TW201143183A - Photoelectric conversion device and imaging device - Google Patents

Abstract

A photoelectric conversion device having an organic photoelectric conversion layer between a first electrode and a second electrode, wherein a material used for forming the organic photoelectric conversion layer has a purity of 96.5% or above as determined by liquid chromatography.

Description

1 1201143183 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a photoelectric conversion device and an image forming device which perform photoelectric conversion in respective organic photoelectric conversion layers. x [Prior Art] Most of the visible light sensors currently used are devices each manufactured by forming a photoelectric conversion region including a PN junction in a surface portion of a semiconductor substrate such as a stone substrate. As for the solid-state imaging device, such a planar type photoreceptor is mainly used, in which a plurality of photoelectric conversion regions are formed in a two-dimensional array arrangement in a surface portion of a semiconductor substrate, each photoelectric conversion region is used as a pixel, and by means of a CCD type Or a CMOS type signal readout circuit reads out a signal generated by photoelectric conversion to the outside in each pixel. The use of a color filter that transmits only light of certain wavelengths to achieve color separation (c 〇1〇°r separation) toward the side of the incident light to form a solid-state color imaging device has become A general method and more particularly, is a well-known single-board sensor commonly used in digital cameras and the like, in which blue (B), green (G), and red light can be transmitted, respectively. The color filters of R) are regularly placed on respective pixels formed in a two-dimensional array arrangement. b However, the single-plate sensor of such a structure has a problem of low light utilization efficiency. This is because the color filter transmits only light of a certain finite wavelength and cannot use light of other wavelengths that the color filter does not transmit. Further, in recent years, the number of pixels mounted on a wafer has increased to 10 million pixels or more than 10 million pixels, and thus the pixel size has become smaller and the surface of the photodiode region has decreased. In addition, the signal readout circuit also needs to be formed on the same semiconductor substrate. Therefore, a reduction in the aperture ratio and a decrease in light collection efficiency become problems. A method for solving these problems has been devised in that a photoelectric conversion region capable of detecting light of different wavelengths is stacked in a direction perpendicular to the surface of the semiconductor substrate. An example of an imaging device of this type is disclosed in U.S. Patent No. 5,965, 875, which is based on the use of the optical absorption coefficient of the bismuth and the wavelength dependence, and in the case where the detectable light is limited to light in the visible region. A plurality of photoelectric conversion regions forming a structure stacked in the depth direction of the semiconductor substrate, thereby achieving color separation according to the difference in their respective depths. Further, an image forming apparatus having an organic photoelectric conversion layer stacked over a semiconductor substrate is disclosed in JP-A-2〇〇3-33255l. However, in the case of utilizing the difference in the depth direction of the crucible, the wavelength ranges of the light absorbed by the side photoelectric conversion regions forming the finance portion (fourth portion) substantially overlap each other and the spectrum of the device is characteristically poor. The device has another problem of poor color separation. It is known that another technique for increasing the aperture ratio is to form a structure in which a layer of an amorphous photoelectric conversion film and an organic conversion conversion film is provided over a semiconductor substrate on which a signal readout circuit is formed. Heretofore, several examples of each of the photoelectric conversion device, the imaging device, the light sensing H, and the solar cell using the organic photoelectric conversion film have been known. Among them, there are special concerns (4) that the photoelectric conversion efficiency is insufficient and the dark electricity is generated: The method of introducing the pn junction and introducing the heterogeneous structure of the body (5) is introduced, and the method of introducing the barrier layer or the _ thing is introduced. However, there is neither a description of the method disclosed in 4 201143183. applied to a photoelectric conversion device for use in an image forming apparatus, nor a description of the application proposed. Although in recent years, a compound capable of exhibiting high performance has been successfully found as a material for a photoelectric conversion layer, the process from synthesis to a manufacturing apparatus has not been sufficiently considered to exhibit the performance of the compound, so that the influence of impurities cannot be eliminated. . Furthermore, although the effectiveness of the electron blocking layer is also disclosed in jp-A-2007-59517, under the above circumstances, sufficient attention has been paid to the process conditions and the influence of impurities. On the other hand, in the field of OLEDs (which represent organic light-emitting diodes), it is disclosed in JP-A-2004-327455 and JP-A-2005-240011 that tooth impurities and palladium impurities have an effect on the lifetime of the OLED. However, the influence of impurities in the case of application to a photoelectric conversion device has not been described. In addition, as time passes, the amount of excitons generated and the amount of luminescence are reduced, thereby shortening the lifetime of the OLED. Therefore, impurities can cause a decrease in the amount of light emission to be accelerated. On the other hand, with regard to the photoelectric conversion device, the presence of impurities causes the device itself to change, rather than its life. The light emission process is doubled, and during the photoelectric conversion process, its excited state immediately causes charge separation. Z-turning is obviously not obvious in the paving of its ability to show its performance. 〇 The amount of luminescence of LEDs decreases with time, and the phenomenon of organic thin charge separation cannot be treated equally. In the field of electricity generation, Tongfu knows that the purification of the chowder by sublimation will improve. However, what impurities affect power generation is still unknown. What is the effect of the dark current and fast-turning of the Wei device? 201143183 The current is high in photoelectric conversion efficiency, and the weak dark electricity meets the following requirements: 1. The organic photoelectric conversion film in the device is 1. In response, the money photoelectric conversion is:: The signal charge generated after dissociation can be transmitted to the two electrodes, and the cuts of the scorpion are lost: more specifically, the film is required to ensure a reduced number of ▲ capture sites (carrier ping site) High charge migration and charge transport capability. It is known that impurities contained in an organic semiconductor material serve as a capture site for charges, resulting in a decrease in mobility and charge transport capability, but hitherto no known impurities have been found in known examples. The conversion efficiency requires that the stability of the excitons is low, whereby the excitons can be rapidly dissociated by an applied electric field or an electric field generated internally by a pn junction or the like (the exciton dissociation efficiency is high). It is known that the mixing of impurities in an organic dye causes exciton deactivation, thereby deteriorating the exciton dissociation efficiency. However, a detailed description about impurities has not been found so far in the known examples. 3. In order to minimize the number of carriers generated inside the film under dark conditions, such film structures and materials are appropriately selected so that the intermediate energy level inside the film is low and serves as an intermediate energy level. The total content of impurities is reduced. However, no specific description about impurities has been found so far in the known examples. SUMMARY OF THE INVENTION An object of the present invention is to provide a photoelectric conversion device and an image forming device each having an organic photoelectric conversion layer, which are reduced in price by adjusting the impurity content of the organic photoelectric layer 6 201143183. The organic photoelectric conversion layer is manufactured at low cost, thereby exhibiting high photoelectric conversion efficiency, weak dark current characteristics, and fast response. And the photoelectric conversion device with organic materials is affected by impurities, so it is used

The purity of the material is important. For example, regarding a semiconductor wafer forming a currently used CCD type or CMOS type image sensor, the purity of a semiconductor as a material thereof is required to be 99.9999 or more than 99.9999, and the purity of the semiconductor is required to be cut or clarified. It can be better. Fine, paste material ^ the higher the purity, the greater the total material cost. Therefore, there is a problem that the cost of the device is increased. . However, the impurities affecting the performance of the photoelectric conversion device vary depending on the structure of the photoelectric conversion material used in the device. It is found that the material contained in the material exerts the same degree of influence on the performance of the photoelectric conversion device, but different energy is given to the photoelectric conversion device according to the structure of the material and the purpose of use of the material (middle) ====== The photoelectric conversion of the embodiment of the invention: μ, so as to achieve the purity of the material of the photoelectric conversion layer of the object of the present invention, does not need to be: / it has at least a few of it, thereby reducing the material in &quot;9999, but can be a case SOLUTION &lt;1&gt; A photoelectric conversion device, = in the above-mentioned invention, but the organic photoelectric conversion layer between the following actual electrodes can be found in the invention, which is in the first electrode and the second electrical layer The material was measured by liquid chromatography (d) to form the organic photoelectric conversion '疋 having a purity of 96.5% or more than 96.5% 20114313⁄4. &lt;2&gt; The photoelectric conversion device according to the above, wherein the material for forming the organic photoelectric conversion layer has an oxidized compound impurity content of 9, ah or less than 9, _ ppm. The photoelectric conversion device according to <1>, wherein the material for forming the organic photoelectric conversion layer is a material which has been purified by solution refining. The photoelectric conversion device according to the above, wherein the material for forming the organic photoelectric conversion layer is a material which has been purified by sublimati refining. The photoelectric conversion device according to any one of <1>, wherein a charge blocking layer is provided between the electrode and the organic photoelectric conversion layer. &lt;6&gt; The photoelectric conversion device of &lt;5&gt;, wherein the charge blocking layer is an electron blocking layer. &lt;7&gt; The photoelectric conversion device of &lt;6&gt;, wherein the electronic p-combat material used in the electron blocking layer has a purity of 96.7% or more than 96.7% as determined by liquid chromatography 9. Halide impurity content of 〇〇〇ppm or less than 9 〇〇〇ppm. &lt;8&gt; The photoelectric conversion device according to <6>, wherein the electron blocking material used in the electron P and in the seed layer has a purity of 96.7% or more than 96.7% as determined by liquid chromatography and 4 〇〇〇卯111 or less than 4, 〇〇〇卯111 heavy metal impurity content. &lt;9&gt; The photoelectric conversion device according to &lt;6&gt;, wherein the electron blocking material used in the electron blocking layer is a material which has been purified by solution refining 8 1. 1.201143183. &lt;10&gt; The photoelectric conversion device according to <6>, wherein the electron blocking material used in the electron blocking layer is a material which has been purified by sublimation purification. &lt;11&gt; The photoelectric conversion device according to &lt;6&gt;, wherein the electron blocking material used in the electron blocking layer is a triarylamine compound. The photoelectric conversion device according to <1>, wherein the material for forming the organic photoelectric conversion layer is contained in a visible light wavelength region extending from 4 nanometers to 8 nanometers. The photoelectric conversion device of any one of &lt;1&gt; to &lt;12&gt;, wherein the electric field is set to l4 volts/cm to 1 x 〇7 volts/cm. Between the first electrode and the second electrode. &lt;14&gt; The photoelectric conversion device of &lt;1&gt;, wherein the organic photoelectric conversion layer comprises a novele. &lt;15&gt; An image forming apparatus comprising: the photoelectric conversion device according to &lt;1&gt;, and a semiconductor substrate, wherein the photoelectric conversion device is stacked on a surface of the semiconductor substrate. According to the present invention, even a material having a purity of 96.5% can be used to form a photoelectric conversion layer that ensures high photoelectric conversion efficiency and a weak dark current characteristic response, and is currently used for a photoelectric conversion device: The material can therefore reduce the cost of manufacturing the photoelectric conversion device for imaging. [Embodiment] 201143183 A preferred embodiment of the present invention is described below. The I is set as a photoelectric conversion device, each of which has an organic photoelectric conversion film containing at least one material, and a coarsely-formed ancient shoal, and each device is characterized by a material for a shouting device having HPLC (high efficiency liquid) Phase chromatography (_Yang Yi

Llqmd Chr〇matography)) % measured or more than % pure. The photoelectric conversion device according to the embodiment of the present invention is affected by impurities because the photoelectric conversion device has an organic material, and therefore the purity of the material is important to it. Since the purity of the organic material cannot be measured after the material is incorporated into the device, the purity of the material prior to the clue is becoming important. At least 96.5% of the purity is suitable for the chopped organic material of the present invention. However, unless the sum of material costs is high, '99% or more than 99% is particularly advantageous. Preferably, practical general-purpose HPLC (high performance liquid chromatography) is used as a purity determination method. The purity value can be determined by monitoring the peak of the light-absorbing lining in the whole chromatogram under the absorption of light (for example, 254 nm) in almost all organic materials. The percentage. The organic photoelectric conversion film is a film containing a photoelectric conversion material, and an organic dye is preferably used as the photoelectric conversion material because the material is required to completely absorb the visible light involved in photoelectric conversion, and more preferably, the organic dye is in 400 nm. The maximum value is in the visible light region of rice to _ nanometer. In order to check the absorption characteristics, the organic dye is suitably in a film state, but it may also be in a solution (e.g., a gas-like solution), which provides almost equal results. The larger the absorption constant, the better, and more specifically, the value is preferably 2〇, 〇〇°〇201143183 I.-I-factory liter/mole/cm (L/mol/cm) or more than 2〇, _ Liter / Moule / cm, more preferably 40,000 liters / Moule / cm or more than 4 liters / Moule / cm. For charge separation and signal readout, ageing materials are preferred and have a set value of oxidation potential, and more specifically 'for Ag/AgCl in acetonitrile solution, the oxidation potential is preferably 〇4 volts to 〗 〇 volts, especially good for 〇. 5 volts to 0.8 volts. Since the organic dye is used in a film state, the film IP (free potential) value is preferably 5 〇 electron volts to 5 7 electron volts, particularly preferably 5.2 electron volts to 6 electron volts. As for the structure of the photoelectric conversion material, examples are shown as jp_A 2〇〇6 86157, JP-A-2006-86160, JP-A-2006-100502, JP-A-2006-100508, JP-A-2006-100767 &gt; JP- A-2006-339424 ^ The dye disclosed in JP-A-2008-244296 and JP-A-2009-088291. In particular, the compounds disclosed in JP-A-2000-297068 can be used. The compound represented by the following formula (I) is suitable as a photoelectric conversion material.

In the formula (I), Zi represents a fused ring containing at least two carbon atoms and containing at least one 5-membered ring or 6-membered ring or a combination thereof, and each of the groups represents an unsubstituted methine group or The substituted methine group represents an aryl group or a heteroaryl group, and η represents an integer equal to or greater than 0. Ζ! denotes a fused ring containing at least two carbon atoms and containing at least one 5-membered ring or 6-membered ring or a combination thereof. It is generally used as the acid core in the mer〇cyanine 11 201143183 wi dye as a minor ring having at least a 5-membered ring or a 6-membered ring or a combination thereof and examples thereof include the following: (a) 1 a 3-dicarbonyl nucleus such as a u-fedone diketone nucleus, a cyclohexanedione, a 5,5-dimercapto-1,3-cyclohexanedifluorene, and a diterpenoid. (b) Pyrazolone nucleus, such as μphenyl-2-pyrazoline-5-one, 3-methyl-1·stupyl-2♦ sitting _5__ and Η2·benzoxanthyl) _3_methyl·2·η is more than saliva ^^•5-brew). (C) Isoxazolinone nucleus, for example, 3-phenyl-2-isoxazoline ML S _ii produced. yen λ 3-methyl-2-iso. Evil saliva _5_ class (4) hydroxy nucleus, such as burning base · 2, 3 _ two gas - 2. through ten. (e) 2,4,6-three steel hexahydrogen + nucleation, such as barbituric acid (^ her 2. thiobarbituric acid and its younger. Examples of derivatives package! Ship base (such as Or ethyl or 2-thiobarbituric acid, which has 2 calcinations in place.

