JP2018019034A - Organic photoelectric conversion element, solid-state imaging element, and electronic device - Google Patents

Abstract

An organic photoelectric conversion element capable of further improving image quality and reliability is provided. A first electrode, a first buffer layer, a photoelectric conversion layer, a second buffer layer, and a second electrode are stacked in this order, and the first buffer layer includes a first organic semiconductor material. The photoelectric conversion layer includes the second organic semiconductor material, the first organic semiconductor material has the first organic crystal, the second organic semiconductor material has the second organic crystal, and the interplanar spacing of the first organic crystal The ratio between the two organic crystals is 0.55: 1 to 1: 0.55, and the orientation of the first organic crystal and the orientation of the second organic crystal substantially coincide with each other. . [Selection figure] None

Description

  The present technology relates to an organic photoelectric conversion element, a solid-state imaging element, and an electronic device.

  In recent years, not only digital cameras and video camcorders, but also applications for imaging devices have been attracting attention as smartphone cameras, surveillance cameras, automobile back monitors, and collision safety prevention sensors. In order to respond to various applications, the performance of organic photoelectric conversion elements has been improved and functions have been diversified.

  For example, a method for forming an organic photoelectric conversion layer provided in an organic photoelectric conversion element, in which a substrate is prepared and the substrate is installed in a vacuum deposition chamber, and the temperature of the installed substrate is The first photoelectric conversion layer is formed by co-evaporating an n-type organic semiconductor and a p-type organic semiconductor constituting the organic photoelectric conversion layer on the substrate while controlling the temperature range to be 5 ° C. or higher and 15 ° C. or lower. The first photoelectric conversion layer forming step of forming a film, and the second photoelectric conversion in which the control is stopped and the second photoelectric conversion layer is formed by performing the co-evaporation on the first photoelectric conversion layer. A method of forming an organic photoelectric conversion layer having a layer forming step has been proposed (see Patent Document 1). According to this technique, it is possible to stably manufacture a bulk hetero layer that is easily changed by a film forming apparatus and has good film characteristics that directly affect afterimage characteristics.

JP2015-15415A

  However, the technique proposed in Patent Document 1 may not be able to further improve image quality and reliability.

  Therefore, the present technology has been made in view of such a situation, and provides an organic photoelectric conversion element, a solid-state imaging element, and an electronic apparatus that can realize further improvement in image quality and further improvement in reliability. The main purpose is to do.

  As a result of intensive studies to solve the above-mentioned object, the present inventor has surprisingly succeeded in dramatically improving the image quality and reliability, and has completed the present technology.

  That is, in the present technology, first, the first electrode, the first buffer layer, the photoelectric conversion layer, the second buffer layer, and the second electrode are stacked in this order, and the first buffer layer is the first buffer layer. An organic semiconductor material, the photoelectric conversion layer includes a second organic semiconductor material, the first organic semiconductor material includes a first organic crystal, the second organic semiconductor material includes a second organic crystal, The ratio between the face spacing of the first organic crystal and the face spacing of the second organic crystal is 0.55: 1 to 1: 0.55, and the orientation of the first organic crystal and the orientation of the second organic crystal And an organic photoelectric conversion element substantially matching the above.

In the organic photoelectric conversion element according to the present technology, at least a part of the organic molecules included in the first organic crystal may be ππ stacked in the direction of the first electrode or the second electrode.
In the organic photoelectric conversion element according to the present technology, the ππ stacking may be formed at an angle of 30 ° or more with respect to the main surface of the first electrode or the second electrode.

  In the organic photoelectric conversion element according to the present technology, at least a part of the organic molecules contained in the first organic crystal is ππ stacked in the direction of the first electrode or the second electrode, and the first buffer layer is The film thickness may be 4 times or more the length of the major axis of the organic molecule.

  In the organic photoelectric conversion element according to the present technology, the first buffer layer may have a film thickness that is less than four times the length of the long axis of the organic molecule contained in the first organic crystal. The major axis direction may be an angle of 45 ° or more with respect to the main surface of the first electrode or the second electrode.

  In the organic photoelectric conversion element according to the present technology, the first buffer layer may further include a high mobility material.

  The organic photoelectric conversion element according to the present technology may further include an organic crystal adjustment layer, and the organic crystal adjustment layer may be disposed between the photoelectric conversion layer and the first buffer layer.

The organic photoelectric conversion element according to the present technology may further include an organic crystal adjustment layer, the organic crystal adjustment layer may be disposed between the photoelectric conversion layer and the first buffer layer, and the organic crystal adjustment layer includes The second organic semiconductor material may include the second organic semiconductor material, and the second organic semiconductor material may include the second organic crystal, and a ratio between a face spacing of the first organic crystal and a face spacing of the second organic crystal is 0.55: 1 to 1: 0.55.
The organic crystal adjustment layer may further include a third organic semiconductor material, and the third organic semiconductor material includes a third organic crystal, and a face spacing of the first organic crystal and a face spacing of the third organic crystal. The ratio of the interplanar spacing of the second organic crystal to the interplanar spacing of the third organic crystal may be 0.55: 1 to 1: 0. 55 may be sufficient.

  The organic photoelectric conversion element according to the present technology may further include an organic crystal adjustment layer, the organic crystal adjustment layer may be disposed between the photoelectric conversion layer and the first buffer layer, and the organic crystal adjustment layer includes A third organic semiconductor material may be included, and the third organic semiconductor material may include a third organic crystal, and a ratio of a face spacing of the first organic crystal to a face spacing of the third organic crystal is 0. .55: 1 to 1: 0.55.

  The present technology also provides a solid-state imaging device in which at least an organic photoelectric conversion device according to the present technology and a semiconductor substrate are stacked for each of a plurality of pixels arranged one-dimensionally or two-dimensionally.

  Furthermore, the present technology provides an electronic device including the solid-state imaging device according to the present technology.

  According to the present technology, image quality and reliability can be improved. In addition, the effect described here is not necessarily limited, and may be any effect described in the present technology.

