基、酞嗪基、三嗪基、噁唑基、苯并噁唑基、噻唑基、苯并噻唑基、咪唑基、苯并咪唑基、吡唑基、吲唑基、異噁唑基、苯并異噁唑基、異噻唑基、苯并異噻唑基、噁二唑基、噻二唑基、***基、四唑基、呋喃基、苯并呋喃基、噻吩基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、吡咯基、吲哚基、咪唑并吡啶基、咔唑基等。 Examples of the heteroaryl group include pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, pteridinyl, pyrazinyl, quinoxalinyl, and pyrimidinyl , Quinazolinyl, pyridazinyl, fluorenyl, phthalazinyl, triazinyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, imidazolyl, benzimidazolyl, pyrazole Base, indazolyl, isoxazolyl, benzoisoxazolyl, isothiazolyl, benzoisothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, furanyl, benzene Benzofuryl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, pyrrolyl, indolyl, imidazopyridyl, carbazolyl, and the like.
對本說明書中的取代基W加以記載。 The substituent W in this specification is described.
取代基W可列舉鹵素原子、烷基(包含環烷基、雙環烷基、 三環烷基)、烯基(包含環烯基、雙環烯基)、炔基、芳基、雜環基(亦可記載為雜環基)、氰基、羥基、硝基、羧基、烷氧基、芳氧基、矽烷氧基、雜環氧基、醯氧基、胺甲醯基氧基、烷氧基羰氧基、芳氧基羰氧基、胺基(包含苯胺基)、銨基、醯基胺基、胺基羰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、胺磺醯基胺基、烷基或芳基磺醯基胺基、巰基、烷硫基、芳硫基、雜環硫基、胺磺醯基、磺基、烷基或芳基亞磺醯基、烷基或芳基磺醯基、醯基、芳氧基羰基、烷氧基羰基、胺甲醯基、芳基或雜環偶氮基、醯亞胺基、膦基(phosphino)、氧膦基(phosphinyl)、氧膦基氧基、氧膦基胺基、膦醯基(phosphono)、矽烷基、肼基、脲基、硼酸基(-B(OH)2)、磷酸基(phosphato)(-OPO(OH)2)、硫酸基(sulfato)(-OSO3H)、其他公知的取代基。 Examples of the substituent W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group, a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group (also (Can be described as heterocyclyl), cyano, hydroxyl, nitro, carboxyl, alkoxy, aryloxy, silyloxy, heterocyclooxy, fluorenyloxy, carbamateoxy, alkoxycarbonyl Oxy, aryloxycarbonyloxy, amine (including aniline), ammonium, fluorenylamino, aminecarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoyl Amine, alkyl, or arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclicthio, sulfamoyl, sulfo, alkyl, or arylsulfinyl, alkyl, or Arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl or heterocyclic azo, phosphoimino, phosphino, phosphinoyl , Phosphinyloxy, phosphinylamino, phosphono, silane, hydrazine, urea, borate (-B (OH) 2 ), phosphate (-OPO (OH () 2), sulfate (sulfato) - OSO 3 H) , take other well-known Groups.
另外，關於取代基W的詳細，在日本專利特開2007-234651號公報的段落[0023]中有所記載。 The details of the substituent W are described in paragraph [0023] of Japanese Patent Laid-Open No. 2007-234651.
R11、R12、R13及R14分別獨立地表示烷基、芳基或雜芳基。另外，R11及R12的至少一方、以及R13及R14的至少一方表示芳基或雜芳基。其中，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，R11、R12、R13及R14較佳的是芳基。 R 11 , R 12 , R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group. In addition, at least one of R 11 and R 12 and at least one of R 13 and R 14 each represent an aryl group or a heteroaryl group. Among these, R 11 , R 12 , R 13, and R 14 are preferably an aryl group, from the viewpoint that the characteristics (heat resistance and responsiveness) of the photoelectric conversion film are more excellent.
R11、R12、R13及R14所表示的烷基、芳基及雜芳基的定義及適宜形態與上述R1及R2所表示的烷基、芳基及雜芳基的定義及適宜形態相同。 R 11, R 12, R 13, and Definition of a suitable shape alkyl, aryl, and heteroaryl groups represented by R 14 to R 1 and the above-described alkyl group, aryl group and heteroaryl group represented by R 2 are defined and The appropriate shape is the same.
Ar1及Ar2分別獨立地表示伸芳基或伸雜芳基。其中， 自光電轉換膜的特性(耐熱性及響應性)更優異的方而而言，Ar1及Ar2較佳的是伸芳基。 Ar 1 and Ar 2 each independently represent an arylene group or an arylene group. Among them, Ar 1 and Ar 2 are preferably an arylene group from the viewpoint that the characteristics (heat resistance and responsiveness) of the photoelectric conversion film are more excellent.
伸芳基中的碳數並無特別限制，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，較佳的是6~30，更佳的是6~20。 The number of carbons in the arylidene group is not particularly limited, and from the viewpoint of better characteristics (heat resistance and responsiveness) of the photoelectric conversion film, it is preferably 6 to 30, and more preferably 6 to 20.
伸芳基例如可列舉伸苯基、伸聯苯基(biphenylene)、伸聯三苯基(terphenylene)、伸萘基、伸蒽基、伸菲基、芘二基、苝二基、茀二基、
伸雜芳基中的碳數並無特別限制，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，較佳的是1~20，更佳的是2~12。 The number of carbons in the extended heteroaryl group is not particularly limited, and from the viewpoint of more excellent characteristics (heat resistance and responsiveness) of the photoelectric conversion film, it is preferably 1 to 20, and more preferably 2 to 12.
伸雜芳基例如可列舉伸吡啶基、伸喹啉基、伸異喹啉基、吖啶二基、啡啶二基、吡嗪二基、喹噁啉二基、嘧啶二基、三嗪二基、咪唑二基、吡唑二基、噁二唑二基、***二基、伸呋喃基、伸噻吩基、吡咯二基、吲哚二基、咔唑二基等。 Examples of the extended heteroaryl group include extended pyridyl, extended quinolinyl, extended isoquinolinyl, acridine diyl, morphinyl diyl, pyrazine diyl, quinoxaline diyl, pyrimidine diyl, and triazine di Base, imidazole diyl, pyrazole diyl, oxadiazole diyl, triazole diyl, furfuryl, thienyl, pyrrole diyl, indole diyl, carbazole diyl, and the like.
X1及X2分別獨立地表示O(氧原子)、S(硫原子)、或NRA。其中，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，較佳的是O(氧原子)或S(硫原子)，更佳的是O(氧原子)。 X 1 and X 2 each independently represent O (oxygen atom), S (sulfur atom), or NR A. Among these, from the viewpoint that the characteristics (heat resistance and responsiveness) of the photoelectric conversion film are more excellent, O (oxygen atom) or S (sulfur atom) is preferred, and O (oxygen atom) is more preferred.
RA表示烷基、芳基、或雜芳基。其中，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，較佳的是烷基。 R A represents an alkyl group, an aryl group, or a heteroaryl group. Among these, an alkyl group is preferable from the point which the characteristic (heat resistance and responsiveness) of a photoelectric conversion film is more excellent.
RA所表示的烷基、芳基及雜芳基的定義及適宜形態與上述R1 及R2所表示的烷基、芳基及雜芳基的定義及適宜形態相同。 The definitions and suitable forms of the alkyl, aryl, and heteroaryl groups represented by R A are the same as the definitions and suitable forms of the alkyl, aryl, and heteroaryl groups represented by R 1 and R 2 described above.
Q是選自由通式(A)所表示的基、通式(B)所表示的基、通式(C)所表示的基、通式(D)所表示的基、及通式(E)所表示的基所構成的群組的任意一個基。 Q is selected from the group represented by the general formula (A), the group represented by the general formula (B), the group represented by the general formula (C), the group represented by the general formula (D), and the general formula (E) Any one of the groups of the indicated basis.
通式(A)~通式(E)中，RQ1~RQ22分別獨立地表示氫原子或取代基。取代基可列舉上述取代基W，例如可列舉烷基、烷氧基、鹵素原子等。其中，自光電轉換元件的特性(耐熱性或響應性)更優異的方面而言，RQ1~RQ22較佳的是氫原子。 In the general formulae (A) to (E), R Q1 to R Q22 each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W, and examples thereof include an alkyl group, an alkoxy group, and a halogen atom. Among these, R Q1 to R Q22 are more preferably a hydrogen atom from the viewpoint that the characteristics (heat resistance or responsiveness) of the photoelectric conversion element are more excellent.
另外，通式(A)~通式(E)中的*1~*4所表示的碳原子分別與通式(1)~通式(3)中的*1~*4所表示的碳原子對應。更具體而言，以下表示通式(A)~通式(E)所表示的基導入至通式(1)~通式(3)中的Q的情況下的結構式的例子。 In addition, the carbon atoms represented by * 1 to * 4 in the general formulae (A) to (E) and the carbon atoms represented by * 1 to * 4 in the general formulae (1) to (3), respectively. correspond. More specifically, the following is an example of a structural formula when a group represented by the general formula (A) to the general formula (E) is introduced into Q in the general formula (1) to the general formula (3).
[化4]
在通式(1)~通式(3)中，Ar1與R11、Ar1與R12、R11與R12、Ar2與R13、Ar2與R14、R13與R14亦可分別相互鍵結而形成環。另外，在鍵結時，較佳的是Ar1與R11、Ar1與R12、R11與R12、Ar2與R13、Ar2與R14、R13與R14分別相互直接地或經由連結基鍵結而形成環，自光電轉換膜的特性(耐熱性及響應性)更優異的方面而言，更佳的是直接鍵結而形成環。 In the general formulae (1) to (3), Ar 1 and R 11 , Ar 1 and R 12 , R 11 and R 12 , Ar 2 and R 13 , Ar 2 and R 14 , R 13 and R 14 are also They can be bonded to each other to form a ring. In addition, at the time of bonding, it is preferable that Ar 1 and R 11 , Ar 1 and R 12 , R 11 and R 12 , Ar 2 and R 13 , Ar 2 and R 14 , and R 13 and R 14 be directly and directly with each other. Alternatively, a ring is formed through a linking group, and from the viewpoint that the characteristics (heat resistance and responsiveness) of the photoelectric conversion film are more excellent, it is more preferable that the ring is formed by direct bonding.
藉由形成該環結構，通式(1)~通式(3)所表示的化合物的耐熱性提高，可在高溫條件下以高蒸鍍率製造光電轉換元件，另外響應性亦可進一步提高。 By forming this ring structure, the heat resistance of the compounds represented by the general formulae (1) to (3) is improved, and a photoelectric conversion element can be manufactured with a high evaporation rate under high temperature conditions, and the responsiveness can be further improved.
另外，連結基的結構並無特別限制，例如可列舉氧原子、硫原子、伸烷基、亞矽烷基(silylene)、伸烯基、伸環烷基、伸環烯基、伸芳基、2價雜環基、亞胺基、或該些基組合而成的基，該些基亦可進一步具有取代基。較佳的是伸烷基、亞矽烷基、伸烯基、伸環烷基、伸環烯基、伸芳基等。 The structure of the linking group is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, an alkylene group, a silylene group, an alkylene group, a cycloalkylene group, a cycloalkylene group, an alkylene group, A valent heterocyclic group, an imino group, or a combination of these groups, and these groups may further have a substituent. Preferred are alkylene, silylene, alkylene, cycloalkyl, cycloalkenyl, alkylene, and the like.