Such as phenyl, phenyl), or have two aryl groups at the 1 and 3 positions C=; or t ethoxylate phenyl), or at 1 position and = have 1 alkyl group (such as ethyl) And i aryl groups (or two heterocyclic groups at the 1 and 3 positions (such as 2-n ratio bite A). Factory and ^i^2, 4 ships °&quot; dilemma, (four) Luo materials Crhodanin, f Kiro ^ \ ^ examples include 3_ unified base rhodamine (such as: tannin (such as 3, 3 broken silk), 3 lone 1 Pang" Ben Kirodin) and each in the 3rd via gamma (four) Rodenin (such as 3 like bite base) Luo Daning). Heterocyclic group substitution·&lt; 12 201143183^ (g) 2-sulfo-2,4-oxazolidinedione (2-sulfo-2,4-(3H,5H)-oxazolidinedione core), for example 3 -Ethyl-2-sulfo-2,4-° stagnation diketone. (h) A thioheterocyclenone nucleus such as 3(2H)-thiacyclenone-1,1-dioxide. (i) a 2-sulfo-2,5-thiazolidinone core such as 3-ethyl-2-sulfur-2,5-sigh bite II. (j) 2,4-° sputum bite two-nucleus, eg 2,4-bite two-brew), 3-ethyl-2,4-thiazolidinone and 3-phenyl-2,4- Thiazolidinedione. (k) 嗤 嗤 -4- -4- ketone nucleus, such as 4- 嗔嗤 _ _ and 2-ethyl -4- 嗟 β sitinone. (l) 2,4-Imidazolidinedione (beta), such as 2,4-imidazolidinium II and 3-ethyl-2,4-^β. (m) 2-Sulpho-2,4-n-myzolopyridinone (2-thioethyl carbazide) nucleus, for example, 2-thio-2,4-imidazolidinone and 3-ethyl-2_ Sulfur-2,4-oxazolidinone. (η) Imidazoline-5-one nucleus, for example 2-propyl decyl-2-imidazolinium 5-one. (ο) 3,5-pyrazolidinedione core, such as i, 2, diphenyl-3, 5-pyrazolidinedione and 1,2-dimethyl-3,5-σ ratio two_. (Ρ) Benzophene-3-one nucleus, such as benzophenone _3_ 嗣, pendant oxy thiophene-3-one, and di- oxybenzothiophene -3- ketone. (q) Indanone core, for example [fluorenone, 3 phenyl hydrazine, thrift, 3-mercapto-1 ketone, 3,3 diphenyl ketone and 3,3 _ The dimethyl quinone 鲷0 is preferably formed by the y, 3 nd nucleus, B saliline nucleus, ns. ketone hexahydropyrimidine nucleus (including thione bodies such as barbituric acid nucleus or 2_ sulfur 'generation 13 201143183 barbituric acid nucleus), 2-sulfo-2,4-thiazolidinone nucleus, 2 sulphur 2,4 oxazolidine di-nuclear 1 nucleus, 2-sulfur - 2, 5- oxazolidinedione nucleus, 2,4-oxazolidinone nucleus, 2,4-oxadazoledione nucleus, 2-sulfo-2,4-imidazolidindione nucleus, 2·imidazoline _ a 5-keto nucleus, a 3,5-pyrazolidinedione nucleus or a benzothiophene -3- ketone nucleus; more preferably an anthracene, a 3-dicarbonyl nucleus, a 2,4,6-trione hexahydropyrimidine nucleus (including a thione body, such as a barbituric acid di- or 2-thiobarbituric acid nucleus, a 3,5-pyrazolidinedione nucleus or a benzothiophene _ or a knuckle _; more preferably a second nucleus or 2, 4,6-tris-hexahydropyridinium nucleus (including thione bodies, such as barbituric acid nucleus or 2 thiobarbituric acid nucleus); especially preferably 1,3 bismuth, barbital a 2, thiobarbituric acid nucleus or a derivative of each nucleus. L, L2 and L3 each independently represent an unsubstituted indenyl or methine group. L1 to L3 may be combined with each other to form a ring, and the formed sulfhydryl ring, cyclopentane, benzene ring, naphthalene ring, porphin ring or ruthenium substituted fluorenyl may have a substituent as described below. However, it is preferred that all of the ethylene 2^3 are unsubstituted subunits. IM4 It is not an integer or an integer of G. It is recorded as an integer from G to 3. The increase in the i/n value of the county makes the absorption wavelength region of the compound shift to more visible ====. The aryl or heteroaryl group, preferably an aryl group, is represented by the formation of κιαλ 1 by thermal deposition in the thermal fractionation of the compound. The aryl group represented by 〇, which is represented by a certain D1, is preferably an aromatic aryl group having 6 to 3 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent W as described below, and it is preferably an aryl group having 6 to 18 carbon atoms and which may have an alkyl substituent having 1 to 4 carbon atoms. Examples of the aryl group include a strepyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a phenanthryl group, a nonylphenyl group, and a nonylphenyl group. Among these groups, stupyl and naphthyl are superior to other groups. The heteroaryl group represented by Di is preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably a heteroaryl group having 4 to 18 carbon atoms. The heteroaryl group I has a substituent w as described below, and it is preferably a heteroaryl group having 4 to 18 stone anodic atoms and which may have a silk substituent of 1 to 4 carbon atoms. Examples of preferred heteroaryl structures include thiophene, furan, pyrrole, oxazole, oxadiazole, thiazole, and benzo or thienofused ring derivatives of these heterocyclic compounds. Among these compounds, thiophene, benzophenone, thienothiophene, dibenzothiophene and bithienothiophene are superior to other compounds. The substituent represented by each of Rb includes a substituent such as the following, which is preferably an aliphatic hydrocarbon group (preferably having a residual or a base group), preferably having a substituent. Phenyl) or heterocyclic group. The aryl group each independently represented by Ra and Rb is preferably a aryl group having 6 to 3 fluorenes, more preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent ' and is preferably an aryl group having 6 to 18 carbon atoms and having / to 4 carbon atoms or a aryl group having 6 to 18 substituents. Examples of the aryl group include a phenyl group, a naphthoquinone group, a benzyl group, a phenanthryl group, a methylphenyl group, a bisfylphenyl group, and a phenyl group. Among these groups are a phenyl group, a naphthyl group and a fluorenyl group. The heterocyclic ring, which is independently represented by R and R, contains a ring group of 3 to 15 201143183. The ring group 'more preferably is a heterocarbon having 3 to 18 carbon atoms; 4^ County may have a wire, and the record (4) contains 3 to 18 and 6 to 7 has a 1 to 4 carbon material for silk generation. a heterocyclic group or a heterocyclic group having an aryl substituent of one carbon atom. The Ra&amp; Rb case includes a county with a dense lion structure. (4) The better structure of the structure 5 == combination (4) ring, singer ring 'sele- s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s , Ming ring, Zhihuan, three, and evil two. The fused ring structure formed by the same or different rings selected from the group consisting of pure and sold money, and more specifically, includes a quinoline ring, an isoquinoline ring, a stupid thiophene ring, a dibenzothiophene ring. a thienothiophene ring, a bithiophene ring, and a bithiophene thiophene ring. The aryl group represented by each of D!, Ra and Rb preferably has a fused ring structure, preferably a fused ring structure having a benzene ring, more preferably a ring structure of naphthalene, anthracene, anthracene or phenanthrene. Among these ring structures, the ring structure of naphthalene and anthracene is superior to other ring structures. Examples of the substituent w include an atom of an atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), a dilute group (including a cycloalkenyl group and a bicyclic group), an alkynyl group, an aryl group, and a hetero group. Cyclo, cyano, hydroxy, nitro, carboxy, alkoxy, aryloxy, decyloxy, heterocyclic oxy, decyloxy, amine methoxycarbonyl, oxycarbonyl, aryloxycarbonyl, amine (containing an anilino group), a sulphonyl group, a decylamino group, an amino group, an amine group, an oxoamino group, an aryloxyamino group, an amine arylamino group, an alkylsulfonylamino group, Arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfonate, alkylsulfinyl, arylsulfinyl, alkyl Sulfonyl, arylsulfonyl, fluorenyl, aryloxycarbonyl, oxy-oxyl, amine sulfhydryl, arylazo group, hetero-201143183 heterocyclylazo group, quinone imine Phosphyl, phosphinyl group, phosphinyloxy, phosphinylamino, phosphonic acid, decyl, decyl, ureido, boronic acid (_b(〇h)2), phosphoric acid Ester group (-OPO(OH)2), sulfur Foundation (-〇S〇3H) and other known substituents. When the substituent represented by each of Ra and fluorene is an aliphatic hydrocarbon group (preferably an alkyl group or an alkenyl group), it may have an aromatic ring structure (preferably benzene) which is substituted with an aryl group substituted with ·NRa(Rb). The hydrogen atom or substituent on the ring structure is combined to form a ring (preferably a 6-membered ring).

Ra and Rb may be combined with each other to form a ring (preferably a 5 or 6 membered ring, more preferably a 6 membered ring), or a substituent of Ra&amp;Rb&amp; and from 1 (Li, L2 &amp; L3) The combination forms a loop (preferably a 5 or 6 membered ring, more preferably a 6-membered ring). The compound represented by the formula (I) includes the compound disclosed in JP-A-2000-297068, and the compound which is not the compound disclosed in JP-A-2000-297068 can also be synthesized according to the synthesis method disclosed in the literature. To manufacture. The compound represented by the formula (I) is preferably a compound represented by the following formula (π).

, __ Ρ22 ^-Ν (II) 〇23 In the formula (II), Z2, L21, L22, L23 and η have the same meanings as Z1, B1, B2, L3 and η in the formula, respectively, and The preferred examples thereof are the same as in the formula (1), and d2i represents a substituted silk substituted by a substituted silk. The compound is preferably substituted with 6 to 3 carbon atoms. Stretching; there are Γί 】 8 carbon atoms of the extended aryl group. The substituent w described above on the aryl group, and preferably contains 6 to =: atoms and may have an alkyl substituent base having from 4 to 4 carbon atoms. Examples of the aryl group include a phenyl group, a phenyl group, a phenyl group and a naphthyl group. In the diradical group, the exo-olefin ring, the anthracene ring, the ring of the ring, the ring of the ring, the ring of the ring of the ring, the ring of H ring, the group of the structure: the group of the structure, and ^^ 裱,忐%, phenanthrene ring, quinoline ring, isoquinoline exhibiting J, singular ring, benzophenone or dimer: good: ^, more than ring, axis ring structure, especially good for Cai = Good _, pyridine ring, pyrazine ring, pyrimidine ring, oxazole ring, thiazole ring %3 201143183 fused ring structure formed by the same or different rings selected from the group consisting of a ring, an oxadiazole ring and a thiadiazole ring In particular, it is a ring structure of a quinoline ring, an isoquinoline ring, a benzothiophene ring, a dibenzothiophene ring, a thienothiophene ring, a bithiophene ring or a bithiophenethiophene ring. Preferred examples of the photoelectric conversion material represented by the formula (I) are shown by the following formula (III), but these examples should not be construed as limiting the scope of the invention. Λ

, rLW (III) D33 In the formula (III), Z3 represents any one of A-1 to A-12 in Table 1, L31 represents a minor fluorenyl group, and η represents 0. D31 is any one of B-1 to B-9, and D32 and D33 each represent any of C-1 to C-15. Table 1: (The asterisk (*) shown in each ring in the table indicates the bonding position of each ring) A-1 A-2 A-3 A-4 A-5 A-6. hair . Office A-7 A-8 A-9 a-ίο A-ll A 0jh A ό 201143183r B-1 B-2 B-3 Β-4 Β-5 Β-6 ·00· CO will οοα •Ολ •CQ ·Λ&gt;· B-7 B-8 Β-9 / / / .0. y / C-1 C-2 C-3 C-4 C-5 C-6 •C0 CO 〇〇〇000 You C- 7 C-8 C-9 C-10 C-ll C-12 •C^O 03⁄4 # &gt;8u C-13 C-14 C-15 / /〆03⁄4 * Ό / / / Represented by equation (I) More preferred examples of the photoelectric conversion material are the following combinations of the substituents, the linking groups and the partial structures in the formula (III), but these combinations should not be construed as limiting the scope of the invention. 201143183. Table 2 Compound Ί, '* / \ \ \ , V · 〆 L31 η d31 D32 D33 1 Α-1 CH 0 B-9 C-1 C-1 2 Α-2 CH 0 B-9 C-15 C -15 3 Α-3 CH 0 B-9 C-15 C-15 4 Α-4 CH 0 B-9 C-15 C-15 5 Α-5 CH 0 B-9 C-15 C-15 6 Α- 10 CH 0 B-9 C-15 C-15 7 Α-11 CH 0 B-9 C-15 C-15 8 Α-6 CH 0 B-1 C-15 C-15 9 Α-7 CH 0 B- 1 C-15 C-15 10 Α-8 CH 0 B-1 C-15 C-15 11 Α-9 CH 0 B-1 C-15 C-15 12 Α-12 CH 0 B-1 C-15 C -15 13 Α-2 CH 0 B-2 C-15 C-15 14 Α-2 CH 0 B-3 C-15 C-15 15 Α-2 CH 0 B-4 C-15 C-15 16 Α- 2 CH 0 B-5 C-15 C-15 17 Α-2 CH 0 B-6 C-15 C-15 18 Α-2 CH 0 B-7 C-15 C-15 19 Α-2 CH 0 B- 8 C-15 C-15 20 Α-2 CH 0 B-1 C-1 C-1 22 Α-2 CH 0 B-1 C-1 C-3 23 Α-2 CH 0 B-9 C-15 C -4 24 Α-2 CH 0 B-9 C-15 C-5 25 Α-2 CH 0 B-9 C-15 C-6 26 Α-2 CH 0 B-9 C-1 C-7 27 Α- 2 CH 0 B-9 C-8 C-8 28 Α-2 CH 0 B-1 C-10 C-10 29 Α-2 CH 0 B-9 C-ll C-ll 30 Α-2 CH 0 B- 9 C-12 C-12 In addition, A-1 to A-12, B-1 to B-9, and C-1 to 21 201143183 C-15 in Table 2 have the same meanings as those shown in Table 1, respectively. The content of impurities in each of these materials is preferably 1 〇, 〇〇〇 _ or less than 10,000 ppm ′ and the lower the better, the higher the purity of the target material, and more specifically, the purity is preferably 99% or more than 99%, more preferably 99 or more than 99.5%. ‘· 〇 As described above, impurities affecting the performance of the photoelectric conversion device vary depending on the structure of the photoelectric conversion material used. However, this does not mean that all the impurities contained in the photoelectric conversion material have the same degree of influence on the performance of the obtained photoelectric conversion device, but the degree of influence of the impurities on the photoelectric conversion device depends on the material structure and the purpose of use of the material (for example, the material is used for Which layer) is different. Examples of the impurities in the photoelectric conversion material for the organic photoelectric conversion film include a raw material, a reagent, a solvent, a reaction intermediate, and various decomposition products derived from a side reaction. When an oxidation reaction occurs as a side reaction, an oxidized compound impurity is formed; when a reduction reaction occurs as a side reaction, a reducing impurity is generated; when a decomposition reaction occurs as a side reaction, a decomposition impurity is generated; and when an isomerization reaction occurs as a side reaction At the time, isomerization impurities are generated. Among these many impurities, it has been found that the oxidizing compound impurities have a particularly large influence on the performance of the photoelectric conversion device. In the case of employing the synthetic route as shown in Scheme 1, the oxidizing compound impurities include oxidizing compounds of the starting materials used and oxidizing compounds of the synthesized products. The less the amount of these oxidized compound impurities, the better the performance achieved. In the present invention, the purity of the material for forming the organic photoelectric conversion layer is 96.5% or more, and the content of the oxidized compound impurity is preferably 9,000 ppm or less, as determined by liquid chromatography. 201143183 ppm 'better is 3, 〇〇〇ppm or less than 3 〇〇〇ppjn, more preferably 1 〇〇〇ppm or less than i, 〇〇〇ppm. A photoelectric conversion device that delivers higher efficiency can be manufactured as long as the content of the oxidized compound impurity is within the range specified above. In detail, the content of the oxidized compound impurity is 9, 〇〇〇ppm or less than 9.000 Ppm and the purity of the material for forming the organic photoelectric conversion layer is determined by liquid chromatography in the range of 96.5% to 99 9%. The inside is preferable because in these cases, a high-performance photoelectric conversion device can be manufactured and the cost of the purified material can be reduced. The lower limit of the content of the oxidizing compound impurity is 0, and it is preferable to make the content as close as possible to zero. However, for the apparatus according to the embodiment of the present invention, the impurity content is not so low. For example, the experimental examples described later show that the device performance is not degraded as long as the total content of the oxidized compound impurities is 9, 〇〇〇 ppm or less than 9.000 ppm. In view of these experimental results, it is presumed that the influence of impurities on the photoelectric conversion device of the present invention is smaller than that on the organic electroluminescence device (although at almost equal driving voltage) because the current flowing under the driving of the photoelectric conversion device is at most The current flowing under the driving of the organic electroluminescence device is 1/1 〇, and even when the organic film has some defects caused by impurities, the influence of the resistance caused by these defects is also small. Process 1 23 201143183t