FIG. 1 is a TEM image of a cross-sectional view illustrating a configuration example of the organic photoelectric conversion element according to the first embodiment to which the present technology is applied. FIG. 2 is a TEM image and a cross-sectional schematic diagram of the first organic crystal and the second organic crystal that constitute the organic photoelectric conversion element of the first embodiment to which the present technology is applied. FIG. 3 is a TEM image of a layer containing pentacene that can be applied to the organic photoelectric conversion element of the first embodiment to which the present technology is applied. FIG. 4 is a cross-sectional view illustrating a configuration example of the solid-state imaging device according to the second embodiment to which the present technology is applied. FIG. 5 is a diagram illustrating a usage example of the solid-state imaging device according to the second embodiment to which the present technology is applied.

  Hereinafter, preferred embodiments for carrying out the present technology will be described. The embodiment described below shows an example of a typical embodiment of the present technology, and the scope of the present technology is not interpreted narrowly.

The description will be given in the following order.
1. 1st Embodiment (example of an organic photoelectric conversion element)
1-1. Organic photoelectric conversion element 1-2. First buffer layer 1-3. Photoelectric conversion layer 1-4. Second buffer layer 1-5. First electrode and second electrode 1-6. Organic crystal adjustment layer 1-7. High mobility material 1-8. Substrate for organic photoelectric conversion element 1-9. 1. Manufacturing method of organic photoelectric conversion element Second Embodiment (Example of Solid-State Image Sensor)
2-1. Solid-state image sensor 2-2. Back-illuminated solid-state imaging device 2-3. 2. Surface irradiation type solid-state imaging device Third Embodiment (Example of Electronic Device)
4). Usage example of solid-state image sensor to which this technology is applied

<1. First Embodiment (Example of Organic Photoelectric Conversion Element)>
[1-1. Organic photoelectric conversion element]
In the organic photoelectric conversion element according to the first embodiment of the present technology, the first electrode, the first buffer layer, the photoelectric conversion layer, the second buffer layer, and the second electrode are stacked in this order, The first buffer layer includes a first organic semiconductor material, the photoelectric conversion layer includes a second organic semiconductor material, the first organic semiconductor material includes a first organic crystal, and the second organic semiconductor material includes a second organic crystal. The ratio of the face spacing of the first organic crystal to the face spacing of the second organic crystal is 0.55: 1 to 1: 0.55, and the orientation of the first organic crystal and the second organic crystal It is an organic photoelectric conversion element whose orientation substantially matches.

  In the organic photoelectric conversion element according to the first embodiment of the present technology, for example, carriers generated in a photoelectric conversion layer having a bulk hetero structure reach an electrode, and then are converted into a voltage and output as an image. At this time, when the electric capacity of the organic module and its peripheral structure is large, the voltage change is small, and the S / N ratio may be lowered. In order to reduce the electric capacity, it is necessary to increase the thickness of the photoelectric conversion layer and increase the distance between the electrodes. However, increasing the thickness of the photoelectric conversion layer causes a decrease in quantum efficiency and an afterimage. There are restrictions on increasing the film thickness.

  In the organic photoelectric conversion element of the first embodiment according to the present technology, a photoelectric conversion layer is stacked on a p-type or n-type first buffer layer that is ππ-stacked with respect to the first electrode. The contained organic molecules can be epitaxially grown on the first buffer layer. As a result, the transfer efficiency is improved, the quantum efficiency is not lowered and the afterimage is not deteriorated, and the electric capacity can be reduced.

  FIG. 1 is a cross-sectional view of the organic photoelectric conversion element 1 according to the first embodiment of the present technology, which is shown by an image of a transmission electron microscope (TEM). The TEM image was taken using a model name: JEM-4000FX manufactured by JEOL Ltd. with an acceleration voltage of 400 kV and an exposure time of 3 seconds.

  As for the organic photoelectric conversion element 1, the 1st electrode 11, the 1st buffer layer 12, the photoelectric converting layer 13, the 2nd buffer layer 14, and the 2nd electrode 15 are laminated | stacked in this order. The first buffer layer 12 includes a first organic semiconductor material, and the photoelectric conversion layer 13 includes a second organic semiconductor material. The first organic semiconductor material has a first organic crystal, and the second organic semiconductor material has a second organic crystal.

  As shown in FIG. 1, organic molecules contained in the first organic crystal are crystallized in a substantially vertical direction (vertical direction in FIG. 1) toward the upper and lower electrodes (that is, the first electrode 11 and the second electrode 15). Lattice fringes are formed and ππ stacking is performed. ππ stacking can be defined as a stable state in which two aromatic rings are stacked. When ππ stacking is performed between organic molecules, the distance between the organic molecules is shortened. Therefore, the mobility is increased, and the charge generated in the photoelectric conversion layer 13 can be efficiently transported to the electrode. Also called ππ interaction.

  The crystal lattice fringes formed by ππ stacking are preferably formed at an angle of 30 ° or more with respect to the main surfaces of the upper and lower electrodes (first electrode 11 and second electrode 15). In FIG. And the angle formed by the main surfaces of the upper and lower electrodes (the first electrode 11 and the second electrode 15) is about 83 °.

  FIG. 2A is a transmission electron microscope (TEM) image of the first organic crystal and the second organic crystal constituting the organic photoelectric conversion element of the first embodiment to which the present technology is applied. is there. The TEM image was taken using a model name: JEM-4000FX manufactured by JEOL Ltd. with an acceleration voltage of 400 kV and an exposure time of 3 seconds.

  FIG. 2B is a schematic cross-sectional view corresponding to the TEM image of the first organic crystal and the second organic crystal constituting the organic photoelectric conversion element of the first embodiment to which the present technology is applied.

  When the photoelectric conversion layer is thickened, the photoelectric conversion layer and the first buffer layer are not lattice matched. Further, when only the first buffer layer is thickened, the quantum efficiency decreases as the film thickness increases. As shown in FIG. 1 and FIG. 2A (TEM image) and FIG. 2B (cross-sectional schematic diagram), the photoelectric conversion layer 13 is formed on the first organic crystal contained in the first buffer layer 12. In the structure in which the second organic crystal contained in (for example, the bulk hetero layer) is lattice-matched, a decrease in transfer efficiency can be suppressed. In addition, by suppressing the formation of random grain boundaries between the crystal grains contained in the photoelectric conversion layer 13 (bulk hetero layer) and the first buffer layer 12, it is possible to suppress carriers from being trapped in the grain boundaries, It is possible to reduce deterioration of afterimages and reduction of quantum efficiency.

