Image pickup element, stacked image pickup element, and solid-state image pickup device

Abstract

An imaging device is provided that has a configuration and structure that enables more reliable transfer of charges accumulated in a photoelectric conversion layer to a first electrode during charge transfer. [Solution] The imaging element comprises a first electrode (11), a charge storage electrode (14) spaced apart from the first electrode (11), a photoelectric conversion layer (13) in contact with the first electrode (11) and formed above the charge storage electrode (14) via an insulating layer, and a second electrode (12) formed on the photoelectric conversion layer (13), and the portion of the insulating layer located between the charge storage electrode (14) and the photoelectric conversion layer (13) has a first region (82a1) and a second region (82a2), the portion of the insulating layer occupying the first region (82a1) is made of a first insulating layer (82A1), and the portion of the insulating layer occupying the second region (82a2) is made of a second insulating layer (82A2), and the absolute value of the fixed charge of the material composing the second insulating layer (82A2) is smaller than the absolute value of the fixed charge of the material composing the first insulating layer (82A1).

Description

[Technical field]

[0001] The present disclosure relates to an imaging element, a stacked imaging element, and a solid-state imaging device. [Background technology]

[0002] An imaging element using an organic semiconductor material for the photoelectric conversion layer is capable of photoelectrically converting a specific color (wavelength band). Because of this characteristic, when used as an imaging element in a solid-state imaging device, it is possible to obtain a structure in which sub-pixels are stacked (stacked imaging element) that is not possible in conventional solid-state imaging devices, in which sub-pixels are formed by combining an on-chip color filter (OCCF) and an imaging element, and the sub-pixels are arranged two-dimensionally (see, for example, JP 2011-138927 A). In addition, since demosaicing is not required, there is an advantage that false colors do not occur. In the following description, an imaging element having a photoelectric conversion unit provided on or above a semiconductor substrate is conveniently referred to as a "first type imaging element," a photoelectric conversion unit constituting the first type imaging element is conveniently referred to as a "first type photoelectric conversion unit," an imaging element provided in a semiconductor substrate is conveniently referred to as a "second type imaging element," and a photoelectric conversion unit constituting the second type imaging element is conveniently referred to as a "second type photoelectric conversion unit."

[0003] FIG. 95 shows a structural example of a stacked type imaging element (stacked type solid-state imaging device) disclosed in JP 2017-157816 A. In the example shown in FIG. 95, a third photoelectric conversion unit 331 and a second photoelectric conversion unit 321 which are second type photoelectric conversion units constituting a third imaging element 330 and a second imaging element 320 which are second type imaging elements are stacked and formed in a semiconductor substrate 370. In addition, a first photoelectric conversion unit 310' which is a first type photoelectric conversion unit is disposed above the semiconductor substrate 370 (specifically, above the second imaging element 320). Here, the first photoelectric conversion unit 310' includes a first electrode 311, a photoelectric conversion layer 313 made of an organic material, and a second electrode 312, and constitutes the first imaging element 310 which is a first type imaging element. A charge storage electrode 314 is provided spaced apart from the first electrode 311, and a photoelectric conversion layer 313 is located above the charge storage electrode 314 via an insulating layer 382. In the second photoelectric conversion section 321 and the third photoelectric conversion section 331, for example, blue light and red light are photoelectrically converted, respectively, due to differences in absorption coefficients. In the first photoelectric conversion section 310', for example, green light is photoelectrically converted.

[0004] The charges generated by photoelectric conversion in the second photoelectric conversion section 321 and the third photoelectric conversion section 331 are temporarily stored in the second photoelectric conversion section 321 and the third photoelectric conversion section 331, and then transferred to the second floating diffusion layer FD2 and the third floating diffusion layer FD3 by the vertical transistor (gate section 322 is shown) and the transfer transistor (gate section 332 is shown), respectively, and further output to an external read circuit (not shown). These transistors and the floating diffusion layers FD2 and FD3 are also formed on the semiconductor substrate 370.