A description of the process 1 is given below. Despite the examples! To synthesize, but the reaction conditions of the raw material i are oxidized, and the partial impurity fl is converted into a hetero-up'== part of the raw material 丨 is oxidized, and the raw material i is converted into the t-side, although a similar reaction occurs in the exemplified compound 1. , instantiate 'J is impurity 3. The term "oxidation compound impurity" as used herein hereinafter The specific structure of the oxidized compound impurity includes a structure of the following formula (AI). When a complex reaction occurs, the amount of impurity compounds also increases. Ton~ 24 201143183⁄4 or2 o&gt;2VL2v w In the formula (AI), 'l21, L22, L23, 〇21 and n2 have the same meanings as L!, L2, L3, D and n in the formula (1), respectively, and The examples of the former are also the same as the examples corresponding to the latter. R2 represents a hydrogen source or an alkyl group having 1 to 3 carbon atoms. The specific structure of the oxidized compound impurity is, for example, the structure of the impurities j to 4 in the scheme. The structural change of the photoelectric conversion material to be used involves the structural changes of the exemplified compound 1 and the raw materials 1 and 2, and the impurities 1 to 4 corresponding to these structural changes are produced. Examples of the method for reducing the content of impurities of these oxidizing compounds include various methods. When it comes to the production process, the use of higher purity reaction materials and reagents is more suitable for reducing the level of impurities in the resulting product. The raw material to be used can be purified by sublimation refining, steaming refining, solution refining or the like, and the purity of the raw material is preferably 99% or more than 99%. The interior of the reaction vessel is suitably kept filled with an inert gas atmosphere during the preparation of the reaction and during the course of the reaction. In order to create the conditions, it is suitable to start the reaction operation after replacing the atmosphere inside the reaction vessel with an inert gas and to keep the internal pressure of the reaction vessel slightly higher than the pressure generated by the use of the inert gas during the reaction. Thereby, formation of oxidized compound impurities of the raw materials used and the reaction products can be suppressed. In order to create an inert atmosphere, it is preferred to use nitrogen or argon. 25 201143183 Further, it is suitable to carry out a synthesis reaction under the condition that light is shielded by a metal film, a metal plate, a black cloth or the like to avoid side reactions caused by light, such as an oxidation reaction, an isomerization reaction, and a reduction reaction. In order to reduce the impurity content, the photoelectric conversion material is suitably purified in a refining process. In the refining process, it is preferred to use either a sublimation refining method, a solution refining method (recrystallization, reprecipitation or purification using an adsorbent) or a zone melting method, and a combination of these methods is more preferable. Alternatively, the same method can be performed more than two or more times. Sublimation refining, as usual, can be carried out by heating the material in a boat under a high vacuum of 1 Pa or below under a high vacuum atmosphere, and can be adjusted by adjusting to a lower temperature. The gasification material is solidified in the collection zone or liquefied in some cases. The boat used was a boat made of quartz glass, Pyrex (trademark) glass or metal. The temperature of the heating zone is preferably from 200 Torr to 4 Torr, and the temperature of the collection zone is preferably from 20 ° C to 1 Torr lower than the heating zone. Hey. Although a recrystallization method, a reprecipitation method, or a purification method using an adsorbent can be used as the solution refining method, the recrystallization method and the reprecipitation method are preferable from the viewpoint of cost. In the present specification, when the obtained solid is in a crystalline state, the purification method is classified into a recrystallization method, and when the obtained solid is in an amorphous state, it is classified into a reprecipitation method. However, the operations in both methods are the same. In these methods, by dissolving in a hot solvent, followed by cooling (more specifically, by preparing a solution having a concentration close to saturation at a temperature close to the boiling point, the solution is passed under hot conditions] and then the filtrate is cooled to room temperature. Or below room temperature, or by dissolving in a good solvent, filtering, followed by the addition of a poor solvent to obtain a solid. In addition, it is preferable to selectively evaporate the excellent solvent under a reduced pressure to a certain degree of 26 201143183 and to increase the ratio of the poor solvent, preferably in an inert atmosphere. , carried out under air conditions. c U may be exposed to the time when it is needed. The difficult method is as follows: = = for example, the chemical or activated carbon). Separately, the chromatographic form of the column is used to achieve a process for achieving high purity, filter oo/gluten, and subsequent washing of the filtrate. θ is an alternative to the recrystallization or reprecipitation method. The sample is stirred under heating and reflux, and the sample is not completely dissolved. As one of the methods of refining the cold liquid, and exceptionally, a method of decomposing impurities by reaction can also be employed. More specifically, there is a case of τ: it is possible to reduce impurities by setting conditions suitable for occurrence of a county reaction when an impurity is generated by an oxidation reaction or by setting a condition suitable for a condensation reaction when the impurity is generated by hydrolysis. The zone melting method represents a hydrazine refining process, and it is also suitable for purifying organic materials. More specifically, it is a method of eliminating impurities in the following processes: feeding the material to be purified into a tubular container, melting the material in an area near one end of the container, and then moving the melted portion of the material to the other end, Thereby, impurities are concentrated into the melted portion. In each of the embodiments of the present invention, each of the photoelectric conversion devices preferably has a charge blocking layer between the electrode and the organic photoelectric conversion layer. The charge blocking layer can be any of a hole blocking layer and an electron blocking layer. In various embodiments of the invention, a hole blocking layer or an electron 27 201143183 resist layer is suitably provided to suppress dark current. In the hole blocking layer provided for preventing the hole from being injected into the electrode, the electron transporting material disclosed in JP-A-2007-59515 can be used. Further, JP-A-2007-59515 describes not only the structure of the chemical suitable for the material, but also the preferred characteristics of these compounds, and information on the same is disclosed. In order not to hinder the absorption of light by the photoelectric conversion layer, the electron blocking material used in the electron blocking layer is preferably at a wavelength of 働 nanometer or less than 4 (8) nm, preferably 380 纟m or less. It exhibits its absorption maximum at the wavelength. Only the material has a small absorption constant, and it does not matter even if the material is made above. If this is the case, then the absorption number of the material is preferably 5,0 liters/mole/cm or less, 5 liters, mur / gram, more preferably 2, liters liters/mo Ears/cm or less than 2 liters/mole/much. In view of the necessity of transporting signal charges from the photoelectric conversion layer, it is required that the oxidation potential and the Ιρ value of the electron blocking material are lower than those of the photoelectric conversion layer. The electronic resistance # material itself has similar values as described in the fiscal conversion material. As an example of the electron blocking material, an aromatic hydrocarbon compound or a composite compound can be used as long as it satisfies the characteristics specified above. Among the compounds, the triarylamine compound is superior to the other compounds, and can be used particularly advantageously as disclosed in Chem. Rev. 2〇〇7, 1〇7, 953 and scarely 7 5^7 The hole transport material. In addition, other materials known as novel materials can be used. The content of impurities in these materials is preferably 1_G PPm or less than 1 〇, 〇〇〇 PPm, and the lower the better. In addition, the higher the target material content, the better the performance. The target material content is preferably from 96.7 to 99.9%, more preferably from 99.5 to 99.9%. Examples of the impurities in the electron blocking material used in the electron blocking layer include a starting material, a reagent, a solvent, a reaction intermediate, and various decomposition products derived from the side reaction. When an oxidation reaction occurs as a side reaction, an oxidized compound impurity is formed; when a reduction reaction occurs as a side reaction, a reducing impurity is generated; when a decomposition reaction occurs as a side reaction, a decomposition impurity is generated; and when an isomerization reaction occurs as a side reaction At the time, isomerization impurities are generated. Among these impurities, it has been found that a halide formed as a reaction intermediate and a heavy metal derived from a reaction reagent have a particularly large influence on the performance of the photoelectric conversion device. (Electronic barrier layer) In the electron blocking layer, an electron donating organic material can be used. Examples of useful low molecular electron donating materials include aromatic diamine compounds (such as hydrazine, ν, bis(3-methylphenyl)-(1,1'-linked stupid) _4,4,-diamine (butyl)卩0) and 4,4,-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (a-NPD)), oxazole, oxadiazole, triazole, imidazole, imidazolinone (imdaz 〇l〇ne), stilbene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene, 4,4,,4,,_ gin (N-(3-methylbenzene) N-phenylamino)triphenylamine (m_MTDATA;), porphyrin compound (such as porphin, tetraphenylporphin copper phthalocyanine, copper phthalocyanine and titanium oxide ugly), three Saliva derivatives, β-causal derivatives, sodium saliva derivatives, polyalkylene hydrocarbon derivatives, π-saliva derivatives, indolizin derivatives, stupid amine derivatives, arylamine derivatives A chalcone derivative, an oxazole derivative, a styrylpurine derivative, a fluorenone derivative, an anthracene derivative, and a decazane derivative substituted with an amine group. And examples of the polymer electron-donating materials of 29 201143183 include phenyl-terminated vinyl polymers, fluorene polymers, carbazole polymers, fluorene polymers, fluorene polymers, pyrrole polymers, picoline polymers. , thiophene polymers, acetylene polymers, monoacetylene polymers and derivatives of these polymers. In addition, a compound having sufficient hole transport properties can be used for the electron blocking layer even if it does not have electron donating properties. The thickness of the electron blocking layer is preferably from 1 G nm to Schneider: 3 〇 nanometer to 150 nm. Especially preferably 5 〇 nanometer to 1 〇〇 nanometer. When the layer is too thin, the effect of suppressing dark current is suppressed. It will decrease, and when this layer is too thick, the photoelectric conversion efficiency will decrease. Examples of the too-to-two-body = electron-blocking include the following materials, which are referred to as ΕΒ-5, TPD, and TDATA, respectively. 30 201143183 E8-1 : Ea=1.9, lp=4.9 EB-2 : Ea*1.7, lp=4.7

The choice of materials that are practically usable in the electron blocking layer is limited by the electrode material adjacent to the electron blocking layer and the photoelectric conversion layer material 31 201143183 near the electronic barrier layer. The material suitable for the electron blocking layer is close to the electron blocking layer - a ‘, ,, the electron affinity (E) ratio, the work function (Wf) of the electric material 4, and at least the material of the electric conversion layer material. λ pre-blocking light (halide impurity) The content of the toothed impurity in the Q ^ η sub-blocking layer is preferably 9, _ ppm or low. The second part of the PPm is preferably 4, _ _ or lower than 4 , _ PPm. The lower limit of the amount of the toothing is 〇, and it is preferable to make the content as close as possible to 〇. In detail, the impurity content of the toothing is 9, qing or less than 9, and is used statically to form an organic photoelectric conversion material. It is preferable to determine the ratio of 96.5 to 99.9% by the Latitude phase chromatography, because in these cases, a high-efficiency photo-electrical device can be manufactured and the cost of the purified material can be reduced. Depending on the raw materials used, examples of the self-chemicals include fluorides, vapors, evolutions, broken compounds, and perfluoric acid vinegar. From the viewpoint of synthetic yield, bromide or iodide is usually selected as a raw material. When the compound to be used as the reaction product is an arylamine, the halide as a raw material is an aryl telluride. The case of the following Scheme 2 is taken as an example. In this case, a compound called a halide is used as a raw material. 4 4, _ a odorous biphenyl and a compound described as a reaction intermediate, and the reaction intermediate may further undergo a reduction reaction and thereby be converted into its hydride. Scheme 2 32 201143183^

The functional impurities in the case where EB_1 to EB-5, TPD and m-MTDATA are respectively used as the electron blocking materials are explained below, but the impurities of the present invention should not be construed as being limited to the following impurities. 33 201143183 Table 3 Electron Blocking Material Halide Impurity ΕΒ-1 ΕΒ-2 Λ ^ ^ An, ΕΒ-3 er-€HD-Br °§^-ΒΓ ΕΒ-4 ΕΒ-5 δ CaHs' 34 201143183 Table 3 (Continued )

The toothed impurity is thus a compound represented by the following formula (AII). ^32

In the formula (All), ^1, ]132 and ]133 each represent a filament having 6 to 3 carbon atoms or a (tetra) group having 4 to 3 carbon atoms and at least one of R32 and 33 has A dentate substituent.

Rh, R32 and the aryl group each independently represented are preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent, and it is preferably an aryl group having 6 to 18 carbon atoms, and may have a group as a group: an alkyl group having 1 to 4 carbon atoms (such as a methyl group or an ethyl group: N-propyl, isopropyl, tert-butyl or n-butyl), an aryl group having 6 to 18 carbon atoms 35 201143183 (such as phenyl or naphthyl) or a heteroaryl group having 4 to 18 carbon atoms (such as 9H-9-aza-tricyclic benzo[a,c,e]cycloheptene). Examples of the aryl group having 6 to 30 carbon atoms represented by each of R31, R32 and the ruler 33 include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group and an anthracenyl group. Among these groups, a phenyl group is superior to other groups. Examples of the substituent suitable for the aryl group include 9H-9-aza-tricyclic benzo[a,c,e]cycloheptene, a methyl group and an ethyl group. Examples of the heteroaryl group having 4 to 30 carbon atoms represented by each of Rm and 32 and R33 include &quot;pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinalyl, anthracene. If fluorenyl, Cinn〇Hnyl gr〇Up, isoindolyl, acridinyl, acridine, cyanozinyl, morpholinyl, tetrazolyl, oxazolyl, imidazolyl, thiazolyl , oxazolyl, oxazolyl, benzimidazolyl, benzotriazolyl, benzoxazolyl, benzothiazolyl and aminoxime. Hi, R32 and R33 may be the same or different from each other, and any adjacent one of them may be combined with each other to form an aromatic ring or a heteroaryl ring. Examples of aromatic rings formed by combining any two of RS1, R32 and R33 include acenes such as benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, anthracene rings and naphthacene. )ring. Examples of the aromatic ring formed by combining any of R32 and R33 include a thiophene ring, a pyrrole ring, a furan ring, a thiazole ring, a bicyclic H ring, and a phenyl copper derivative of these rings. Substituting ^- as described above may be carried out with a substituent. Examples of the configuration in the case where the nitrogen-containing heterocyclic ring is formed by any adjacent two of the groups 3i R*32 and R33 include an acyclic ring, a 9-dihydro ((tetra) (tetra) ring, a ring, a ring of phenol, and ten Seychelles and this confusing derivative of Wei. 36 201143183 The halogen atom replaced by r31, r32 and R. 3!, ruler 32 and R„ is a fluorine cadaver.

The number of bases is preferably 1 or 2. a bromine atom or an iodine atom, preferably a bromine atom or an iodine atom

f When the desired material is required to be a heavy metal catalyst, the amount of heavy impurities of the material is preferably 4,0 〇〇 ppm or less, 〇〇〇ppm, or lower! , 〇〇〇 ppm. From the viewpoint of productivity, heavy metal catalysis is preferably copper catalyzed lysine. When the impurities are contained, copper, copper (1), copper (11) and copper salts, copper chloride, copper bromide and copper iodide are used. When a palladium catalyst is used, the impurities are included. , oxidation peak) and Rugao (such as acetic acid, stone, acid, gas, her, desertification and deuteration). When used as a catalyst, a trialkylphosphine or a triarylphosphine is used as a ligand for the activation catalyst. The complex formed by these ligands with _) is also included in (4) of the impurities. The material of the organic photoelectric conversion layer formed by & had a heavy metal catalyst content of 4, (8) 〇 PPm or less, 〇〇〇 ppm and purity as determined by liquid chromatography to be 96.5/. A specific case of 99.9% is preferable because in these cases, a high-performance photoelectric conversion device can be manufactured and in addition, the cost of purification &amp; The electron blocking material should also be purified, and the purification details are similar to those of 37 201143183 regarding the purification of the photoelectric conversion material. There is a case where water and a solvent are contained in the photoelectric conversion material of the photoelectric conversion material. The solvent is a solvent used in the reaction and purification process. Examples of the solvent include alcohol compounds (such as methanol, ethanol, and propanol), acetonitrile, acetone, ethyl acetate, toluene, diphenylbenzene, hexane, n, n-dimethylamine N, N_- Ethylethylamine, sulfhydryl. Called the bite and the mystery. These impurities are removed by mechanical drying, drying, heat drying or the like before the completion of the refining process. ... In order to avoid the increase of impurities during storage, it is better to use the inert gas atmosphere in the case of shading. As for the temperature, there is no problem with the room temperature, but a lower temperature is preferred. (Curtain barrier layer) In the hole barrier layer, an electron-accepting organic material can be used. An example package of a compound that can be used as an electron-accepting material (IV) diphtheria, such as 13 bis(4-t-butylphenyl- succinyl)-extension base (〇xd 7), onion bismuth derivative , diphenyl eye organism, bath copper (bath () eupn)ine), red phenophyllin (bathophenanthroline) and its derivatives, triterpenoids, ginseng (8_ via base) ablation, double German A complex compound, a stilbene extended aryl derivative, and a heterocyclic pentane hybrid. In addition, materials having sufficient electron transport properties may be used, although they are not subjected to electronic organic materials in 4 cases. Buwei compound, phenethyl compound (such as DMC (4-dicyanodecyl)|methyl·6·(4) didecylaminophenyl)-4-anthracene) and 4Η-scent Compound. The preferred use of 'special s' is as for example in the claw eight _2 〇〇 8_72 〇 9 38 38 201143183

The following compounds disclosed by r I. "HB" in HB-l to HB-5 is an abbreviation for hole blocking. : Ea=3.5, lp=62