  When ππ stacking is performed between organic molecules, the intermolecular distance is shortened. Therefore, the mobility is increased, and the charge generated in the photoelectric conversion layer 13 can be efficiently transported to the first electrode 11. In the present technology, photoelectric conversion is performed by laminating the photoelectric conversion layer 13 (for example, a bulk hetero layer) on the first buffer layer including the first organic crystal including the organic molecules subjected to ππ stacking with respect to the first electrode 11. Organic molecules contained in the second organic crystal contained in the layer 13 can be epitaxially grown on the first buffer layer 12. As a result, the transfer efficiency is improved, the quantum efficiency is not lowered and the afterimage is not deteriorated, and the electric capacity can be reduced. The organic photoelectric conversion element of the first embodiment according to the present technology can be applied to, for example, a backside illumination type and a frontside illumination type solid-state imaging element.

  As shown in FIG. 2B, the organic molecules of the first organic crystal contained in the first buffer layer 12 are ππ stacked, and the orientation of the second organic crystal contained in the photoelectric conversion layer 13 and the first organic crystal The organic molecules of the second organic crystal are epitaxially grown on the first buffer layer 12 with the orientation substantially coincident. FIG. 2B shows the interplanar spacing X of the first organic crystal and the interplanar spacing Y of the second organic crystal. Since the ratio between the interplanar spacing X of the first organic crystal and the interplanar spacing Y of the second organic crystal is 1: 0.55, the organic molecules of the second organic crystal are epitaxially deposited on the first buffer layer 12. Can grow. If the ratio of the interplanar spacing X of the first organic crystal to the interplanar spacing Y of the second organic crystal is 0.55: 1 to 1: 0.55, the first buffer layer containing ππ-stacked organic molecules On 12, the organic molecules of the second organic crystal can grow epitaxially.

  When the ratio of the interplanar spacing X of the first organic crystal to the interplanar spacing Y of the second organic crystal is 0.55: 1 to 1: 0.55, the organic molecules and the second organic contained in the first organic crystal The organic molecules contained in the crystal may be the same or different, but if the organic molecules contained in the first organic crystal and the organic molecules contained in the second organic crystal are the same, the first organic crystal The ratio of the interplanar spacing X to the interplanar spacing Y of the second organic crystal is 1: 1. The organic molecule contained in the first organic crystal and the organic molecule contained in the second organic crystal shown in FIG. 2 (b) are different from each other, so that the two organic molecules are different from the same case. It is.

  As shown in FIGS. 2A and 2B, the face spacing X corresponds to the fringe spacing of the crystal lattice fringes of the first organic crystal, and the face spacing Y corresponds to the fringe spacing of the crystal lattice fringes of the second organic crystal. Correspond. Further, as shown in FIG. 2 (b), the face spacing X substantially matches the length of one major axis of the organic molecules of the first organic crystal, and the face spacing Y is the organic spacing of the second organic crystal. It approximately corresponds to the length of the long axis of one molecule.

FIG. 3 is a TEM image of the layer 100 containing pentacene, which can be applied to the organic photoelectric conversion element of the first embodiment according to the present technology. Referring to FIG. 3, a layer 100 containing pentacene having a thickness of about 30 nm is formed on a substrate of SiO ₂ (145 nm) / Si (not shown).

  From FIG. 3, it is possible to confirm the crystal lattice fringes of the pentacene crystal that is substantially parallel to the interface between the layer 100 containing pentacene and the substrate (the horizontal direction in FIG. 3). Crystal lattice fringes correspond to the (001) lattice plane of the pentacene crystal. Therefore, the stack direction of the π plane of the pentacene molecule is substantially parallel to the interface between the pentacene-containing layer 100 and the substrate (the left-right direction in FIG. 3).

  Then, the overlap of π conjugation increases in the stack direction of the π plane, and the layer 100 containing pentacene has a signal charge flow in a direction substantially parallel to the interface between the layer 100 containing pentacene and the substrate (the left-right direction in FIG. 3). (Transfer) is improved, transfer efficiency is improved, and a decrease in quantum efficiency and an afterimage can be prevented.

[1-2. First buffer layer]
The first buffer layer 12 will be described in detail.
The first buffer layer 12 includes a first organic semiconductor material, and the first organic semiconductor material has a first organic crystal. The first organic semiconductor material is a p-type organic semiconductor material or an n-type organic semiconductor material. When a p-type organic semiconductor material is used for the first buffer layer 12, it acts as an electron injection barrier layer (electron blocking layer), and when an n-type semiconductor material is used, a hole injection barrier is used. Acts as a layer (hole blocking layer).

  The p-type organic semiconductor material (compound) is a donor-type organic semiconductor material (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound.

  Examples of the p-type organic semiconductor mother nucleus used in the first buffer layer 12 include condensed polycyclic aromatic compounds. For example, oligothiophene, oligoparaphenylene, fluorene, carbazole, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovarene, circumcamanthracene, bisanthene, zeslen, Heptazesulene, pyranthrene, violanthene, isoviolanthene, cirabiphenyl, thienothiophene, benzodithiophene, cyclopentadithiophene, dithienopyrrole, dithienosilole, dithienonaphthalene, benzothiophenobenzothiophene, anthradithiophene, thienopyrazine, benzothiadiazole, di Compounds such as ketopyrrolopyrrole and pyrazolotriazole, porphyrin and copper phthalocyanine Tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ), bisethylenedithiatetrathiafulvalene (BEDTTTF), compounds having a thieno [3,2-b] thiophene structure, derivatives thereof, quinacridone derivatives, etc. Can be mentioned. Also, triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, phthalocyanine compounds, cyanine compounds, merocyanine compounds, oxonol compounds, polyamine compounds, indoles A compound, a pyrrole compound, a pyrazole compound, a polyarylene compound and the like can be mentioned, but not limited thereto.

  An n-type organic semiconductor material (compound) is an acceptor-type organic semiconductor material, which is typified by an organic compound having mainly excellent electron transport properties, and has a property of accepting electrons relatively more easily than a p-type organic semiconductor material. Refers to an organic compound.

