JP2013183056A - Photoelectric conversion element, manufacturing method therefor, solid state image pickup device and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion element reliability of which can be enhanced, and to provide a manufacturing method of photoelectric conversion element, a solid state image pickup device and an electronic apparatus.SOLUTION: The photoelectric conversion element includes a first electrode, an inorganic insulation film provided on the first electrode, and having an aperture and a first uneven shape on the periphery of the aperture, an organic photoelectric conversion layer formed on the inorganic insulation film from the inside of the aperture across the peripheral region thereof, and a second electrode provided on the organic photoelectric conversion layer. Since the first uneven shape is provided in the peripheral region of the aperture in the inorganic insulation film on the first electrode, and the organic photoelectric conversion layer is provided from the inside of the aperture across the peripheral region thereof, adhesion of the inorganic insulation film and the organic photoelectric conversion layer is enhanced.

Description

  The present disclosure relates to a photoelectric conversion element using an organic photoelectric conversion film, a manufacturing method thereof, a solid-state imaging device, and an electronic apparatus.

  In a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal Oxide Semiconductor) image sensor, a color filter of red, green, or blue is generally provided for each pixel. In this case, since each pixel can obtain only a single color signal, signal processing called demosaic processing is performed after signal acquisition. For example, in a green pixel, red and blue signals are generated by interpolation processing using signals of respective colors acquired from adjacent red and blue pixels. When such signal processing is performed, image quality deterioration due to so-called false color occurs.

  Therefore, a solid-state imaging device has been proposed in which three photoelectric conversion layers are stacked in one pixel and three color signals are obtained in one pixel (for example, Patent Document 1). In the solid-state imaging device of Patent Document 1, for example, an organic photoelectric conversion unit that detects green light and generates a signal charge according to the green light is provided on a silicon substrate, and red light and blue light are detected in the silicon substrate, respectively. A photodiode (inorganic photoelectric conversion unit) is provided.

JP 2011-29337 A

  In the solid-state imaging device as described above, the organic photoelectric conversion unit has a laminated structure of an inorganic film such as an insulating film and an organic film as a photoelectric conversion layer. For this reason, the organic film is easily peeled off, which affects the reliability of the solid-state imaging device.

  The present disclosure has been made in view of such problems, and an object thereof is to provide a photoelectric conversion element, a method for manufacturing the photoelectric conversion element, a solid-state imaging device, and an electronic apparatus that can improve reliability. .

  A photoelectric conversion element of the present disclosure is provided on a first electrode, an inorganic insulating film that is provided on the first electrode, has an opening, and has a first uneven shape in a peripheral region of the opening; and the inorganic insulating film The organic photoelectric conversion layer formed from the inside of the opening to the peripheral region of the opening, and the second electrode provided on the organic photoelectric conversion layer are provided.

  In the photoelectric conversion element of the present disclosure, on the first electrode, the first uneven shape is provided in the peripheral region of the opening of the inorganic insulating film, and the organic photoelectric conversion layer is provided from the inside of the opening to the peripheral region. Thereby, the adhesiveness of an inorganic insulating film and an organic photoelectric converting layer increases.

  The method for manufacturing a photoelectric conversion element of the present disclosure includes a step of forming a first electrode, a step of forming an inorganic insulating film having an opening and a first uneven shape in a peripheral region of the opening on the first electrode, And a step of forming an organic photoelectric conversion layer on the inorganic insulating film from the inside of the opening to a peripheral region of the opening, and a step of forming the second electrode on the organic photoelectric conversion layer.

  In the manufacturing method of the photoelectric conversion element of the present disclosure, after forming the first uneven shape in the peripheral region of the opening of the inorganic insulating film on the first electrode, the organic photoelectric conversion layer is formed from the inside of the opening to the peripheral region By doing, the adhesiveness of an inorganic insulating film and an organic photoelectric converting layer increases.

  A solid-state imaging device of the present disclosure includes the photoelectric conversion element of the present disclosure as a pixel.

  An electronic apparatus according to the present disclosure includes a solid-state imaging device including the photoelectric conversion element according to the present disclosure as a pixel.

  In the solid-state imaging device and the electronic apparatus of the present disclosure, the adhesion between the inorganic insulating film and the organic photoelectric conversion layer is increased by including the photoelectric conversion element of the present disclosure as a pixel.

  According to the photoelectric conversion element, the photoelectric conversion element manufacturing method, the solid-state imaging device, and the electronic apparatus of the present disclosure, the first uneven shape is provided in the peripheral region of the opening of the inorganic insulating film on the first electrode. By forming the organic photoelectric conversion layer from the inside to the peripheral region, the adhesion between the inorganic insulating film and the organic photoelectric conversion layer can be increased. Therefore, reliability can be improved.

It is sectional drawing showing the structure of the photoelectric conversion element of one embodiment of this indication. It is sectional drawing showing the structural example of an inorganic photoelectric conversion part. It is sectional drawing showing the structural example of the electric charge (electron) storage layer of an organic photoelectric conversion part. It is a schematic diagram showing the plane structure of the light shielding layer shown in FIG. 5 is a cross-sectional view illustrating an example of contact between an upper electrode and a multilayer wiring layer 51. FIG. It is sectional drawing for demonstrating the manufacturing method of the photoelectric conversion element shown in FIG. FIG. 7 is a cross-sectional view illustrating a process following FIG. 6. FIG. 8 is a cross-sectional diagram illustrating a process following the process in FIG. 7. FIG. 9 is a cross-sectional diagram illustrating a process following the process in FIG. 8. It is a characteristic view for demonstrating the film-forming conditions at the time of light shielding layer formation. The surface state of the light shielding layer of an Example was image | photographed. The surface state of the light shielding layer of the comparative example is photographed. FIG. 10 is a cross-sectional diagram illustrating a process following the process in FIG. 9. FIG. 14 is a cross-sectional diagram illustrating a process following the process in FIG. 13. FIG. 15 is a cross-sectional view illustrating a process following FIG. 14. FIG. 16 is a cross-sectional diagram illustrating a process following the process in FIG. 15. FIG. 17 is a cross-sectional diagram illustrating a process following the process in FIG. 16. It is sectional drawing showing the principal part structure of the photoelectric conversion element which concerns on a comparative example. It is the figure showing the mode of peeling of the organic photoelectric converting layer of the photoelectric conversion element shown in FIG. It is sectional drawing showing the principal part structure of the photoelectric conversion element which concerns on a modification. It is a one part expanded sectional view of the photoelectric conversion element shown in FIG. 12 is a functional block diagram of a solid-state imaging device according to application example 1. FIG. 12 is a functional block diagram of an electronic device according to application example 2. FIG.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. The order of explanation is as follows.
1. Embodiment (an example of a photoelectric conversion element in which an inorganic insulating film and an organic photoelectric conversion layer are stacked on a light-shielding portion having an uneven shape)
2. Modified example (example when patterning irregularities on the surface of an inorganic insulating film)
3. Application example 1 (example of solid-state imaging device)
4). Application example 2 (Example of electronic device (camera))

<Embodiment>
[Constitution]
FIG. 1 illustrates a cross-sectional configuration of a photoelectric conversion element (photoelectric conversion element 10) according to an embodiment of the present disclosure. The photoelectric conversion element 10 constitutes one pixel in a solid-state imaging device (described later) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor) image sensor. In the photoelectric conversion element 10, pixel transistors (including transfer transistors Tr1 to 3 described later) are formed on the surface of the semiconductor substrate 11 (surface S2 opposite to the light receiving surface), and multilayer wiring is formed on the surface S2 side. A layer (multilayer wiring layer 51) is provided.