HB*2 : Ea=3.3·丨p=6.0 HB-3: Ea=3.7, lp»7.2

Ηβ·&lt;: Ea*3.6· Ιρ*7.β HB-5: Ea=3.6, lp=7.6 BCP : Eas32, Ιρββ.7

For the ί ==: I photoelectric conversion layer containing the material of the 祠 兔 兔 】 】 】 】 & & & & & & & , , , , , , , , , , , 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合99 ^ In the case of °6 ° laugh, included in the example of 3 = non-C6. The oxidative solution of the impurity of the allotrope, the role of the barrier layer II. Although the rainbow is mentioned by 39 201143183 The formation of the resistive layer also has the effect of "controlling the self-charge::: another effect of dark current. Electron" to weakly control the charge injected from the electrode, weighs I β &gt; === the wall and makes the charge resist The push layer is in contact with the layer (photoelectric conversion layer) under the barrier layer. The former is a method of providing an energy barrier against the angle of the implant, thereby preventing the electrode material from being in a small defect and in contact with the photoelectric conversion layer, thereby Forming a leak point ^ 派 =======- can refer to the adjustment of the barrier to the difference between the barrier layer and the electrode layer of the electrode, such as the round and the quality, so that it can be prevented by using None of the inorganic materials:: What barrier layer and organic material include == barrier layer can be more significant The suppression of the charge/supply of the supplied/charged electric charge. In Fig. i, the spear ', the 'avoidable signal first layer 103' is intended to be an inorganic material layer, and Lu, the material of the side of the electrode 104 And the first layer l3b is assigned to have a preferred use of Si, Mo, Ce, Li, Hf, Ta, Ai, Ti, zn, 201143183. W and Zr as the inorganic material layer Inorganic material 2 with an oxide material inorganic (four) 'and in detail SiC> suitable as this oxygen to prevent the injection of charge from the electrode, the inorganic material layer needs to have the free energy of the energy barrier between the energy and the adjacent electrode work function, Moreover, there is a large Ip. However, when the inorganic material layer separately constitutes the charge blocking layer, the decrease in the thickness of the layer causes the formation of the electrode between the electrode and the photoelectric conversion layer, and the increase in the thickness of the layer weakens the charge. Transport properties and make signal charge difficult to read. In addition to the inorganic material layer, it is important to provide a layer under the inorganic material layer. The material (4) is better for the charge transfer property of the signal charge generated by the forest, and t The organic material used therein is preferably caused A material for reducing the carrier current derived from the dark current in the material. By providing the organic material layer, the charge blocking layer can be homogenized and thickened, and the dark current derived from the charge resistance is not reluctant = electric r Combining these effects with the action of the inorganic material layer, and then referring to the structure of the device according to the present invention, Fig. 1 is a cross-sectional view of the photoelectric conversion device according to the first embodiment of the present invention. The photoelectric conversion device 100 of this embodiment is (four) such that the photoelectric conversion layer 102 is stacked on the first electrode film 101, : (10) on the stack_light_奂 layer and the second electrode film is doubled: step 201143183 is stacked on the charge blocking layer 103 on. The device may be designed to allow light to be incident from the side of the first electrode film 1〇1, or it may be designed to allow light to be emitted from the side of the second electrode film 1G4. In the case where light is incident from the side of the first electrode film 104, the second electrode film is the upper electrode ' and the lower electrode 101 is stacked on the substrate not shown. In the implementation of the present invention, the electric noise barrier layer 1G3 has a two-layer structure composed of a first charge blocking layer 10a3a and a second charge blocking layer 1?3b. Since the incident light needs to enter the photoelectric conversion layer 1〇2, the upper electrode 104 is suitably formed of a material which is transparent. As for the highly transparent electrode, a transparent conductive oxide (then) is given as an example thereof. (d) The lower electrode 1〇1 is preferably formed of a highly transparent material because there may be a case where light is required to propagate in a downward direction as seen in the structure of the image forming apparatus mentioned below. The charge blocking layer 103 is a layer that suppresses transfer of charges from the electrode 104 into the photoelectric conversion layer 102 when a voltage is applied between the electrodes 1〇1 and 104. When the charge blocking layer 103 has a single layer structure, there is an intermediate energy level (such as an impurity level) in the material itself constituting the charge blocking layer 1〇3, and charge (electron, hole) transfer occurs via these intermediate energy levels, This leads to dark electricity &amp; enhancement. To prevent this from occurring, the charge blocking layer 1〇3 in this embodiment is designed to have a two-layer structure instead of a single layer structure. By creating an interface between the first layer i03a and the second layer 103b constituting the charge blocking layer 103, a discontinuity is generated in the intermediate energy level existing in each of the layers and i〇3b, thereby causing the carrier It is difficult to move via an intermediate energy level or the like. Therefore, it is considered that the dark current can be controlled. However, when the layer 42 201143183 l〇3a and the layer i〇3b are formed of the same material, it may occur that the intermediate energy present in the layer can be exactly the same as the energy level existing in the layer of the layer 1G3b. In order to further enhance the dark current control side, the materials forming the layers 103a and 103b, respectively, are preferably different from each other. Although FIG. 1 illustrates the case where a charge blocking layer is provided between the photoelectric conversion layer 1〇2 and the upper electrode 1〇4, it is also possible to provide another electric hybrid H _ between the photoelectric conversion layer 1G2 and the power-off, ιοί. The charge blocking layer is designed as an electron blocking layer and is additionally designed as a hole blocking layer. As described in the description of the charge blocking layer, each of the electron blocking layer and the hole blocking layer is preferably a two-layer structure. Alternatively, it is preferable that the respective layers have a multilayer structure including three or more layers and the materials forming the plurality of layers are different from each other. Fig. 2 is a schematic cross-sectional view showing a single pixel portion of an image forming apparatus according to a second embodiment of the present invention, and Fig. 3 is a schematic cross-sectional view of Fig. 2. Imaging device 2. . The pixels for the same 4:::= are shown in Figure 2, arranged in an array, and the signals emitted from each individual pixel produce a single pixel of image data. One pixel of the image forming apparatus shown in FIG. 2 is equipped with an n-type germanium substrate 1, a transparent insulating film 7 formed on the substrate 11, a lower photoelectric conversion region formed on the insulating film 7, and provided on the photoelectric conversion region. A light-shielding mold 14 having a hole and a transparent insulating film μ laminated on the light-shielding film 14. The photoelectric conversion region is composed of an intermediate layer 12 in which the first electrode film 1 is formed on the first electrode film u and a second electrode film 13 formed on the intermediate layer 12. The light receiving region of the intermediate layer 12 is restricted by laminating the light-shielding film 14 having the holes on the photoelectric conversion region. In this photoelectric conversion region, the structure of the photoelectric conversion described in Fig. 1 of 43 201143183 can be employed. The intermediate layer 12 as shown in FIG. 3 is configured such that the barrier layer 122, the photoelectric conversion layer 19 _ layer is combined with the mils &amp; gram * I 23 and the hole barrier layer and buffer layer 124 as mentioned The steps are stacked on the first electrode film u, and the hole blocking layer and the buffer layer 124 each have the multi-layered conjunct film structure as mentioned above, and the charge is generated from the light of the fourth electrode (including) The electrons and the holes, the 'quality, and the other' cause the electron mobility to be smaller than the holes, and in addition to this, the number of electrons and holes generated in the vicinity of the second electrode film 13 is larger than that in the vicinity of the first electrode film 11. Representative examples of light f-conversion (4) having a miscellaneous f include organic materials. In the structure shown in Fig. 2, materials for generating electrons and holes in response to green light absorption are used. Since the photoelectric conversion layer 123 can be shared by all, it can be a film in a single chip form, and it is not necessary to be based on pixels. The photoelectric conversion layer 123 can preferably be constructed by using a material as described above in combination. When the organic material other than the above is incorporated in the constituent material of the photoelectric conversion layer 123, it is preferable to include at least an organic p-type semiconductor or an organic n-type semiconductor. Any one of a quinacridone derivative, a naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a tetracene derivative, an anthracene derivative, and an alkadiene derivative is particularly preferably used as an organic p. Each of a semiconductor and an organic n-type semiconductor. The organic ruthenium type semiconductor (compound) is an organic semiconductor (compound) having donor characteristics and refers to an organic compound having a property of easily supplying electrons. The product is mainly represented by a hole transporting organic compound. More specifically, when two organic materials are used in contact with each other, the organic compound having a donor property means an organic compound having a free potential lower than the other. Therefore, any organic compound can be used as an organic compound having a donor property as long as it has an electron donating property. Examples of the organic compound usable as an organic compound having an electron donating property include a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, an anthracene compound, a tribylene compound, and a taste σ. Sitting compound, Ju Shi Xi Yuan compound, β-thin compound, enantiomeric compound, cyanine compound, merocyanine compound, oxonol compound, polyamine compound, π-dial compound, oxime compound, carbazole compound a polycondensed aryl compound, a fused aromatic carbocyclic compound (such as a naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a naphthacene derivative, an anthracene derivative, an anthracene derivative, and a propadiene oxime derivative) And the ligand is a metal complex of a nitrogen-containing heterocyclic compound. However, the organic compound usable as an organic compound having an electron donating property is not limited to the above-exemplified compounds, but is as mentioned above as long as the free potential of the organic compound is lower than that used as the n-type compound (having receptor characteristics). An organic compound which can be used as an organic semiconductor having donor characteristics. The organic n-type semiconductor (compound) is an organic semiconductor (compound) having acceptor characteristics and refers to an organic compound having a property of easily accepting electrons, and is mainly represented by an electron transporting organic compound. More specifically, when two organic materials are used in contact with each other, the organic compound having an acceptor property means an organic compound having an electron affinity higher than the other. Therefore, any organic compound can be used as an organic compound having a receptor property as long as it has an electron accepting property. Examples of the organic compound usable as an organic compound having an electron-accepting property include a fused aromatic carbocyclic compound (such as a naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a naphthacene derivative, a benedict derivative, an anthracene derivative). And a propadiene derivative), a gas-, oxygen- or/and sulfur-containing 5 to 7 member compound (such as beta ratio bite, D ratio 嘻, ton, scuttle, triazine, quinoline, Quinoxaline, quinazoline, pyridazine, porphyrin, isoquinoline, acridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, oxazole, benzimidazole, Benzotriazole, benzoxazole, benzothiazole, oxazole, hydrazine, triterpenoid hydrazine, triterpenoid pyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyrrolidine (pyralidine), pyrrolopyridine, 嗔°°°°, bite, dibenzazepine and tribenzoxazine, poly-arylene compound, compound, cyclopentadiene compound, Shi Xi The alkyl compound and the ligand are metal complexes of a nitrogen-containing heterocyclic compound. However, the organic compound which can be used as the organic compound having electron-accepting properties is not limited to the above-exemplified compounds, but is as mentioned above as long as the electron affinity of the organic compound is higher than that of the organic compound used as an organic compound having donor characteristics. It can be used as an organic semiconductor having acceptor characteristics. An η-type organic dye or a p-type organic dye can also be used. Although any dye can be used as the dye, examples of preferred dyes include cyanine dyes, the present ethylene-based dyes, hemicyanine dyes, and merocyanine dyes (including zero-twisted basal cyanine ( Simple part cyanine)), trinuclear cyanine dye, tetranuclear cyanine dye, rhoddacyanine dye, composite cyanine dye, complex part cyanine dye, pole change (all〇p〇lar Dyes, oxygen beta, dyes, semi-oxo dyes, squarylium dyes, ketoacids 46 201143183 (croconium) dyes, azamethine dyes, coumarin dyes, arylene dyes, Anthraquinone dyes, triphenyl decane dyes, azo dyes, azomethine dyes, spiro compounds, metallocene dyes, ketone dyes, fulgide dyes, anthraquinone dyes, Morphazine dye, phenothiazine dye, anthraquinone dye, anthraquinone dye, diphenylmethane dye, polyene dye, acridine dye, acridone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, brown Oxazine dye, phthalate Rylene ) dyes, phthalocyanine dyes, chlorophyll dyes, phthalocyanine dyes, metal complex dyes and fused aromatic carbocyclic dyes (such as naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, flowers) Derivatives, anthracene derivatives and allene derivatives. In a consistent embodiment of the invention, the inter-turn layer 12 has a p-type semiconductor layer and an n-type semiconductor layer, and preferably, at least one of the p-type semiconductor or the n-type semiconductor is an organic semiconductor, and further, A photoelectric conversion layer having a bulk heterojunction structure of a p-type semiconductor and an n-type semiconductor is sandwiched between the semiconductor layers. In this case, the bulk heterojunction structure is incorporated in the intermediate layer 12, and thereby the defect of the carrier diffusion length of the photoelectric conversion layer 123 can be compensated for in order to improve the photoelectric conversion efficiency of the photoelectric conversion layer 123. Further, the photoelectric conversion layer included in the intermediate layer 12 has a p-type half = body layer and an n-type semiconductor layer ' preferably (the bulk heterojunction structure) of the opening and the dispersion layer. Here, it is difficult to include a directional control agent compound in at least one of a p-type semiconductor or an n-type semiconductor, and each of the ί-type conductors has directional control (controllable). The situation of things is better. A compound having π·co-light electrons 47 201143183 is used as the organic compound. And the planes of these π-electrons are preferably not oriented perpendicular to the substrate (electrode substrate). As for the orientation angle of the plane, the more parallel the substrate is, the better. More specifically, the angle between the π-electron plane and the substrate is preferably 〇. To 80. More preferably 0. To 60. Better for you. To 4 〇. More preferably 0° to 20. , especially good for you. To 10. , the best is 0. (i.e., the organic compound layer is preferably included in the entire intermediate layer 12 in parallel with respect to the substrate orientation control, and more specifically, the ratio of the orientation control organic compound portion to the entire intermediate layer 12 is preferably 10% or more. More preferably 3〇% or more than 30% 'more preferably 50% or more than 50%, more preferably 7〇% or more than 7〇%, especially preferably 90% or more than 90%, preferably ι〇0 By controlling the orientation of the organic compound contained in the intermediate layer 12 t to satisfy the above conditions, %β can compensate for the short defect of the carrier diffusion length of the photoelectric conversion layer, so as to improve the photoelectric conversion efficiency of the photoelectric conversion layer. In the case of orientation, it is more preferable that the heterojunction (for example, a pn junction) is not parallel to the substrate (electrode substrate). The orientation angle of the heterojunction is not parallel to the substrate, but the more perpendicular to the substrate, the better. The angle of formation of the heterojunction of the special s and the substrate is preferably from 1 〇 to 9 〇, more preferably from 30 to 90. More preferably from 50 to 90. More preferably from 70 to 90. , preferably 80. to 90., preferably 90. (ie perpendicular to the substrate; ^ The organic compound layer under the control of the heterojunction is preferably contained in even a portion of the entire intermediate layer 12' and more specifically, the ratio of the orientation control portion to the entire intermediate layer 12 is preferably 10% or more, more preferably More preferably 3% or more than 30% 'more preferably 50% or more than 50%, more preferably 70% or more than 70%, especially preferably 90°/❶ or more than 90%, most preferably loo%. In the case, 48 201143183 the area of the heterojunction in the intermediate layer 12 is increased, whereby the number of carriers (such as electrons, holes, and electron hole pairs) generated at the interface is increased, thereby improving the photoelectric conversion efficiency. The photoelectric conversion layer in which the heterojunction of the organic compound and the orientation of the π_electron plane are controlled as described above can particularly ensure an improvement in the electrical conversion efficiency. A detailed description of these conditions can be given to each of the lions (Japanese Patent Application No. 31) No.), medium. As for the absorption of light, the thickness of the organic layer is as large as possible. However, the sweetness does not promote the balance of the electric separation. The thickness of the money is preferably from 3G to 300 nm, and more preferably 5G. Rice to 25 nanometers, especially good for 8 meters and 200 nanometers. The intermediate layer including these organic layers can be provided by using a dry film forming method or a wet film forming method. Examples of the dry type method include a true evaporation method, a slit method, an ion method, and a physical gas phase. ^ MBE) and ah (such as electricity polymerization). Wet film forming method = casting method, spin coating method, dipping method and LB method. When polymer compound is used as a type semiconductor (compound m- The polymer compound is preferably formed into a film by a French method. When a film such as vapor deposition is used, the film formation method is not suitable for polymerization because of fear of decomposition; Polymer. When using a low score; acre is preferred to use a dry film formation method. It is especially preferred to use a vacuum evaporation method. The basic factors of the steaming &amp; method include the method for heating the compound, the second resistance heating evaporation method or the electron beam heating evaporation method; the shape, such as the shape of a crucible or a boat; the degree of vacuum; evaporation 49 201143183 ; substrate temperature; evaporation rate, etc. In order to make the evaporation as uniform as possible, it is preferred to carry out evaporation under the rotation of the substrate. As for the degree of vacuum, the higher the degree, the better the results obtained. More specifically, the vacuum evaporation should be between 1 〇 -4 Torr or less than 1 〇 -4 Torr ' preferably 10 · 6 Torr or less than 1 〇 - 6 Torr, especially preferably 1 〇 8 Torr or less than 1 Torr. • Perform in a vacuum of 8 torr and allow the compound to be evaporated to avoid direct contact with oxygen and moisture in the outside air. Preferably, the compound evaporates in a vacuum throughout the evaporation step so as not to come into contact with oxygen and moisture in the outside air. The conditions for vacuum evaporation need to be strictly controlled because they affect, for example, the crystallinity, amorphousness, density, and tightness of the formed organic film. Further, it is preferable to employ an evaporation rate PI or I &gt; ID control by using a film thickness monitor such as a quartz resonator or an interferometer. In the case where two or more than two compounds are simultaneously evaporated, a co-evaporation method, a flash evaporation method or the like can be employed. When the photoelectric conversion layer 123 containing the organic material in the above device structure obtains light incident from the upward direction of the second electrode 13, the light absorption generally generates a large amount of electrons and holes near the second electrode 13 at the first electrode. There are not so many electrons and holes in the vicinity of 11. This is because most of the light having a wavelength near the absorption peak of the photoelectric conversion layer 123 is absorbed in the vicinity of the second electrode 13 and the absorbance of the light decreases as the distance from the vicinity of the second electrode 13 increases. Therefore, unless electrons or holes generated in the vicinity of the second electrode 13 are efficiently transferred to the Shih-hs substrate, the photoelectric conversion efficiency is lowered, resulting in a decrease in sensitivity of the resulting device. In addition, the signal reduction from the wavelength of light strongly absorbed near the second electrode 13 is such that the spectral sensitivity range is expanded or so-called widened. In addition, in the photoelectric conversion layer 123 containing an organic material, a general tendency is that the electron mobility is much smaller than the hole mobility. Further, it has been confirmed that electron mobility is easily affected by oxygen in the photoelectric conversion layer 123 containing an organic material and that the photoelectric conversion layer 123 is exposed to air to further lower the electron mobility. Here, when it is desired to move electrons onto the ruthenium substrate 1, as long as electrons generated in the vicinity of the second electrode 13 have a long travel distance in the photoelectric conversion layer 123, part of the electrons are deactivated during their travel and cannot be Collected into the electrode' resulting in reduced sensitivity and widened spectral sensitivity range. In order to prevent the sensitivity from being lowered and the spectral sensitivity range to be widened, an effective method is to efficiently advance electrons or holes generated in the vicinity of the second electrode 13 to the Shih-kung substrate 1. In order to achieve efficient travel of electrons or holes, managing electrons or holes generated in the photoelectric conversion layer 123 becomes a problem. The image forming apparatus 200 shown in Fig. 2 has the photoelectric conversion layer 123 having the properties specified above, and thus, as mentioned above, the holes are collected into the first electrode film U opposed to the electrodes on the incident light side. It is also used to increase the external quantum efficiency, thereby improving sensitivity and narrowing the spectral sensitivity range. In the image forming apparatus 200, a voltage is thus applied between the first electrode film Μ and the second electrode film 13 so that electrons generated in the photoelectric conversion layer 123 are transferred into the first electrode film 13 and generated in the photoelectric conversion layer 123. The holes are transferred to the first electrode film 11. The function of the undercoat layer and electron blocking layer 122 is to reduce the asperity on the first electrode film U. When the first electrode film u has a bump on the surface or adheres to the surface of the dust and the low molecular organic compound evaporates thereon and enters the photoelectric leaking wiper, the film is recorded in 201143183 with the bump dust. Small cracks are produced in the part. In other words, the thickness of the photoelectric conversion layer 123 is reduced. Here, := cover step and a 増 = when:,::== advance to the second is obvious. Therefore, the undercoat layer and the electron blocking layer 122 suppress the upper layer 11, and the influence of the bumps is reduced, and the iff sub-blocking layer handle material can be easily referred to. Examples of materials suitable for forming one thousand include, in particular, organic high molecular polymer materials such as polyaniline, polythiophene, polypyrrole, polycarbazole, PTPDES and PTPDEK, and the film can also be formed by spin coating. A, for the purpose of attenuating the dark current generated by the injection of electrons from the first electrode film u, the electron blocking layer 122 is provided, and is suppressed from the first electrode film u &gt; main incoming electrons into the photoelectric conversion layer 123. The hole blocking and buffer layer 125 is provided as a hole barrier layer for the purpose of attenuating the dark current generated by the injection of the holes from the second electrode film 13, and it not only performs suppression of injection of holes from the second electrode film 13. To the work side in the photoelectric conversion layer 123, and in some cases, the function of reducing the damage caused on the photoelectric conversion layer 123 at the time of formation of the second electrode film 13 is also performed" when the second electrode film 13 functions as the photoelectric conversion layer 123 When the upper layer is formed, the case may be such that, in the case of, for example, a sputtering method, high energy such as sputtering particles, secondary electrons, Ar particles, and oxygen anions present in the apparatus for forming the second electrode film 13 The particles collide with the photoelectric conversion layer 123 to hit 52 201143183, whereby the photoelectric conversion layer 123 changes its quality and causes performance degradation such as an increase in leakage current and a decrease in sensitivity. A method of providing the buffer layer 125 on the photoelectric conversion layer 123 can be preferably employed as a method of preventing these cases. Returning now to Fig. 2'p-type semiconductor region (hereinafter abbreviated as p region) 4, an n-type semiconductor region (hereinafter abbreviated as n region) 3 and a p region 2 are formed in the n-type germanium substrate 1 in order of increasing depth. In a portion of the surface portion of the P+ region 4 where the light is blocked by the light shielding film 14, a high-density p region (referred to as a p region) 6' is formed and the p+ region 6 is surrounded by the n region 5. The depth of the pn junction between the ρ region 4 and the η region 3 is adjusted from the depth of the surface of the n-type germanium substrate i to a depth (about 2 μm) which allows absorption of blue light. Therefore, the p region 4 and the η region 3 absorb blue light and generate a hole in response to the absorbed light, and form a photodiode (Β photodiode) which accumulates the hole. The holes generated in the xenon photodiode are stored in the p region 4. The depth of the pn junction between the germanium region 2 and the germanium substrate 1 is adjusted from the depth of the surface of the germanium substrate to the depth of absorption of red light (about 2 micrometers). Therefore, the ρ region. 2 and the η-type 矽 substrate 丨 absorb red light and generate holes in response to the absorbed light, and form a photodiode (R photodiode) that accumulates holes. The holes generated in the R photodiode are accumulated in the crucible region 2. The P+ region 6 is electrically connected to the first electrode film n' via the connection region 9 formed in the hole drilled in the insulating film 7, and the holes accumulated in the first electrode film 11 are accumulated via the connection region 9. The connection region 9 is electrically insulated from the environment around the periphery of the first electrode film 11 and the p+ region 6 by the insulating film 8. The holes accumulated in the ρ region 2 are converted into signals in response to the charge amount thereof by means of a MOS circuit (not shown) 53 201143183 formed of a p-channel MOS transistor formed in the n-type germanium substrate 1, accumulating in p The holes in the region 4 are converted into signals in response to the amount of charge by means of a MOS circuit (not shown) formed of a p-channel MOS transistor formed in the n region 3, and the electrons accumulated in the Ρ+ region 6 are A MOS circuit (not shown) composed of a p-channel MOS transistor formed in the n region 5 is converted into a signal in response to the amount of charge thereof, and these signals are output to the outside of the image forming apparatus 200. These MOS circuits constitute a signal readout area. In addition, the MOS circuits are each connected to a signal readout pad (not shown) by wiring 10. Further, the ρ region 2 and the ρ region 4 are provided with extraction electrodes. When the reset potential is assigned to these electrodes, each region reaches a depletion state and minimizes the capacitance of the bonding. Therefore, the capacitance generated on the junction can be made small. By designing the device having the structure, photoelectric conversion of G light can be performed in, for example, the photoelectric conversion layer 123, and stepwise in the photodiode and the R photodiode formed in the heart dream substrate, respectively. carried out

—, a similar / νπ tanzanite thermal microlayer.