  The n-type organic semiconductor is not particularly limited. For example, fullerene, octaazaporphyrin, and the like, perfluoro compounds in which the hydrogen atom of the nucleus of the p-type organic semiconductor is replaced with a fluorine atom (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene Examples thereof include aromatic carboxylic acid anhydrides such as tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and polymer compounds containing the imidized product thereof as a skeleton. Examples of fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240, fullerene 540, mixed fullerene, fullerene nanotubes and the like. . The compound in which a substituent is added to fullerene is an alkyl group, an aryl group, or a heterocyclic group as a substituent of the fullerene derivative. More preferably, the alkyl group is an alkyl group having 1 to 12 carbon atoms, and the aryl group and the heterocyclic group are preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring. , Biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran Ring, benzimidazole ring, imidazopyridine ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline , Thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, or phenazine ring, more preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyridine ring, imidazole ring, oxazole ring, or A thiazole ring, particularly preferably a benzene ring, a naphthalene ring, or a pyridine ring. These may further have a substituent, and the substituents may be bonded as much as possible to form a ring. In addition, you may have a some substituent and they may be the same or different. A plurality of substituents may be combined as much as possible to form a ring.

  The first buffer layer 12 preferably has a film thickness that is at least four times the length of the major axis of the organic molecules contained in the first organic crystal. Accordingly, the film thickness of the first buffer layer 12 varies depending on the type of organic molecules used, since the major axis length of the organic molecules varies, but is preferably 6 nm to 150 nm. According to this preferred embodiment, the transfer efficiency is further improved, the quantum efficiency is not lowered, and the afterimage is not deteriorated, and the electric capacity can be lowered.

  The first buffer layer 12 may have a film thickness that is less than four times the length of the major axis of the organic molecules contained in the first organic crystal. Accordingly, the film thickness of the first buffer layer 12 varies depending on the type of organic molecule used, since the length of the major axis of the organic molecule varies, but is preferably 1.5 nm to 12 nm. In this case, the major axis direction of the organic molecule is an angle of 45 ° or more with respect to the main surface of the first electrode 11 or the second electrode 15. According to this aspect, the transfer efficiency is further improved, the quantum efficiency is not lowered and the afterimage is not deteriorated, and the electric capacity can be reduced.

[1-3. Photoelectric conversion layer]
The photoelectric conversion layer 13 will be described in detail.
The photoelectric conversion layer 13 includes a second organic semiconductor material, and the second organic semiconductor material has a second organic crystal. The second organic semiconductor material is a p-type organic semiconductor material or an n-type organic semiconductor material. When a p-type organic semiconductor material is used for the first buffer layer 12, the second organic semiconductor material is a p-type organic semiconductor material, and when an n-type semiconductor material is used for the first buffer layer 12, The two organic semiconductor material is an n-type organic semiconductor material. Specific examples of the p-type organic semiconductor material and the n-type organic semiconductor material are as described above.

  The photoelectric conversion layer 13 can also be comprised from the laminated structure of a p-type organic-semiconductor layer / n-type organic-semiconductor layer, and the mixed layer (bulk heterolayer of p-type organic-semiconductor layer / p-type organic semiconductor and n-type organic semiconductor) ) / N-type organic semiconductor layer, or p-type organic semiconductor layer / p-type organic semiconductor / n-type organic semiconductor mixed layer (bulk heterolayer). In addition, it can be configured by a laminated structure of an n-type organic semiconductor layer / a mixed layer (bulk heterolayer) of a p-type organic semiconductor and an n-type organic semiconductor, or a mixed (bulk heterolayer) of a p-type organic semiconductor and an n-type organic semiconductor. ).

  Moreover, the photoelectric converting layer 13 can also be comprised from a p-type organic semiconductor, and can also be comprised from an n-type organic semiconductor.

  The p-type organic semiconductor material and the n-type organic semiconductor material may be included in the same bulk hetero layer one by one, or may be included in two or more types, or the p-type organic semiconductor material and n One of the type organic semiconductor materials may be one type and the other may be two or more types. The p-type organic semiconductor layer may include at least one p-type organic semiconductor material, and the n-type organic semiconductor layer may include at least one n-type organic semiconductor material.

[1-4. Second buffer layer]
The second buffer layer 14 will be described in detail.
When a p-type organic semiconductor material is used for the second buffer layer 14, it acts as an electron injection barrier layer (electron blocking layer), and when an n-type semiconductor material is used, a hole injection barrier layer (hole Acts as a blocking layer). When a p-type organic semiconductor material is used for the first buffer layer 12, an n-type organic semiconductor material is used for the second buffer layer 14, and an n-type organic semiconductor material is used for the first buffer layer 12. The second buffer layer 14 is made of a p-type organic semiconductor material. Specific examples of the p-type organic semiconductor material or the n-type organic semiconductor material are as described above.

[1-5. First electrode and second electrode]
The first electrode 11 and the second electrode 15 will be described in detail.
When the first organic semiconductor material included in the first buffer layer 12 is a p-type organic semiconductor material and the second buffer layer 14 includes an n-type organic semiconductor material, the first electrode 11 has holes (signal charges). The second electrode 15 takes out electrons. When the first organic semiconductor material included in the first buffer layer 12 is an n-type organic semiconductor material and the second buffer layer 14 includes a p-type organic semiconductor material, the first electrode 11 receives electrons (signal charges). The second electrode 15 is for extracting holes.

The first electrode 11 is made of, for example, a light transmissive conductive material, specifically, ITO (Indium-Tin-Oxide). The first electrode 11 may be made of a tin oxide (SnO ₂ ) -based material or a zinc oxide (ZnO) -based material. The tin oxide-based material is a tin oxide added with a dopant, and the zinc oxide-based material is, for example, aluminum zinc oxide (AZO) obtained by adding aluminum (Al) as a dopant to zinc oxide, and zinc oxide as a dopant. Examples thereof include gallium zinc oxide (GZO) to which gallium (Ga) is added, indium zinc oxide (IZO) to which zinc oxide is added with indium (In) as a dopant. In addition, IGZO, CuI, InSbO ₄ , ZnMgO, CuInO ₂ , MgIn ₂ O ₄ , CdO, ZnSnO _3, or the like can be used. Although the thickness of the 1st electrode 11 may be arbitrary thickness, they are 50 nm-500 nm, for example.