  The photoelectric conversion element 10 has a structure in which an organic photoelectric conversion unit that selectively detects light in different wavelength ranges and performs photoelectric conversion and an inorganic photoelectric conversion unit are stacked in the vertical direction. Thereby, in the solid-state imaging device described later, a plurality of types of color signals can be acquired in one pixel without using a color filter. In the present embodiment, the photoelectric conversion element 10 has a stacked structure of one organic photoelectric conversion unit 11G and two inorganic photoelectric conversion units 11B and 11R, whereby red (R), green (G ) And blue (B) color signals. The organic photoelectric conversion unit 11 </ b> G is formed on the back surface (surface S <b> 1) side of the semiconductor substrate 11, and the inorganic photoelectric conversion units 11 </ b> B and 11 </ b> R are embedded in the semiconductor substrate 11. The semiconductor substrate 11 corresponds to a specific example of “substrate” in the present disclosure. Hereinafter, the structure of each part is demonstrated.

(Semiconductor substrate 11)
The semiconductor substrate 11 is, for example, one in which inorganic photoelectric conversion units 11B and 11R and a green power storage layer 110G are embedded in a predetermined region of an n-type silicon (Si) layer 110. Also embedded in the semiconductor substrate 11 is a conductive plug 120a1 serving as a transmission path for charges (electrons or holes) from the organic photoelectric conversion unit 11G. In the present embodiment, the back surface (surface S1) of the semiconductor substrate 11 is a light receiving surface. On the surface (surface S2) side of the semiconductor substrate 11, a plurality of pixel transistors (including transfer transistors Tr1 to Tr3) corresponding to the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R are formed. A peripheral circuit composed of a logic circuit or the like is formed.

  Examples of the pixel transistor include a transfer transistor, a reset transistor, an amplification transistor, and a selection transistor. Each of these pixel transistors is formed of a MOS transistor, for example, and is formed in the p-type semiconductor well region on the surface S2. A circuit including such a pixel transistor is formed for each of the red, green, and blue photoelectric conversion units. Each circuit may have a three-transistor configuration including a total of three transistors, such as a transfer transistor, a reset transistor, and an amplifying transistor, among these pixel transistors, or four transistors including a selection transistor. It may be a configuration. Here, among these pixel transistors, only the transfer transistors Tr1 to Tr3 are illustrated. The pixel transistors other than the transfer transistor can be shared between the photoelectric conversion units or between the pixels. Further, a so-called pixel sharing structure that shares a floating diffusion can also be applied.

  The transfer transistors Tr1 to Tr3 include gate electrodes (gate electrodes TG1 to TG3) and floating diffusions (FDs 113, 114, and 116). The transfer transistor Tr1 transfers the signal charge corresponding to green (electrons in the present embodiment) generated in the organic photoelectric conversion unit 11G and accumulated in the green power storage layer 110G to a vertical signal line Lsig described later. It is. The transfer transistor Tr2 transfers the signal charge (electrons in the present embodiment) corresponding to blue generated and accumulated in the inorganic photoelectric conversion unit 11B to a vertical signal line Lsig described later. Similarly, the transfer transistor Tr3 transfers signal charges (electrons in the present embodiment) corresponding to red color generated and accumulated in the inorganic photoelectric conversion unit 11R to a vertical signal line Lsig described later.

  Each of the inorganic photoelectric conversion units 11B and 11R is a photodiode having a pn junction, and is formed in the semiconductor substrate 11 in the order of, for example, the inorganic photoelectric conversion units 11B and 11R from the surface S1 side. Among these, the inorganic photoelectric conversion unit 11B selectively detects blue light and accumulates signal charges corresponding to blue. For example, from the selective region along the surface S1 of the semiconductor substrate 11, multiple layers are formed. It is formed to extend over a region near the interface with the wiring layer 51. The inorganic photoelectric conversion unit 11R selectively detects red light and accumulates signal charges corresponding to red. For example, the inorganic photoelectric conversion unit 11R is formed in a lower layer (surface S2 side) region than the inorganic photoelectric conversion unit 11B. . In addition, blue (B) is a color corresponding to a wavelength range of 450 nm to 495 nm, for example, and red (R) is a color corresponding to a wavelength range of 620 nm to 750 nm, for example. The inorganic photoelectric conversion units 11B and 11R are each in the wavelength range described above. It is sufficient that light in a part or all of the wavelength region can be detected.

  FIG. 2A illustrates a detailed configuration example of the inorganic photoelectric conversion units 11B and 11R. FIG. 2B corresponds to a structure in another cross section of FIG. Note that in this embodiment, a case where electrons out of a pair of electrons and holes generated by photoelectric conversion are read as signal charges (when an n-type semiconductor region is a photoelectric conversion layer) will be described. In the figure, “+ (plus)” superscripted on “p” and “n” represents a high p-type or n-type impurity concentration. In addition, among the pixel transistors, the gate electrodes TG2 and TG3 of the transfer transistors Tr2 and Tr3 are also shown.

  The inorganic photoelectric conversion unit 11B includes, for example, a p-type semiconductor region serving as a hole accumulation layer (hereinafter also referred to simply as a p-type region, the same applies to an n-type case) 111p and an n-type photoelectric conversion layer serving as an electron accumulation layer ( n-type region) 111n. Each of the p-type region 111p and the n-type photoelectric conversion layer 111n is formed in a selective region in the vicinity of the surface S1, and a part thereof is bent so as to extend to reach the interface with the surface S2. . The p-type region 111p is connected to a p-type semiconductor well region (not shown) on the surface S1 side. The n-type photoelectric conversion layer 111n is connected to the FD 113 (n-type region) of the blue transfer transistor Tr2. Note that a p-type region 113p (a hole accumulation layer) is formed in the vicinity of the interface between each surface S2 side end of the p-type region 111p and the n-type photoelectric conversion layer 111n and the surface S2.

  The inorganic photoelectric conversion unit 11R is formed, for example, by sandwiching an n-type photoelectric conversion layer 112n (electron storage layer) between p-type regions 112p1 and 112p2 (hole storage layer) (stacked structure of pnp). Have). A part of the n-type photoelectric conversion layer 112n is bent and extended so as to reach the interface with the surface S2. The n-type photoelectric conversion layer 112n is connected to the FD 114 (n-type region) of the red transfer transistor Tr3. Note that a p-type region 113p (hole accumulation layer) is formed at least near the interface between the end of the n-type photoelectric conversion layer 111n on the surface S2 side and the surface S2.

  FIG. 3 illustrates a detailed configuration example of the green power storage layer 110G. Here, a description will be given of a case where electrons are read out from the lower electrode 14a side as signal charges out of a pair of electrons and holes generated by the organic photoelectric conversion unit 11G. FIG. 3 also shows the gate electrode TG1 of the transfer transistor Tr1 among the pixel transistors.

  The green power storage layer 110G includes an n-type region 115n that serves as an electron storage layer. A part of the n-type region 115n is connected to the conductive plug 120a1, and accumulates electrons supplied from the lower electrode 14a side through the conductive plug 120a1. The n-type region 115n is also connected to the FD 116 (n-type region) of the green transfer transistor Tr1. A p-type region 115p (hole accumulation layer) is formed in the vicinity of the interface between the n-type region 115n and the surface S2.

  The conductive plug 120a1, together with a conductive plug 120a2 described later, functions as a connector between the organic photoelectric conversion unit 11G and the semiconductor substrate 11, and forms a transmission path for electrons or holes generated in the organic photoelectric conversion unit 11G. is there. Here, the conductive plug 120a1 is electrically connected to the lower electrode 14a of the organic photoelectric conversion unit 11G and is connected to the green power storage layer 110G.

The conductive plug 120a1 is formed of, for example, a conductive semiconductor layer and is embedded in the semiconductor substrate 11. In this case, since it becomes an electron transmission path, the conductive plug 120a1 is preferably an n-type. Alternatively, the conductive plug 120a1 may be, for example, a through via filled with a conductive film material such as tungsten. In this case, for example, in order to suppress a short circuit with silicon, it is desirable that the via side surface be covered with an insulating film such as silicon oxide (SiO ₂ ) or silicon nitride (SiN).