For example, between the % tantalum film 7 and the n-type germanium substrate JR spear-pole film 11 (between the examples), an inorganic photoelectric conversion region 'of the inorganic material 54 201143183 is formed to allow absorption of light that has passed through the photoelectric conversion layer 123. 'Respond to this light to generate charge and accumulate these charges. In this case, an M〇s circuit for reading out a signal in response to charges accumulated in the charge accumulation region of the inorganic photoelectric conversion region is provided substantially only inside the n-type germanium substrate 1 and the wiring 10 is also connected to this MOS circuit. The first electrode film 11 has a function of collecting holes generated in the photoelectric conversion layer 123 and having traveled to the electrode film 11. The first electrode film u is divided based on the pixels, whereby image data can be generated. According to the structure shown in Fig. 2, photoelectric conversion is also performed in the 11-type germanium substrate 1, and therefore the first electrode film 11 preferably has a visible light transmittance of 60% or more, preferably 90% or more than 90%. In the case where the device has a structure in which the photoelectric conversion region is not present under the first electrode film U, the transparency of the first electrode film 11 can be low. Any of the best 1TO, IZ0, zn〇2, Sn02, Ti02, FTO, Al, Ag, and Au can be used for the first electrode film 11. Details of the first electrode film 11 will be described later. The second electrode film 13 has a function of discharging electrons generated in the photoelectric conversion layer 123 and being driven into the electrode film 13. The second electrode film 13 can be shared by all the pixels. Therefore, in the image forming apparatus 2GG, the second electrode film 13 is a film in a monolithic form to be shared by all the pixels. Since the incident light must be made to be the conversion layer 123, the second electrode film 13 needs to be formed by using a material which is permeable to visible light. Therefore, the visible transmittance of the second electrode film 13 is preferably 6. % or more than 60%, preferably 90% or more than 90%. most

The material of the Ti electrode film 13 may be any one of 1T 〇, IZ 〇, Zn 〇 2, Sn 〇 2, A1 Ag, and au. The details of the second film 55 201143183 polar film 13 will be described later. As the inorganic layer, a pn junction or a shirt joint formed of a crystalline semiconductor, an amorphous stone, and a compound semiconductor including GaAs is generally used. In these cases, the spectral range of the light-receiving area stacked on each other is widened by the fact that the color separation is performed according to the depth at which the light travels inside the substrate. However, the color separation can be remarkably improved by using the photoelectric conversion layer 123 as the upper layer as shown in Fig. 2, that is, by cutting the light which has passed through the photoelectric conversion layer 123 in the depth direction of the substrate. In the special case where the g light is detected by the photoelectric conversion layer 123 as shown in FIG. 2, the light passing through the photoelectric conversion layer 123 includes B light and R light, so that separation of light in the depth direction of the recording board is only required. Riding in the B-area R light. Therefore, the color separation is improved. Even when the photo-electric conversion layer 123 detects BS or R light, the color separation can be significantly improved by appropriately selecting the depth of each pn junction in the germanium substrate. The configuration of the inorganic layer is preferably npn*pnpn from the light incident side. Further, Ρηρη is connected, more preferably, because the dark current can be attenuated by trapping a hole and a dark current generated near the surface at a potential of ν, particularly by forming a p-layer on the surface. Although FIG. 2 shows a photoelectric conversion region located above the n-type dream substrate 1, the device may have two or more than two photoelectric conversion regions stacked on the n-type slab substrate 1 Structure above each other. A description of a structure in which two or more photoelectric conversion regions are stacked on each other in layers is given in the description of another embodiment of the present invention. In this case, the inorganic layer The detected light can be a kind of light of color, and can achieve good color separation. In the case of imaging another image of "one of the four colors of one of the pixels on the side of one of the four 2011 20111313⁄4", the following structure can be envisaged, such as (1)_ _Color light is made of electric conversion zone and the light of three colors is made up of three inorganic layers; (7) Two photoelectric conversions are stacked on top of each other in two layers and light of side color, while the inorganic layer side is other The structure of the light of two colors; and (3) the three photoelectric conversion regions are stacked on each other in three layers and the light of three colors, and the structure of the light of the other color on the side of the inorganic layer. The imaging device 200 can have a separate debt test allowed by a pixel A structure of light of a color. The structure in this case corresponds to a structure which does not have the p region 2, the n region 3, and the p region 4 in the diagram shown in Fig. 2. The inorganic layer will now be described in more detail. Examples of suitable structures for the layer include not only the light guide type, the pn junction type, the Schottky junction type, the PIN junction type, and the MSM (metal-semiconductor_metal) type photoreceptor structure, but also the photonic crystal type. The structure of the photoreceptor. As shown in FIG. 2, it is particularly suitable to use an inorganic layer formed by alternately stacking first and second conductive regions in a layer in a single semiconductor substrate, wherein the first conductive region is of a conductive type Contrary to the second conductive region, and establishing a junction between the first conductive region and the second conductive region at a depth suitable for photoelectric conversion of light generally included in any of the different wavelength bands. Single crystal germanium is suitable as a single The semiconductor substrate can be separated by the absorption wavelength characteristic depending on the depth direction of the viewing plate. InGaN type, inAIN type, ΙnΑΙΡ type or InGaAlP type semiconductor can also be used as the inorganic layer. Semiconductors. InGaN-type semiconductors are designed to have their respective absorption maxima in the wavelength range of blue light by changing their In content as appropriate. In other words, the composition is in the formula InxGa^N (0$X&lt;1). Table 57 201143183 These compound semiconductors are produced by a metal organic chemical vapor deposition method (M0CVD method), and an InAIN type nitride semiconductor such as an InGaN type semiconductor having A1 (which is the same as Ga as the 13th group) can be generally used. As a short-wave photoreceptor, alternatively, ΙηΑΙΡ and InGaAlP which are lattice-matched to a GaAs substrate can be used. Each inorganic semiconductor can form an embedded structure. The term "embedded structure" means that the two ends of the short-wave photoreceptor portion are different from the short-wavelength photosensitive. A semiconductor-covered structure of a semiconductor used in the device. The semiconductor covering both ends is preferably a conductor having a band gap wavelength equal to or shorter than the band gap wavelength of the short wave photoreceptor. Materials which can be used for the first electrode film 11 and the second electrode film 13 are, for example, metals, alloys, metal oxides, conductive compounds or various mixtures of these. Examples of useful metal species include a combination of meta-series selected from the group consisting of mK, Ca, Rb, Sr, Cs, Ba, t2.

Sc, Ti, Y, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc,

Re, Fe, RU, 〇s, c〇, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, A, Ga, In, Ή, Si, Ge, Sn, Pb, p, As,

Sb, Bi, Se, Te, P〇, Br, I, At, B, C, N, F, 〇, s, and N. Examples of particularly suitable metallic materials include A1, Dan, cargo, and

Ag, Ta, Cu, Cr, Mo, Ti, Ni, Pd and Zn. The first electrode film 11 can transport the photoelectric conversion layer or the hole transport layer from the hole included in the intermediate layer 12 to take out the hole and collect it, so the selection is made in consideration of the following factors: the photoelectric conversion layer can be transported to a hole such as a hole Adhesion, electron affinity, free potential, stability, etc. of adjacent layers of the hole transport layer 1 58 201143183 On the other hand, the 'second electrode film 13 from the electron transportable photoelectric conversion layer or electron transport layer included in the intermediate layer 12 The electrons are taken out and released, so the selection is made in consideration of adhesion to an adjacent layer such as an electron transportable photoelectric conversion layer and an electron f-feed layer, electron affinity, free potential, stable land, and the like. Examples of materials for these films include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO); metals such as gold di silver, chromium, and nickel; these metals and conductive metal oxides Mixture or laminate; inorganic conductive materials such as copper iodide and copper sulfide; organic conductive materials such as polyaniline, polythiophene and polypyrrole; anthraquinone compounds; and laminates of bismuth compounds with ITO. Among these materials, conductive metal oxides are superior to other materials, and ITO and IZO are particularly suitable for productivity, high electrical conductivity, and transparency. Various methods are used to fabricate the electrodes depending on the materials used. In the case of IT0, for example, a film can be formed by a method of sewing an indium tin oxide dispersion by an electron beam method, a sputtering method, a resistance heating evaporation method, or a chemical reaction method (sol-gel method). In the case of ruthenium, the formed ruthenium film may be subjected to UV-ozone treatment or plasma treatment. The conditions at the time of forming the transparent electrode film are mentioned below. When the transparent electrode film is formed, the temperature of the wire plate is 5 W (or lower than · C, more 300 ° C or lower than 30 (TC, more preferably 200. (or less than · c, better). It is = 〇 ° C or lower than 15 ° ° C. In addition, 'the gas can be introduced during the transparent electrode. The type of the introduced gas is not limited to a specific one, but can be introduced into the eight, He, oxygen, nitrogen and the like. Or the gas can be mixed. Especially in the case of oxide materials, the formation of 59 201143183 〇 / ozjpif 臈 often shows oxygen defects, so it is appropriate to introduce oxygen β β with 3, the surface resistance of the film The suitable range is based on whether the transparent electrode film is used for the first electrode film 11 or for the second electrode film. The signal electrode readout region of the moon electrode film has a CMOS structure, and the transparent electrode = when ϊίΓ, 000 ohms/square (Ω/□) Or less than 1 〇, _ ohms / ping is better than 1,000 ohms / square or less, when the ohmic / horn reading area has a CCD structure, the surface resistance is relatively. When the letter squared or low At 1,000 ohms/square, mg 1 () ^ , ohm / 100 ohm / 芈 * £ ohm / square or lower

, m / thousand. On the other hand, the surface resistance used as the second electrode 臈U pole film is preferably _, _ ohm / flat = 1 '〇〇〇, 〇〇〇 ohm / square ' is preferably 1 〇〇〇〇〇 戍Below 100,000 ohms/square. Ding Nai and lower than the materials especially suitable for transparent electrode film materials are ITO, Izo, Sn02, yttrium (yttria-doped tin oxide), Ζη〇, ΑΖ〇 (pushing αι oxidized), GZO (gallium-doped zinc oxide), Ti 〇2 and FT〇 (aerated tin oxide) ten of any. The light transmittance of the transparent electrode film at the Wei peak wavelength of the photoelectric conversion in the photoelectric conversion region including the transparent electrode film is preferably more than 60%, more preferably 80% or more, more preferably 90%. % or more than 9〇%, more preferably 95% or more than 95%. When stacking more than one intermediate layer 丨2, the first electrode film U and the second electrode film 13 included in each intermediate layer 12 need to allow light whose wavelength is not detected by the photoelectric conversion layer included in the relevant intermediate layer The wavelength of light passes through 'whether the photoelectric conversion layer is located near the light incident side or away from the light incident 201143183 side'. Therefore, it is preferable to use visible light that can transmit 90% or more, preferably 95% or more than 95%. The material as the electrode film 祠° The second electrode film 13 is preferably formed under no plasma conditions. By forming the second electrode film 13 in the absence of plasma, the effect of electropolymerization on the substrate can be reduced, whereby the photoelectric conversion characteristics can be made better. The term "plasma-free conditions" as used herein means that the &amp;amplifier which does not generate plasma during the formation of the second electrode film 13 or the distance between the plasma source and the substrate is 2 cm or more, preferably 10 cm or more than 10 cm 'better 20 cm or more than 2 cm, thereby reducing the amount of plasma reaching the substrate. As for the apparatus which does not generate plasma during the formation of the second electrode film 13, for example, an electron beam evaporation apparatus (EB evaporation apparatus) and a pulse-laser evaporation apparatus. Examples of electron beam evaporation devices and pulsed laser evaporation devices that can be used include, for example, the devices described in the following book: "T〇umd"

Dendoumaku no Shin-Tenkai" was published under the editorial of Sawada Yutaka (CMC publishing CaLtd., 1999); the name r T〇umd Dendoumaku no Shin-Tenkai II was issued under the editor of Sawada Ymaka (CMC publishing Co.Ltd. '2002' book; name is r T〇umei

Dendoumaku no Gijutsu" is edited by Nippon Gakujutsxi Shinkoukai (japan Society for the Promotion of Science) (and published by Ohmsha Ltd. in 1999); and references attached to these books. Hereinafter, a method of forming a transparent electrode film by means of an EB evaporation apparatus is called an EV evaporation method, and a method of forming a transparent electrode film by means of a pulsed laser evaporation apparatus is called a pulsed laser evaporation method. For example, an opposite target sputtering apparatus and an arc plasma evaporation apparatus 201143183 can be considered as a device capable of achieving a condition that the distance between the plasma source and the substrate is 2 cm or more and the amount of plasma reaching the substrate is reduced (under This is called a plasmaless film forming equipment). Examples of equipment include, for example, § exemption as described in the following book. The name is "Toumei Dendoumaku no Shin-Tenkai" at