[0005] During charge accumulation, the charge generated by photoelectric conversion in the first photoelectric conversion section 310' is attracted to the charge accumulation electrode 314 and accumulated in the photoelectric conversion layer 313. During charge transfer, the charge accumulated in the photoelectric conversion layer 313 is accumulated in a first floating diffusion layer FD1 formed in the semiconductor substrate 370 via the first electrode 311, the contact hole section 361, and the wiring layer 362. The first photoelectric conversion section 310' is also connected, via the contact hole section 361 and the wiring layer 362, to a gate section 318 of an amplifying transistor that converts the amount of charge into a voltage. The first floating diffusion layer FD1 constitutes a part of a reset transistor (gate section 317 is shown). Reference numeral 371 denotes an element isolation region, reference numeral 372 denotes an oxide film formed on the surface of the semiconductor substrate 370, reference numerals 376 and 381 denote interlayer insulating layers, reference numeral 383 denotes a protective layer, and reference numeral 390 denotes an on-chip microlens. Reference numerals 63, 64, 65, 66, and 81 will be described in the sixth embodiment. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2017-157816 A Summary of the Invention [Problem to be solved by the invention]

[0007] Although the imaging element disclosed in the above-mentioned patent publication has excellent characteristics, there is a demand for more reliable transfer of the charges accumulated in the photoelectric conversion layer 313 to the first electrode 311 during charge transfer.

[0008] Therefore, an object of the present disclosure is to provide an imaging element having a configuration and structure that enables more reliable transfer of charges accumulated in a photoelectric conversion layer to a first electrode during charge transfer, a stacked imaging element composed of such an imaging element, and a solid-state imaging device including such an imaging element or a stacked imaging element. [Means for solving the problem]

[0009] In order to achieve the above object, an image sensor according to a first aspect of the present disclosure includes: first electrode, a charge storage electrode disposed spaced apart from the first electrode; a photoelectric conversion layer in contact with the first electrode and formed above the charge storage electrode with an insulating layer interposed therebetween; and A second electrode formed on the photoelectric conversion layer; Equipped with a portion of the insulating layer located between the charge storage electrode and the photoelectric conversion layer has a first region and a second region; the portion of the insulating layer occupying the first region comprises a first insulating layer; the portion of the insulating layer occupying the second region comprises a second insulating layer; The absolute value of the fixed charge of the material constituting the second insulating layer is smaller than the absolute value of the fixed charge of the material constituting the first insulating layer.

[0010] In order to achieve the above object, an image sensor according to a second aspect of the present disclosure includes: first electrode, a charge storage electrode disposed spaced apart from the first electrode; a photoelectric conversion layer in contact with the first electrode and formed above the charge storage electrode with an insulating layer interposed therebetween; and A second electrode formed on the photoelectric conversion layer; Equipped with an insulating material layer is provided between the first electrode and the charge storage electrode; The material constituting the insulating material layer has a polarity different from the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode.

[0011] In order to achieve the above object, an image sensor according to a third aspect of the present disclosure includes: first electrode, a charge storage electrode disposed spaced apart from the first electrode; a photoelectric conversion layer in contact with the first electrode and formed above the charge storage electrode with an insulating layer interposed therebetween; and A second electrode formed on the photoelectric conversion layer; Equipped with an insulating material layer is provided in contact with at least a part of a portion of the charge storage electrode that does not face the first electrode; The material constituting the insulating material layer has the same polarity as the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode.

[0012] In order to achieve the above object, a stacked imaging element of the present disclosure includes at least one imaging element according to the first to third aspects of the present disclosure.

[0013] A solid-state imaging device according to a first aspect of the present disclosure for achieving the above object includes a plurality of imaging elements according to the first to third aspects of the present disclosure. Also, a solid-state imaging device according to a second aspect of the present disclosure for achieving the above object includes a plurality of stacked imaging elements according to the present disclosure. [Brief description of the drawings]