  A support substrate 53 made of, for example, silicon is bonded to the surface S2 side of the semiconductor substrate 11 with a multilayer wiring layer 51 interposed therebetween. In the multilayer wiring layer 51, a plurality of wirings 51 a and wirings 51 b are arranged via an interlayer insulating film 52. Thus, in the photoelectric conversion element 10, the multilayer wiring layer 51 is formed on the side opposite to the light receiving surface, and a so-called back-illuminated solid-state imaging device can be realized.

  On the other hand, an organic photoelectric conversion unit 11G is formed on the surface S1 side of the semiconductor substrate 11. Hereinafter, the configuration on the surface S1 side of the semiconductor substrate 11 will be described.

(Organic photoelectric conversion unit 11G)
The organic photoelectric conversion unit 11G is an organic photoelectric conversion element that generates an electron / hole pair by absorbing light in a selective wavelength range (here, green light) using an organic semiconductor. The organic photoelectric conversion unit 11G has a configuration in which the organic photoelectric conversion layer 17 is sandwiched between a pair of electrodes (lower electrode 14a and upper electrode 18) for extracting signal charges. The lower electrode 14a (first electrode) is electrically connected to a conductive plug 120a1 embedded in the semiconductor substrate 11. The upper electrode 18 (second electrode) is connected to the wiring 51a in the multilayer wiring layer 51 via a contact portion described later, for example, at the periphery of the solid-state imaging device, and thereby charges (here, holes) are discharged. It has come to be.

  The organic photoelectric conversion unit 11G is formed on the surface S1 of the semiconductor substrate 11 via interlayer insulating films 12A and 12B. In the interlayer insulating film 12A, a conductive plug 120a2 is embedded in a region facing the conductive plug 120a1, and in the interlayer insulating film 12B, a wiring layer 13a is embedded in a region facing the conductive plug 120a2. A lower electrode 14a is disposed on the interlayer insulating film 12B. On the lower electrode 14a, inorganic insulating films 15A and 15B having openings H are formed. The organic photoelectric conversion layer 17 is formed from the inside of the opening H of the inorganic insulating films 15A and 15B (the upper surface of the lower electrode 14a) to the peripheral region thereof. An upper electrode 18 is provided so as to cover the organic photoelectric conversion layer 17, and a protective film 19 and a planarizing layer 20 are laminated on the upper electrode 18 in this order.

  As described above, the conductive plug 120a2 functions as a connector together with the conductive plug 120a1, and together with the conductive plug 120a1 and the wiring layer 13a, a conductive (electron) transmission path from the lower electrode 14a to the green power storage layer 110G. To form. The conductive plug 120a2 may function as a light shielding film. In this case, it is desirable that the conductive plug 120a2 is formed of a laminated film of a metal material such as titanium (Ti), titanium nitride (TiN), and tungsten.

The interlayer insulating film 12A is made of an insulating film having a small interface state in order to reduce the interface state with the semiconductor substrate 11 (silicon layer 110) and to suppress the generation of dark current from the interface with the silicon layer 110. It is desirable to be configured. As such an insulating film, for example, a stacked film of a hafnium oxide (HfO ₂ ) film and a silicon oxide (SiO ₂ ) film can be used. The interlayer insulating film 12B is composed of, for example, a single layer film made of one of silicon oxide, silicon nitride, silicon oxynitride (SiON), or a laminated film made of two or more of these.

The lower electrode 14a is provided in a region that faces the light receiving surfaces of the inorganic photoelectric conversion units 11B and 11R formed in the semiconductor substrate 11 and covers these light receiving surfaces. The lower electrode 14a has optical transparency and is made of, for example, a conductive film having a refractive index of 1.8 to 2.0, such as ITO (indium tin oxide). However, in addition to this, tin oxide (TO), tin oxide (SnO ₂ ) -based material added with a dopant, or zinc oxide-based material obtained by adding a dopant to zinc oxide (ZnO) may be used. Examples of the zinc oxide-based material include aluminum zinc oxide (AZO) to which aluminum (Al) is added as a dopant, gallium zinc oxide (GZO) to which gallium (Ga) is added, and indium zinc oxide to which indium (In) is added. (IZO). In addition, CuI, InSbO ₄ , ZnMgO, CuInO ₂ , MgIN ₂ O ₄ , CdO, ZnSnO _3, or the like may be used. In the present embodiment, signal charges (electrons) are extracted from the lower electrode 14a as described above. Therefore, in the solid-state imaging device described later using the photoelectric conversion element 10 as a pixel, the lower electrode 14a is inorganic. Each pixel is separated by insulating films 15A and 15B.

  The inorganic insulating films 15A and 15B are composed of, for example, a single layer film made of one of silicon oxide, silicon nitride, and silicon oxynitride (SiON), or a laminated film made of two or more of these. Yes. These inorganic insulating films 15A and 15B have a function of electrically separating the lower electrodes 14a of each pixel and sandwiching the light shielding layer 16 when the photoelectric conversion element 10 is used as a pixel of a solid-state imaging device. Are stacked. By these inorganic insulating films 15A and 15B, insulation between the light shielding layer 16, the lower electrode 14a, and the organic photoelectric conversion layer 17 is secured. The inorganic insulating film 15B corresponds to a specific example of “an inorganic insulating film” in the present disclosure, and the inorganic insulating film 15A corresponds to a specific example of “another insulating film” in the present disclosure.

  In the present embodiment, the inorganic insulating film 15B provided on the upper side of these inorganic insulating films 15A and 15B has an uneven shape A1 (first uneven shape) in the peripheral region of the opening H. The uneven shape A1 is formed following the uneven shape A2 (second uneven shape) of the light shielding layer 16 (reflecting the shape of the uneven shape A2). The uneven shape A1 of the inorganic insulating film 15B is also reflected on the upper surface (surface on the upper electrode 18 side) of the organic photoelectric conversion layer 17, and the upper surface of the organic photoelectric conversion layer 17 is uneven according to the uneven shape A1. It has a shape A3. In FIG. 1, the uneven shape A2 of the light shielding layer 16, the uneven shape A1 of the inorganic insulating film 15B, and the uneven shape A3 of the organic photoelectric conversion layer 17 are schematically shown.

  The light shielding layer 16 suppresses the incidence of external light (noise light) to the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R. Usually, such a layer having a light shielding function is provided in the same layer as a metal (for example, conductive plug 120a2) provided below the lower electrode 14a, or the conductive plug 120a2 also serves as a light shielding layer. There are many cases. In the present embodiment, the light shielding layer 16 is provided above the lower electrode 14a, and the uneven shape A2 is formed on the surface of the light shielding layer 16. Thereby, the uneven shape A1 following the uneven shape A2 of the light shielding layer 16 is formed on the surface of the inorganic insulating film 15B on the organic photoelectric conversion layer 17 side.

  The light shielding layer 16 is formed in the peripheral region of the opening H, and for example, the entire surface thereof has an uneven shape A2. For example, in the solid-state imaging device described later, as shown in FIG. 4, the light shielding layer 16 having the openings H is formed in a lattice shape as a whole. The concavo-convex shape A2 may be formed only in a partial region of the surface of the light shielding layer 16, but it is preferable that the uneven shape A2 is formed over the entire surface of the light shielding layer 16 as in the present embodiment. It is desirable from the viewpoint of improving adhesion.

  Specifically, the surface of the light shielding layer 16 is a rough surface formed in a later-described CVD (Chemical Vapor Deposition) process, and the rough surface includes the uneven shape A2. Specifically, the RMS granularity (Root Mean Square granularity) is preferably a rough surface of, for example, 8 nm or more, and more preferably about 10 nm or more. This is because in the film forming process of the inorganic insulating film 15B, it is easy to form a shape (uneven shape A1) that follows the uneven shape A2 on the upper surface of the inorganic insulating film 15B (it is easy to reflect the uneven shape A2). .