The book entitled "Toumei Dendoumaku no Shin-Tenkai II" issued by Sawada Yutaka under the editorial release (CMC publishing Co. Ltd., 1999) is published under the editor of Sawada Yutaka (CMC publishing Co. Ltd., 2002). The name "T〇umei Dendoumaku no Gijutsu" is edited by Nippon Gakujutsu Shinkoukai (published by Ohmsha Ltd. in 1999); and the references attached to these books. When a transparent conductive film such as a tco film is used as the second electrode film 13, a DC short circuit or an increase in leakage current may occur. One of the reasons for considering these cases is that fine cracks generated in the photoelectric conversion layer 123 are covered by a dense film such as a TCO film, resulting in a gap between the second electrode film 13 and the first electrode film u provided on the opposite faces of the photoelectric conversion layer. The conductivity increases. Therefore, in an electrode such as an A1 film whose film quality is not as good as TCO, it is not easy to cause an increase in leakage current. By controlling the thickness of the second electrode film 13 at the thickness (or the trace thickness) of the photoelectric conversion layer 123, the leakage current can be greatly suppressed. The thickness of the second electrode film 13 should be adjusted to at most the photoelectric conversion layer 123. One fifth of the thickness, preferably one tenth. However, although the resistance is steeply increased, the thickness of the conductive film is reduced by more than a certain range, but the preferable sheet resistance in the solid-state imaging device 200 according to the embodiment of the present invention may be 1 (8) ohm/square to 10, _ ohm / square 62 201143183 range, so the film thickness of the device can reduce the thickness of the film is thinner 'the amount of light absorbed by the film, the light absorption increases and the photoelectric conversion power increases with the film thickness reduction ^ (10) Nano, more preferably 5 nm to 2 N. Materials suitable for transparent electrorotation are materials which can be formed into films by means of an electroless I film forming apparatus, a helium evaporation apparatus or a pulsed laser evaporation apparatus. The material is preferably a metal, an alloy, a metal oxide, a metal nitride, a metal halide, an organic derivative, or a mixture of both or both. Examples of such materials include conductive gold; | oxides such as antimony telluride, oxidized words: indium oxide, indium oxide (indium oxide), indium tin oxide (yttrium) and oxidized steel (IWO); metal nitrides, such as Titanium nitride; metals such as gold, platinum, silver, chromium, nickel and aluminum; mixtures or laminates of these metals with conductive metal oxides; inorganic conductive materials such as copper iodide and copper sulfide; organic conductive materials such as Polyaniline, polythiophene and polypyrrole; and laminates of these conductive materials with ruthenium. In addition, you can also use the material described in detail in the following book: "Toumei Dendoumaku no Shin-Tenkai", published under the editor of Sawada Yutaka (CMC Publishing Co. Ltd., 1999), entitled "Toumei Dendoumaku no" Shin-Tenkai II" is published under the editorial of Sawada Yutaka (CMC Publishing Co. Ltd., 2002); the name "Toumei Dendoumaku no Gijutsu" was edited by Nippon Gakujutsu Shinkoukai (Sakamoto Academic Promotion Association) (and 63 201143183f by OhmshaLtd . published in 1999) and so on. Fig. 4 is a schematic cross-sectional view showing an image forming apparatus relating to a third embodiment of the present invention. The image forming apparatus according to the embodiment shown in Fig. 2 is configured to have two photodiodes stacked in layers on each other inside the panel: and the image forming apparatus according to this embodiment is different in that It is configured to have two photodiodes juxtaposed in a state parallel to the surface of the semiconductor substrate in a horizontal direction. One of the pixels of the image forming apparatus 300 is configured to include an n-type germanium substrate, and an intermediate layer 31 formed on the first electrode film 30 and formed by the first electrode film 3 formed on the n-type germanium substrate 17 and formed. The photoelectric conversion region constituted by the second electrode film 32 on the intermediate layer 31 forms a light shielding film 34 having a hole on the photoelectric conversion region, thereby restricting the light receiving region of the intermediate layer 31. Further, a transparent insulating film 33 is formed on the light shielding film 34. The compositions of the first electrode film 30, the intermediate layer 31, and the second electrode film 32 are the same as those of the first electrode film u, the intermediate layer 12, and the second electrode film 13 described in the description of Fig. 1, respectively. In the surface portion of the n-type germanium substrate 17 located under the hole of the light shielding film 34, a photodiode composed of the n region 19 and the p region 18 and a photodiode composed of the n region 21 and the p region 20 are formed side by side. ^ Any direction on the surface of the n-type germanium substrate 17 is perpendicular to the incident direction of the incident light. The color filter 28 is formed on the photodiode composed of the n region 19 and the p region 18 via the transparent insulating film 24, and the first electrode film 30» is formed thereon and the color filter is transmitted through the R light. 29 is formed on the photodiode 64 20114313 body formed of the n region 21 and the p region 2 经由 via the transparent insulating film 24 and the first electrode film 30 is formed on the upper surface. The periphery of the color filter 28 and the periphery of the color filter 29 are covered with a transparent insulating film 25. The photodiode composed of the η region 19 and the p region 18 absorbs the luminescence passing through the color filter 28, and generates a hole in response to the absorbed luminescence. The resulting holes accumulate in the p region 18. On the other hand, the photodiode composed of the η region 21 and the ρ region 20 absorbs the R light' passing through the color filter 29 and generates a hole in response to the absorbed R light. The resulting holes accumulate in the ρ region 20. In the surface portion of the n-type germanium substrate 17 which shields light by the light shielding film 34, the Ρ+ region 23 is formed, and the ρ+ region is surrounded by the η region 22. The ρ+ region 23 is electrically connected to the first electrode film 30 via the connection region 27 formed in the holes drilled in the insulating films 24 and 25, and the holes collected in the first electrode film 30 are accumulated via the connection region 27. The connection region 27 is electrically insulated from the environment around the first electrode film 30 and the p+ region 23 by the insulating film 26. The holes accumulated in the p region 18 are converted into signals in response to the charge amount thereof by means of a MOS circuit (not shown) formed of a p-channel MOS transistor formed in the n-type germanium substrate, and accumulated in the p region 20 The hole in the middle is converted into a hole in the ρ+ region 23 by means of a MOS circuit (not shown) formed of a p-channel MOS transistor formed in the n-type germanium substrate 17 in response to a signal of its charge amount. A MOS circuit (not shown) composed of a p-channel MOS transistor formed in the n region 22 is converted into a signal responsive to the amount of charge thereof, and all of these signals are output to the outside of the image forming apparatus 300. These MOS circuits constitute a signal readout area. Each MOS circuit is connected to the signal readout pad by wiring 35 (not shown in Fig. 65 201143183). Alternatively, the signal readout area may be formed by a CCD and an amplifier instead of an M〇s circuit. More specifically, the signal readout area can be configured to read the holes accumulated in the p-region 18, the p-region 2〇, and the p+ region 23 in the CCD formed inside the n-type germanium substrate, and the electricity is charged by the CCD. The hole is transferred to the amplifier, and the output signal response from the hole of the amplifier can be CCD structure or CMOS structure, but in terms of power consumption, high-speed readout, pixel addition, partial readout, etc., CMOS The structure is better. Although the color separation between the R light and the B light in the apparatus shown in FIG. 4 is performed by the color filters 28 and 29, the apparatus does not have to be provided with the color filters 28 and 29, but can be configured to The depths of the pn junction between the p region 2 〇 and the η region 21 and between the ρ region 18 and the η region 19 are appropriately adjusted, and the photodiode absorbs r light and luminescence. In this case, an inorganic photoelectric conversion region composed of an inorganic material may be formed between the n-type germanium substrate 17 and the first electrode film 30 (for example, between the insulating film 24 and the n-type germanium substrate 17) to allow absorption. Light passing through the intermediate layer 31 generates charges and accumulates these charges in response to the light. In this case, the MOS circuit for reading out the signal of the charge accumulated in the charge accumulation region of the inorganic photoelectric conversion region is provided substantially only inside the n-type germanium substrate 17 and the wiring 35 is also connected to this MOS circuit. In another case, the device may have a structure in which one photodiode is provided inside the n-type germanium substrate 17 and two or more than two photoelectric conversion regions are stacked on each other in a layer form above the n-type germanium substrate 17. . In another case, the device may have the following structure: two or more than two photodiodes 66 201143183 are provided inside the n-type germanium substrate π, and in addition, two or more than two photoelectric conversion regions are n The ruthenium substrate 17 is stacked on top of each other in layers. On the other hand, unless a color image needs to be formed, the device may have a structure in which one photodiode is provided inside the germanium substrate 17 and only one photoelectric conversion region is stacked in one layer. Fig. 5 is a schematic cross-sectional view showing a single pixel portion of an image forming apparatus according to a fourth embodiment of the present invention. According to the embodiment described with reference to FIGS. 2 and 4, the photodiode for photoelectric conversion is provided inside the semiconductor substrate, and the device in this embodiment has the following structure: only the signal readout circuit is provided inside the semiconductor substrate and three The photoelectric conversion layers (that is, the photoelectric conversion layer for detecting R light, the photoelectric conversion layer for detecting G light, and the photoelectric conversion layer for detecting b light) are stacked on each other over the semiconductor substrate. More specifically, the image forming apparatus 400 shown in FIG. 5 has the following structure: a first electrode film 56, an intermediate layer 57 stacked on the first electrode film 56, and a second electrode film 58 stacked on the intermediate layer 57. R photoelectric conversion region, including a first electrode film 6〇, an intermediate layer 61 stacked on the first electrode film 6〇, and a B photoelectric conversion region of the second electrode film 62 stacked on the intermediate layer 61 in a layer form, and A G photoelectric conversion region including a first electrode film 64, an intermediate layer 65 stacked on the first electrode film 64, and a second electrode film 66 stacked on the intermediate layer 65 is stacked in a layer form on the germanium substrate in the order mentioned Above 41 is a state in which each of the first electrode films faces the side of the substrate 々I. A transparent insulating film 48 is formed on the ruthenium substrate 41 and has an R photoelectric conversion region formed thereon. A transparent insulating film 59 is further formed on the upper surface. The B photoelectric conversion region is further formed above. A transparent insulating film 63 is formed on this region. G photoelectric 67 201143183

A conversion region is formed on the film 63, and a light shielding film having a hole is formed thereon. A transparent insulating film 67 is formed on the light shielding film 68. The composition of the first electrode film 64, the intermediate layer phantom, and the second electric surface 66 included in the G photoelectric conversion region is respectively composed of the first film η, the intermediate layer 12, and the second electrode film 13 described in the description of FIG. the same. Similarly, the composition of the first electrode film 6 (), the intermediate layer &amp; and the = electrode film 62 which are included in the photoelectric conversion region of the ruthenium, respectively, and the first electrode 12 and the intermediate layer 12 described in the description of FIG. The composition of the two-electrode film 13 is the same, and the composition of the first electrode film 56, the intermediate layer 57, and the second electrode 58 included in the photoelectric conversion region and the first electrode film (1), 12 and The composition of the second electrode film 13 is the same. However, the photoelectric conversion layer incorporated in the B photoelectric conversion region uses a material capable of absorbing blue light and generating electrons and holes in response to the light thus absorbed, and into the R photoelectric conversion region (4) photoelectric conversion dissimilarity can touch red light and ring The light thus absorbed produces electron and hole material. 'As for the damage and composition of the barrier layers of the electron and hole blocking layers in each of the inter-panel layers 61 and 57, it should be appropriately selected to avoid the H0M0 of the photoelectric conversion film in each intermediate layer. The LUM〇 energy level and the energy barrier of the signal charge transport between the adjacent layers of the transition layer 1J HQMQ and the LUM〇 energy level in each intermediate layer. In the surface portion of the ruthenium substrate 41 which is shielded by the light shielding film 68, P+ regions: 43, 45, and 47 are formed, and are surrounded by the n region 42, the material, and the milk, respectively. The Ρ+ region 43 is electrically connected to the first electrode film 56 via the connection region 54 formed in the hole drilled in the insulating film 48, and the hole collected in the electrode film 56 of the 68201143183 is accumulated via the connection region%. The connection region 54 is electrically insulated from the environment around the first electrode film 56 and the p+ region 43 by the insulating film 51. The P+ region 45 is electrically connected to the first electrode film 60' via the connection region 53 formed in the hole drilled in the insulating film 48, the R photoelectric conversion region, and the insulating film 59, and is accumulated in the first electrode film 60 via the connection region 53. Collect the holes. The connection region 53 is electrically insulated from the environment around the first electrode film 60 and the p+ region 45 by the insulating film 50. The P+ region 47 is electrically connected to the first electrode film 64 via the connection region 52 formed in the hole drilled in the insulating film 48, the R photoelectric conversion region, the insulating film 59, the B photoelectric conversion region, and the insulating film 63, and via the connection region 52 accumulates the holes collected in the first electrode film 64. The connection region 52 is electrically insulated from the environment except the first electrode film 64 and the p+ region 47 by the insulating film 49. The holes accumulated in the P+ region 43 are converted into a signal in response to the amount of charge thereof by means of a MOS circuit (not shown) formed of a p-channel MOS transistor formed in the n region 42, and accumulated in the ρ+ region 45. The hole is converted into a signal responsive to the amount of charge thereof by a MOS circuit (not shown) formed of a p-channel MOS transistor formed in the n region 44, and the hole accumulated in the Ρ+ region 47 is thereby The MOS circuit (not shown) formed by the p-channel MOS transistor formed in the n region 46 is converted into a signal responsive to its charge amount, and all of these signals are output to the outside of the imaging device 400. These MOS circuits constitute a signal readout area. Each]v[〇s circuit is connected to the signal readout pad (not shown) by wiring 55. Alternatively, the signal readout area may be constructed of a CCD and an amplifier as mentioned above. On the other hand, an inorganic photoelectric conversion region made of an inorganic material may be formed between the n-type germanium substrate 41 and the first electrode 貘 56 69 201143183t (for example, between the insulating film 48 and the germanium substrate 41) to allow reception. The light passing through the intermediate layers 57, 61 and 65 'generates and accumulates these charges in response to the received light. In this case, the MOS circuit for reading out the signal of the charge accumulated in the charge accumulation region of the inorganic photoelectric conversion region is provided substantially only inside the germanium substrate 41 and the wiring 55 is connected to this MOS circuit. In the above description, the term "photoelectric conversion layer absorbing B light" means that light having a wavelength in the range of 400 nm to 500 nm can be absorbed at least and preferably 50% at a peak wavelength in the wavelength range or The layer of the absorption factor exceeding 50%, the term "light-transfer layer for absorbing G light" means that light having a wavelength in the range of 500 nm to 600 nm can be absorbed at least and preferably at a peak wavelength within the wavelength range. A layer having an absorption factor of 50% or more than 50% and the term "photoelectric conversion layer for absorbing R light" means light which absorbs at least a wavelength in the range of from 600 nm to 700 nm and preferably in the wavelength range A layer having an absorption factor of 50% or more at a peak wavelength within. In the present embodiment, three photoelectric conversion layers are provided. The colors of the light respectively detected by these photoelectric conversion layers are not in a particular order. From the side of the incident light side (upper side), it is conceivable to detect the pattern of colors in the order of BGR, BRG, GBR, GRB, RBG or RGB. Among these patterns, 〇 detects that the pattern appearing in the uppermost layer is superior to other patterns. On the other hand, in the embodiment shown in FIG. 4, the following combination can be employed: the upper layer of the R layer and the lower layer and the upper layer of the B layer are formed by placing the B layer and the G layer in the same plane. The combination of the G layer and the R layer in the same plane to form the lower layer 201143183 _ 1 , or the upper layer of the G layer and the lower layer by the B layer and the R layer in the same plane. In these combination tissues, the combination of the upper layer of the G layer and the lower layer by the B layer and the R layer are placed in the same plane towel is superior to the other combination. One, six is a cross-sectional view of the image forming apparatus 5 in the fifth embodiment of the present invention. In FIG. 6, a cross-sectional view of two pixel portions in a pixel region where light is detected and accumulated charges is described together, a wiring connected to electrodes in the pixel region, and a cross section of a peripheral circuit region forming a bonding pad connected to the wiring. Figure. The p region 421 is formed in the surface portion of the n-type germanium substrate 413 in the pixel region, and the n region 422 is formed in the surface portion of the p region 421. The meander region 423 is formed in the surface portion of the n region 422. The n region each numbered "424" is further formed in the surface portion of the p region 423. The ρ region 421 accumulates a hole of a red (R) component which is photoelectrically converted by pn bonding with the n-type germanium substrate 413. The potential change of the ρ region 421 caused by the hole accumulation of the R component is connected to the metal wiring 419 of the signal readout pad 427 formed by the MOS transistor 426 formed inside the n-type germanium substrate 413, and enters the signal reading from the MOS transistor 426. Read out of the pad 427. The ρ region 423 accumulates a hole of a blue (Β) component photoelectrically converted by π η bonding with the η region 422. The potential change of the ρ region 423 due to the hole accumulation of the component is connected to the MOS transistor 426' formed inside the n region 422 and the metal wiring 419 of the signal readout pad 427, and the signal is read from the MOS transistor 426. Read out of the pad 427. A hole accumulation region 425 is formed inside the ? region 424, which includes a p region of a hole of a green (G) component which is generated in the photoelectric conversion layer 123 stacked on the n-type germanium substrate 413. The potential change of the hole accumulation region 425 caused by the hole accumulation of the G component is connected via the MOS transistor 426 formed inside the n region 424, and the metal wiring 419 of the signal readout pad 427 from the MOS transistor 426" Read into the signal readout pad 427. In general, different signal readout pads 427 are provided for each of the three color component readings respectively. Ρ region, η region, transistor, metal wiring, etc. In the above, the respective structures and the like are not limited to the illustrated structure, but the best one may be selected as appropriate. Since the light and the R light are separated according to the depth of the germanium substrate, the ρη bonding under the surface of the stone substrate is The choice of depth, concentration of impurities such as _agents, etc. is important. The technique of the CM 〇 像 像 sensor can be applied to the CM 〇 circuit acting as a money readout area. Not only low noise readout lines can be applied. Amplifier (5) umnamp cerebral palsy and (10) circuit: and it is also possible to apply a circuit which allows the number of f crystals in each pixel region to be reduced, such as ruthenium, tantalum nitride or the like as a main component. Above. Contains oxygen cut Nitrogen, two? as the main component of the transparent insulating film 4U formed in the singer *, the thinner the thickness of the film 412, the better the results. Details _ ~ ~ thickness is 5 « or less than 5 microns, compare It is 3 micrometers, more preferably 2 micrometers or less, and 2 micrometers is less than 1 micrometer. The size of the horse is 1 micro-not! Contains, for example, a crane as a main component and electrically connects the first electrode film 41q 72 201143183 as a hole accumulation region The plug 415 of the p region 425 is formed inside the insulating films 411 and 412. The plug 415 is in a state of being joined and joined at the interface between the insulating film 411 and the insulating film 412 via the pad 416. The pad 416 used is preferably A pad containing aluminum as a main component, a gate electrode of the metal wiring 419, transistors 426, 426, and 426" is formed inside the insulating film 412. A barrier layer comprising metal wiring is preferably provided. A plug 415 is provided based on the pixels. The light shielding film 417 is provided inside the insulating film 411 for the purpose of preventing noise generated by the pn junction between the n region 424 and the p region 425. A film containing tungsten, aluminum or the like as a main component is generally used as the light shielding film 417. A bonding pad 42 (a pad for supplying power from the outside) and a signal readout pad 427 are formed inside the insulating film 411, and an electrical connection for the bonding pad 420 to the first electrode film 414 described later is also formed. The metal wiring (not shown) β forms a first transparent electrode film 414 on the plug 415 provided for each pixel inside the insulating film 411. The first electrode film is divided according to the number of pixels, and the size of each divided film determines the area of light reception. Applying a bias voltage from the bonding pad 420 to the first electrode 414 via wiring is preferably designed to be in the hole by applying a negative bias voltage to the first electrode film 414 with respect to the second electrode film 405 described later. The structure of the electric holes is accumulated in the accumulation area 425. An intermediate layer 12 having the same structure as that shown in Fig. 2 is formed on the first electrode film 414, and a second electrode film 4?5 is formed on this layer. A protective film 404 having a function of protecting the intermediate layer 12 and containing tantalum nitride or the like as a main component is formed on the second electrode film 405. At 73 201143183 2 film 404 towel 'there is no - first electrode-cut 14 existing at the pixel area to make - hole. Further holes are formed in the insulating film and the protective film 4〇4 at a position above the portion of the bonding crucible 420. And a wiring 418 electrically connecting the second electrode film 405 and the portion of the connection pad 420 exposed by the two holes is formed in the inside of the hole and the protective film 4〇4 via the wiring, and the potential is included It is applied to the second electrode film 4〇5. An alloy containing aluminum such as A1_Si or Al_Cu may also be used as the material of the wiring 418. A protective film 403 containing tantalum nitride or the like as a main component and protecting the wiring 418 is formed on the wiring 418, the infrared-shielding multilayer dielectric film 402 is formed on the protective film 403, and the anti-reflection film 4〇1 is formed in the infrared ray. The multilayer dielectric film 402 is protected. The first electrode film 414 performs the same function as the first electrode film 11 shown in Fig. 2. And the second electrode film 405 performs the same function as the second electrode film 13 shown in Fig. 2. By constituting the above device, color imaging can be realized by detecting light of three colors of BGR with each pixel. According to the structure shown in Fig. 6, R and B are used as the common values in the two pixels, and the B values are used separately. Since the sensitivity of G is important for image formation, the structure just allows for the formation of good quality color images. The image forming apparatus described above is applied to a digital camera, a video camera, a fax machine, a scanner, a photocopier, and other imaging devices. Further, it can be used as a light sensor including a biosensor and a chemical sensor. Examples of materials for insulating films in the description of the embodiments of the present invention 201143183 include metal oxides such as Si〇x, SiNx, BSG, PSG, BPSG,