  The second electrode 15 may be made of a conductive material such as gold (Au), silver (Ag), copper (Cu), and aluminum (Al). Similar to the first electrode 11, the second electrode 15 may be made of a transparent conductive material. Although the thickness of the 2nd electrode 15 may be arbitrary thickness, they are 0.5 nm-100 nm, for example.

[1-6. Organic crystal adjustment layer]
The organic photoelectric conversion element of the first embodiment according to the present technology may further include an organic crystal adjustment layer. The organic crystal adjustment layer (not shown in FIGS. 1 and 2) may be disposed between the photoelectric conversion layer 13 and the first buffer layer 12. By including the organic crystal adjustment layer in the organic photoelectric conversion element of the first embodiment according to the present technology, the transfer efficiency is further improved, the quantum efficiency is not lowered, the afterimage is not lowered, and the electric capacity is lowered. Can do.

  The organic crystal adjustment layer may include a second organic semiconductor material, and the second organic semiconductor material has a second organic crystal. The ratio between the face spacing of the first organic crystal and the face spacing of the second organic crystal is 0.55: 1 to 1: 0.55. The details of the second organic semiconductor material are as described above.

  The organic crystal adjustment layer may include a third organic semiconductor material. The organic crystal adjustment layer may include two organic semiconductor materials, a second organic semiconductor material and a third organic semiconductor material. When the organic crystal adjustment layer includes two organic semiconductor materials of the second organic semiconductor material and the third organic semiconductor material, the mass% ratio of the second organic semiconductor material to the third organic semiconductor material is an arbitrary mass%. The ratio may be, but is preferably 30% by mass: 70% by mass to 70% by mass: 30% by mass.

  The third organic semiconductor material has a third organic crystal, and the ratio between the face spacing of the first organic crystal and the face spacing of the third organic crystal is 0.55: 1 to 1: 0.55, The ratio between the face spacing of the organic crystal and the face spacing of the third organic crystal is 0.55: 1 to 1: 0.55.

  The third organic semiconductor material is a p-type organic semiconductor material or an n-type organic semiconductor material. When a p-type organic semiconductor material is used for the first buffer layer 12, the third organic semiconductor material is a p-type organic semiconductor material, and when an n-type organic semiconductor material is used for the first buffer layer 12, The third organic semiconductor material is an n-type organic semiconductor material. Specific examples of the p-type organic semiconductor material and the n-type organic semiconductor material are as described above.

  [1-7. High Mobility Material] The first buffer layer 12 may further include a high mobility material. Examples of the high mobility material include P3HT (poly (3-hexylthiophene-2,5-diyl)), P3OT (poly (3-octylthiophene-2,5-diyl)), and P3DDT (poly (3-dodecyl). Thiophene-2,5-diyl)), PTAA (poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine]), F8BT (poly [(9,9-di-n-octylfluore) Nyl-2,7-diyl) -alt- (benzo [2,1,3] thiadiazole-4,8-diyl)]), MEH-PPV, PCDTBT, and other P-type organic semiconductor polymers, poly (2,5 -Di (3,7-dimethyloctyloxy) cyanoterephthalylidene), poly (5- (3,7-dimethyloctyloxy) -2-methoxy-cyanoterephthalylidene), poly (5- (2-ethylhexyl) N-type such as (xy) -2-methoxy-cyanoterephthalylidene), poly (2,5-di (octyloxy) cyanoterephthalylidene), poly (2,5-di (hexyloxy) cyanoterephthalylidene) Examples thereof include conductive polymers.

[1-8. Substrate for organic photoelectric conversion element]
The organic photoelectric conversion element 1 may be formed on a substrate (not shown in FIGS. 1 and 2). Here, as a substrate, polymethyl methacrylate (polymethyl methacrylate, PMMA), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyethersulfone (PES), polyimide, polycarbonate (PC), polyethylene terephthalate (PET), An organic polymer exemplified by polyethylene naphthalate (PEN) (having a form of a polymer material such as a flexible plastic film, plastic sheet, or plastic substrate made of a polymer material) can be given.

If a substrate composed of such a flexible polymer material is used, for example, an image sensor can be incorporated into or integrated with an electronic device having a curved shape. Alternatively, various glass substrates, various glass substrates with an insulating film formed on the surface, quartz substrates, quartz substrates with an insulating film formed on the surface, silicon semiconductor substrates, stainless steel with an insulating film formed on the surface Examples thereof include metal substrates made of various alloys such as various metals and various metals. As the insulating film, a silicon oxide-based material (for example, SiO _x or spin-on glass (SOG)); silicon nitride (SiN _Y ); silicon oxynitride (SiON); aluminum oxide (Al ₂ O ₃ ); metal oxide, Mention may be made of metal salts. It is also possible to form an organic insulating film. Examples include lithographic polyphenolic materials, polyvinylphenolic materials, polyimide materials, polyamide materials, polyamideimide materials, fluorine polymer materials, borazine-silicon polymer materials, torquesen materials, and the like. Furthermore, a conductive substrate (a substrate made of metal such as gold or aluminum, a substrate made of highly oriented graphite) having these insulating films formed on the surface can also be used.

[1-9. Manufacturing method of organic photoelectric conversion element]
The manufacturing method of the organic photoelectric conversion element 1 will be described.

  First, the first electrode 11 is formed. In addition, when forming the organic photoelectric conversion element 1 on the board | substrate demonstrated above, the 1st electrode 11 can be formed on the board | substrate for organic photoelectric conversion elements. The first electrode 11 is formed, for example, by forming an ITO film by a sputtering method, patterning the ITO film by a photolithography technique, and performing dry etching or wet etching.

  Next, the first buffer layer 12 is formed on the first electrode 11. For deposition of the first buffer layer 12, it is desirable to use a vapor deposition method, but a coating method (including a casting method and a spin coating method) can also be used. A photoelectric conversion layer 13 is formed on the first buffer layer 12. In addition, as a method of matching the organic molecules of the second organic semiconductor material included in the photoelectric conversion layer 13 with the crystal orientation of the organic molecules of the first organic semiconductor material included in the first buffer layer 12, a substrate temperature at the time of film formation is used. There are a method of promoting surface diffusion by adjusting the thickness, a method of adding a thermal history after film formation, and the like, but other methods may be used. The temperature during organic vapor deposition is 0 ° C. or higher, and the film formation rate is preferably 0.5 A / sec to 2 A / sec, but not limited thereto. A second buffer layer 14 is formed on the photoelectric conversion layer 13. For the film formation of the second buffer layer 14, it is desirable to use a vapor deposition method as in the case of the film formation of the first buffer layer 12, but a coating method (including a casting method and a spin coating method) can also be used. .