所形成的環的結構並無特別限制，例如可列舉苯環、萘環、蒽環、菲環、茀環、聯伸三苯(triphenylene)環、稠四苯環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、吲哚嗪環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹嗪環、喹啉環、酞嗪環、萘啶環、喹噁啉環、喹噁唑啉環(quinoxazoline ring)、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環(thianthrene ring)、苯并哌喃環(chromene ring)、二苯并哌喃環(xanthene ring)、啡噁噻環、啡噻嗪環、啡嗪環、環戊烷環、環己烷環、吡咯啶環、哌啶環、四氫呋喃環、四氫吡喃環、四氫噻吩環、四氫噻喃環等。 The structure of the formed ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a thick tetraphenyl ring, a biphenyl ring, a pyrrole ring, and a furan. Ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoxazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzene Benzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, morphine ring, acridine Ring, morpholine ring, thianthrene ring, chromene ring, xanthene ring, phenoxaline ring, phenothiazine ring, morphazine ring, ring A pentane ring, a cyclohexane ring, a pyrrolidine ring, a piperidine ring, a tetrahydrofuran ring, a tetrahydropyran ring, a tetrahydrothiophene ring, a tetrahydrothioan ring, and the like.
另外，較佳的是Ar1與R11、Ar1與R12、及R11與R12中的至少1者分別相互鍵結而形成環，且Ar2與R13、Ar2與R14、及R13與R14中的至少1者分別相互鍵結而形成環。若為此種形態，則光電轉換膜的耐熱性及響應性進一步提高。 In addition, it is preferred that at least one of Ar 1 and R 11 , Ar 1 and R 12 , and R 11 and R 12 be bonded to each other to form a ring, and Ar 2 and R 13 , Ar 2 and R 14 , And at least one of R 13 and R 14 is bonded to each other to form a ring. With this configuration, the heat resistance and responsiveness of the photoelectric conversion film are further improved.
n表示0或1。其中，自光電轉換元件的特性(耐熱性或響應性)更優異的方面而言，較佳的是n為0。 n represents 0 or 1. Among these, from the viewpoint that the characteristics (heat resistance or responsiveness) of the photoelectric conversion element are more excellent, n is preferably 0.
在n為1的情況下，例示上述通式(1A)~通式(3E)所表 示的化合物。 When n is 1, the formula (1A) to the formula (3E) are exemplified. Shown compound.
另外，在n為0的情況下，*1所表示的碳原子與*3所表示的碳原子成為同一碳原子，*2所表示的碳原子與*4所表示的碳原子成為同一碳原子。亦即，在通式(1)~通式(3)中，n=0的情況下，表示以下的通式(4)~通式(6)所表示的化合物。 In addition, when n is 0, the carbon atom represented by * 1 and the carbon atom represented by * 3 become the same carbon atom, and the carbon atom represented by * 2 and the carbon atom represented by * 4 become the same carbon atom. That is, in the general formulae (1) to (3), when n = 0, the compounds represented by the following general formulae (4) to (6) are shown.
另外，通式(4)~通式(6)中的各基的定義如上所述。 The definition of each group in the general formulae (4) to (6) is as described above.
其中，自本發明的效果更優異的方面而言，特佳的是通式(4)所表示的化合物。通式(4)所表示的化合物是所謂的二酮基吡咯并吡咯化合物。 Among them, the compound represented by the general formula (4) is particularly preferable from the viewpoint that the effect of the present invention is more excellent. The compound represented by the general formula (4) is a so-called diketopyrrolopyrrole compound.
以下例示通式(1)~通式(3)所表示的化合物。 The compounds represented by the general formulae (1) to (3) are exemplified below.
[化6]
[化9]
[化17]
[化23]
較佳的是通式(1)~通式(3)所表示的化合物在紫外可見吸收光譜中的400nm以上且不足720nm中具有極大吸收。 自可範圍廣泛地吸收可見區域的光的觀點考慮，吸收光譜的峰值波長(極大吸收波長)更佳的是450nm以上、700nm以下，進一步更佳的是480nm以上、700nm以下，特佳的是510nm以上、680nm以下。 It is preferable that the compounds represented by the general formulae (1) to (3) have a maximum absorption in the ultraviolet-visible absorption spectrum of 400 nm or more and less than 720 nm. From the viewpoint of absorbing light in the visible region in a wide range, the peak wavelength (maximum absorption wavelength) of the absorption spectrum is more preferably 450 nm or more and 700 nm or less, even more preferably 480 nm or more and 700 nm or less, and particularly preferably 510 nm. Above and below 680nm.
化合物的極大吸收波長可使用化合物的氯仿溶液且使用島津製作所公司製造的UV-2550而測定。氯仿溶液的濃度較佳的是5×10-5mol/l~1×10-7mol/l，更佳的是3×10-5mol/l~2×10-6mol/l，特佳的是2×10-5mol/l~5×10-6mol/l。 The maximum absorption wavelength of a compound can be measured using a chloroform solution of the compound and UV-2550 manufactured by Shimadzu Corporation. The concentration of the chloroform solution is preferably 5 × 10 -5 mol / l ~ 1 × 10 -7 mol / l, and more preferably 3 × 10 -5 mol / l ~ 2 × 10 -6 mol / l, particularly preferably It is 2 × 10 -5 mol / l ~ 5 × 10 -6 mol / l.
通式(1)~通式(3)所表示的化合物在紫外可見吸收光譜中的400nm以上且不足720nm中具有極大吸收，該極大吸收波長的莫耳吸光係數較佳的是10000mol-1．l．cm-1以上。為了使光電轉換膜的膜厚變薄，製成高電荷捕獲效率、高速響應性、高感度特性的元件，較佳的是莫耳吸光係數大的材料。通式(1)~通式(3)所表示的化合物的莫耳吸光係數更佳的是30000 mol-1．l．cm-1以上，進一步更佳的是50000mol-1．l．cm-1以上。通式(1)~通式(3)所表示的化合物的莫耳吸光係數是使用氯仿溶液而測定者。 The compounds represented by the general formulae (1) to (3) have a maximum absorption in the ultraviolet-visible absorption spectrum of 400 nm or more and less than 720 nm. The Mohr absorption coefficient of the maximum absorption wavelength is preferably 10,000 mol -1 . l. cm -1 or more. In order to make the film thickness of the photoelectric conversion film thin, and to make an element with high charge trapping efficiency, high-speed response, and high sensitivity characteristics, a material with a large Mohr absorption coefficient is preferred. The Mohr absorption coefficient of the compounds represented by the general formulae (1) to (3) is more preferably 30,000 mol -1 . l. cm -1 or more, more preferably 50,000 mol -1 . l. cm -1 or more. Molar absorption coefficients of the compounds represented by the general formulae (1) to (3) were measured using a chloroform solution.
通式(1)~通式(3)所表示的化合物的熔點與蒸鍍溫度的差(熔點-蒸鍍溫度)越大，則越難在蒸鍍時分解，可施加高的溫度而增大蒸鍍速度。而且，熔點與蒸鍍溫度的差(熔點-蒸鍍溫度)較佳的是40℃以上，更佳的是50℃以上，進一步更佳的是60℃以上，特佳的是80℃以上。 The larger the difference between the melting point and the evaporation temperature (melting point-evaporation temperature) of the compounds represented by the general formulae (1) to (3), the more difficult it is to decompose during evaporation, and it can be increased by applying a high temperature Evaporation speed. The difference between the melting point and the evaporation temperature (melting point-evaporation temperature) is preferably 40 ° C or higher, more preferably 50 ° C or higher, even more preferably 60 ° C or higher, and particularly preferably 80 ° C or higher.
通式(1)~通式(3)所表示的化合物的分子量較佳的是300~1500，更佳的是500~1000，特佳的是500~900。化合物的分子量若為1500以下，則蒸鍍溫度並不變高，難以產生化合物的分解。化合物的分子量若為300以上，則蒸鍍膜的玻璃轉移點並不變低，元件的耐熱性難以降低。 The molecular weight of the compound represented by the general formula (1) to the general formula (3) is preferably 300 to 1500, more preferably 500 to 1,000, and particularly preferably 500 to 900. If the molecular weight of the compound is 1500 or less, the vapor deposition temperature does not increase, and it is difficult to cause decomposition of the compound. When the molecular weight of the compound is 300 or more, the glass transition point of the vapor-deposited film does not decrease, and it is difficult to reduce the heat resistance of the device.
通式(1)~通式(3)所表示的化合物的玻璃轉移點(Tg)較佳的是95℃以上，更佳的是110℃以上，進一步更佳的是135℃以上，特佳的是150℃以上，最佳的是160℃以上。若玻璃轉移點變高，則元件的耐熱性提高，因此較佳。 The glass transition point (Tg) of the compounds represented by the general formulae (1) to (3) is preferably 95 ° C or higher, more preferably 110 ° C or higher, and even more preferably 135 ° C or higher. It is 150 ° C or more, and most preferably 160 ° C or more. When the glass transition point becomes higher, the heat resistance of the element is improved, which is preferable.
通式(1)~通式(3)所表示的化合物特別是可有效用作攝影元件、光感測器、或光電池中所使用的光電轉換膜的材料。 另外，通常情況下，通式(1)所表示的化合物在光電轉換膜內作為有機p型化合物而發揮功能。而且，作為其他用途，亦可用作著色材料、液晶材料、有機半導體材料、有機發光元件材料、電 荷傳輸材料、醫藥材料、螢光診斷試劑材料等。 The compounds represented by the general formulae (1) to (3) are particularly useful as a material for a photoelectric conversion film used in a photographic element, a light sensor, or a photovoltaic cell. In general, the compound represented by the general formula (1) functions as an organic p-type compound in a photoelectric conversion film. In addition, it can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, an organic light-emitting element material, and Charge transfer materials, medical materials, fluorescent diagnostic reagent materials, etc.
(其他材料) (other materials)
光電轉換膜亦可進一步含有有機p型化合物或有機n型化合物的光電轉換材料。 The photoelectric conversion film may further contain a photoelectric conversion material of an organic p-type compound or an organic n-type compound.
有機p型半導體(化合物)是施體性有機半導體(化合物)，主要是指以電洞傳輸性有機化合物為代表、具有容易提供電子的性質的有機化合物。更詳細而言，是指在使2種有機材料接觸而使用時，游離電位小的有機化合物。因此，施體性有機化合物若為具有供電子性的有機化合物，則可使用任意有機化合物。例如可使用三芳基胺化合物、聯苯胺化合物、吡唑啉化合物、苯乙烯基胺化合物、腙化合物、三苯基甲烷化合物、咔唑化合物等。 Organic p-type semiconductors (compounds) are donor organic semiconductors (compounds), and mainly refer to organic compounds represented by hole-transporting organic compounds and having the property of easily supplying electrons. More specifically, it refers to an organic compound having a small free potential when two types of organic materials are used in contact. Therefore, if the donor organic compound is an organic compound having an electron donating property, any organic compound can be used. For example, a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, a fluorene compound, a triphenylmethane compound, a carbazole compound, or the like can be used.
所謂有機n型半導體(化合物)是受體性有機半導體，主要是指以電子傳輸性有機化合物為代表、具有容易接受電子的性質的有機化合物。更詳細而言，是指在使2種有機化合物接觸而使用時，電子親和力大的有機化合物。因此，受體性有機半導體若為具有電子接受性的有機化合物，則可使用任意有機化合物。較佳的是富勒烯或富勒烯衍生物、縮合芳香族碳環化合物(萘衍生物、蒽衍生物、菲衍生物、稠四苯衍生物、芘衍生物、苝衍生物、螢蒽衍生物)、含有氮原子、氧原子、硫原子的5員~7員的雜環化合物(例如吡啶、吡嗪、嘧啶、噠嗪、三嗪、喹啉、喹噁啉、喹唑啉、酞嗪、噌啉、異喹啉、喋啶、吖啶、啡嗪、啡啉、四唑、吡唑、咪唑、噻唑、噁唑、吲唑、苯并咪唑、苯并***、
苯并噁唑、苯并噻唑、咔唑、嘌呤、***并噠嗪、***并嘧啶、四氮雜茚(tetrazaindene)、噁二唑、咪唑并吡啶、
上述有機n型化合物較佳的是選自由富勒烯及富勒烯衍生物所構成的群組的富勒烯類。所謂富勒烯是表示富勒烯C60、富勒烯C70、富勒烯C76、富勒烯C78、富勒烯C80、富勒烯C82、富勒烯C84、富勒烯C90、富勒烯C96、富勒烯C240、富勒烯C540、混合富勒烯，所謂富勒烯衍生物是表示於該些富勒烯上加成有取代基的化合物。取代基較佳的是烷基、芳基、或雜環基。富勒烯衍生物較佳的是日本專利特開2007-123707號公報中所記載的化合物。 The organic n-type compound is preferably fullerenes selected from the group consisting of fullerenes and fullerene derivatives. The so-called fullerene indicates fullerene C 60, fullerene C 70, fullerene C 76, fullerene C 78, fullerene C 80, fullerene C 82, fullerene C 84, fullerene alkenyl C 90, fullerene C 96, fullerene C 240, fullerene C 540, a mixed fullerene, the fullerene derivative is represented by the so-called on the fullerene addition these compounds have a substituent. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. The fullerene derivative is preferably a compound described in Japanese Patent Laid-Open No. 2007-123707.