  Such a light shielding layer 16 is made of a material having low transmittance with respect to visible light, such as tungsten (W), titanium (Ti), aluminum (Al), or copper (Cu). In this case, a laminate (TiN / W) in which titanium nitride (TiN) and tungsten are stacked in this order from the inorganic insulating film 15A side can be mentioned. Or the thing (Ti / TiN / W) by which titanium, TiN, and tungsten were laminated | stacked in order from the inorganic insulating film 15A side is mentioned. Among these, the laminated film of the Ti layer and the TiN layer or the TiN single layer film mainly has a function of improving the adhesion to the inorganic insulating film 15A, and the thickness thereof is, for example, 10 nm to 40 nm. The W layer is provided mainly to ensure light shielding properties, and the thickness thereof is, for example, 150 nm to 250 nm.

  The organic photoelectric conversion layer 17 is composed of an organic semiconductor that absorbs light in a selective wavelength range and performs photoelectric conversion while transmitting light in other wavelength ranges. The organic semiconductor is preferably configured to include one or both of an organic p-type semiconductor and an organic n-type semiconductor. As such an organic semiconductor, any one of quinacridone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives is preferably used. Alternatively, a polymer such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, or a derivative thereof may be used. In addition, metal complex dyes, rhodamine dyes, cyanine dyes, merocyanine dyes, phenylxanthene dyes, triphenylmethane dyes, rhodacyanine dyes, xanthene dyes, macrocyclic azaannulene dyes, azulene dyes, naphthoquinones , Anthraquinone dyes, condensed polycyclic aromatics such as anthracene and pyrene, chain compounds condensed with aromatic rings or heterocyclic compounds, or quinoline, benzothiazole, benzoxazole having a squarylium group and a croconic methine group as a bonding chain Or the like, or a cyanine-like dye bonded by two nitrogen-containing heterocycles or the like, or a squarylium group and a croconite methine group can be preferably used. The metal complex dye is preferably a dithiol metal complex dye, a metal phthalocyanine dye, a metal porphyrin dye, or a ruthenium complex dye, but is not limited thereto. In the present embodiment, the organic photoelectric conversion layer 17 can photoelectrically convert green light corresponding to a part or all of the wavelength range of 495 nm to 570 nm, for example, and one or more of the above materials It is comprised including the material of. The thickness of such an organic photoelectric conversion layer 17 is, for example, 50 nm to 500 nm.

  Two or more organic semiconductors (for example, a p-type organic semiconductor and an n-type organic semiconductor) are vapor-deposited at the same time, whereby an organic co-deposition film that is a composite film of these organic semiconductors is used as the organic photoelectric conversion layer 17. May be. Further, other layers (not shown) may be provided between the lower electrode 14 a of the organic photoelectric conversion layer 17 and the upper electrode 18. For example, an undercoat film, an electron blocking film, an organic photoelectric conversion layer 17, a hole blocking film, a buffer film, a work function adjusting film, and the like may be stacked sequentially from the lower electrode 14a side.

  The upper electrode 18 is composed of an inorganic conductive film having the same light transmittance as that of the lower electrode 14a. The upper electrode 18 is provided in contact with the concavo-convex shape A3 of the organic photoelectric conversion layer 17 in the peripheral region of the opening H.

  Further, as shown in FIG. 5, the upper electrode 18 is connected to the multilayer wiring layer 51 via the contact metal layer 18c (not shown in FIG. 1) in the selective region. In FIG. 5, illustration of the multilayer wiring layer 51 and the support substrate 53, the protective layer 19, and the planarizing layer 20 is omitted for simplification. The contact metal layer 18c is formed by removing the upper electrode 18 from the lower wiring layer (conductive plugs 120b1, 12b2, and wiring layer 13b) in order to extract charges from the upper electrode 18 (discharge of holes in the present embodiment). , 14b). In the case where signal charges are extracted from the lower electrode 18 side as in the present embodiment, in the solid-state imaging device described later, the upper electrode 18 is provided in common for each pixel, and the contact metal layer 18c It is sufficient that at least one location is provided for the upper electrode 18.

  The protective film 19 is made of, for example, a light-transmitting inorganic material, and is made of, for example, a single-layer film made of any of silicon oxide, silicon nitride, silicon oxynitride, or the like, or two or more of them. It is a laminated film. The thickness of the protective film 19 is, for example, 0.1 μm to 30 μm.

  The planarization layer 20 is made of, for example, an acrylic resin material, a styrene resin material, an epoxy resin material, or the like. An on-chip lens 21 is provided on the planarizing layer 20. The planarization layer 20 may be provided as necessary, and the protective layer 19 may also serve as the planarization layer 20.

  The on-chip lens 21 collects light incident from above on the light receiving surfaces of the organic photoelectric conversion layer 11G and the inorganic photoelectric conversion layers 11B and 11R. In the present embodiment, since the multilayer wiring layer 51 is formed on the surface S2 side of the semiconductor substrate 11, the light receiving surfaces of the organic photoelectric conversion layer 11G and the inorganic photoelectric conversion layers 11B and 11R are arranged close to each other. Thus, it is possible to reduce the variation in sensitivity between the colors depending on the F value of the on-chip lens 21.

[Production method]
The photoelectric conversion element 10 as described above can be manufactured, for example, as follows. 6-9 and FIGS. 13-17 show the manufacturing method of the photoelectric conversion element 10 in process order. However, here, only the main configuration of the photoelectric conversion element 10 is illustrated, and a procedure for forming the organic photoelectric conversion unit 11G on the surface S1 side of the semiconductor substrate 11 will be specifically described.

  Although not shown, the semiconductor substrate 11 having the inorganic photoelectric conversion portions 11A and 11B is formed before the organic photoelectric conversion portion 11G is formed, and the multilayer wiring layer 51 and the support are formed on the surface S2 side of the semiconductor substrate 11. A substrate 53 is formed. Specifically, first, a silicon layer 110 is formed on a temporary substrate made of, for example, a silicon oxide film, and the conductive plug 120a1, the green storage layer 110G, and the inorganic photoelectric conversion units 11B and 11R are formed on the silicon layer 110. For example, the semiconductor substrate 11 is formed by embedding by ion implantation. Thereafter, a pixel transistor including transfer transistors Tr1 to Tr3, a peripheral circuit such as a logic circuit, and a multilayer wiring layer 51 are formed on the surface S2 side of the semiconductor substrate 11. Subsequently, after the support substrate 53 is bonded onto the multilayer wiring layer 51, the temporary substrate is peeled off from the surface S1 side of the semiconductor substrate 11 to expose the surface S1 of the semiconductor substrate 11.

  First, as shown in FIG. 6, interlayer insulating films 12 </ b> A and 12 </ b> B are formed on the surface S <b> 1 of the semiconductor substrate 11. Specifically, first, an interlayer insulating film 12A made of a laminated film of a hafnium oxide film and a silicon oxide film as described above is formed on the surface S1 of the semiconductor substrate 11. At this time, for example, after a hafnium oxide film is formed by an ALD (atomic layer deposition) method, a silicon oxide film is formed by a plasma CVD method, for example. Thereafter, a region facing the conductive plug 120a1 of the interlayer insulating film 12A is opened, and the conductive plug 120a2 made of the above-described material is formed. Subsequently, an interlayer insulating film 12B made of the above-described material is formed on the interlayer insulating film 12A by, for example, a plasma CVD method. Next, a region of the interlayer insulating film 12B facing the conductive plug 120a2 is opened, and the wiring layer 13a made of the above-described material is formed.