  Finally, the second electrode 15 is formed on the second buffer layer 14 by vacuum vapor deposition or the like, and the organic photoelectric conversion element 1 is manufactured.

<2. Second Embodiment (Example of Solid-State Image Sensor)>
[2-1. Solid-state image sensor]
The solid-state imaging device according to the second embodiment of the present technology includes at least the organic photoelectric conversion device (organic photoelectric conversion) of the first embodiment according to the present technology for each of a plurality of pixels arranged one-dimensionally or two-dimensionally. This is a solid-state imaging device in which an element 1) and a semiconductor substrate are stacked. Examples of the solid-state image sensor according to the second embodiment of the present technology include a back-illuminated solid-state image sensor and a front-illuminated solid-state image sensor. First, a backside illumination type solid-state imaging device will be described. The details of the organic photoelectric conversion device of the first embodiment provided in the solid-state imaging device of the second embodiment according to the present technology are as described above. Since the solid-state imaging device according to the second embodiment of the present technology has stacked organic photoelectric conversion devices having excellent image quality and excellent reliability, it can contribute to improvement in performance such as image quality of color images. it can.

[2-2. Back-illuminated solid-state image sensor]
An example of a back-illuminated solid-state imaging device will be described with reference to FIG. FIG. 4 is a cross-sectional view illustrating a configuration example of one pixel 20 of the backside illumination type solid-state imaging device 10.

  The pixel 20 includes a single organic photoelectric conversion element 41 stacked in the depth direction, a photodiode 36 having a pn junction, and a photodiode 37 in one pixel. The pixel 20 includes a semiconductor substrate (silicon substrate) 35 on which a photodiode 36 and a photodiode 37 are formed, and light reception is performed such that light is incident on the back side of the semiconductor substrate 35 (upper side of the semiconductor substrate 35 in FIG. 4). A surface is formed, and a circuit including a readout circuit and the like is formed on the surface side of the semiconductor substrate 35. That is, the pixel 20 has a light receiving surface on the back surface side of the substrate 35 and a circuit forming surface formed on the substrate surface side opposite to the light receiving surface. The semiconductor substrate 35 may be formed of a first conductivity type, for example, an n-type semiconductor substrate.

  In the semiconductor substrate 35, an inorganic photoelectric conversion unit having two pn junctions, that is, a first photodiode 36 and a second photodiode 37 are formed so as to be stacked in the depth direction from the back side. In the semiconductor substrate 35, the first photodiode 36 is formed and the second photodiode 37 is formed from the reverse side to the depth direction (downward in the figure). In FIG. 4, the first photodiode 36 is for blue (B), and the second photodiode 37 is for red (R).

  A first electrode (lower electrode) 33, a first buffer layer 47, a photoelectric conversion layer 32, and a second buffer layer are formed on the back surface of the semiconductor substrate 35 in the region where the first photodiode 36 and the second photodiode 37 are formed. An organic photoelectric conversion element 41 for the first color in which 46 and the second electrode (upper electrode) 31 are stacked in this order is disposed. In the example of the backside illumination type solid-state imaging device 10 shown in FIG. 4, the organic photoelectric conversion device 41 is for green (G). For example, the second electrode (upper electrode) 31 and the first electrode (lower electrode) 33 may be formed of a transparent conductive film such as an indium tin oxide film or an indium zinc oxide film.

  In the example of the back-illuminated solid-state imaging device 10 shown in FIG. 4, the organic photoelectric conversion element 41 is green, the first photodiode 36 is blue, and the second photodiode 37 is red. Any combination of colors is possible. For example, the organic photoelectric conversion element 41 can be set to red or blue, and the first photodiode 36 and the second photodiode 37 can be set to other corresponding colors. In this case, the position in the depth direction of the first photodiode 36 and the second photodiode 37 is set according to the color.

  Further, without using the first photodiode 36 and the second photodiode 37, three photoelectric conversion elements, that is, an organic photoelectric conversion element 41B for blue, an organic photoelectric conversion element 41G for green, and an organic photoelectric conversion for red are used. The element 41R may be applied to the solid-state imaging device (backside illumination type solid-state imaging device and front-side illumination type solid-state imaging device) of the second embodiment according to the present technology. As the organic photoelectric conversion element 41B that performs photoelectric conversion with blue wavelength light, an organic photoelectric conversion material containing a coumarin dye, tris-8-hydroxyquinoline A1 (A1q3), a melocyanine dye, or the like can be used. As the photoelectric conversion element 41G that performs photoelectric conversion with green wavelength light, for example, an organic photoelectric conversion material containing a rhodamine dye, a melocyanine dye, quinacridone, or the like can be used. As the photoelectric conversion element 41R that performs photoelectric conversion with red wavelength light, an organic photoelectric conversion material containing a phthalocyanine dye can be used.

  Further, in addition to the organic photoelectric conversion element 41B for blue, the organic photoelectric conversion element 41G for green, and the organic photoelectric conversion element 41R for red, the organic photoelectric conversion element 41UV for ultraviolet light and / or the organic for infrared light is used. The photoelectric conversion element 41IR may be applied to the solid-state imaging device (back-illuminated solid-state imaging device and front-illuminated solid-state imaging device) according to the second embodiment of the present technology. By providing the photoelectric conversion element 41UV for ultraviolet light and / or the photoelectric conversion element 41IR for infrared light, it becomes possible to detect light having a wavelength other than the visible light region.

  In the organic photoelectric conversion element 41, a first electrode (lower electrode) 33 is formed, and an insulating film 34 for insulating and isolating the first electrode (lower electrode) 33 is shown in the figure of the first electrode (lower electrode) 33. Formed at the bottom.