光電轉換膜較佳的是成為以上述化合物X與富勒烯類混合的狀態而形成的本體異質結構。本體異質結構是在光電轉換膜內，p型有機半導體(化合物X)與n型有機半導體混合、分散而成的層，可藉由濕式法、乾式法中的任一者而形成，較佳的是藉由共蒸鍍法而形成。藉由含有異質接合結構，可彌補光電轉換膜的載子擴散長度短的缺點，可使光電轉換膜的光電轉換效率提高。另外，關於本體異質接合結構，在日本專利特開2005-303266號公報的[0013]~[0014]等中有所詳細說明。 The photoelectric conversion film preferably has a bulk heterostructure formed in a state where the compound X and the fullerenes are mixed. The bulk heterostructure is a layer in which a p-type organic semiconductor (compound X) and an n-type organic semiconductor are mixed and dispersed in a photoelectric conversion film, and can be formed by any of a wet method and a dry method, and is preferably It is formed by a co-evaporation method. By including the heterojunction structure, the shortcomings of the short carrier diffusion length of the photoelectric conversion film can be compensated, and the photoelectric conversion efficiency of the photoelectric conversion film can be improved. In addition, the bulk heterojunction structure is described in detail in [0013] to [0014] of Japanese Patent Laid-Open No. 2005-303266.
光電轉換膜中的有機n型化合物相對於上述化合物X的 莫耳比率(有機n型化合物/上述化合物X)較佳的是1.0以上，更佳的是1以上、10以下，進一步更佳的是2以上、8以下。 Relative to the above-mentioned compound X, the organic n-type compound in the photoelectric conversion film The molar ratio (organic n-type compound / the above-mentioned compound X) is preferably 1.0 or more, more preferably 1 or more and 10 or less, even more preferably 2 or more and 8 or less.
包含本發明的化合物X及有機n型化合物的光電轉換膜是非發光性膜，具有與有機發光二極體(Organic Light Emission Diode，OLED)不同的特徵。所謂非發光性膜是發光量子效率為1%以下的膜的情況，較佳的是0.5%以下，更佳的是0.1%以下。 The photoelectric conversion film containing the compound X and the organic n-type compound of the present invention is a non-luminescent film, and has a characteristic different from that of an organic light emitting diode (OLED). When the non-luminescent film is a film having a light emitting quantum efficiency of 1% or less, it is preferably 0.5% or less, and more preferably 0.1% or less.
(成膜方法) (Film forming method)
光電轉換膜12可藉由乾式成膜法或濕式成膜法而成膜。乾式成膜法的具體例可列舉真空蒸鍍法、濺鍍法、離子鍍法，分子束磊晶(Molecular-Beam Epitaxy，MBE)法等物理氣相沈積(physical Vapor Deposition，PVD)法、或電漿聚合等化學氣相沈積(Chemical Vapor Deposition，CVD)法。濕式成膜法使用澆鑄法、旋塗法、浸漬法、LB法等。較佳的是乾式成膜法，更佳的是真空蒸鍍法。 在藉由真空蒸鍍法進行成膜的情況下，真空度、蒸鍍溫度等製造條件可依照常法而設定。 The photoelectric conversion film 12 can be formed by a dry film formation method or a wet film formation method. Specific examples of the dry film formation method include a physical vapor deposition (PVD) method such as a vacuum evaporation method, a sputtering method, an ion plating method, and a molecular beam epitaxy (MBE) method, or Chemical vapor deposition (CVD) methods such as plasma polymerization. As the wet film formation method, a casting method, a spin coating method, a dipping method, an LB method, or the like is used. A dry film-forming method is preferable, and a vacuum evaporation method is more preferable. When forming a film by a vacuum vapor deposition method, manufacturing conditions such as a degree of vacuum and a vapor deposition temperature can be set in accordance with a conventional method.
光電轉換膜12的厚度較佳的是10nm以上、1000nm以下，更佳的是50nm以上、800nm以下，特佳的是100nm以上、500nm以下。藉由設為10nm以上，可獲得適宜的暗電流抑制效果；藉由設為1000nm以下，可獲得適宜的光電轉換效率。 The thickness of the photoelectric conversion film 12 is preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 800 nm or less, and particularly preferably 100 nm or more and 500 nm or less. When it is set to 10 nm or more, a suitable dark current suppression effect can be obtained; when it is set to 1000 nm or less, a suitable photoelectric conversion efficiency can be obtained.
[電極] [electrode]
電極(上部電極(透明導電性膜)15與下部電極(導電性膜)11)包含導電性材料。導電性材料可使用金屬、合金、金屬氧化 物、導電性化合物、或該些的混合物等。 The electrodes (the upper electrode (transparent conductive film) 15 and the lower electrode (conductive film) 11) include a conductive material. Conductive materials can use metals, alloys, and metal oxidation Materials, conductive compounds, or mixtures thereof.
為了自上部電極15射入光，上部電極15必須相對於所欲檢測的光而言充分透明。具體而言可列舉摻雜有銻或氟等的氧化錫(ATO、FTO)、氧化錫、氧化鋅、氧化銦、氧化銦錫(ITO)、氧化鋅銦(IZO)等導電性金屬氧化物，金、銀、鉻、鎳等的金屬薄膜，以及該些金屬與導電性金屬氧化物的混合物或積層物，碘化銅、硫化銅等無機導電性物質，聚苯胺、聚噻吩、聚吡咯等有機導電性材料，及該些與ITO的積層物等。自高導電性、透明性等方面考慮，其中較佳的是透明導電性金屬氧化物。 In order to enter light from the upper electrode 15, the upper electrode 15 must be sufficiently transparent to the light to be detected. Specific examples include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metal thin films of gold, silver, chromium, nickel, etc., as well as mixtures or laminates of these metals with conductive metal oxides, inorganic conductive materials such as copper iodide, copper sulfide, organics such as polyaniline, polythiophene, polypyrrole, etc. Conductive materials, and these laminates with ITO. From the viewpoints of high conductivity and transparency, a transparent conductive metal oxide is preferred.
通常情況下，若使導電性膜比某範圍更薄，則導致電阻值急遽增加，在內裝有本實施方式的光電轉換元件的固態攝影元件中，薄片電阻較佳的是100Ω/□~10000Ω/□即可，可薄膜化的膜厚的範圍的自由度大。而且，上部電極(透明導電性膜)15的厚度越薄則所吸收的光的量越少，一般情況下透光率越增加。透光率的增加使光電轉換膜12中的光吸收增大，使光電轉換能力增大，因此非常佳。隨著薄膜化，若考慮洩漏電流的抑制、薄膜的電阻值的增大、穿透率的增加，則理想的是上部電極15的膜厚較佳的是5nm~100nm，更佳的是5nm~20nm。 In general, if the conductive film is made thinner than a certain range, the resistance value will increase sharply. Among the solid-state imaging elements containing the photoelectric conversion element of this embodiment, the sheet resistance is preferably 100Ω / □ ~ 10000Ω / □, and there is a large degree of freedom in the range of film thicknesses that can be reduced. In addition, the thinner the upper electrode (transparent conductive film) 15 is, the less the amount of light absorbed is, and the light transmittance is generally increased. The increase in light transmittance increases the light absorption in the photoelectric conversion film 12 and increases the photoelectric conversion capability, so it is very good. As the thickness of the thin film is increased, the thickness of the upper electrode 15 is preferably 5 nm to 100 nm, and more preferably 5 nm to the thickness of the upper electrode 15 in consideration of suppression of leakage current, increase in resistance value of the film, and increase in transmittance. 20nm.
下部電極11根據用途存在有具有透明性的情況、相反地使用不透明而使光反射的材料的情況等。具體而言可列舉摻雜有銻或氟等的氧化錫(ATO、FTO)、氧化錫、氧化鋅、氧化銦、氧化銦錫(ITO)、氧化鋅銦(IZO)等導電性金屬氧化物，金、銀、 鉻、鎳、鈦、鎢、鋁等金屬及該些金屬的氧化物或氮化物等導電性化合物(可列舉氮化鈦(TiN)作為一例)，進一步可列舉該些金屬與導電性金屬氧化物的混合物或積層物，碘化銅、硫化銅等無機導電性物質，聚苯胺、聚噻吩、聚吡咯等有機導電性材料，及該些與ITO或氮化鈦的積層物等。 The lower electrode 11 may have transparency depending on the application, and may instead use a material that is opaque and reflects light. Specific examples include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Gold, silver, Metals such as chromium, nickel, titanium, tungsten, aluminum, and conductive compounds such as oxides or nitrides of these metals (for example, titanium nitride (TiN) can be cited as an example), and these metals and conductive metal oxides can also be mentioned Mixtures or laminates, inorganic conductive materials such as copper iodide, copper sulfide, organic conductive materials such as polyaniline, polythiophene, polypyrrole, and these laminates with ITO or titanium nitride.
形成電極的方法並無特別限定，可根據電極材料而適宜選擇。具體而言可列舉印刷方式、塗佈方式等濕式方式，真空蒸鍍法、濺鍍法、離子鍍法等物理方式，CVD、電漿CVD法等化學方式等而形成。 The method of forming the electrode is not particularly limited, and can be appropriately selected depending on the electrode material. Specific examples include wet methods such as printing methods and coating methods, physical methods such as vacuum evaporation, sputtering, and ion plating, and chemical methods such as CVD and plasma CVD.
在電極的材料為ITO的情況下，可藉由電子束法、濺鍍法、電阻加熱蒸鍍法、化學反應法(溶膠-凝膠法等)、塗佈氧化銦錫的分散物等方法而形成。另外，可對使用ITO而製作的膜實施紫外線(UltraViolet，UV)-臭氧處理、電漿處理等。在電極的材料為TiN的情況下，使用以反應性濺鍍法為首的各種方法，另外可實施UV-臭氧處理、電漿處理等。 When the material of the electrode is ITO, the electron beam method, the sputtering method, the resistance heating evaporation method, the chemical reaction method (sol-gel method, etc.), and the method of applying a dispersion of indium tin oxide can be used. form. In addition, a film made using ITO may be subjected to an ultraviolet (UltraViolet, UV) -ozone treatment, a plasma treatment, or the like. When the material of the electrode is TiN, various methods including a reactive sputtering method are used, and UV-ozone treatment, plasma treatment, and the like can be performed.
[電荷阻斷膜：電子阻斷膜、電洞阻斷膜] [Charge blocking film: electron blocking film, hole blocking film]
本發明的光電轉換元件亦可包含電荷阻斷膜。藉由包含該膜，所得的光電轉換元件的特性(光電轉換效率、響應速度等)更優異。電荷阻斷膜可列舉電子阻斷膜與電洞阻斷膜。以下對各個膜加以詳述。 The photoelectric conversion element of the present invention may include a charge blocking film. By including this film, the characteristics (photoelectric conversion efficiency, response speed, etc.) of the obtained photoelectric conversion element are more excellent. Examples of the charge blocking film include an electron blocking film and a hole blocking film. Each film is described in detail below.