[0014] [Figure 1] 1A and 1B are schematic partial cross-sectional views of an image sensor according to a first embodiment and a modification thereof. [Diagram 2] FIG. 2 is a diagram illustrating a schematic arrangement of a first electrode, an insulating layer, and the like in the image sensor of the first embodiment. [Diagram 3] 3A and 3B are schematic partial cross-sectional views of an image sensor according to a second embodiment and a modified example thereof, and FIG. 3C is a schematic partial cross-sectional view of an image sensor according to a third embodiment. [Figure 4] FIG. 4 is a diagram illustrating a schematic arrangement of a first electrode, an insulating layer, and the like in an image sensor according to a second embodiment. [Diagram 5] FIG. 5 is a diagram illustrating a schematic arrangement of a first electrode, an insulating layer, and the like in an image sensor according to a third embodiment. [Figure 6] 6A and 6B are schematic partial cross-sectional views of an image sensor according to a fourth embodiment and a modification thereof. [Figure 7] FIG. 7 is a diagram illustrating a schematic arrangement of a first electrode, an insulating layer, and the like in an image sensor according to a fourth embodiment. [Figure 8]8A and 8B are schematic partial cross-sectional views of an image sensor according to a fifth embodiment and a modification thereof. [Figure 9] FIG. 9 is a diagram illustrating a schematic arrangement relationship between the first electrode, the insulating layer, and the like in the image sensor of the fifth embodiment illustrated in FIG. 8A. In FIG. [Figure 10] FIG. 10 is a diagram illustrating a schematic arrangement of a first electrode, an insulating layer, and the like in a modified example of the imaging element of Example 5 shown in FIG. 8B (a combination of the imaging element of Example 4 and the imaging element of Example 5). [Figure 11] FIG. 11 is a schematic cross-sectional view of a portion of an imaging element (two imaging elements arranged side by side) of Example 6. In FIG. [Figure 12] FIG. 12 is a schematic partial cross-sectional view of an imaging element, a stacked imaging element, according to a sixth embodiment. [Figure 13] FIG. 13 is an equivalent circuit diagram of the imaging element, the stacked-type imaging element, of the sixth embodiment. [Figure 14] FIG. 14 is an equivalent circuit diagram of the imaging element, the stacked-type imaging element, of the sixth embodiment. [Figure 15] FIG. 15 is a schematic layout diagram of a first electrode and a charge storage electrode constituting an image sensor according to a sixth embodiment, and a transistor constituting a control unit. [Figure 16] FIG. 16 is a schematic layout diagram of the first electrodes and charge storage electrodes constituting the image sensor of the sixth embodiment. [Figure 17] FIG. 17 is a schematic layout diagram of a modification (Modification 1 of the Sixth Embodiment) of the first electrode and the charge storage electrode constituting the image sensor of the Sixth Embodiment. [Figure 18] FIG. 18 is a diagram showing a schematic diagram of a potential state at each portion during operation of the image pickup device of Example 6. In FIG. [Figure 19] 19A, 19B, and 19C are equivalent circuit diagrams of the imaging element and the stacked imaging element of Examples 6, 10, and 11 to explain the respective parts of FIG. 18 (Example 6), FIG. 46 (Example 10), and FIG. 53 (Example 11). [Figure 20] FIG. 20 is a conceptual diagram of a solid-state imaging device according to the sixth embodiment. [Figure 21]FIG. 21 is an equivalent circuit diagram of the imaging element of the sixth embodiment and a modified example (modification 2 of the sixth embodiment) of the stacked imaging element. [Figure 22] FIG. 22 is a schematic layout diagram of a first electrode and a charge storage electrode constituting a modification (Modification 2 of Example 6) of the image sensor of Example 6 shown in FIG. 21, and a transistor constituting a control unit. [Figure 23] FIG. 23 is a schematic layout diagram of a modification (Modification 3 of Example 6) of the first electrodes and charge accumulation electrodes constituting the image sensor of Example 6. In FIG. [Figure 24] FIG. 24 is a schematic layout diagram of a modification (Modification 4 of Example 6) of the first electrodes and charge storage electrodes constituting the image sensor of Example 6. In FIG. [Diagram 25] FIG. 25 is a schematic layout diagram of a modification (Modification 5 of Example 6) of the first electrodes and charge accumulation electrodes constituting