  In one pixel 20, a wiring 39 connected to the first electrode (lower electrode) 33 and a wiring (not shown) connected to the second electrode (upper electrode) 31 are formed. As the wiring connected to the wiring 39 and the second electrode (upper electrode) 31, for example, a tungsten (W) plug having an SiO 2 or SiN insulating layer in the periphery or ion implantation to suppress a short circuit with Si. It can be formed by a semiconductor layer or the like. In the example of the back-illuminated solid-state imaging device shown in FIG. 2, since the signal charges are holes, the wiring 39 becomes a p-type semiconductor layer when formed by a semiconductor layer by ion implantation. The wiring connected to the second electrode (upper electrode) 31 can use an n-type semiconductor layer because the second electrode (upper electrode) 31 extracts electrons.

  In this example, an n-type region 38 for charge accumulation is formed on the surface side of the semiconductor substrate 35. This n-type region 38 functions as a floating diffusion portion of the photoelectric conversion element 41.

  As the insulating film 34 on the back surface of the semiconductor substrate 35, a film having a negative fixed charge can be used. As a film having a negative fixed charge, for example, a hafnium oxide film can be used. That is, the insulating film 34 may be formed to have a three-layer structure in which a silicon oxide film, a hafnium oxide film, and a silicon oxide film are sequentially formed from the back surface.

  A wiring layer 45 is formed on the front surface side (lower side in FIG. 4) of the semiconductor substrate 35, and on the other hand, on the back surface side (upper side in FIG. 4) of the semiconductor substrate 35 and on the organic photoelectric conversion element 41. A protective layer 44 is formed, and a planarizing layer 43 is formed on the protective layer 44. An on-chip lens 42 is formed on the planarization layer 43. Although not shown, a color filter may be formed on the back-illuminated solid-state imaging device 10.

[2-3. Surface irradiation type solid-state imaging device]
The solid-state image sensor according to the second embodiment of the present technology can be applied not only to a back-illuminated solid-state image sensor but also to a front-illuminated solid-state image sensor. A surface irradiation type solid-state imaging device will be described.

  In the example of the front-illuminated solid-state image sensor, the wiring layer 92 formed below the semiconductor substrate 35 is different from the back-illuminated solid-state image sensor 10 described above in that the organic photoelectric conversion element 41, the semiconductor substrate 35, and the like. The only difference is that the wiring layer 92 is formed between the two. Other points may be the same as those of the back-illuminated solid-state imaging device 10 described above, and a description thereof is omitted here.

<3. Third Embodiment (Example of Electronic Device)>
The electronic device according to the third embodiment of the present technology is a device including the solid-state imaging device according to the second embodiment of the present technology. Since the solid-state imaging device according to the second embodiment of the present technology is as described above, the description thereof is omitted here. Since the electronic apparatus according to the third embodiment of the present technology includes a solid-state imaging device having excellent image quality and excellent reliability, it is possible to improve performance such as image quality of a color image.

<4. Example of use of solid-state image sensor to which this technology is applied
FIG. 5 is a diagram illustrating a usage example of the solid-state imaging device according to the second embodiment of the present technology as an image sensor.

  The solid-state imaging device of the second embodiment described above can be used in various cases for sensing light such as visible light, infrared light, ultraviolet light, and X-ray as follows. That is, as shown in FIG. 5, for example, the field of appreciation for taking images for appreciation, the field of transportation, the field of home appliances, the field of medical / healthcare, the field of security, the field of beauty, sports The solid-state imaging device of the second embodiment can be used for devices (for example, the electronic device of the third embodiment described above) used in the fields of No. 1, agriculture and the like.

  Specifically, in the field of viewing, for example, the solid-state display according to the second embodiment is applied to an apparatus for shooting an image provided for viewing, such as a digital camera, a smartphone, or a mobile phone with a camera function. An image sensor can be used.

  In the field of traffic, for example, in-vehicle sensors that capture images of the front, rear, surroundings, and interior of a vehicle for safe driving such as automatic stop and recognition of the driver's condition, traveling vehicles and roads are monitored. The solid-state image sensor according to the second embodiment can be used in a device used for traffic, such as a surveillance camera that performs distance measurement between vehicles, a distance measurement sensor that performs distance measurement between vehicles, and the like.

  In the field of home appliances, for example, a device used for home appliances such as a television receiver, a refrigerator, an air conditioner, etc. in order to photograph a user's gesture and perform device operations in accordance with the gesture. The solid-state imaging device of the embodiment can be used.

  In the medical / healthcare field, for example, the solid state of the second embodiment is applied to a device used for medical or healthcare, such as an endoscope or a device that performs angiography by receiving infrared light. An image sensor can be used.

  In the field of security, for example, the solid-state imaging device according to the second embodiment can be used in devices used for security, such as surveillance cameras for crime prevention and cameras for personal authentication.

  In the field of beauty, for example, the solid-state image sensor according to the second embodiment may be used in a device used for beauty, such as a skin measuring device that photographs skin and a microscope that photographs the scalp. it can.

  In the field of sports, for example, the solid-state imaging device according to the second embodiment can be used in devices used for sports, such as action cameras and wearable cameras for sports applications.

  In the field of agriculture, for example, the solid-state imaging device of the second embodiment can be used in an apparatus used for agriculture, such as a camera for monitoring the state of fields and crops.

  The embodiments according to the present technology are not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present technology.

  Moreover, the effect described in this specification is an illustration to the last, and is not limited, Moreover, there may exist another effect.