(電子阻斷膜) (Electronic blocking film)
電子阻斷膜中可使用供電子性有機材料。具體而言，低分子 材料可使用N,N'-雙(3-甲基苯基)-(1,1'-聯苯基)-4,4'-二胺(TPD)或4,4'-雙[N-(萘基)-N-苯基-胺基]聯苯(α-NPD)等芳香族二胺化合物、噁唑、噁二唑、***、咪唑、咪唑酮、二苯乙烯衍生物、吡唑啉衍生物、四氫咪唑、多芳基烷烴、丁二烯、4,4',4"-三(N-(3-甲基苯基)-N-苯基胺基)三苯基胺(m-MTDATA)、卟啉、四苯基卟啉銅、酞菁、銅酞菁、鈦酞菁氧化物等卟啉化合物、***衍生物、噁二唑衍生物、咪唑衍生物、多芳基烷烴衍生物、吡唑啉衍生物、吡唑啉酮衍生物、苯二胺衍生物、芳基胺衍生物、胺基取代查耳酮衍生物、噁唑衍生物、苯乙烯基蒽衍生物、茀酮衍生物、腙衍生物、矽氮烷衍生物等，高分子材料可使用苯乙炔(phenylene vinylene)、茀、咔唑、吲哚、芘、吡咯、甲基吡啶(picoline)、噻吩、乙炔、丁二炔(diacetylene)等的聚合物或其衍生物。即使不是供電子性化合物，若為具有充分的電洞傳輸性的化合物則可使用。具體而言較佳的是日本專利特開2008-72090號公報的[0083]~[0089]中所記載的化合物。 An electron-donating organic material can be used in the electron blocking film. Specifically, low molecular Materials can use N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD) or 4,4'-bis [N- ( (Naphthyl) -N-phenyl-amino] biphenyl (α-NPD) and other aromatic diamine compounds, oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivative, pyrazoline Derivatives, tetrahydroimidazole, polyarylalkanes, butadiene, 4,4 ', 4 "-tris (N- (3-methylphenyl) -N-phenylamino) triphenylamine (m -MTDATA), porphyrin, porphyrin, copper tetraphenylporphyrin, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide and other porphyrin compounds, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkanes Derivatives, pyrazoline derivatives, pyrazolinone derivatives, phenylenediamine derivatives, arylamine derivatives, amine-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, pyrene Ketone derivatives, fluorene derivatives, silazane derivatives, etc., polymer materials can be phenylene vinylene, fluorene, carbazole, indole, fluorene, pyrrole, picoline, thiophene, acetylene, A polymer or a derivative thereof such as diacetylene. Even if it is not an electron-donating compound, if Sufficient hole transporting compound may be used. Specifically preferred is Japanese Patent Laid-Open Patent Publication No. 2008-72090 [0083] - Compound [0089] are described.
亦較佳的是電子阻斷膜含有通式(F-1)所表示的化合物。藉由使用該化合物，所得的光電轉換膜的響應速度更優異，且進一步抑制各製造批間的響應速度的不均一。 It is also preferable that the electron blocking film contains a compound represented by the general formula (F-1). By using this compound, the response speed of the obtained photoelectric conversion film is more excellent, and the non-uniformity of the response speed between manufacturing lots is further suppressed.
[化24]
(通式(F-1)中，R"11~R"18、R'11~R'18分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、羥基、胺基、或巰基，該些基亦可進一步具有取代基。R"15~R"18中的任意一個與R'15~R'18中的任意一個連結而形成單鍵。A11及A12分別獨立地表示下述通式(A-1)所表示的基，作為R"11~R"14、及R'11~R'14中的任意一個而進行取代。Y分別獨立地表示碳原子、氮原子、氧原子、硫原子、或矽原子，該些亦可進一步具有取代基)
(通式(A-1)中，Ra1~Ra8分別獨立地表示氫原子、鹵素原子、烷基、芳基、或雜環基，該些亦可進一步具有取代基。
*表示鍵結位置。Xa表示單鍵、氧原子、硫原子、伸烷基、亞矽烷基、伸烯基、伸環烷基、伸環烯基、伸芳基、2價雜環基、或亞
胺基，該些亦可進一步具有取代基。S11分別獨立地表示下述取代基(S11)，作為Ra1~Ra8中的任意一個而進行取代。n'表示0~4的整數)
(R'1~R'3分別獨立地表示氫原子或烷基) (R ' 1 to R' 3 each independently represent a hydrogen atom or an alkyl group)
通式(F-1)中，R"11~R"18、R'11~R'18分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、羥基、胺基、或巰基，該些亦可進一步具有取代基。進一步的取代基的具體例可列舉上述取代基W，較佳的是鹵素原子、烷基、芳基、雜環基、羥基、胺基、或巰基，更佳的是鹵素原子、烷基、芳基、或雜環基，進一步更佳的是氟原子、烷基、或芳基，特佳的是烷基、芳基，最佳的是烷基。 In the general formula (F-1), R " 11 to R" 18 and R '11 to R' 18 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amine group, or These mercapto groups may further have a substituent. Specific examples of the further substituent include the above-mentioned substituent W, preferably a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amine group, or a mercapto group, and more preferably a halogen atom, an alkyl group, or an aromatic group. Group, or heterocyclic group, more preferably a fluorine atom, an alkyl group, or an aryl group, particularly preferably an alkyl group or an aryl group, and most preferably an alkyl group.
R"11~R"18、R'11~R'18較佳的是氫原子、亦可具有取代基的烷基、芳基、或雜環基，更佳的是氫原子、亦可具有取代基的碳數為1~18的烷基、碳數為6~18的芳基、或碳數為4~16的雜環基。其中，較佳的是通式(A-1)所表示的取代基分別獨立地取代 R"12及R'12，更佳的是通式(A-1)所表示的取代基分別獨立地取代R"12及R'12，R"11、R"13~R"18、R'11、R'13~R'18為氫原子、亦可具有取代基的碳數為1~18的烷基，特佳的是通式(A-1)所表示的取代基分別獨立地取代R"12及R'12，R"11、R"13~R"18、R'11、R'13~R'18為氫原子。 R " 11 ~ R" 18 and R '11 ~ R' 18 are preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group which may have a substituent, more preferably a hydrogen atom and may have a substitution. The carbon number of the group is an alkyl group having 1 to 18 carbon atoms, the aryl group having 6 to 18 carbon atoms, or the heterocyclic group having 4 to 16 carbon atoms. Among them, it is preferable that the substituents represented by the general formula (A-1) independently independently substitute R " 12 and R '12 , and the more preferable ones are the substituents independently represented by the general formula (A-1). R "12 and R '12, R" 11, R "13 ~ R" 18, R' 11, R '13 ~ R' 18 is a hydrogen atom, it can be a substituent having a carbon number of alkyl group having 1 to 18 It is particularly preferred that the substituents represented by the general formula (A-1) independently substitute R " 12 and R '12 , R" 11, R " 13 ~ R" 18 , R' 11, R '13 ~ R '18 is a hydrogen atom.
Y分別獨立地表示碳原子、氮原子、氧原子、硫原子、或矽原子，該些亦可進一步具有取代基。亦即，Y表示包含碳原子、氮原子、氧原子、硫原子、或矽原子的二價連結基。其中較佳的是-C(R'21)(R'22)-、-Si(R'23)(R'24)-、-N(R'20)-，更佳的是-C(R'21)(R'22)-、-N(R'20)-，特佳的是-C(R'21)(R'22)-。 Y each independently represents a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, and these may further have a substituent. That is, Y represents a divalent linking group containing a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom. Among them, -C (R '21 ) (R' 22 )-, -Si (R '23 ) (R' 24 )-, -N (R '20 )-, and more preferably -C (R '21) (R' 22) -, - N (R '20) -, particularly preferably is -C (R' 21) (R '22) -.
R'20~R'24分別獨立地表示氫原子、鹵素原子、亦可具有取代基的烷基、芳基、雜環基、羥基、胺基、或巰基。其進一步的取代基的具體例可列舉取代基W。R'20~R'24較佳的是氫原子、亦可具有取代基的烷基、芳基、或雜環基，更佳的是氫原子、亦可具有取代基的碳數為1~18的烷基、碳數為6~18的芳基、或碳數為4~16的雜環基，進一步更佳的是氫原子、或亦可具有取代基的碳數為1~18的烷基，特佳的是碳數為1~18的烷基。 R '20 to R' 24 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amine group, or a mercapto group which may have a substituent. Specific examples of the further substituent include the substituent W. R '20 to R' 24 are preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group which may have a substituent, more preferably a hydrogen atom and a carbon number of 1 to 18 which may also have a substituent. Alkyl group, aryl group having 6 to 18 carbon atoms, or heterocyclic group having 4 to 16 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a substituent Particularly preferred is an alkyl group having 1 to 18 carbon atoms.
通式(A-1)中的Ra1~Ra8分別獨立地表示氫原子、鹵素原子、亦可具有取代基的烷基、芳基、雜環基、羥基、胺基、或巰基。其進一步的取代基的具體例可列舉取代基W。而且，該些取代基亦可多個相互鍵結而形成環。 Ra 1 to Ra 8 in the general formula (A-1) each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amine group, or a mercapto group which may have a substituent. Specific examples of the further substituent include the substituent W. Moreover, a plurality of these substituents may be bonded to each other to form a ring.
Ra1~Ra8較佳的是氫原子、鹵素原子、碳數為1~18的 烷基、碳數為6~18的芳基、或碳數為4~16的雜環基，更佳的是氫原子、碳數為1~12的烷基、或碳數為6~14的芳基，進一步更佳的是氫原子、碳數為1~6的烷基、或碳數為6~10的芳基。 烷基亦可具有分支。 Ra 1 to Ra 8 are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms, and more preferably Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 6 to 10 carbon atoms Aryl. Alkyl groups may also have branches.
較佳的具體例可列舉氫原子、甲基、乙基、丙基、丁基、己基、環己基、苯基、或萘基。 Preferable specific examples include a hydrogen atom, methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, phenyl, or naphthyl.
而且，特佳的是Ra3及Ra6為氫原子或碳數為1~6的烷基，且Ra1、Ra2、Ra4、Ra5、Ra7、Ra8為氫原子的情況。 Further, it is particularly preferable that Ra 3 and Ra 6 are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, and Ra 1 , Ra 2 , Ra 4 , Ra 5 , Ra 7 , and Ra 8 are hydrogen atoms.
Xa表示單鍵、氧原子、硫原子、伸烷基、亞矽烷基、伸烯基、伸環烷基、伸環烯基、伸芳基、2價雜環基、或亞胺基，該些亦可進一步具有取代基。 Xa represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, an alkenyl group, a cycloalkylene group, a cycloalkenyl group, an alkylene group, a divalent heterocyclic group, or an imino group, and these It may further have a substituent.
Xa較佳的是單鍵、碳數為1~12的伸烷基、碳數為2~12的伸烯基、碳數為6~14的伸芳基、碳數為4~13的雜環基、氧原子、硫原子、具有碳數為1~12的烴基(較佳的是芳基或烷基)的亞胺基(例如苯基亞胺基、甲基亞胺基、第三丁基亞胺基)、或亞矽烷基，更佳的是單鍵、氧原子、碳數為1~6的伸烷基(例如亞甲基、1,2-伸乙基、1,1-二甲基亞甲基)、碳數為2的伸烯基(例如-CH2=CH2-)、碳數為6~10的伸芳基(例如1,2-伸苯基、2,3-伸萘基)、或亞矽烷基，進一步更佳的是單鍵、氧原子、碳數為1~6的伸烷基(例如亞甲基、1,2-伸乙基、1,1-二甲基亞甲基)。該些取代基亦可進一步具有取代基W。 Xa is preferably a single bond, an alkylene group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an arylene group having 6 to 14 carbon atoms, and a heterocyclic ring having 4 to 13 carbon atoms. Group, oxygen atom, sulfur atom, imine group (for example, phenylimide group, methylimide group, third butyl group) having a hydrocarbon group (preferably aryl group or alkyl group) having 1 to 12 carbon atoms Imine), or silylene, more preferably a single bond, an oxygen atom, and an alkylene group having 1 to 6 carbon atoms (e.g., methylene, 1,2-ethylene, 1,1-dimethyl) Methylene), an alkenyl group having 2 carbon atoms (e.g. -CH 2 = CH 2- ), and an arylene group having 6 to 10 carbon atoms (e.g. 1,2-phenylene, 2,3-phenylene) Naphthyl), or silylene, and more preferably a single bond, an oxygen atom, or an alkylene group having 1 to 6 carbon atoms (e.g., methylene, 1,2-ethylene, 1,1-dimethyl) Methylene). These substituents may further have a substituent W.