the image sensor of Example 6. In FIG. [Figure 26] FIG. 26 is a schematic cross-sectional view of a modification (Modification 6 of Example 6) of the imaging element (two imaging elements arranged side by side) of Example 6. [Figure 27] FIG. 27 is a schematic cross-sectional view of a portion of an imaging element (two imaging elements arranged side by side) of Example 7. In FIG. [Figure 28] FIG. 28 is a schematic plan view of a portion of the imaging element (2×2 imaging elements arranged side by side) of the seventh embodiment. [Figure 29] FIG. 29 is a schematic plan view of a part of a modified example (modification 1 of embodiment 7) of the imaging element (2×2 imaging elements arranged side by side) of embodiment 7. In FIG. [Diagram 30] 30A and 30B are schematic plan views of a part of a modification (Modification 2 of Example 7) of the imaging element of Example 7. FIG. [Diagram 31] 31A and 31B are schematic plan views of a part of a modification (Modification 3 of Example 7) of the imaging element of Example 7. FIG. [Diagram 32] 32A and 32B are schematic cross-sectional views of a portion of modified examples (modified examples 4A and 4B of the seventh embodiment) of the imaging element (two imaging elements arranged side by side) of the seventh embodiment. [Diagram 33]33A and 33B are schematic plan views of a portion of a modification (Modification 4A of Example 7) of the imaging element of Example 7. FIG. [Diagram 34] 34A and 34B are schematic plan views of a portion of a modification of the imaging element of the seventh embodiment (Modification 4B of the seventh embodiment). [Diagram 35] 35A and 35B are schematic plan views of a portion of a modification of the imaging element of the seventh embodiment (Modification 4C of the seventh embodiment). [Diagram 36] 36A and 36B are schematic plan views of a portion of a modification (Modification 4D of Example 7) of the imaging element of Example 7. FIG. [Figure 37] FIG. 37 is a schematic partial cross-sectional view of an imaging element, a stacked imaging element, according to an eighth embodiment. [Figure 38] FIG. 38 is a schematic partial cross-sectional view of an imaging element, a stacked imaging element, according to a ninth embodiment. [Figure 39] FIG. 39 is a schematic partial cross-sectional view of a modified example of the imaging element of the ninth embodiment, the stack-type imaging element. [Diagram 40] FIG. 40 is a schematic partial cross-sectional view of another modified example of the image pickup element of the ninth embodiment. [Diagram 41] FIG. 41 is a schematic partial cross-sectional view of still another modified example of the image pickup element of the ninth embodiment. [Diagram 42] FIG. 42 is a schematic partial cross-sectional view of a part of the imaging element, the stack-type imaging element, of Example 10. In FIG. [Diagram 43] FIG. 43 is an equivalent circuit diagram of the imaging element, the stacked-type imaging element, of the tenth embodiment. [Diagram 44] FIG. 44 is an equivalent circuit diagram of the imaging element, the stacked-type imaging element, of the tenth embodiment. [Diagram 45] FIG. 45 is a schematic layout diagram of the first electrode, the transfer control electrode, and the charge storage electrode constituting the image sensor of the tenth embodiment, as well as transistors constituting the control section. [Diagram 46] FIG. 46 is a diagram showing a schematic diagram of the state of electric potential at each portion during operation of the image pickup device of Example 10. In FIG. [Figure 47]FIG. 47 is a diagram showing a schematic diagram of the state of electric potential at each portion during another operation of the image pickup device of Example 10. In FIG. [Figure 48] FIG. 48 is a schematic layout diagram of the first electrode, the transfer control electrode, and the charge storage electrode constituting the modified image sensor of the tenth embodiment, as well as transistors constituting the control section. [Figure 49] FIG. 49 is a schematic partial cross-sectional view of a part of the imaging element, the stack-type imaging element, of Example 11. In FIG. [Figure 50] FIG. 50 is an equivalent circuit diagram of the imaging element, the stacked-type imaging element, of the eleventh embodiment. [Figure 51] FIG. 51 is an equivalent circuit diagram of the imaging element, the stacked-type imaging element, of the eleventh embodiment. [Figure 52] FIG. 52 is a schematic layout diagram of a first electrode and a charge storage electrode constituting the image sensor of the eleventh embodiment, and a transistor constituting