  Next, as shown in FIG. 7, the lower electrode 14a is formed on the interlayer insulating film 12B. Specifically, first, the above-described transparent conductive film is formed over the entire surface of the interlayer insulating film 12B. Examples of film forming methods include sol-gel method, spin coating method, spray method, roll coating method, ion beam deposition method, electron beam deposition method, laser ablation method, CVD Method or sputtering method. However, in order to form the lower electrode 14a having a particularly large area and a uniform thickness, it is desirable to use the sputtering method among the above methods. Thereafter, the lower electrode 14a is formed by patterning, for example, using dry etching (or wet etching) using a photolithography method. At this time, by forming the lower electrode 14a in a region facing the wiring layer 13a, the lower electrode 14a is electrically connected to the green power storage layer 110G via the wiring layer 13a and the conductive plugs 120a1 and 120a2. Like that.

  Subsequently, as shown in FIG. 8, an inorganic insulating film 15A is formed. Specifically, the inorganic insulating film 15A made of the above-described material is formed by, for example, a plasma CVD method so as to cover the entire surface of the semiconductor substrate 11 so as to cover the interlayer insulating film 12B and the lower electrode 14a. Next, the surface of the formed inorganic insulating film 15A is planarized using, for example, a CMP (Chemical Mechanical Polishing) method.

  In each of the steps of forming the conductive plug 120a2, the wiring layer 13a and the light shielding layer 16 described later, the conductive plug 120b2 and the wiring layers 13b and 14b in the contact portion 18c shown in FIG. 5 are formed.

(Light shielding layer forming process)
Thereafter, the light shielding layer 16 is formed as follows. Specifically, first, as shown in FIG. 9, the light shielding layer 16 made of the above-described material or the like is formed over the entire surface of the inorganic insulating film 15A. Specifically, first, for example, a laminated film of a Ti layer and a TiN layer, or a TiN layer (single layer film) is formed by, for example, a sputtering method or a CVD method, and then a W layer is formed by, for example, a CVD method. Form a film.

  Here, when forming the W layer, film forming conditions are used so that the concavo-convex shape A2 is formed on the surface thereof. When the CVD method is used as the film forming method, in detail, a W layer is formed through a nucleation (nucleation generation) step and a growth step of the nuclei. It is recommended to set such conditions.

(1) Nucleation step Film formation temperature: 450 ° C
WF ₆ flow rate: 15sccm
SiH ₄ flow rate: 4 sccm
H ₂ flow rate: 400sccm
Deposition pressure: 500Pa
Film thickness: 20-30nm
(2) Growth step Deposition temperature: 450 ° C
WF ₆ flow rate: 80sccm
SiH ₄ flow rate: 0 sccm
H ₂ flow rate: 720sccm
Deposition pressure: 10500 Pa
Film thickness: 200nm

The surface of the W layer formed under the above conditions is a rough surface including the uneven shape A2 as described above, and its RMS granularity is about 10 nm. The formation of such a rough surface is greatly influenced by the film formation temperature and the flow rate ratio of WF _{6 to} H ₂ among the film formation conditions. Specifically, especially in the growth step, the RMS granularity of the surface of the W layer is increased by allowing film formation to proceed at a relatively low temperature or setting the flow ratio of WF _{6 to} H ₂ higher than usual. Thus, a rough surface including the uneven shape A2 can be formed.

  For example, when only the film forming temperature is changed among the film forming conditions as described above, the following effects are exerted on the surface shape of the W layer. FIG. 10A shows the relationship between the film formation temperature (° C.) in the growth step and the reflectance (%) of the surface of the formed W layer. FIG. 10B shows the film formation temperature (° C.) The relationship with the roughness (nm) of the surface of the deposited W layer is shown. Thus, when the film forming temperature is changed stepwise in the range of 350 to 500 ° C., for example, when the film is formed at a lower temperature, the reflectance is lowered and the surface roughness is increased. . From this result, it is understood that the RMS granularity of the surface of the light shielding layer 16 tends to increase (the surface becomes rough) due to the decrease in the film formation temperature. Further, since the RMS granularity is increased, the uneven shape A2 is reflected on the inorganic insulating film 15B and the organic photoelectric conversion layer 17 to be formed in a later step, and the uneven shapes A1 and A3 as described above are easily formed. Become.

FIG. 11A shows a photograph of the surface state (RMS granularity: 9.934 nm) of the W layer formed under the film forming conditions (1) and (2) as an example. However, FIG. 11A shows the W layer as viewed obliquely from above, and FIG. 11B shows the W layer as viewed from above. Further, as a comparative example, when the flow rate of WF ₆ is set to 20 sccm and the flow rate of H ₂ is set to 2000 sccm in the film forming step (the conditions other than the flow rates of WF ₆ and H ₂ are the same as in the above embodiment). 12A and 12B show the surface state of the W layer. That is, in the comparative example, the ratio of the flow rate of WF _{6 to} H ₂ is set lower than in the example. In this case, the RMS granularity is lower than in the example (3.525 nm), and the surface of the W layer Has a relatively smooth surface. From this result, it is understood that the RMS granularity of the surface of the light shielding layer 16 tends to increase (the surface becomes rough) by increasing the flow rate ratio of WF ₆ to H ₂ . Therefore, even when the flow rate ratio of WF _{6 to} H ₂ is set high, it is easy to form the uneven shapes A1 and A3 as described above, as in the case where the film forming temperature is lowered.

  Subsequently, the light shielding layer 16 formed as described above is patterned. Specifically, as shown in FIG. 13, a region facing the lower electrode 14a is opened by, for example, dry etching using a photolithography method.

  Next, as shown in FIG. 14, an inorganic insulating film 15B is formed. Specifically, the inorganic insulating film 15B made of the above-described material is formed by, for example, a CVD method so as to cover the light shielding layer 16 and its opening. Thereby, an uneven shape A1 is formed on the surface of the inorganic insulating film 15B, following the uneven shape A2 of the surface of the light shielding layer 16.

  Thereafter, an opening H is formed as shown in FIG. Specifically, the regions facing the lower electrode 14a of the inorganic insulating films 15A and 15B are selectively removed by, for example, dry etching using a photolithography method. Thereby, the surface of the lower electrode 14a is exposed from the inorganic insulating films 15A and 15B.

  Subsequently, as shown in FIG. 16, the organic photoelectric conversion layer 17 made of the above-described material or the like is formed using, for example, a vacuum evaporation method. As a result, the organic photoelectric conversion layer 17 is formed from the inside of the opening H to the peripheral region of the open height H as described above, and in the peripheral region, the organic photoelectric conversion layer 17 has the uneven shape A1 of the inorganic insulating film 15B. It is formed in contact with. Further, in the peripheral region of the opening H, an uneven shape A3 that follows the uneven shape A1 of the surface of the insulating layer 15B is formed on the surface of the organic photoelectric conversion layer 17.

  Thereafter, as shown in FIG. 17, the upper electrode 18 is formed. Specifically, the above-described conductive film is formed over the entire surface of the semiconductor substrate 11 on the organic photoelectric conversion layer 17 by, for example, a vacuum deposition method, a sputtering method, or the like. At this time, it is desirable to form the conductive film continuously with the organic photoelectric conversion layer 17 in a vacuum atmosphere (by a consistent vacuum process). After forming the conductive film in this way, the upper electrode 18 is formed by patterning the conductive film by etching using, for example, a photolithography method. At this time, the organic photoelectric conversion layer 17 may be patterned at the same time.

  Finally, although not shown, after the protective layer 19 is formed on the upper electrode 18 by, for example, plasma CVD, the planarizing layer 20 is formed by, for example, spin coating. Thereafter, an on-chip lens 21 is formed on the planarizing layer 20 to complete the photoelectric conversion element 10 shown in FIG.

[Action, effect]
In the photoelectric conversion element 10 of the present embodiment, signal charges are acquired as follows, for example, as a pixel of a solid-state imaging device. That is, when light enters the photoelectric conversion element 10 through the on-chip lens 21, the incident light passes through the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R in this order, and red, green in the passing process. , Photoelectric conversion is performed for each blue color light.