通式(A-1)所表示的基的具體例可列舉下述N1~N11所例 示的基。但並不限定於該些基。通式(A-1)所表示的基較佳的是N-1~N-7，更佳的是N-1~N-6，更佳的是N-1~N-3，特佳的是N-1~N-2，最佳的是N-1。 Specific examples of the group represented by the general formula (A-1) include the following examples of N1 to N11 示 基。 Showed base. But it is not limited to these bases. The group represented by the general formula (A-1) is preferably N-1 to N-7, more preferably N-1 to N-6, more preferably N-1 to N-3, and particularly preferably It is N-1 ~ N-2, and the best is N-1.
取代基(S11)中，R'1表示氫原子或烷基。R'1較佳的是甲基、乙基、丙基、異丙基、丁基、或第三丁基，更佳的是甲基、乙基、丙基、異丙基、或第三丁基，進一步更佳的是甲基、乙基、異丙基、或第三丁基，特佳的是甲基、乙基、或第三丁基。 In the substituent (S 11 ), R ′ 1 represents a hydrogen atom or an alkyl group. R '1 is preferably methyl, ethyl, propyl, isopropyl, butyl, or tert-butyl, more preferably methyl, ethyl, propyl, isopropyl, or tertiary butyl The methyl group is more preferably a methyl group, an ethyl group, an isopropyl group, or a third butyl group, and particularly preferably a methyl group, an ethyl group, or a third butyl group.
R'2表示氫原子或烷基。R'2較佳的是氫原子、甲基、乙 基、丙基、異丙基、丁基、或第三丁基，進一步較佳的是氫原子、甲基、乙基、或丙基，更佳的是氫原子、甲基，特佳的是甲基。 R ' 2 represents a hydrogen atom or an alkyl group. R ′ 2 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a third butyl group, and still more preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, More preferred are a hydrogen atom and a methyl group, and particularly preferred is a methyl group.
R'3表示氫原子或烷基。R'3較佳的是氫原子、或甲基，更佳的是甲基。 R ' 3 represents a hydrogen atom or an alkyl group. R '3 is preferably a hydrogen atom, or a methyl, more preferably methyl.
而且，R'1~R'3亦可分別相互鍵結而形成環。在形成環的情況下，環員數並無特別限定，較佳的是5員環或6員環，進一步較佳的是6員環。 R ' 1 to R' 3 may be bonded to each other to form a ring. In the case of forming a ring, the number of ring members is not particularly limited, and a 5-member ring or a 6-member ring is preferable, and a 6-member ring is more preferable.
S11表示上述取代基(S11)，作為Ra1~Ra8中的任意一個而進行取代。較佳的是通式(A-1)中的Ra3及Ra6的至少任意1個分別獨立地表示上述取代基(S11)。 S 11 represents the aforementioned substituent (S 11 ), and is substituted as any one of Ra 1 to Ra 8 . It is preferable that at least any one of Ra 3 and Ra 6 in the general formula (A-1) independently represents the substituent (S 11 ).
取代基(S11)較佳的是可列舉下述(a)~(x)，更佳的是(a)~(j)，更佳的是(a)~(h)，特佳的是(a)~(f)，進一步較佳的是(a)~(c)，最佳的是(a)。 The substituents (S 11 ) are preferably the following (a) to (x), more preferably (a) to (j), more preferably (a) to (h), and particularly preferably (a) to (f), more preferably (a) to (c), and most preferably (a).
[化28]
n'分別獨立地表示0~4的整數，較佳的是0~3，更佳的是0~2，進一步更佳的是1~2，特佳的是2。 n 'each independently represents an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, even more preferably 1 to 2, and particularly preferably 2.
上述通式(A-1)亦可為下述通式(A-3)所表示的基、下述通式(A-4)所表示的基、或下述通式(A-5)所表示的基。 The general formula (A-1) may be a group represented by the following general formula (A-3), a group represented by the following general formula (A-4), or a group represented by the following general formula (A-5) Represented base.
[化29]
(通式(A-3)~通式(A-5)中，Ra33~Ra38、Ra41、Ra44~Ra48、Ra51、Ra52、Ra55~Ra58分別獨立地表示氫原子、鹵素原子、或烷基，該些亦可進一步具有取代基。*表示鍵結位置。 Xc1、Xc2、及Xc3分別獨立地表示單鍵、氧原子、硫原子、伸烷基、亞矽烷基、伸烯基、伸環烷基、伸環烯基、伸芳基、2價的雜環基、或亞胺基，該些亦可進一步具有取代基。Z31、Z41、及Z51分別獨立地表示環烷基環、芳香族烴環、或芳香族雜環，該些亦可進一步具有取代基) (In general formula (A-3) to general formula (A-5), Ra 33 to Ra 38 , Ra 41 , Ra 44 to Ra 48 , Ra 51 , Ra 52 , Ra 55 to Ra 58 each independently represent a hydrogen atom. , Halogen atom, or alkyl group, which may further have a substituent. * Indicates a bonding position. Xc 1 , Xc 2 , and Xc 3 each independently represent a single bond, an oxygen atom, a sulfur atom, an alkylene group, or an alkylene group. Silyl group, alkenyl group, cycloalkylene group, cycloalkenyl group, arylene group, divalent heterocyclic group, or imino group, which may further have a substituent. Z 31 , Z 41 , and Z 51 each independently represents a cycloalkyl ring, an aromatic hydrocarbon ring, or an aromatic heterocyclic ring, and these may further have a substituent)
通式(A-3)~通式(A-5)中，Ra33~Ra38、Ra41、Ra44~Ra48、Ra51、Ra52、Ra55~Ra58分別獨立地表示氫原子、鹵素原子(較佳的是氟原子、氯原子、溴原子、或碘原子)、或烷基。自 若為極性低的取代基則有利於電洞的傳輸的理由考慮，較佳的是氫原子、或烷基，更佳的是氫原子。 In the general formulae (A-3) to (A-5), Ra 33 to Ra 38 , Ra 41 , Ra 44 to Ra 48 , Ra 51 , Ra 52 , and Ra 55 to Ra 58 each independently represent a hydrogen atom, A halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), or an alkyl group. Considering the reason that if the substituent is low in polarity, the hole is facilitated, a hydrogen atom or an alkyl group is preferred, and a hydrogen atom is more preferred.
在Ra33~Ra38、Ra41、Ra44~Ra48、Ra51、Ra52、Ra55~Ra58表示烷基的情況下，該烷基較佳的是碳數為1~18的烷基，更佳的是碳數為1~12的烷基，進一步更佳的是碳數為1~6的烷基。具體而言較佳的是甲基、乙基、丙基、丁基、己基、或環己基。 When Ra 33 to Ra 38 , Ra 41 , Ra 44 to Ra 48 , Ra 51 , Ra 52 , Ra 55 to Ra 58 represent alkyl groups, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms. An alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is even more preferable. Specifically, methyl, ethyl, propyl, butyl, hexyl, or cyclohexyl is preferred.
通式(A-3)~通式(A-5)中，Ra33~Ra38、Ra41、Ra44~Ra48、Ra51、Ra52、Ra55~Ra58中鄰接的基彼此之間亦可相互鍵結而形成環。環可列舉前述的環R。該環較佳的是苯環、萘環、蒽環、吡啶環、嘧啶環等。 In the general formulae (A-3) to (A-5), the adjacent groups in Ra 33 to Ra 38 , Ra 41 , Ra 44 to Ra 48 , Ra 51 , Ra 52 , and Ra 55 to Ra 58 are adjacent to each other. They may also be bonded to each other to form a ring. Examples of the ring include the aforementioned ring R. The ring is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring, or the like.
Xc1、Xc2、及Xc3分別獨立地表示單鍵、氧原子、硫原子、伸烷基、亞矽烷基、伸烯基、伸環烷基、伸環烯基、伸芳基、2價的雜環基、或亞胺基。在Xc1、Xc2、及Xc3表示伸烷基、亞矽烷基、伸烯基、伸環烷基、伸環烯基、伸芳基、2價的雜環基、或亞胺基的情況下，該些亦可進一步具有取代基。該進一步的取代基可列舉取代基W。 Xc 1 , Xc 2 , and Xc 3 each independently represent a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, an alkenyl group, a cycloalkylene group, a cycloalkenyl group, an alkylene group, or a divalent group. Heterocyclyl, or imino. When Xc 1 , Xc 2 , and Xc 3 represent an alkylene group, a silylene group, an alkylene group, a cycloalkylene group, a cycloalkenyl group, an alkylene group, a divalent heterocyclic group, or an imino group These may further have a substituent. Examples of the further substituent include the substituent W.
Xc1、Xc2、及Xc3較佳的是單鍵、碳數為1~12的伸烷基、碳數為2~12的伸烯基、碳數為6~14的伸芳基、碳數為4~13的雜環基、氧原子、硫原子、具有碳數為1~12的烴基(較佳的是芳基或烷基)的亞胺基(例如苯基亞胺基、甲基亞胺基、第三丁基亞胺基)，更佳的是單鍵、碳數為1~6的伸烷基(例如亞甲基、1,2-伸乙基、1,1-二甲基亞甲基)、碳數為2的伸烯基(例 如-CH2=CH2-)、碳數為6~10的伸芳基(例如1,2-伸苯基、2,3-伸萘基)。 Xc 1 , Xc 2 , and Xc 3 are preferably a single bond, an alkylene group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an arylene group having 6 to 14 carbon atoms, and carbon. Heterocyclic groups of 4 to 13, oxygen atoms, sulfur atoms, imine groups (e.g., phenylimide, methyl) having a hydrocarbon group (preferably aryl or alkyl) of 1 to 12 carbons Imino, third butylimino), more preferably a single bond, 1 to 6 carbon alkylene (e.g., methylene, 1,2-ethylene, 1,1-dimethyl) Methylene), an alkenyl group having 2 carbon atoms (e.g. -CH 2 = CH 2- ), and an arylene group having 6 to 10 carbon atoms (e.g. 1,2-phenylene, 2,3-phenylene) Naphthyl).
Z31、Z41、及Z51分別獨立地表示環烷基環、芳香族烴環、或芳香族雜環。通式(A-3)~通式(A-5)中，Z31、Z41、及Z51與苯環縮合。自可期待光電轉換元件的高耐熱性與高電洞傳輸能力的理由考慮，較佳的是Z31、Z41、及Z51為芳香族烴環。 Z 31 , Z 41 , and Z 51 each independently represent a cycloalkyl ring, an aromatic hydrocarbon ring, or an aromatic heterocyclic ring. In the general formulae (A-3) to (A-5), Z 31 , Z 41 , and Z 51 are condensed with a benzene ring. Considering the reason that the high heat resistance and high hole transmission ability of the photoelectric conversion element can be expected, it is preferable that Z 31 , Z 41 , and Z 51 are aromatic hydrocarbon rings.
另外，電子阻斷膜亦可由多個膜而構成。 The electron blocking film may be composed of a plurality of films.