Moreover, this technique can also take the following structures.
[1]
The first electrode, the first buffer layer, the photoelectric conversion layer, the second buffer layer, and the second electrode are stacked in this order,
The first buffer layer comprises a first organic semiconductor material;
The photoelectric conversion layer includes a second organic semiconductor material;
The first organic semiconductor material has a first organic crystal;
The second organic semiconductor material has a second organic crystal;
The ratio of the spacing between the first organic crystals and the spacing between the second organic crystals is 0.55: 1 to 1: 0.55,
An organic photoelectric conversion element in which the orientation of the first organic crystal and the orientation of the second organic crystal are substantially the same.
[2]
The organic photoelectric conversion element according to [1], wherein at least a part of organic molecules contained in the first organic crystal is ππ stacking toward the first electrode or the second electrode.
[3]
The organic photoelectric conversion element according to [2], wherein the ππ stacking is formed at an angle of 30 ° or more with respect to a main surface of the first electrode or the second electrode.
[4]
At least a part of the organic molecules contained in the first organic crystal is ππ stacked toward the first electrode or the second electrode,
The organic photoelectric conversion element according to any one of [1] to [3], wherein the first buffer layer has a film thickness that is at least four times the length of the long axis of the organic molecule.
[5]
The first buffer layer has a film thickness that is less than four times the length of the major axis of the organic molecule contained in the first organic crystal, and the major axis direction of the organic molecule is the first electrode or the first The organic photoelectric conversion element according to any one of [1] to [4], which has an angle of 45 ° or more with respect to the main surface of the two electrodes.
[6]
The organic photoelectric conversion element according to any one of [1] to [5], wherein the first buffer layer further includes a high mobility material.
[7]
Further comprising an organic crystal adjustment layer,
The organic photoelectric conversion element according to any one of [1] to [6], wherein the organic crystal adjustment layer is disposed between the photoelectric conversion layer and the first buffer layer.
[8]
Further comprising an organic crystal adjustment layer,
The organic crystal adjustment layer is disposed between the photoelectric conversion layer and the first buffer layer,
The organic crystal adjustment layer includes the second organic semiconductor material;
The second organic semiconductor material has the second organic crystal;
The ratio between the face spacing of the first organic crystal and the face spacing of the second organic crystal is 0.55: 1 to 1: 0.55, and any one of [1] to [6] Organic photoelectric conversion element.
[9]
The organic crystal adjustment layer further includes a third organic semiconductor material;
The third organic semiconductor material has a third organic crystal;
The ratio of the spacing between the first organic crystals and the spacing between the third organic crystals is 0.55: 1 to 1: 0.55,
The organic photoelectric conversion device according to [8], wherein a ratio between a face spacing of the second organic crystal and a face spacing of the third organic crystal is 0.55: 1 to 1: 0.55.
[10]
Further comprising an organic crystal adjustment layer,
The organic crystal adjustment layer is disposed between the photoelectric conversion layer and the first buffer layer,
The organic crystal adjustment layer includes a third organic semiconductor material;
The third organic semiconductor material has a third organic crystal;
The ratio between the face spacing of the first organic crystal and the face spacing of the third organic crystal is 0.55: 1 to 1: 0.55, and any one of [1] to [6] Organic photoelectric conversion element.
[11]
For each of a plurality of pixels arranged in one or two dimensions,
A solid-state imaging device in which at least the organic photoelectric conversion device according to any one of [1] to [10] and a semiconductor substrate are stacked.
[12]
[11] An electronic apparatus comprising the solid-state imaging device according to [11].

DESCRIPTION OF SYMBOLS 1 ... Organic photoelectric conversion element, 10 ... Back surface irradiation type solid-state image sensor, 11 ... 1st electrode, 12 ... 1st buffer layer, 13 ... Photoelectric conversion layer, 14 ... 2nd buffer layer, 15 ... 2nd electrode

Claims (12)

The first electrode, the first buffer layer, the photoelectric conversion layer, the second buffer layer, and the second electrode are stacked in this order,
The first buffer layer comprises a first organic semiconductor material;
The photoelectric conversion layer includes a second organic semiconductor material;
The first organic semiconductor material has a first organic crystal;
The second organic semiconductor material has a second organic crystal;
The ratio of the spacing between the first organic crystals and the spacing between the second organic crystals is 0.55: 1 to 1: 0.55,
An organic photoelectric conversion element in which the orientation of the first organic crystal and the orientation of the second organic crystal are substantially the same.   2. The organic photoelectric conversion element according to claim 1, wherein at least a part of organic molecules contained in the first organic crystal is ππ-stacked toward the first electrode or the second electrode.   The organic photoelectric conversion element according to claim 2, wherein the ππ stacking is formed at an angle of 30 ° or more with respect to a main surface of the first electrode or the second electrode. At least a part of the organic molecules contained in the first organic crystal is ππ stacked toward the first electrode or the second electrode,
The organic photoelectric conversion element according to claim 1, wherein the first buffer layer has a film thickness that is at least four times the length of the major axis of the organic molecule.   The first buffer layer has a film thickness that is less than four times the length of the major axis of the organic molecule contained in the first organic crystal, and the major axis direction of the organic molecule is the first electrode or the first The organic photoelectric conversion element of Claim 1 which is an angle of 45 degrees or more with respect to the main surface of 2 electrodes.   The organic photoelectric conversion element according to claim 1, wherein the first buffer layer further includes a high mobility material. Further comprising an organic crystal adjustment layer,
The organic photoelectric conversion element according to claim 1, wherein the organic crystal adjustment layer is disposed between the photoelectric conversion layer and the first buffer layer. Further comprising an organic crystal adjustment layer,
The organic crystal adjustment layer is disposed between the photoelectric conversion layer and the first buffer layer,
The organic crystal adjustment layer includes the second organic semiconductor material;
The second organic semiconductor material has the second organic crystal;
2. The organic photoelectric conversion element according to claim 1, wherein a ratio of a spacing between the first organic crystals and a spacing between the second organic crystals is 0.55: 1 to 1: 0.55. The organic crystal adjustment layer further includes a third organic semiconductor material;
The third organic semiconductor material has a third organic crystal;
The ratio of the spacing between the first organic crystals and the spacing between the third organic crystals is 0.55: 1 to 1: 0.55,
The organic photoelectric conversion device according to claim 8, wherein a ratio of a face spacing of the second organic crystal and a face spacing of the third organic crystal is 0.55: 1 to 1: 0.55. Further comprising an organic crystal adjustment layer,
The organic crystal adjustment layer is disposed between the photoelectric conversion layer and the first buffer layer,
The organic crystal adjustment layer includes a third organic semiconductor material;
The third organic semiconductor material has a third organic crystal;
2. The organic photoelectric conversion device according to claim 1, wherein a ratio of a spacing between the first organic crystals and a spacing between the third organic crystals is 0.55: 1 to 1: 0.55. For each of a plurality of pixels arranged in one or two dimensions,
A solid-state imaging device in which at least the organic photoelectric conversion device according to claim 1 and a semiconductor substrate are laminated.   An electronic apparatus comprising the solid-state imaging device according to claim 11.