  Specifically, first, green light is selectively detected (absorbed) in the organic photoelectric conversion unit 11G and subjected to photoelectric conversion. Thereby, for example, electrons out of the generated electron / hole pairs are extracted from the lower electrode 14a side, and then stored in the green power storage layer 110G via the wiring layer 13a and the conductive plugs 120a1 and 120a2. The holes are discharged from the upper electrode 18 side through the contact metal layer 18c, the wiring layers 14b and 13b, the conductive plugs 120b2 and 120b1, and the wiring layer 51a. Thereafter, among the light transmitted through the organic photoelectric conversion unit 11G, blue light is absorbed and photoelectrically converted in this order by the inorganic photoelectric conversion unit 11B and red light by the inorganic photoelectric conversion unit 11R. In the inorganic photoelectric conversion unit 11B, electrons corresponding to blue light are accumulated in the n-type region (n-type photoelectric conversion layer 111n). Similarly, in the inorganic photoelectric conversion unit 11R, electrons corresponding to red light are accumulated in the n-type region (n-type photoelectric conversion layer 112n).

  During the read operation, the transfer transistors Tr1, Tr2, and Tr3 are turned on, and the electrons accumulated in the green power storage layer 110G and the n-type photoelectric conversion layers 111n and 112n are transferred to the FDs 113, 114, and 116, respectively. . As a result, the light reception signals of the respective colors are read out to a vertical signal line Lsig described later through other pixel transistors (not shown). Thus, by stacking the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R in the vertical direction, the color light of red, green, and blue is separated and detected without providing a color filter, and the signal of each color Charge can be obtained.

  Here, in the organic photoelectric conversion unit 11G of the photoelectric conversion element 10 as described above, the organic photoelectric conversion layer 17 is sandwiched between the insulating layers 15A and 15B made of an inorganic film and the upper electrode 18 in the region on the lower electrode 14a. Have a configuration. For this reason, film peeling occurs between the organic film and the inorganic film as described below.

(Comparative example)
FIG. 18 illustrates a main configuration of a photoelectric conversion element (photoelectric conversion element 100) of a comparative example of the present embodiment. As in the present embodiment, the photoelectric conversion element 100 is obtained by stacking an organic photoelectric conversion unit 100G on a semiconductor substrate 11 including inorganic photoelectric conversion units 11B and 11R. However, unlike this embodiment, a light shielding layer 101b is provided between the interlayer insulating films 102A and 102B provided on the semiconductor substrate 11. The conductive plug 101a also serves as a light shielding layer. Further, the lower electrode 104 is disposed on the interlayer insulating film 102B, on the lower electrode 104, an inorganic insulating film 105 is provided with an opening H _100. The surface of the inorganic insulating film 105 is a flat surface. An organic photoelectric conversion layer 106 is formed so as to cover the inside and the peripheral region of the opening H100 of the inorganic insulating film 105, and an upper electrode 107 is provided on the organic photoelectric conversion layer 106.

  In the photoelectric conversion element 100 of the comparative example, the organic photoelectric conversion layer 106 is sandwiched between the inorganic insulating film 105 and the upper electrode 106, but film peeling occurs due to poor adhesion between the organic film and the inorganic film. . For example, as shown in FIG. 19, a part of the organic photoelectric conversion layer 106 is peeled off from the surface of the inorganic insulating film 105 provided thereunder. This also affects the electrical characteristics, which causes a decrease in reliability.

  On the other hand, in the present embodiment, the uneven shape A1 is provided in the peripheral region of the opening H of the inorganic insulating film 15B, and the organic photoelectric conversion layer 17 is formed from the inside of the opening H to the peripheral region. The uneven surface shape A1 increases the surface area of the interface between the inorganic insulating film 15B and the organic photoelectric conversion layer 17, and improves the adhesion of the organic photoelectric conversion layer 17 to the inorganic insulating film 15B. For this reason, the organic photoelectric conversion layer 17 is hardly peeled off from the insulating layer 15B, and the influence on the electrical characteristics is suppressed.

  Moreover, since this uneven | corrugated shape A1 is provided in the peripheral region of the opening H, the light scattering in an uneven surface does not affect a device characteristic easily.

  Further, in the present embodiment, the light shielding layer 16 having the uneven shape A2 is provided between the inorganic insulating films 15A and 15B, and the inorganic insulating film 15B is provided thereon. Here, generally, as in the comparative example, the light shielding layer 101b (and the conductive plug 102a also serving as the light shielding layer) is provided below the lower electrode 104. In the present embodiment, by providing the light shielding layer 16 above the lower electrode 14a, the uneven shape A1 can be formed in the inorganic insulating film 15B by using the uneven shape A2 of the light shielding layer 16 in the manufacturing process. it can. Further, the uneven shape A2 of the light shielding layer 16 can be formed by appropriately adjusting the film forming conditions using, for example, a CVD method.

  In addition, in this Embodiment, the uneven | corrugated shape A3 which followed the uneven | corrugated shape A1 is provided in the surface (surface by the side of the upper electrode 18) of the organic photoelectric converting layer 17. FIG. That is, the uneven shape A1 of the light shielding layer 16 is reflected not only on the surface of the inorganic insulating film 15B but also on the surface of the organic photoelectric conversion layer 17. Thereby, the surface area of the interface between the organic photoelectric conversion layer 17 and the upper electrode 18 increases, and the adhesion of the organic photoelectric conversion layer 17 to the upper electrode 18 can also be improved.

  Moreover, since the effect of releasing the shrinkage stress caused by heat or the like is enhanced by the above-described concavo-convex shapes A1 to A3, between the organic photoelectric conversion layer 17 and the inorganic insulating film 15B, or between the organic photoelectric conversion layer 17 and the upper electrode 18 The stress generated during the period is relaxed. Thus, film peeling is also suppressed by the heat dissipation effect of the uneven shapes A1 to A3, and the adhesion is improved.

  As described above, in the present embodiment, the uneven shape A1 is provided in the peripheral region of the opening H of the inorganic insulating film 15B made of an inorganic film on the lower electrode 14a, and the organic photoelectric conversion layer 17 is formed from the inside of the opening A1. By forming over the peripheral region, the adhesion between the inorganic insulating film 15B and the organic photoelectric conversion layer 17 can be improved. Therefore, reliability can be improved.

<Modification>
Next, a modification of the photoelectric conversion element of the above embodiment will be described. In the following, the same components as those in the above embodiment are denoted by the same reference numerals, and the description thereof is omitted as appropriate.

  FIG. 20 illustrates a configuration of a main part of a photoelectric conversion element (photoelectric conversion element 10A) according to a modification. FIG. 21 shows an enlarged part of the photoelectric conversion element 10A. In the above embodiment, the concavo-convex shape A1 of the inorganic insulating film 15B is formed using the concavo-convex shape A2 of the light shielding layer 16, but by patterning the surface of the inorganic insulating film 15 as in this modification, An uneven shape (uneven shape A1a) may be formed. That is, in the above embodiment, film formation is performed so that the surface of the light shielding layer 16 is a rough surface, and the uneven shape A1 is formed following the uneven shape A2 included in the rough surface. For this reason, the arrangement of the concave portions (or convex portions) in the concavo-convex shape A1 is random, but pattern formation is performed directly or regularly on the surface of the inorganic insulating film 15 as in this modification. It may be what was done. In this modification, the light shielding layer (light shielding layer 16A) is provided between the interlayer insulating films 12A and 12B together with the conductive plug 120a2.

  The inorganic insulating film 15 is made of the same material as the inorganic insulating films 15A and 15B of the above embodiment, and has a thickness of, for example, 500 nm to 800 nm. The uneven shape A1a of the inorganic insulating film 15 is formed by arranging a plurality of recesses 15a1. The aspect ratio (width d1 / depth d2) of each recess 15a1 and the interval (pitch) between the recesses 15a1 are designed to appropriate values according to the respective film thicknesses of the inorganic insulating film 15 and the organic photoelectric conversion layer 17. ing. Such a recess 15a1 may be a groove extending in one direction, or may be a hole formed in a matrix. The aspect ratio of the recess 15a1 is preferably set to about 0.25 to 1.0 from the viewpoint of adhesion.