電子阻斷膜亦可使用無機材料。一般情況下，無機材料比有機材料的介電常數大，因此在用於電子阻斷膜中的情況下，變得對光電轉換膜施加多的電壓，可提高光電轉換效率。可成為電子阻斷膜的材料存在有氧化鈣、氧化鉻、氧化鉻銅、氧化錳、氧化鈷、氧化鎳、氧化銅、氧化鎵銅、氧化鍶銅、氧化鈮、氧化鉬、氧化銦銅、氧化銦銀、氧化銥等。在電子阻斷膜為單層的情況下，可將該層設為包含無機材料的層，或者在多層的情況下，可將1個或2個以上的層設為包含無機材料的層。 The electron blocking film may also use an inorganic material. In general, the dielectric constant of an inorganic material is larger than that of an organic material. Therefore, when it is used in an electron blocking film, a large amount of voltage is applied to the photoelectric conversion film, which can improve the photoelectric conversion efficiency. Materials that can be used as electron blocking films include calcium oxide, chromium oxide, chromium oxide copper, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, copper strontium oxide, niobium oxide, molybdenum oxide, indium copper oxide, Indium silver oxide, iridium oxide, etc. When the electron blocking film is a single layer, the layer may be a layer including an inorganic material, or in the case of a plurality of layers, one or two or more layers may be a layer including an inorganic material.
(電洞阻斷膜) (Hole blocking film)
電洞阻斷膜中可使用電子接受性有機材料。 Electron-accepting organic materials can be used in the hole blocking film.
電子接受性材料可使用1,3-雙(4-第三丁基苯基-1,3,4-噁二唑基)苯(OXD-7)等噁二唑衍生物、蒽醌二甲烷衍生物、聯苯醌衍生物、浴銅靈(bathocuproine)、浴菲繞啉(bathophenanthroline)、及該些的衍生物、***化合物、三(8-羥基喹啉)鋁錯合物、雙(4-甲基-8-喹啉)鋁錯合物、二苯乙烯基芳烴衍生物、矽雜環戊二烯 (silole)化合物等。而且，不僅僅是電子接受性有機材料，若為 具有充分的電子傳輸性的材料則亦可使用。可使用卟啉系化合物、或DCM(4-二氰基亞甲基-2-甲基-6-(4-(二甲基胺基苯乙烯基))-4H吡喃)等苯乙烯基系化合物、4H吡喃系化合物。具體而言較佳的是日本專利特開2008-72090號公報的[0073]~[0078]中所記載的化合物。 Electron-accepting materials can be derived from oxadiazole derivatives such as 1,3-bis (4-third butylphenyl-1,3,4-oxadiazolyl) benzene (OXD-7), and anthraquinone dimethane Compounds, biphenylquinone derivatives, bathhoproproine, bathhophenanthroline, and their derivatives, triazole compounds, tris (8-hydroxyquinoline) aluminum complexes, bis (4 -Methyl-8-quinoline) aluminum complex, distyryl aromatic hydrocarbon derivative, silapentadiene (silole) compounds and the like. And, it ’s not just electron-accepting organic materials. Materials having sufficient electron-transport properties can also be used. A porphyrin-based compound or a styrene-based system such as DCM (4-dicyanomethylene-2-methyl-6- (4- (dimethylaminostyryl))-4H pyran) can be used Compound, 4H pyran compound. Specifically, compounds described in [0073] to [0078] of Japanese Patent Laid-Open No. 2008-72090 are preferable.
電荷阻斷膜的製造方法並無特別限制，可藉由乾式成膜法或濕式成膜法而成膜。乾式成膜法可使用蒸鍍法、濺鍍法等。 蒸鍍可為物理蒸鍍(PVD)、化學蒸鍍(CVD)中的任一者，較佳的是真空蒸鍍等物理蒸鍍。濕式成膜法可使用噴墨法、噴霧法、噴嘴印刷法、旋塗法、浸塗法、澆鑄法、模塗法、輥塗法、棒塗法、凹版印刷塗佈法等，自高精度圖案化的觀點考慮，較佳的是噴墨法。 The method for manufacturing the charge blocking film is not particularly limited, and a film can be formed by a dry film formation method or a wet film formation method. As the dry film formation method, a vapor deposition method, a sputtering method, or the like can be used. The vapor deposition may be any one of physical vapor deposition (PVD) and chemical vapor deposition (CVD). Physical vapor deposition such as vacuum vapor deposition is preferred. The wet film forming method can be inkjet method, spray method, nozzle printing method, spin coating method, dip coating method, casting method, die coating method, roll coating method, bar coating method, gravure printing coating method, etc. From the viewpoint of precision patterning, the inkjet method is preferred.
電荷阻斷膜(電子阻斷膜及電洞阻斷膜)的厚度分別較佳的是10nm~200nm，更佳的是30nm~150nm，特佳的是50nm~100nm。其原因在於：若其厚度過薄，則暗電流抑制效果降低；若過厚，則光電轉換效率降低。 The thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 10 nm to 200 nm, more preferably 30 nm to 150 nm, and particularly preferably 50 nm to 100 nm. The reason is that if the thickness is too thin, the dark current suppression effect is reduced; if it is too thick, the photoelectric conversion efficiency is reduced.
[基板] [Substrate]
光電轉換元件亦可進一步包含基板。所使用的基板的種類並無特別限制，可使用半導體基板、玻璃基板、或塑膠基板。 The photoelectric conversion element may further include a substrate. The type of the substrate used is not particularly limited, and a semiconductor substrate, a glass substrate, or a plastic substrate can be used.
另外，基板的位置並無特別限制，通常在基板上依序積層導電性膜、光電轉換膜、及透明導電性膜。 In addition, the position of the substrate is not particularly limited, and generally a conductive film, a photoelectric conversion film, and a transparent conductive film are sequentially laminated on the substrate.
[密封層] [Sealing layer]
光電轉換元件亦可進一步包含密封層。光電轉換材料存在由於水分子等劣化因素的存在而顯著地造成其性能劣化的現象，如下方式可防止上述劣化：藉由不滲透水分子的緻密的金屬氧化物、金屬氮化物、金屬氮氧化物等陶瓷或金剛石狀碳(DLC)等的密封層對光電轉換膜全體進行包覆而進行密封。 The photoelectric conversion element may further include a sealing layer. The photoelectric conversion material has a phenomenon that significantly deteriorates its performance due to the presence of degradation factors such as water molecules, which can be prevented by the following methods: dense metal oxides, metal nitrides, and metal oxynitrides that are impermeable to water molecules A sealing layer such as ceramic or diamond-like carbon (DLC) covers the entire photoelectric conversion film and seals it.
另外，密封層可依照日本專利特開2011-082508號公報的段落[0210]~段落[0215]的記載而進行材料的選擇及製造。 The sealing layer can be selected and manufactured in accordance with the description in paragraphs [0210] to [0215] of Japanese Patent Laid-Open No. 2011-082508.
[光感測器] [Light sensor]
光電轉換元件的用途例如可列舉光電池與光感測器，本發明的光電轉換元件較佳的是用作光感測器。光感測器可為單獨使用上述光電轉換元件的光感測器，較佳的是將上述光電轉換元件配置為直線狀的線感測器或者設為配置在平面上的2維感測器的形態的光感測器。本發明的光電轉換元件在線感測器中，藉由如掃描機等那樣使用光學系統及驅動部將光影像信息轉換為電訊號而作為攝影元件發揮功能，在2維感測器中，藉由如攝影模組那樣以光學系統在感測器上成像而將光影像信息轉換為電訊號而作為攝影元件發揮功能。 The use of the photoelectric conversion element includes, for example, a photovoltaic cell and a light sensor. The photoelectric conversion element of the present invention is preferably used as a light sensor. The light sensor may be a light sensor using the above-mentioned photoelectric conversion element alone. Preferably, the above-mentioned photoelectric conversion element is configured as a linear line sensor or a two-dimensional sensor arranged on a plane. Morphological light sensor. In the on-line sensor of the photoelectric conversion element of the present invention, the optical system and the driving unit are used to convert the optical image information into an electric signal, such as a scanner, and function as a photographic element. In a two-dimensional sensor, Like a photographing module, an optical system forms an image on a sensor, and converts light image information into an electrical signal to function as a photographing element.
光電池是發電裝置，因此將光能轉換為電能的效率成為重要的性能，但作為在暗處的電流即暗電流在功能上並不成為問題。 另外，無需設置彩色濾光片等的後段的加熱步驟。作為光感測器，將明暗訊號高精度地轉換為電訊號成為重要的性能，因此將光量 轉換為電流的效率亦為重要的性能，若在暗處輸出訊號，則成為雜訊，因此要求低的暗電流。另外，對於後段步驟的耐受性亦重要。 Since a photovoltaic cell is a power generation device, the efficiency of converting light energy into electrical energy becomes an important performance, but as a current in a dark place, that is, a dark current, there is no functional problem. In addition, it is not necessary to provide a subsequent heating step such as a color filter. As a light sensor, it is important to convert light and dark signals into electrical signals with high accuracy. The efficiency of conversion to current is also an important performance. If a signal is output in a dark place, it becomes noise, so a low dark current is required. In addition, tolerance to subsequent steps is also important.
[攝影元件] [Photographic element]
其次，對包含光電轉換元件10a的攝影元件的構成例加以說明。 Next, a configuration example of a photographing element including the photoelectric conversion element 10a will be described.
另外，在以下所說明的構成例中，關於具有與已經加以說明的構件等同等構成、作用的構件等，藉由在圖中附以同一符號或相當符號而使說明簡略化或省略說明。 In addition, in the configuration examples described below, descriptions of components having a structure equivalent to or equivalent to the components already described and functions are simplified or omitted by attaching the same or equivalent symbols to the drawings.
所謂攝影元件是將影像的光信息轉換為電訊號的元件，是指多個光電轉換元件以同一平面狀配置於矩陣上，可在各個光電轉換元件(畫素)中將光訊號轉換為電訊號，將該電訊號按照每個畫素而逐次地輸出至攝影元件外的元件。因此，每一個畫素中包含一個光電轉換元件、一個以上電晶體。 The so-called photographic element is an element that converts the optical information of an image into an electrical signal. It means that a plurality of photoelectric conversion elements are arranged on the matrix in the same plane. The optical signals can be converted into electrical signals in each photoelectric conversion element (pixel). , And output the electric signal to the elements outside the photographing element successively for each pixel. Therefore, each pixel contains one photoelectric conversion element and one or more transistors.
圖2是表示用以說明本發明的一實施方式的攝影元件的概略構成的示意性剖面圖。該攝影元件可搭載於數位相機、數位錄影機等攝影裝置、電子內視鏡、行動電話機等的攝影模組等中而使用。 FIG. 2 is a schematic cross-sectional view illustrating a schematic configuration of an imaging element according to an embodiment of the present invention. This photographing element can be used by being mounted in photographing devices such as digital cameras and digital video recorders, photographing modules such as electronic endoscopes and mobile phones.
該攝影元件包含如圖1(a)及圖1(b)所示的構成的多個光電轉換元件、形成有讀出電路(上述讀出電路讀出與各光電轉換元件的光電轉換膜中所產生的電荷對應的訊號)的電路基板，在該電路基板上方的同一面上，多個光電轉換元件成為排列為1維 狀或二維狀的構成。 This photographic element includes a plurality of photoelectric conversion elements having a structure as shown in FIG. 1 (a) and FIG. 1 (b), and a reading circuit formed in the photoelectric conversion film of the reading circuit and each photoelectric conversion element. (The signal corresponding to the generated electric charge) circuit board, on the same surface above the circuit board, a plurality of photoelectric conversion elements are arranged in one dimension Shape or two-dimensional shape.