Al2〇3, MgO, Geo, Nio, CaO, BaO, Fe203, Y2〇3 and

Ti02; and metal fluorides such as MgF2, LiF, a1F3 and CaF2. Among these materials, 'SiOx, SiNx, BSG, PSG and BPSG are superior to other materials. In the embodiments of the present invention as shown in Figs. 2, 4, 5 and 5, signal reading from the photoelectric conversion layer can be performed using holes or electrons. More specifically, as mentioned above, the device may be configured such that the hole is in the inorganic photoelectric conversion region provided between the semiconductor substrate and the photoelectric conversion region stacked over the semiconductor substrate or in the photovoltaic formed inside the semiconductor substrate The diodes accumulate and read signals in response to the holes through the signal readout region, or they may be configured such that the electrons are hidden and borrowed in the inorganic photoelectric conversion region and the photodiode formed in the (four) part of the semi-conducting county. Signals responsive to these electrons are read from the signal readout area. In the embodiments of the present invention as shown in FIG. 2, FIG. 4, FIG. 5 and FIG. 6, although the structure shown in FIG. 3 is used as the photoelectric conversion region provided on the germanium substrate, it may be used. Has the structure shown in Figure 。. According to the structure of the figure, it can be _ electrons and holes, so the effect of riding current is ', enhanced. When the electrode placed on the opposite side to the light incident side serves as a temple for collecting electrons, only the connection region 9 in Fig. 2 is connected to the second electrode or the connection region 27 in Fig. 4 is connected to the second electrode 13. The imaging devices 200, 3, 400, and 200, each of which are described as embodiments of the present invention, are configured to "make a large number of pixels arranged in an array on the same side, and the color signals of RGB are available from Each pixel is obtained. Each of these pixels can be considered as an electrical conversion device for converting RGB light into an electrical signal as a result of 75 201143183l. Therefore, each of the image forming apparatuses described in the embodiment of the present invention has a structure in which each of the photoelectric conversion devices as shown in Figs. 2 to 6 is arranged in a large number on the same plane in an array form. Fig. 7 and Fig. 8 are explanatory views of an image forming apparatus according to a sixth embodiment of the present invention. ® 7 is a schematic view of a part of the surface of the imaging device, and Fig. 8 is a schematic view showing a vertical section taken in the χ_χ line in Fig. 7. In the image forming apparatus 6A according to an embodiment of the present invention, the p-well layer 602 is formed on the n-type stone substrate 601. Hereinafter, the combination of the n-type slab substrate 601 and the p-well layer 602 is referred to as a semiconductor substrate. Each of the three kinds of color filters is arranged in a large number in the column direction and the row direction orthogonal to the same plane above the semiconductor substrate, that is, the color filter 613r mainly transmitting the R light, and the color filter mainly transmitting the G light. The sheet 613g and the color filter 613b mainly transmitting the B light. It is known that a material that transmits R light can be used for the color filter 6i3r, a material that is known to pass through G light can be used for the color filter 613g, and a material that is known to transmit B light can be used for the color filter 613b. An arrangement pattern of color filters for a known single-plate solid-state imaging device such as a Bayer pattern, which is a vertical stripe pattern and a horizontal stripe pattern, may be employed as the color filters 613, 613 g, and 613b. Arrangement pattern. The transparent electrode 611r is formed over the n region 604r, the transparent electrode 611g is formed over the n region 604g, and the transparent electrode 611b is formed over the n region 76 201143183 604b. The transparent electrodes 61 lr, 611g, and 611b corresponding to the color filters 613f, 613g, and 613b, respectively, are kept separated from each other. The functions of each of the transparent electrodes 611r, 61 lg and 611b are the same as those of the lower electrode η in Fig. 1. A monolithic structure photoelectric conversion film 612 is formed on each of the transparent electrodes 611r, 611g, and 611b and shared by the color filters 613r, 613g, and 613b. The monolithic structure upper electrode 613 is formed on the photoelectric conversion film 612 and shared by the color filters 613r, 613g, and 613b. The photoelectric conversion element corresponding to the color filter 613r is formed of a transparent electrode 611r, a part of the upper electrode 613 opposed to the electrode 611r, and a part of the photoelectric conversion film 612 therebetween. Hereinafter, such a photoelectric conversion element will be referred to as an R photoelectric conversion device because this element is an element formed on a semiconductor substrate. The photoelectric conversion element corresponding to the color filter 613g is formed of a transparent electrode 611g, a part of the upper electrode 613 opposed to the electrode 611g, and a part of the photoelectric conversion film 612 interposed therebetween. Hereinafter, such a photoelectric conversion element will be referred to as a G photoelectric conversion device. The photoelectric conversion element corresponding to the color filter 613b is formed of a transparent electrode 611b, a part of the upper electrode 613 opposed to the electrode 611b, and a part of the photoelectric conversion film 612 missing therebetween. Hereinafter, such a photoelectric conversion element will be referred to as a B photoelectric conversion device. In the η region of the p-well layer 602, a high-density n-type impurity region (hereinafter referred to as "n+region") 6〇4r' is formed to accumulate in the photo-electric conversion film of the R photoelectric 77 201143183. The charge generated in 612. Further, for the purpose of protecting the n+ region 604r from light, it is preferable to provide a light shielding film on the region 6〇4r. In the η region inside the well layer 602, an η+ region 604g for accumulating electricity generated in the photoelectric conversion film 612 of the G photoelectric conversion device is formed. Further, for the purpose of protecting the n+ region 604g from light, a light shielding film is preferably provided on the n+ region 604g. In the n region inside the p-well layer 602, an n+ region 6〇4b for accumulating electricity generated in the photoelectric conversion film 612 of the B photoelectric conversion device is formed. Further, for the purpose of protecting the n+ region 604b from light, a light shielding film is preferably provided on the n+ region 604b. A contact region 606r including a metal such as a metal is formed on the n+ region 6〇4r' and a transparent electrode 611r is formed on the contact region 606r. The β n+ region 6〇4Γ is electrically connected to the transparent electrode 611r via the contact region 606r. The contact region 606r is embedded in an insulating layer 6〇5 permeable to visible light and infrared rays. A contact region 606g including a metal such as aluminum is formed on the n+ region 6〇4g, and a transparent electrode 611g is formed on the contact region 6〇6g. The n+ region 6〇4g is electrically connected to the transparent electrode 611g by the contact region 6〇6g. The contact region 606g is embedded in the insulating layer 605. A contact region 6〇6b including a metal such as aluminum is formed on the n+ region 6〇4b' and the transparent electrode 611b is formed on the contact region 6〇61). The n++ region 6〇4b and the transparent electrode 611b are contacted by the contact region 6〇6b. Electrically connected together. Contact region 606b is embedded in insulating layer 605. In the region of the P 2011 layer 6〇2 where the n 2011 regions of the n+ regions 604r, 604g, and 604b are not formed, a charge for reading out the charges generated in the R photoelectric conversion device and accumulated in the n+ region 604r is formed. a signal readout area 605r of the signal, a signal readout area 6〇5g for reading out each of the signals generated in response to the charge generated in the G photoelectric conversion device and accumulated in the n+ region 604g, and a readout response at the B photoelectric A signal readout region 605b of each of the signals generated in the conversion device and accumulated in the n+ region 604b. Each of the signal readout areas 605r, 605g, and 605b can employ a known structure using a CCD or MOS circuit. Further, for the purpose of protecting the signal readout regions 6〇5r, 605g, and 6〇5b from light, it is preferable to provide a light shielding film on these regions. Fig. 9 is a view showing an example of a specific configuration of the signal readout area 605r shown in Fig. 8. The same components in Fig. 9 as those in Figs. 7 and 8 are denoted by the same reference numerals as those in the drawings. Further, since the signal readout regions 605r, 605g, and 605b have the same configuration, the description of the signal readout regions 605g and 605b is omitted. The signal readout region 605r is equipped with a reset transistor 543. Its drain is connected to the n region 604f and its source is connected to the power source vn; the output transistor 542 has its gate connected to the drain of the reset transistor 543 and The source is connected to the power supply Vcc' column select transistor 541, the source of which is connected to the drain of the output transistor % and the drain of which is connected to the signal output line 545; the reset transistor 546 whose / and the pole are connected to The η region is 6〇3ι· and its source is connected to the power source %; the output transistor 547 has a gate connected to the reset transistor % of the pole and its source is connected to the power source Vcc; and the column select transistor state, The source is connected to the output transistor 547 and is connected to the signal output line 549. By applying a bias voltage between the transparent electrode 611r and the upper electrode 613, 79201143183 generates charges in response to light incident on the photoelectric conversion film 612, and these charges, 'i, are moved by the transparent electrode 611r to the n+ region 6〇4r. In the n+ region 604r, the accumulated charge is converted by the output transistor 542 into a signal of the amount of response charge. And by switching the column selection transistor 541 to the open position, the signal is output to the signal output line 545. After the signal is output, the charge in the n+ region 604r is reset by resetting the transistor 543. Therefore, the signal readout region 605r can be constituted by a known MOS circuit including three kinds of transistors. Returning to Fig. 8, for the purpose of protecting the photoelectric conversion element, protective layers 615 and 616 of a double-layer structure are formed on the photoelectric conversion layer 612, and color filters 613r, 613g, and 613r are formed on the protective layer 616. This image forming apparatus 600 is manufactured by undergoing a process of first forming the photoelectric conversion film 612, then forming the color filters 613r, 613g, and 613b. The process of forming the color filters 613r, 613g, and 613b includes a photolithography step and a baking step. When the organic material is used for the photoelectric conversion film 612 and the photolithography and baking steps are performed in a state where the photoelectric conversion film 612 is exposed, the properties of the photoelectric conversion film 612 are degraded. The protective layers 615 and 616 are provided for the purpose of preventing degradation of the properties of the photoelectric conversion film 612 by the generation process. The protective film 615 is preferably an inorganic layer comprising an inorganic material and formed by an ALCVD method. The ALCVD method is an atomic layer CVD method and allows formation of a dense inorganic layer. Therefore, the formed layer can be an effective protective layer of the photoelectric conversion layer 612. The ALCVD method is also known as the ALE method or the ALD method. The composition of the inorganic layer formed by the ALCVD method is preferably AI203, SiO 2 , Ti 〇 2, ZrO 2 , MgO, HfCb or Ta 2 〇 5, more preferably A 〇 2 〇 3 or Si 〇 2, and particularly preferably 201143183 AI 2 O 3 ° For the purpose of further improving the ability to protect the photoelectric conversion film 612, a protective layer 616' is formed on the protective layer 615 and it is preferably an organic layer including an organic polymer. The organic polymer is preferably polypyrene, more preferably one gas to two. Alternatively, the protective film 616 may be omitted, or the order of arrangement of the protective film 615 and the protective film 616 may be reversed. The structure shown in Fig. § can protect the photoelectric conversion film 612 particularly efficiently. When a prescribed bias voltage is applied between the transparent electrode 611r and the upper electrode 613, the electric charge generated in the photoelectric conversion film 612 incorporated in the R photoelectric conversion device is moved to the n+ region 604r via the transparent electrode 611r and the contact region 606γ, and Accumulate in this area. The signals of the charges accumulated in the response η+ region 604r are read out by the signal readout region 6〇5γ, and these signals are output to the outside of the image forming apparatus 600. Similarly, when a prescribed bias voltage is applied between the transparent electrode 611g and the upper electrode 613, the electric charge generated in the photoelectric conversion film 612 incorporated in the G photoelectric conversion device is moved to the n+ region 604g via the transparent electrode 611g and the contact region 606g, And accumulate in this area. The signals in response to the charges accumulated in the n+ region 604g are sold by the signal readout area 6〇5g s, and these signals are outputted to the outside of the image forming apparatus 600. Similarly to the above, when a prescribed bias voltage is applied between the transparent electrode 611b and the upper electrode 613, the electric charge generated in the photoelectric conversion film 612 incorporated in the B photoelectric conversion device is moved to n+ via the transparent electrode 6iib and the contact region 606b. Region 604b' and accumulates in this region. And the signal of the charge accumulated in the response n+ region 6〇4b is read out by the signal readout region 605b, and this will be 201143183

a L These signals are output to the outside of the imaging device 600. In this manner, the R component signal responsive to the charge generated in the R photoelectric conversion device, the G component signal responsive to the charge generated in the G photoelectric conversion device, and the B component signal responsive to the charge generated in the B photoelectric conversion device are self-imaging devices 600 output to the outside. Therefore, a color image can be obtained. In this mode, the photoelectric conversion area can be made thinner, thereby improving resolution and reducing false colors such as 祀 color. Further, regardless of the circuit formed in the semiconductor substrate, the aperture can be made higher, whereby sensitivity can be achieved, and in addition, the omission of microlenses can have an effect on reducing the number of parts. According to various embodiments of the present invention, the organic photoelectric conversion film has its maximum absorption wavelength in the high green region, and although it is required to absorb light in the entire visible region, the above materials can satisfactorily satisfy the requirements. Although the embodiment of the present invention using the photoelectric conversion device according to the embodiment of the present invention in an image forming apparatus has been described above, the photoelectric conversion device of the present invention can transmit high performance even when it is used as a solar cell because Has high photoelectric conversion efficiency. The invention will now be explained in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention in any way. EXAMPLES &lt;Sample a&gt; The exemplified compound 1 described above was synthesized in the following manner. The basic part of the illustrated Spider 1 is again indicated by the following reaction procedure. 82 201143183

Q nine. Oxidizing compound impurity 1 After replacing the air in the reaction vessel with nitrogen, 2.7 g of 4-(anthracene, diphenylamino)benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.5 g of 1,3 were placed. -茚满二_ (by Tokyo Chemical

The product was placed in a reaction vessel as a raw material, and 50 ml of ethanol was further added to the reaction vessel, and 1. mM of piperidine was added thereto. Subsequently, the reaction vessel was shielded from light under a nitrogen atmosphere, and the reaction solution was heated under reflux for 3 hours. After the end of the reaction, the resulting solution was cooled to room temperature and was thus produced - and washed with 5 ml of ethanol. In the solution refining process, these crystals were redissolved in 17 ml of a two-gas combustor and passed through a filter. Further, 17 Torr of methanol was added to the obtained filtrate, and the resulting mixture was concentrated and reduced until the total volume thereof was reduced by about 1/2. The crystal obtained by this = "5 liters of methanol yarn = A gram of the compound in the form of a crystalline substance! . This 83 20114318} The crystalline material is refined by sublimation refining equipment (TRS_丨, product of ULVAC_RIK〇, Inc). Under the argon flow, the temperature at the boat was 2 Torr. (: or over 200 ° C, the collection zone is controlled at 200 ° C or below 20 (TC and the pressure in the system is 〇. 1 Pa. Sublimation purification is carried out. After sublimation purification, the crystal yield is 88%. The obtained sublimation crystal was taken out from the sublimation tube in a sealed atmosphere box having a nitrogen atmosphere and transferred to a brown glass vial. Further, the vial was sealed with a lid and stored under a nitrogen atmosphere under a light-shielding condition. The sample thus obtained is referred to as sample a1. &lt;Sample a3&gt; Synthesis of exemplified compound 3

To 10 ml of dehydrated xylene, 4.4 g of a raw material 3, 4 g of decyl 6-bromo-2-naphthoate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.2 g of palladium acetate, and 0.6 g of triphenylphosphine were added. And i 〇 grams of carbon dioxide planer. The resulting mixture was refluxed for 7 hours under a nitrogen stream. The reaction mixture was filtered under suction, and the filtrate was concentrated under reduced pressure, and then purified and purified by EtOAc EtOAc. Then steam the remaining grams of intermediate 3. And 6.4 to add 3 ethoxy ethoxy) sodium hydride to the methyl hydrazine H (double (2-)

Che^cal industries, !〇%ΐ: ^ has an internal temperature of o °c, and the solution is obtained in milliliters of the internal temperature of the solution in dehydrated toluene and is added dropwise thereto: prepared and Concentrated hydrochloric acid was added thereto until the enthalpy reached i. To this: water; B; and washing the separated oil layer with an aqueous solution of sodium hydrogencarbonate: Step: Dry the oil layer with magnesium sulfate, followed by filtration. The solvent is reduced by steaming by means of an evaporator. To the three-part residue, 1.3 g of Izumi 2 mesh and 5 ml of acetonitrile were added. The mixture was refluxed under a stream of nitrogen for 2 hours, followed by standing to cool. After that, the mixture is suction filtered, and the obtained body (4) is added to the test and the money is ordered to be heated under the flow for an hour. The crystals obtained by cooling to room temperature were suctioned through acetonitrile and dried under vacuum. Therefore, 25 grams of Example = Compound 3 was obtained. This sample was subjected to sublimation refining with sample &amp; 1, and thus passed to sample a3, but the yield was 3 〇/〇. In sample a and sample a3, the oxidized compound impurity 1 and the oxidized compound impurity described above as "quality" were respectively detected by means of HPLC.