  Such an inorganic insulating film 15 is not particularly shown, but can be formed as follows, for example. That is, after the insulating film made of the above-described material or the like is formed on the lower electrode 14a, the opening H is formed by dry etching using, for example, a photolithography method. Thereafter, a plurality of recesses 15a1 are formed in the peripheral region of the opening H of the insulating film by, for example, dry etching using a photolithography method, thereby forming the uneven shape A1a. Note that the concavo-convex shape A1a may be formed before the opening H or at the same time.

  As in this modification, the concavo-convex shape A1a provided on the surface of the inorganic insulating film 15 may be a pattern formed, and even in this case, the same effect as in the above embodiment can be obtained. Can do.

<Application example 1>
FIG. 22 is a functional block diagram of a solid-state imaging device (solid-state imaging device 1) that uses the photoelectric conversion elements described in the above-described embodiments and modifications for each pixel. The solid-state imaging device 1 is a CMOS image sensor and includes a pixel unit 1a as an imaging area, and includes a circuit unit 130 including, for example, a row scanning unit 131, a horizontal selection unit 133, a column scanning unit 134, and a system control unit 132. Have. The circuit unit 130 may be provided in the peripheral region of the pixel unit 1a or the pixel unit 1a, and may be provided in the peripheral region of the pixel unit 1a, or may be stacked with the pixel unit 1a (opposing the pixel unit 1a). May be provided).

  The pixel unit 1a has, for example, a plurality of unit pixels P (corresponding to the photoelectric conversion element 10) that are two-dimensionally arranged in a matrix. In the unit pixel P, for example, a pixel drive line Lread (specifically, a row selection line and a reset control line) is wired for each pixel row, and a vertical signal line Lsig is wired for each pixel column. The pixel drive line Lread transmits a drive signal for reading a signal from the pixel. One end of the pixel drive line Lread is connected to an output end corresponding to each row of the row scanning unit 131.

  The row scanning unit 131 includes a shift register, an address decoder, and the like, and is a pixel driving unit that drives each pixel P of the pixel unit 1a, for example, in units of rows. A signal output from each pixel P in the pixel row selected and scanned by the row scanning unit 131 is supplied to the horizontal selection unit 133 through each of the vertical signal lines Lsig. The horizontal selection unit 133 is configured by an amplifier, a horizontal selection switch, and the like provided for each vertical signal line Lsig.

  The column scanning unit 134 includes a shift register, an address decoder, and the like, and drives each of the horizontal selection switches of the horizontal selection unit 133 in order while scanning. By the selective scanning by the column scanning unit 134, the signal of each pixel transmitted through each of the vertical signal lines Lsig is sequentially transmitted to the horizontal signal line 135 and output to the outside through the horizontal signal line 135.

  The system control unit 132 receives a clock supplied from the outside, data for instructing an operation mode, and the like, and outputs data such as internal information of the solid-state imaging device 1. The system control unit 132 further includes a timing generator that generates various timing signals. The row scanning unit 131, the horizontal selection unit 133, the column scanning unit 134, and the like are based on the various timing signals generated by the timing generator. Drive control is performed.

<Application example 2>
The solid-state imaging device 1 using the above-described photoelectric conversion element 10 as a pixel is applied to all types of electronic devices having an imaging function, such as a camera system such as a digital still camera and a video camera, and a mobile phone having an imaging function. can do. FIG. 23 shows a schematic configuration of the electronic apparatus 2 (camera) as an example. The electronic device 2 is, for example, a video camera capable of shooting a still image or a moving image, and drives the solid-state imaging device 1, the optical system (optical lens) 310, the shutter device 311, the solid-state imaging device 1 and the shutter device 311. And a signal processing unit 312.

  The optical system 310 guides image light (incident light) from a subject to the pixel unit 1 a of the solid-state imaging device 1. The optical system 310 may be composed of a plurality of optical lenses. The shutter device 311 controls the light irradiation period and the light shielding period for the solid-state imaging device 1. The drive unit 313 controls the transfer operation of the solid-state imaging device 1 and the shutter operation of the shutter device 311. The signal processing unit 312 performs various types of signal processing on the signal output from the solid-state imaging device 1. The video signal Dout after the signal processing is stored in a storage medium such as a memory, or is output to a monitor or the like.

  As described above, the embodiments and modifications have been described, but the present disclosure is not limited to the above-described embodiments and the like, and various modifications can be made. For example, in the said embodiment etc., it was set as the structure which laminated | stacked the organic photoelectric conversion part 11G which detects green light, and the inorganic photoelectric conversion parts 11B and 11R which each detect blue light and red light as a photoelectric conversion element. However, the present disclosure is not limited to such a structure. That is, red light or blue light may be detected in the organic photoelectric conversion unit, or green light may be detected in the inorganic photoelectric conversion unit. Further, the number and ratio of these organic photoelectric conversion units and inorganic photoelectric conversion units are not limited, and two or more organic photoelectric conversion units may be provided. A signal may be obtained. In addition, the organic photoelectric conversion unit and the inorganic photoelectric conversion unit are not limited to a structure in which the organic photoelectric conversion unit and the inorganic photoelectric conversion unit are stacked in the vertical direction.

  In the above embodiment and the like, the light shielding layer 16 having the concavo-convex shape A2 is provided above the lower electrode 14a. However, the light shielding layer 16 is in the same layer as the lower electrode 14a (on the interlayer insulating film 12B). It may be provided. That is, the formation position of the light shielding layer 16 is not particularly limited as long as the uneven shape can be reflected on the surface of the inorganic insulating film 15B in contact with the organic photoelectric conversion layer 17. However, it is desirable that the light shielding layer 16 is provided directly below the inorganic insulating film 15B as in the above embodiment and the like because the uneven shape A1 is easily reflected.

  Furthermore, the photoelectric conversion element of the present disclosure does not have to include all the constituent elements described in the above-described embodiments and the like, and conversely, may include other layers.