圖2所示的攝影元件100包含：基板101、絕緣層102、連接電極103、畫素電極(下部電極)104、連接部105、連接部106、光電轉換膜107、對向電極(上部電極)108、緩衝層109、密封層110、彩色濾光片(CF)111、隔板112、遮光層113、保護層114、對向電極電壓供給部115、讀出電路116。 The imaging element 100 shown in FIG. 2 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode (lower electrode) 104, a connection portion 105, a connection portion 106, a photoelectric conversion film 107, and a counter electrode (upper electrode). 108, a buffer layer 109, a sealing layer 110, a color filter (CF) 111, a separator 112, a light shielding layer 113, a protective layer 114, a counter electrode voltage supply unit 115, and a readout circuit 116.
畫素電極104具有與圖1(a)及圖1(b)中所示的光電轉換元件10a的下部電極11相同的功能。對向電極108具有與圖1(a)及圖1(b)中所示的光電轉換元件10a的上部電極15相同的功能。光電轉換膜107的構成與圖1(a)及圖1(b)中所示的光電轉換元件10a的下部電極11及上部電極15間所設的層相同。 The pixel electrode 104 has the same function as the lower electrode 11 of the photoelectric conversion element 10a shown in FIGS. 1 (a) and 1 (b). The counter electrode 108 has the same function as the upper electrode 15 of the photoelectric conversion element 10 a shown in FIGS. 1 (a) and 1 (b). The structure of the photoelectric conversion film 107 is the same as the layer provided between the lower electrode 11 and the upper electrode 15 of the photoelectric conversion element 10a shown in FIGS. 1 (a) and 1 (b).
基板101是玻璃基板或Si等的半導體基板。在基板101上形成有絕緣層102。在絕緣層102的表面形成有多個畫素電極104與多個連接電極103。 The substrate 101 is a semiconductor substrate such as a glass substrate or Si. An insulating layer 102 is formed on the substrate 101. A plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.
光電轉換膜107是在多個畫素電極104上覆蓋該些而設置的所有光電轉換元件所共用的層。 The photoelectric conversion film 107 is a layer common to all the photoelectric conversion elements provided on the plurality of pixel electrodes 104 and covering them.
對向電極108是設在光電轉換膜107上的所有光電轉換元件所共用的1個電極。對向電極108形成至配置於光電轉換膜107的更外側的連接電極103上，與連接電極103電性連接。 The counter electrode 108 is one electrode common to all photoelectric conversion elements provided on the photoelectric conversion film 107. The counter electrode 108 is formed on the connection electrode 103 disposed outside the photoelectric conversion film 107 and is electrically connected to the connection electrode 103.
連接部106是埋設於絕緣層102，用以將連接電極103與對向電極電壓供給部115電性連接的插頭(plug)等。對向電極 電壓供給部115形成在基板101上，經由連接部106及連接電極103而給對向電極108施加規定的電壓。在所應施加給對向電極108的電壓比攝影元件的電源電壓高的情況下，藉由電荷泵等升壓電路使電源電壓升壓而供給上述規定的電壓。 The connection portion 106 is a plug or the like buried in the insulating layer 102 and used to electrically connect the connection electrode 103 and the counter electrode voltage supply portion 115. Counter electrode The voltage supply section 115 is formed on the substrate 101 and applies a predetermined voltage to the counter electrode 108 via the connection section 106 and the connection electrode 103. When the voltage to be applied to the counter electrode 108 is higher than the power supply voltage of the imaging element, the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.
讀出電路116與多個畫素電極104的各個對應而設於基板101上，讀出與由對應的畫素電極104所捕獲的電荷對應的訊號。讀出電路116包含例如電荷耦合元件(Charge Coupled Device，CCD)、互補金屬氧化半導體(Complementary Metal Oxide Semiconductor，CMOS)電路、或薄膜電晶體(Thin-Film Transistor，TFT)電路等，藉由在絕緣層102內所配置的未圖示的遮光層而遮光。讀出電路116經由連接部105而和與其對應的畫素電極104電性連接。 The readout circuit 116 is provided on the substrate 101 in correspondence with each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the electric charge captured by the corresponding pixel electrode 104. The readout circuit 116 includes, for example, a Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS) circuit, or a Thin-Film Transistor (TFT) circuit. A light shielding layer (not shown) arranged in the layer 102 blocks light. The readout circuit 116 is electrically connected to the corresponding pixel electrode 104 through the connection portion 105.
緩衝層109覆蓋對向電極108而形成在對向電極108上。密封層110覆蓋緩衝層109而形成在緩衝層109上。彩色濾光片111形成在與密封層110上的各畫素電極104對向的位置。 隔板112是設於彩色濾光片111彼此之間，用以使彩色濾光片111的透光效率提高者。 The buffer layer 109 covers the counter electrode 108 and is formed on the counter electrode 108. The sealing layer 110 covers the buffer layer 109 and is formed on the buffer layer 109. The color filter 111 is formed at a position opposed to each pixel electrode 104 on the sealing layer 110. The spacer 112 is provided between the color filters 111 to improve the light transmission efficiency of the color filters 111.
遮光層113形成在密封層110上的除設有彩色濾光片111及隔板112的區域以外的區域，防止光射入至於有效畫素區域以外所形成的光電轉換膜107。保護層114形成在彩色濾光片111、隔板112、及遮光層113上，保護攝影元件100全體。 The light shielding layer 113 is formed on a region other than the region where the color filter 111 and the spacer 112 are provided on the sealing layer 110, and prevents light from entering the photoelectric conversion film 107 formed outside the effective pixel region. The protective layer 114 is formed on the color filter 111, the spacer 112, and the light-shielding layer 113, and protects the entire imaging element 100.
在如上所述而構成的攝影元件100中，若射入光，則該 光入射至光電轉換膜107，於此處產生電荷。所產生的電荷中的電洞被畫素電極104所捕獲，與其量對應的電壓訊號被讀出電路116輸出至攝影元件100外部。 In the imaging element 100 configured as described above, when light is incident, Light is incident on the photoelectric conversion film 107, and charges are generated there. The hole in the generated electric charge is captured by the pixel electrode 104, and a voltage signal corresponding to the amount of the hole is output by the readout circuit 116 to the outside of the imaging element 100.
攝影元件100的製造方法如下所示。 The manufacturing method of the imaging element 100 is as follows.
在形成有對向電極電壓供給部115與讀出電路116的電路基板上形成連接部105、連接部106、多個連接電極103、多個畫素電極104、及絕緣層102。多個畫素電極104在絕緣層102的表面配置為例如正方格子狀。 A connection portion 105, a connection portion 106, a plurality of connection electrodes 103, a plurality of pixel electrodes 104, and an insulating layer 102 are formed on a circuit substrate on which a counter electrode voltage supply portion 115 and a readout circuit 116 are formed. The plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102 in a square grid shape, for example.
其次，在多個畫素電極104上藉由例如真空加熱蒸鍍法而形成光電轉換膜107。其次，在光電轉換膜107上藉由例如濺鍍法而在真空下形成對向電極108。其次，藉由例如真空加熱蒸鍍法而在對向電極108上依序形成緩衝層109、密封層110。其次，在形成彩色濾光片111、隔板112、遮光層113之後，形成保護層114而完成攝影元件100。 Next, a photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum heating evaporation method. Next, the counter electrode 108 is formed on the photoelectric conversion film 107 under a vacuum by, for example, a sputtering method. Next, a buffer layer 109 and a sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, a vacuum heating evaporation method. Next, after forming the color filter 111, the spacer 112, and the light-shielding layer 113, a protective layer 114 is formed to complete the imaging device 100.
在攝影元件100的製造方法中，亦可在光電轉換膜107的形成步驟與密封層110的形成步驟之間，追加將製作途中的攝影元件100置於非真空下的步驟從而防止多個光電轉換元件的性能劣化。藉由追加該步驟，可防止攝影元件100的性能劣化且抑制製造成本。 In the manufacturing method of the photographic element 100, a step of placing the photographic element 100 in the process of production under a non-vacuum may be added between the step of forming the photoelectric conversion film 107 and the step of forming the sealing layer 110 to prevent multiple photoelectric conversions. The performance of the component is deteriorated. By adding this step, it is possible to prevent performance degradation of the imaging element 100 and suppress manufacturing costs.
[實施例] [Example]
以下表示實施例，但本發明並不限定於該些實施例。 Examples are shown below, but the present invention is not limited to these examples.
(化合物D3的合成) (Synthesis of Compound D3)
在100mL三口圓底燒瓶中加入對溴苄腈5.46g(30mmol)、第三戊醇20mL、第三丁醇鉀5.05g(45mmol)，一面攪拌一面加熱至95℃。在該混合物中，以25分鐘滴加在第三戊醇3mL中溶解有琥珀酸二異丙酯2.73g(13.5mmol)的溶液。在滴加後，對反應混合物進行4小時的加熱回流，其次冷卻至50℃。在該混合物中加入水15mL與甲醇15mL，進行30分鐘的攪拌並濾取沈澱物。用50%水性甲醇、水對所得的紅色粉末加以清洗，在80℃下進行真空乾燥，獲得3.0g(產率為50%)作為紅色粉末的化合物1。 In a 100 mL three-neck round bottom flask, 5.46 g (30 mmol) of p-bromobenzonitrile, 20 mL of tertiary pentanol, and 5.05 g (45 mmol) of potassium tert-butoxide were added, and heated to 95 ° C. while stirring. To this mixture, a solution in which 2.73 g (13.5 mmol) of diisopropyl succinate was dissolved in 3 mL of third pentanol was added dropwise over 25 minutes. After the dropwise addition, the reaction mixture was heated under reflux for 4 hours, followed by cooling to 50 ° C. 15 mL of water and 15 mL of methanol were added to the mixture, and the mixture was stirred for 30 minutes, and the precipitate was collected by filtration. The obtained red powder was washed with 50% aqueous methanol and water, and vacuum-dried at 80 ° C to obtain 3.0 g (yield 50%) of Compound 1 as a red powder.
在200mL三口圓底燒瓶中加入化合物1(1.0g，2.24mmol)、碳酸鉀1.24g(8.97mmol)、N-甲基吡咯啶酮35mL，在氮氣環境下、室溫下進行30分鐘的攪拌。其次，加入碘甲烷4.07g(28.7mmol)而在室溫下進行1小時的攪拌。進一步加入碘甲烷3.18g(22.4mmol)而加熱至55℃，進行5小時的攪拌。冷卻 至室溫後，加入水100mL，濾取所得的固體。藉由矽膠管柱層析法進行純化，獲得319mg(產率為30%)作為橙色粉末的化合物2。 A 200 mL three-necked round-bottom flask was charged with Compound 1 (1.0 g, 2.24 mmol), potassium carbonate 1.24 g (8.97 mmol), and 35 mL of N-methylpyrrolidone, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. Next, 4.07 g (28.7 mmol) of methyl iodide was added and the mixture was stirred at room temperature for 1 hour. Further, 3.18 g (22.4 mmol) of methyl iodide was added, and the mixture was heated to 55 ° C. and stirred for 5 hours. cool down After reaching room temperature, 100 mL of water was added, and the obtained solid was collected by filtration. Purification was performed by silica gel column chromatography to obtain 319 mg (yield 30%) of Compound 2 as an orange powder.
在100mL三口圓底燒瓶中加入化合物2(0.3g，0.63mmol)、Pd2(dba)350mg、1,1'-雙(二苯基膦)二茂鐵(1,1'-Bis(diphenylphosphino)ferrocene，DPPF)30mg、二甲苯(xylene)15mL，在氮氣環境下、室溫下進行15分鐘的攪拌。加入二苯基胺0.32g(1.89mmol)、第三丁醇鈉0.9g(9.45mmol)而在100℃下進行7小時的攪拌，其後冷卻至室溫。在反應混合物中加入水與乙酸乙酯，對有機層進行萃取，將溶劑蒸餾除去。藉由矽膠管柱層析法進行純化，獲得0.26g(產率為64%)作為紅褐色粉末的D3。 In a 100 mL three-necked round-bottomed flask, compound 2 (0.3 g, 0.63 mmol), Pd 2 (dba) 3 50 mg, 1,1'-bis (diphenylphosphine) ferrocene (1,1'-Bis (diphenylphosphino) ) ferrocene (DPPF) 30 mg, xylene 15 mL, and stirred under a nitrogen environment at room temperature for 15 minutes. Diphenylamine 0.32 g (1.89 mmol) and sodium tert-butoxide 0.9 g (9.45 mmol) were added, and the mixture was stirred at 100 ° C. for 7 hours, and then cooled to room temperature. Water and ethyl acetate were added to the reaction mixture, the organic layer was extracted, and the solvent was distilled off. Purification by silica gel column chromatography gave 0.26 g (64% yield) of D3 as a reddish brown powder.