201143183 L 3 ' and its content is 870 ppm or less than 870 ppm. The content of the exemplified compound 1 and the exemplified compound 3 is in the range of 99.9% to 99.5%. The analytical value of HPLC was expressed based on the relative area ratio between the peaks in the chromatogram obtained by using the THF-water mixture solvent as a moving bed and monitoring the absorbance at 254 nm. When the water content in these samples is determined by the Karl Fischer technique and the solvent content is determined by the weight loss due to drying (the weight percentage reduced by heating under vacuum at 1 Torr) When the value obtained by subtracting the respective water contents is subtracted, it is 〇.1% or less than 0.1%. Similar results were obtained even when the solution was refined twice or more times and the sublimation refining was carried out twice or more. &lt;Sample a2 and sample a4&gt; Sample a2 and sample a4 were obtained by omitting the sublimation refining process in the example of sample a1 and sample a3 synthesis, respectively. The content of the oxidized compound impurity 1 in the sample a2 and the oxidized compound impurity 3 in the sample a4 are in the range of 1,100 ppm to 2,800 ppm, and the contents of the exemplified compounds 1 and 3 in these samples are respectively 99.1% to 97.3%. Within the scope. Both the water content and the solvent content are 0.1% or less. &lt;Comparative sample a1 and comparative sample a3&gt; The comparative sample a1 and the comparative sample a3 were obtained by separately eliminating the solution refining process in the example of the synthesis of the sample a2 and the sample a4. Comparing the content of the oxidized compound impurity 1 in the sample a1 and the content of the oxidizing compound impurity 3 in the comparative sample a3 were each 3,200 ppm or more than 3,200 ppm, and the contents of the exemplified compounds 1 and 3 in each of the samples were respectively 96.3% 86 201143183. Less than 96.3%. <Sample bl> The exemplified compound 2 in the above Scheme 2 was synthesized in the following manner. The basic part of Flow 2 is indicated below.

Exemplary Compound 2 After replacing the air in the reaction vessel with nitrogen, 2.4 g of 9H-paraben[b,d,f]azepine is described (according to J. 〇rg. Chem, 56, 3906 (1991) Synthetic) and 2.4 g of 4,4,-di-di-biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed as a raw material in a reaction vessel, and 1.5 g of sodium tributoxide was further added to the reaction vessel (by Wako Pure

Chemical Industries, Ltd., loo mg palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 450 mg of triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.), and 50 ml of toluene. The reaction vessel was then shielded from light under an atmosphere of air and the reaction solution was heated under reflux for 8 hours. After the end of the reaction, the resulting solution was cooled to room temperature, and 50 ml of decyl alcohol was added thereto. The crystals thus produced were filtered off and washed with 5 mL of decyl alcohol. In the solution refining process, these crystals were redissolved in 1 Torr of gas and passed through a filter. Further, 1 ml of sterol was added to the obtained filtrate, and the resulting mixture was concentrated under reduced pressure until the total amount thereof was reduced by about 1/2. The crystals thus obtained were filtered off and washed with 5 ml of methanol. 87 201143183. = nitrogen = lower: further dried by vacuum (〇 2 Torr) (under 朦c). Thus, s 例 exemplified compound 2 was obtained. This crystalline material is subjected to sublimation refining by means of a product of the formula. Under argon flow, the vessel temperature is 300 C or more than 3 〇 (rc, the collection area is controlled at eagle below 200. (: and the pressure in the system is (sub-refined under the condition of U Pa. Sublimation refined) crystal The yield was 85%. The sample thus obtained is referred to as sample b. The sublimation obtained therefrom was taken out from the sublimation tube in a closed operation box with a nitrogen atmosphere and transferred to a brown glass cut, bottle towel. The vial was sealed and stored under light-shielded conditions under nitrogen atmosphere [Sample b3]

After replacing the air in the reaction vessel with nitrogen, the raw material, i.e., 1 gram of material 41 (synthesized according to Journal of Materials Chemistry, Vol. 15, pp. 4753-4760 (2005)) and 1.5 g of raw material 42 ( Synthesized according to Organic Letters, Vol. 9, pp. 797-800 (2007), 100 mg acetate, 300 mg triphenylphosphine, 2.5 g carbonate planer and 50 ml dehydrated benzene (via Wako Pure Chemical Industries, Ltd. was placed in a reaction vessel, and the reaction vessel 88 201143183 ί was heated under a nitrogen atmosphere for 12 hours. After the end of the reaction, the unit was taken to room temperature, and 5 ml of methanol was added thereto. Therefore, the body was then washed with 5 g of methanol. The solution was refined in the solution tr = carcass re-dissolved 10 ml of two gas In the courtyard, and after the addition of acetonitrile to the remainder, the crystal is separated, 2 is dried under nitrogen, and heated by the artificial (eight 〇·=) heating (under the boot). Therefore, the exemplified compound 4 in the form of a ship-f crystal material is obtained. This crystal material is subjected to the same sublimation refining of the sample, and the sample is obtained therefrom. In the sample Μ and the sample b3, respectively, by means of Ηρ] 侦测The impurity described above is the dopant compound #丨 and the self-chemical impurity 4, and the amount thereof is 3,900 ppm or less than 3,9 〇〇ppm. Its towel, the exemplified compound, the content of the compound 4 is in the range of 99.9% to 99.2%. Further, when the content as the catalytic metal was measured by the ICP method, it was found that the impurity content was 960 ppm or less than 960 ppm. When the water content in these samples is determined by the Karl Fischer technique and the volume content is determined by the weight loss due to drying (by the weight reduction under vacuum at 1 〇〇t minus the individual weight minus its individual When the water contains a value of ', it is G.1% or less than 〇.1%. Similar results were obtained even if the solution was refined twice or more times and the money was made twice or more. <Sample b2 and sample b4> Sample b2 and sample b4 were obtained by omitting the liter purification process in the example of sample bl and sample b3 synthesis, respectively. The content of the toothing impurity 89 201143183 2 in the sample b2 and the content of the halide impurity 4 in the sample b4 are in the range of 4,100 ppm to 8,700 ppm. The contents of the compounds 2 and 4 are exemplified in the samples of 98.8% to 96.7%, respectively. Within the range, the palladium content as a metal impurity content is in the range of 1,200 ppm to 3,600 ppm. Both the water content and the solvent content are 0.1% or less. &lt;Comparative Sample Μ and Comparative Sample b3&gt; The comparative sample bl and the comparative sample b3 were obtained by further eliminating the solution refining process in the examples of the synthesis of the sample b2 and the sample b4, respectively. Comparing the content of the halide impurity 2 in the sample bl and the content of the halide impurity 4 in the comparative sample b3 are each 9,000 ppm or more than 9, 〇〇〇ppm, and the contents of the exemplified compounds 2 and 4 in each of the samples are respectively 95.0% or Less than 95_0% and a palladium content of 4, 〇〇〇ppm or more than 4 〇〇〇ppm. <<Example 1>> According to the embodiment of the invention shown in Fig. 2, an image forming apparatus was manufactured as follows. After forming a 30 nm thick amorphous film on a CMOS substrate by sputtering, the film is subjected to light on each photodiode (PD) that causes a pixel to exist on the eM〇s substrate. The lithography is patterned to become a pixel. The sample bl was evaporated by vacuum heating to form an electron blocking layer of 1 Å on the pixel electrode. The co-evaporation samples a and Fu (6) were vacuum-heated by a single layer thickness, 100 nm and 300 nm, respectively, to form a photoelectric conversion layer in the electron-resistant layer. Further, the amorphous IT crucible was formed into a film of 5 '-th' m thick by the impurity to serve as an upper transparent electrode on the photoelectric conversion layer. Further, Si (10) was formed as a clock layer on the upper electrode by heating and evaporation, and the ALA layer was further formed on the &amp; ruthenium film by the ALCVD method. In the true 201143183 electrical conversion layer: true under 4Xl0·4 Pa conditions for the formation of the light before the 'in the (10) volt / cm (difficult ^ to Fang Gong ^ ^ 4; Γ γ electric field conditions to check the provision of Qing Pi An / Flat knife ^ dark electricity a voltage 'and under this money, measure the maximum sensitivity ί 自〇? 2 turn the county's material quantum wealth, dark electric differential response speed [from 0 to 98% signal strength start time). "Case Examples 2 to 8 and Comparative Examples 1 to 4" Examples 2 to 8 and comparative examples! The devices up to 4 were each fabricated in the manner of Example i, except that the samples a1 and bl used in Example 1 were replaced with the samples shown in Table 4 below, respectively. Σ〇 In Table 4, external quantum efficiency, dark current, and response speed at maximum sensitivity wavelengths of each of the photoelectric conversion devices of Examples 1 to 8 and Comparative Examples 丨 to 4 (from 〇 to 98% signal intensity) The start-up time is respectively shown as a relative value, wherein the values of the two values of the external quantum efficiency of the photoelectric conversion device in the example 越大 are larger, which means that the characteristics of the device are better. Conversely, the smaller the value of dark current and response speed, the better the characteristics of the device. Table 4 Samples used in the electron blocking layer Samples used in the photoelectric conversion layer External quantum efficiency (relative value) Dark current (relative value) Response speed (relative value)

201143183 Example 6 b2 a2 0.9 2.0 2.7 Example 7 b3 al 1.0 0.5 0.5 Example 8 b4 al 1.0 0.5 1.0 Comparative Example 1 bl Comparative sample a 0.7 1.2 30 Comparative Example 2 bl Comparative sample a3 0.7 1.5 50 Comparative Example 3 Comparative sample bl al 0.8 70 90 Comparative Example 4 Comparative sample b3 al 0.7 100 130 Here, the contents of the exemplified compounds 1-4 in the samples, respectively, are summarized in Table 5 below. Table 5 Sample Oxidation Compound Impurity or Halide Impurity Exemplary Compound Content Sample a 1 870 ppm or less 870 ppm 1 99.5-99.9% Sample a2 1 1,100-2,800 ppm 1 99.1-97.3% Comparative sample al 1 3.200 ppm or more than 3.200 Ppm 1 96.3% or less 96.3% Sample bl 2 3.900 ppm or less 3.900 ppm 2 99.2% or more than 99.2% 960 ppm or less than 960 ppm Sample b2 2 4,100-8,700 ppm 2 98.8-96.7% 1,200-3,600 ppm Comparison Sample bl 2 9.000 ppm or more than 9.000 ppm 2 95.0% or less than 95.0% 4,000 ppm or more than 4,000 ppm Sample a3 3 8.70 ppm or less than 8.70 ppm 3 99.5-99.9% Sample a4 3 1,100-2,800 ppm 3 99.1-97.3% - Compare sample a3 3 3.200 ppm or more than 3.200 ppm 3 96.3% or less than 96.3% Sample b3 4 3.900 ppm or less 3.900 ppm 4 99.2% or more than 99.2% 960 ppm or less than 960 ppm Sample b4 4 4,100-8,700 ppm 4 98.8-96.7% 1,200-3,600 ppm 92 201143183. Compare sample b3 4 9,000 ppm or more than 4 95.0% or less than _ 4,000 ppm or over 9,000 ppm 95.0% over 4,000 ppm As shown in Table 4, samples used in Examples 1 to 8 Al to one of a4 and samples bl to b4 Each device fabricated in different combinations achieved high external quantum efficiency, weak dark current, and fast response speed, but the device fabricated using the comparative sample a1 in Comparative Example 1 and the device fabricated in Comparative Example 2 using Comparative Sample a3 were externally quantum. The efficiency and response speed were very poor, and the apparatus manufactured using the comparative sample bl in Comparative Example 3 and the apparatus manufactured using the comparative sample b3 in Comparative Example 4 were very inferior in dark current and response speed. Therefore, these tests reveal that high external quantum efficiency can be obtained as long as the image forming apparatus incorporates the exemplified compound 1-4 in an amount of at least 96.5% and does not necessarily require an ultrahigh purity of 99.99% or more than 99.99% of the organic material. An imaging device with weak dark current and fast response speed. The factors of these effects are the reduction of the oxidized compound impurity content, the functional impurity content, and the metal impurity content. According to the present invention, as long as the purity of the material for forming the organic photoelectric conversion layer is at least 96.5%, photoelectric conversion devices and imaging devices each having high external quantum efficiency, weak dark current, and fast response speed can be manufactured, and these devices can be Avoid the use of high-purity materials that are expensive, thus reducing manufacturing costs. Industrial Applicability The photoelectric conversion device and the image forming apparatus according to the embodiments of the present invention can be applied to an image forming apparatus such as a digital camera, a video camera, a facsimile machine, a scanner, and a photocopier. The device of the present invention can also be used as a light sensor including a biosensor and a sensor. While the invention has been described in detail with reference to the specific embodiments of the present invention, it is understood that various changes and modifications may be made without departing from the spirit and scope of the invention. However, it is a Japanese patent application filed on March 8, 2010 (Japanese Patent Application No. 2010-051075), the content of which is incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a photoelectric conversion device according to a first embodiment of the present invention in a schematic form. Fig. 2 is a cross-sectional view showing the image forming apparatus of the second embodiment of the present invention in a schematic form. Figure 3 is a cross-sectional view showing the intermediate layer shown in Figure 2 in a schematic form. Figure 4 is a cross-sectional view showing the image forming apparatus of the third embodiment of the present invention in a schematic form. Fig. 5 is a cross-sectional view showing the image forming apparatus of the fourth embodiment of the present invention in a schematic form. Figure 6 is a cross-sectional view showing the image forming apparatus of the fifth embodiment of the present invention in a schematic form. Fig. 7 is a schematic view showing a part of a surface of an image forming apparatus relating to a sixth embodiment of the present invention. Fig. 8 is a schematic view showing a vertical cross section taken along the line X-X in Fig. 7. 94 201143183. Fig. 9 is a diagram showing an example of a specific configuration of one of the signal readout areas shown in Fig. 8. [Description of main component symbols] Bu 17, 4, 413, 601: 矽 substrate 2, 4, 18, 20 '42, 44, 46, 42 423: p area 3, 5, 19, 2, 22, 422, 424 ' 603r : η region 6, 23, 43, 45, 47: ρ+ regions 7, 8, 15, 24, 25, 26, 33, 48, 49, 50, 51, 59, 63, 67, 4U, 412: Insulating film 9, 27, 52, 53, 54: connection regions 10, 35, 55, 418: wirings η, 30, 56, 60, 64, 101, 414: first electrode film 12, 3, 57, 6 Intermediate layer 13, 32, 58, 62, 66, 104, 405: second electrode film 14, 34, 68, 417: light shielding film 28, 29: color filter 100: photoelectric conversion device 102: photoelectric conversion layer 103 : a charge blocking layer 103a : a first charge blocking layer 103b : a second charge blocking layer 122 : an undercoat layer and an electronic barrier layer 123 : a photoelectric conversion layer 124 : a hole blocking layer and a buffer layer 95 201143183. 125 : hole blocking Buffer layer 200, 300, 400, 500, 600: imaging device 401: anti-reflection film 402: infrared protection multilayer dielectric film 403, 404: protective film 415: plug 416: pad 419: metal wiring 420: bonding pad 425 : Hole accumulation area 426, 426', 426": transistor 427: signal readout pads 541, 548: column selection transistors 542, 547: output transistors 543, 546: reset transistors 545, 549: signal output line 602: p-well Layers 604b, 604g, 604r: n+ region 605: insulating layers 605b, 605g, 605r: signal readout regions 606b, 606g, 606r: contact regions 611b, 611g, 611r: transparent electrode 612: photoelectric conversion film 613: upper electrode 96 201143183 613b 615, Vcc : Vn : , 613g, 613r : color filter 616 : protective layer power supply 97

Claims (1)

201143183 VII. Patent application scope: 1. A photoelectric conversion device comprising an organic photoelectric conversion layer located between a first electrode and a cathode, wherein a material for forming the organic photoelectric conversion layer is used for liquid chromatography The photoelectric conversion device according to claim 1, wherein the material for forming the organic photoelectric conversion layer has a ninth solution or a low value, as determined by the method, having a purity of 96.5% or more. The oxidized compound impurity content at 9,000 ppm. 3. The photoelectric conversion device according to claim 1, wherein the material used for forming the layer of the light (4) is a material which has been purified by solution refining. 4. The photoelectric conversion device according to claim 1, wherein the material for forming the organic photoelectric conversion layer is a material which has been purified by sublimation purification. 5. The photoelectric conversion device of claim 1, wherein a charge blocking layer is provided between the first electrode and the second electrode and the organic photoelectric conversion layer. 6. The photoelectric conversion device of claim 5, wherein the charge blocking layer is an electron blocking layer. 7. The photoelectric conversion device of claim 6, wherein the electron blocking material used in the electron blocking layer has a purity of 96.7% or more and a purity of 9,000 ppm or determined by liquid chromatography. Halogen impurity content below 9,000 ppm. 8. The photoelectric conversion device according to claim 6, wherein the electronic barrier material used in the electron blocking layer of 98 201143183 has a purity of 96.7% or more and a purity of 4,000 as determined by liquid chromatography. Heavy metal impurity content of ppm or less than 4,000 ppm. 9. The photoelectric conversion device of claim 6, wherein the electron blocking material used in the electron blocking layer is a material that has been purified by solution refining. 10. The photoelectric conversion device according to claim 6, wherein the electron blocking material used in the electron blocking layer is a material which has been purified by sublimation purification. 11. The photoelectric conversion device of claim 6, wherein the electron blocking material used in the electron blocking layer is a triarylamine compound. 12. The photoelectric conversion device according to claim 2, wherein the material for forming the organic photoelectric conversion layer comprises a maximum absorption in a visible light wavelength region extending from 4 nm to _ nanometer. A color conversion agent according to any one of claims 12 to 12, wherein an electric field of 1 G. 4 volts/cm to 1 x 1 q7 volts/cm is placed in the first - between the electrode and the second electrode. In the photoelectric conversion device described in claim 1, the organic photoelectric conversion layer in the basin contains a smile __). And an image forming apparatus comprising: the photoelectric conversion device according to the item 1; and a surface on which the photoelectric conversion device is stacked on the semiconductor substrate