The present disclosure may be configured as follows.
(1)
A first electrode;
An inorganic insulating film provided on the first electrode, having an opening, and having a first concavo-convex shape in a peripheral region of the opening;
On the inorganic insulating film, an organic photoelectric conversion layer formed from the inside of the opening to the peripheral region of the opening;
A photoelectric conversion element comprising: a second electrode provided on the organic photoelectric conversion layer.
(2)
A light shielding layer having a second uneven shape in a region between the inorganic insulating film and the substrate and in the peripheral region of the opening;
The photoelectric conversion element according to (1), wherein the first uneven shape of the inorganic insulating film is formed following the second uneven shape of the light shielding layer.
(3)
The photoelectric conversion element according to (2), wherein the light shielding layer has a rough surface including the second uneven shape on a surface on the inorganic insulating film side.
(4)
The photoelectric conversion element according to (2) or (3), wherein the light shielding layer and the inorganic insulating film are provided in this order through another insulating film in a peripheral region of the opening on the first electrode. .
(5)
Said 1st uneven | corrugated shape is the photoelectric conversion element in any one of said (1)-(4) comprised by the some groove | channel or several hole provided in the said organic photoelectric converting layer side.
(6)
The organic photoelectric conversion layer has a third concavo-convex shape formed on the surface on the second electrode side, following the first concavo-convex shape, in the peripheral region of the opening. (1) to (5) The photoelectric conversion element in any one of.
(7)
The organic photoelectric conversion layer performs green light photoelectric conversion,
In the substrate, an inorganic photoelectric conversion unit that performs photoelectric conversion of blue light and an inorganic photoelectric conversion unit that performs photoelectric conversion of red light are stacked. The photoelectric according to any one of (1) to (6) above. Conversion element.
(8)
Forming a first electrode;
Forming an inorganic insulating film having an opening on the first electrode and having a first concavo-convex shape in a peripheral region of the opening;
Forming an organic photoelectric conversion layer on the inorganic insulating film from the inside of the opening to the peripheral region of the opening; and
Forming a second electrode on the organic photoelectric conversion layer. A method for manufacturing a photoelectric conversion element.
(9)
Forming a light-shielding layer having a second concavo-convex shape in a region between the inorganic insulating film and the substrate and in the peripheral region of the opening;
The manufacturing method of the photoelectric conversion element according to (8), wherein the first uneven shape of the inorganic insulating film is formed following the second uneven shape of the light shielding layer.
(10)
In the step of forming the light shielding layer, the rough surface including the second concavo-convex shape is formed on the surface of the light shielding layer on the inorganic insulating film side. The method for manufacturing a photoelectric conversion element according to (9) above.
(11)
The method for producing a photoelectric conversion element according to (10), wherein the rough surface is formed by forming the light shielding layer using a CVD (Chemical Vapor Deposition) method.
(12)
The method for manufacturing a photoelectric conversion element according to (9) or (10), wherein the light shielding layer and the inorganic insulating film are formed in this order through another insulating film in a peripheral region of the opening on the first electrode. .
(13)
In the step of forming the inorganic insulating film,
The manufacturing method of the photoelectric conversion element according to any one of (8) to (12), wherein a plurality of grooves or a plurality of holes are formed on the surface on the organic photoelectric conversion layer side as the first uneven shape.
(14)
The method for manufacturing a photoelectric conversion element according to (13), wherein the groove or hole is formed by etching using a photolithography method.
(15)
In the step of forming the organic photoelectric conversion layer,
In the peripheral region of the opening, a third concavo-convex shape formed in accordance with the first concavo-convex shape is formed on the surface on the second electrode side. The method according to any one of (8) to (14) above. A method for producing a photoelectric conversion element.
(16)
Including a photoelectric conversion element as a pixel,
The photoelectric conversion element is
A first electrode;
An inorganic insulating film provided on the first electrode, having an opening, and having a first concavo-convex shape in a peripheral region of the opening;
On the inorganic insulating film, an organic photoelectric conversion layer formed from the inside of the opening to the peripheral region of the opening;
A solid-state imaging device comprising: a second electrode provided on the organic photoelectric conversion layer.
(17)
A solid-state imaging device including a photoelectric conversion element as a pixel,
The photoelectric conversion element is
A first electrode;
An inorganic insulating film provided on the first electrode, having an opening, and having a first concavo-convex shape in a peripheral region of the opening;
On the inorganic insulating film, an organic photoelectric conversion layer formed from the inside of the opening to the peripheral region of the opening;
An electronic device comprising: a second electrode provided on the organic photoelectric conversion layer.

  DESCRIPTION OF SYMBOLS 10 ... Photoelectric conversion element, 11 ... Semiconductor substrate, 11G ... Organic photoelectric conversion part, 11B, 11R ... Inorganic photoelectric conversion part, 12A, 12B ... Interlayer insulation film, 13a ... Wiring layer, 14a ... Lower electrode, 15a, 15b, 15 Inorganic insulating film 16, 16A ... Light shielding layer, 17 ... Organic photoelectric conversion layer, 18 ... Upper electrode, 19 ... Protective layer, 20 ... Planarization layer, 21 ... On-chip lens, 110 ... Silicon layer, 110G ... For green Storage layer, 120a1, 120a2 ... conductive plug, 51 ... multilayer wiring layer, 53 ... support substrate, A1 to A3, A1a ... uneven shape, 1 ... solid-state imaging device, 2 ... electronic equipment.

Claims (17)

A first electrode;
An inorganic insulating film provided on the first electrode, having an opening, and having a first concavo-convex shape in a peripheral region of the opening;
On the inorganic insulating film, an organic photoelectric conversion layer formed from the inside of the opening to the peripheral region of the opening;
A photoelectric conversion element comprising: a second electrode provided on the organic photoelectric conversion layer. A light shielding layer having a second uneven shape in a region between the inorganic insulating film and the substrate and in the peripheral region of the opening;
The photoelectric conversion element according to claim 1, wherein the first uneven shape of the inorganic insulating film is formed following the second uneven shape of the light shielding layer. The photoelectric conversion element according to claim 2, wherein the light shielding layer has a rough surface including the second uneven shape on a surface on the inorganic insulating film side. The photoelectric conversion element according to claim 2, wherein the light shielding layer and the inorganic insulating film are provided in this order through another insulating film in a peripheral region of the opening on the first electrode. The photoelectric conversion element according to claim 1, wherein the first uneven shape includes a plurality of grooves or a plurality of holes provided on the organic photoelectric conversion layer side. 2. The photoelectric conversion according to claim 1, wherein the organic photoelectric conversion layer has a third concavo-convex shape formed on the surface on the second electrode side following the first concavo-convex shape in a peripheral region of the opening. element. The organic photoelectric conversion layer performs green light photoelectric conversion,
The photoelectric conversion element according to claim 1, wherein an inorganic photoelectric conversion unit that performs photoelectric conversion of blue light and an inorganic photoelectric conversion unit that performs photoelectric conversion of red light are stacked in the substrate. Forming a first electrode;
Forming an inorganic insulating film having an opening on the first electrode and having a first concavo-convex shape in a peripheral region of the opening;
Forming an organic photoelectric conversion layer on the inorganic insulating film from the inside of the opening to the peripheral region of the opening; and
Forming a second electrode on the organic photoelectric conversion layer. A method for manufacturing a photoelectric conversion element. Forming a light-shielding layer having a second concavo-convex shape in a region between the inorganic insulating film and the substrate and in the peripheral region of the opening;
The manufacturing method of the photoelectric conversion element according to claim 8, wherein the first uneven shape of the inorganic insulating film is formed following the second uneven shape of the light shielding layer. The method for manufacturing a photoelectric conversion element according to claim 9, wherein in the step of forming the light shielding layer, a rough surface including the second uneven shape is formed on a surface of the light shielding layer on the inorganic insulating film side. The method for producing a photoelectric conversion element according to claim 10, wherein the rough surface is formed by forming the light shielding layer using a CVD (Chemical Vapor Deposition) method. The method for manufacturing a photoelectric conversion element according to claim 9, wherein the light shielding layer and the inorganic insulating film are formed in this order through another insulating film in a peripheral region of the opening on the first electrode. In the step of forming the inorganic insulating film,
The method for manufacturing a photoelectric conversion element according to claim 8, wherein a plurality of grooves or a plurality of holes are formed on the surface on the organic photoelectric conversion layer side as the first uneven shape. The method for manufacturing a photoelectric conversion element according to claim 13, wherein the groove or hole is formed by etching using a photolithography method. In the step of forming the organic photoelectric conversion layer,
The method for manufacturing a photoelectric conversion element according to claim 8, wherein a third uneven shape formed following the first uneven shape is formed on a surface on the second electrode side in a peripheral region of the opening. Including a photoelectric conversion element as a pixel,
The photoelectric conversion element is
A first electrode;
An inorganic insulating film provided on the first electrode, having an opening, and having a first concavo-convex shape in a peripheral region of the opening;
On the inorganic insulating film, an organic photoelectric conversion layer formed from the inside of the opening to the peripheral region of the opening;
A solid-state imaging device comprising: a second electrode provided on the organic photoelectric conversion layer. A solid-state imaging device including a photoelectric conversion element as a pixel,
The photoelectric conversion element is
A first electrode;
An inorganic insulating film provided on the first electrode, having an opening, and having a first concavo-convex shape in a peripheral region of the opening;
On the inorganic insulating film, an organic photoelectric conversion layer formed from the inside of the opening to the peripheral region of the opening;
An electronic device comprising: a second electrode provided on the organic photoelectric conversion layer.

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