另外，後述的化合物D1~化合物D2、及化合物D4~化合物D14可參照上述化合物D3的合成方法及公知的方法而進行合成。 In addition, the compounds D1 to D2 and D4 to D14 to be described later can be synthesized by referring to the method for synthesizing the compound D3 and a known method.
以下匯總表示本實施例及比較例中所使用的化合物(D1~D14、RD1~RD4)。 The compounds (D1 to D14, RD1 to RD4) used in the examples and comparative examples are collectively shown below.
[化31]
[化32]
<光電轉換元件的製作> <Production of photoelectric conversion element>
製作圖1(a)的形態的光電轉換元件。此處，光電轉換元件 包含下部電極11、電子阻斷膜16A、光電轉換膜12及上部電極15。 A photoelectric conversion element in the form of FIG. 1 (a) was produced. Here, the photoelectric conversion element It includes a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, and an upper electrode 15.
具體而言，藉由濺鍍法在玻璃基板上成膜非晶質性ITO而形成下部電極11(厚度為30nm)，進一步藉由真空加熱蒸鍍法在下部電極11上成膜下述化合物(EB-1)而形成電子阻斷膜16A(厚度為100nm)。進一步在將基板的溫度控制為25℃的狀態下，在電子阻斷膜16A上，以上述化合物(D1~D14、RD1~RD4)與富勒烯(C60)分別按單層換算而成為100nm、300nm的方式藉由真空加熱蒸鍍進行共蒸鍍而成膜，形成光電轉換膜12。進一步在光電轉換膜12上藉由濺鍍法成膜非晶質性ITO，形成上部電極15(透明導電性膜)(厚度為10nm)。在上部電極15上藉由加熱蒸鍍形成SiO膜作為密封層之後，藉由原子層化學氣相沈積(Atomic Layer Chemical Vapor Deposition，ALCVD)法在其上形成氧化鋁(Al2O3)層，製作光電轉換元件。 Specifically, the lower electrode 11 (thickness: 30 nm) was formed by forming an amorphous ITO film on a glass substrate by a sputtering method, and the following compound was further formed on the lower electrode 11 by a vacuum heating evaporation method ( EB-1) to form an electron blocking film 16A (thickness: 100 nm). In a state where the substrate temperature was controlled to 25 ° C, the above compounds (D1 to D14, RD1 to RD4) and fullerene (C 60 ) were converted to 100 nm on a single-layer basis on the electron blocking film 16A. At 300 nm, a film was formed by co-evaporation by vacuum heating vapor deposition, and a photoelectric conversion film 12 was formed. Further, an amorphous ITO was formed on the photoelectric conversion film 12 by a sputtering method to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming a SiO film as a sealing layer on the upper electrode 15 by heating evaporation, an aluminum oxide (Al 2 O 3 ) layer is formed thereon by an atomic layer chemical vapor deposition (ALCVD) method. Production of photoelectric conversion elements.
<元件耐熱性> <Element heat resistance>
將所得的各元件在氮氣環境下、150℃的加熱板上保持20分鐘而進行熱退火，恢復至室溫後測定暗電流，將自退火前起的暗電流的增加率[{(退火後的暗電流值-退火前的暗電流值)/退火前的暗電流值}×100(%)]不足5%的情況作為「A」、將5%以上且不足10%的情況作為「B」、將超過10%的情況作為「C」而記載於表1的「耐熱性」一欄中。另外，實用上必須為A或B。 The obtained elements were thermally annealed in a nitrogen atmosphere on a 150 ° C hot plate for 20 minutes, and the dark current was measured after returning to room temperature. The increase rate of the dark current from before the annealing was [{(after annealing) Dark current value-Dark current value before annealing) / Dark current value before annealing} × 100 (%)] When the value is less than 5%, it is regarded as "A", and when it is 5% or more and less than 10%, it is regarded as "B", Cases exceeding 10% are described as "C" in the "Heat resistance" column of Table 1. In addition, it must be A or B practically.
<響應速度(98%訊號上升時間)的評價> <Evaluation of response speed (98% signal rise time)>
測定對所得的固態攝影元件中的光電轉換元件施加2×105V/cm的電場時的相對響應速度(自0至98%訊號強度的上升時間)，將實施例1設為1而求出相對值，記載於表1的「響應速度(相對值)」一欄中。另外，在測定各元件的光電轉換性能時，自上部電極(透明導電性膜)側射入光。以下表示相對值的求出方法。 The relative response speed (rising time from 0 to 98% signal intensity) when an electric field of 2 × 10 5 V / cm was applied to the photoelectric conversion element in the obtained solid-state imaging element was measured, and Example 1 was set to 1 to obtain The relative value is described in the "Response speed (relative value)" column in Table 1. When measuring the photoelectric conversion performance of each element, light was incident from the upper electrode (transparent conductive film) side. The method of obtaining the relative value is shown below.
(將實施例1設為1的相對值) (Set Example 1 to a relative value of 1.)
=[實施例(或比較例)X中的自0至98%訊號強度的上升時間]/[實施例1中的自0至98%訊號強度的上升時間] = [Rise time from 0 to 98% signal strength in Example (or Comparative Example) X] / [Rise time from 0 to 98% signal strength in Example 1]
另外，實用上較佳的是20以內，更佳的是5以內。 In addition, practically, it is preferably within 20, and more preferably within 5.
如上述表1所示，確認在本發明的光電轉換元件中顯示出優異的耐熱性及響應性。 As shown in Table 1 above, it was confirmed that the photoelectric conversion element of the present invention exhibits excellent heat resistance and responsiveness.
例如，根據實施例1~實施例14的比較可知，確認若Ar1與R11、Ar1與R12、R11與R12、Ar2與R13、Ar2與R14、及R13與R14的至少一者相互鍵結而形成環，則耐熱性更優異。 For example, it can be seen from the comparison of Examples 1 to 14 that if Ar 1 and R 11 , Ar 1 and R 12 , R 11 and R 12 , Ar 2 and R 13 , Ar 2 and R 14 , and R 13 and When at least one of R 14 is bonded to each other to form a ring, the heat resistance is more excellent.
而且，根據實施例1與實施例5的比較可知，確認在通式(1)~通式(3)中的Ar1與R11、Ar1與R12及R11與R12的至少一者相互鍵結而形成環，Ar2與R13、Ar2與R14、及R13與R14的至少一者相互鍵結而形成環的情況下(相當於實施例1)，響應性更優異。 Further, it is known from the comparison between Example 1 and Example 5 that at least one of Ar 1 and R 11 , Ar 1 and R 12, and R 11 and R 12 in the general formulae (1) to (3) was confirmed. When a ring is bonded to each other, at least one of Ar 2 and R 13 , Ar 2 and R 14 , and R 13 and R 14 is bonded to each other to form a ring (equivalent to Example 1), and the response is more excellent. .
而且，根據實施例4與實施例6的比較可知，確認在Ar1與R11、Ar1與R12、R11與R12、Ar2與R13、Ar2與R14、R13與R14分別並不經由連結基而直接鍵結的情況下(相當於實施例6)，響應性更優異。 Furthermore, it can be seen from the comparison between Example 4 and Example 6 that Ar 1 and R 11 , Ar 1 and R 12 , R 11 and R 12 , Ar 2 and R 13 , Ar 2 and R 14 , and R 13 and R were confirmed. In the case where 14 is directly bonded without a linking group (corresponding to Example 6), the responsiveness is more excellent.
而且，根據實施例3與實施例7的比較可知，確認在X1及X2為O(氧原子)的情況下(相當於實施例3)，響應速度及耐熱性更優異。 Further, it is known from the comparison between Example 3 and Example 7 that when X 1 and X 2 are O (oxygen atom) (corresponding to Example 3), the response speed and heat resistance are more excellent.
而且，根據實施例1與實施例8的比較可知，確認在Ar1及Ar2為伸芳基的情況下(相當於實施例1)，響應性更優異。 Further, it is found from a comparison between Example 1 and Example 8 that when Ar 1 and Ar 2 are arylene groups (equivalent to Example 1), the response is more excellent.
另一方面，確認在使用專利文獻1的實施例欄中所使用的RD1的情況下(相常於比較例1)，耐熱性及響應性差。 On the other hand, when the RD1 used in the Example column of Patent Document 1 was used (compared to Comparative Example 1), it was confirmed that the heat resistance and responsiveness were poor.
而且，確認在使用通式(1)~通式(3)中的R1及R2為氫原子的RD2的情況下(相當於比較例2)，響應性差。 Furthermore, when using RD2 in which R 1 and R 2 in the general formulae (1) to (3) were hydrogen atoms (corresponding to Comparative Example 2), it was confirmed that the response was poor.
另外，確認在使用通式(1)~通式(3)中的R11~R14為烷基的RD3的情況下(相當於比較例3)，響應性差。 In addition, when using RD3 in which R 11 to R 14 in the general formulae (1) to (3) were alkyl groups (corresponding to Comparative Example 3), the response was poor.
而且，在使用不具有胺基的RD4的情況下(相當於比較例4)，在蒸鍍時化合物分解，根本無法製造光電轉換膜。 Moreover, when RD4 which does not have an amine group is used (equivalent to the comparative example 4), a compound is decomposed during vapor deposition, and a photoelectric conversion film cannot be manufactured at all.
另外，RD2及RD3相當於日本專利特開2010-192782號公報中所例示的例示化合物(19)及例示化合物(71)，RD4相當於日本專利特開2003-346926號公報的實施例6中所使用的化合物。 In addition, RD2 and RD3 correspond to the exemplified compound (19) and the exemplified compound (71) disclosed in Japanese Patent Laid-Open No. 2010-192782, and RD4 corresponds to that described in Example 6 of Japanese Patent Laid-Open No. 2003-346926. Used compounds.
<攝影元件的製作> <Production of Photographic Elements>
製作與圖2所示的形態同樣的攝影元件。亦即，藉由濺鍍法 在CMOS基板上成膜非晶質性TiN 30nm後，藉由光微影法在CMOS基板上的光電二極體(PD)上以分別存在各1個畫素的方式進行圖案化而製成下部電極，在電子阻斷材料的成膜以後與實施例1~實施例14、比較例1~比較例4同樣地製作。同樣地進行其評價，獲得與表1同樣的結果，可知在攝影元件中亦適用於製造並顯示出優異的性能。 An imaging element having the same configuration as that shown in FIG. 2 was produced. That is, by sputtering After forming an amorphous TiN film on the CMOS substrate at 30 nm, the photodiode method was used to pattern the photodiodes (PD) on the CMOS substrate in such a manner that there is one pixel each to form a lower portion. The electrodes were produced in the same manner as in Examples 1 to 14 and Comparative Examples 1 to 4 after the formation of the electron blocking material. The evaluation was performed in the same manner, and the same results as in Table 1 were obtained. It was found that the imaging element is suitable for manufacturing and exhibits excellent performance.
10a‧‧‧光電轉換元件 10a‧‧‧photoelectric conversion element
11‧‧‧下部電極(導電性膜) 11‧‧‧Lower electrode (conductive film)
12‧‧‧光電轉換膜 12‧‧‧photoelectric conversion film
15‧‧‧上部電極(透明導電性膜) 15‧‧‧upper electrode (transparent conductive film)
16A‧‧‧電子阻斷膜 16A‧‧‧Electronic blocking film
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