the control unit. [Figure 53] FIG. 53 is a diagram showing a schematic diagram of the state of electric potential at each portion during operation of the image pickup device of Example 11. In FIG. [Figure 54] FIG. 54 is a diagram showing a schematic diagram of the state of potential at each portion during another operation (charge transfer) of the image sensor of Example 11. In FIG. [Figure 55] FIG. 55 is a schematic layout diagram of the first electrodes and charge storage electrodes constituting a modified example of the image sensor of the eleventh embodiment. [Figure 56] FIG. 56 is a schematic partial cross-sectional view of an imaging element, a stacked imaging element, of Example 12. [Figure 57] FIG. 57 is a schematic partial cross-sectional view enlarging a portion where a charge storage electrode, a photoelectric conversion layer, and a second electrode are laminated in the image sensor of Example 12. As shown in FIG. [Figure 58] FIG. 58 is a schematic layout diagram of a first electrode and a charge storage electrode constituting a modified example of the image sensor of the twelfth embodiment, and a transistor constituting a control unit. [Figure 59] FIG. 59 is a schematic partial cross-sectional view enlarging a portion where a charge storage electrode, a photoelectric conversion layer, and a second electrode are laminated in the image sensor of Example 13. As shown in FIG. [Figure 60] FIG. 60 is a schematic partial cross-sectional view of an imaging element, a stacked imaging element, of Example 14. [Figure 61] FIG. 61 is a schematic partial cross-sectional view of the imaging element and the stacked imaging element according to the fifteenth and sixteenth embodiments. [Figure 62] 62A and 62B are schematic plan views of a charge storage electrode segment in Example 16. [Figure 63] 63A and 63B are schematic plan views of a charge storage electrode segment in Example 16. [Figure 64] FIG. 64 is a schematic layout diagram of the first electrode and charge storage electrode constituting the image sensor of the sixteenth embodiment, and the transistors constituting the control section. [Figure 65] FIG. 65 is a schematic layout diagram of the first electrodes and charge storage electrodes constituting a modified example of the image sensor of the sixteenth embodiment. [Figure 66] FIG. 66 is a schematic partial cross-sectional view of the imaging elements and stacked imaging element of Examples 17 and 16. [Figure 67] 67A and 67B are schematic plan views of a charge storage electrode segment in Example 17. [Figure 68] FIG. 68 is a schematic plan view of a first electrode and a charge storage electrode segment in a solid-state imaging device according to an eighteenth embodiment. [Figure 69] FIG. 69 is a schematic plan view of a first electrode and a charge storage electrode segment in a first modified example of the solid-state imaging device of the eighteenth embodiment. [Figure 70] FIG. 70 is a schematic plan view of a first electrode and a charge storage electrode segment in a second modified example of the solid-state imaging device of the eighteenth embodiment. [Figure 71] FIG. 71 is a schematic plan view of a first electrode and a charge storage electrode segment in a third modified example of the solid-state imaging device according to the eighteenth embodiment. [Figure 72] FIG. 72 is a schematic plan view of a first electrode and a charge storage electrode segment in a fourth modified example of the solid-state imaging device of the eighteenth embodiment. [Figure 73]FIG. 73 is a schematic plan view of a first electrode and a charge storage electrode segment in a fifth modified example of the solid-state imaging device of the eighteenth embodiment. [Figure 74] FIG. 74 is a schematic plan view of a first electrode and a charge storage electrode segment in a sixth modified example of the solid-state imaging device according to the eighteenth embodiment. [Figure 75] FIG. 75 is a schematic plan view of a first electrode and a charge storage electrode segment in a seventh modified example of the solid-state imaging device according to the eighteenth embodiment. [Figure 76] FIG. 76 is a schematic plan view of a first electrode and a charge storage electrode segment in an eighth modification of the solid-state imaging device according to the eighteenth embodiment. [Figure 77] FIG. 77 is a schematic plan view of a first electrode and a charge storage electrode segment in a ninth modification of the solid-state imaging device according to the eighteenth embodiment. [Figure 78] 78A, 78B, and 78C are charts showing an example of readout driving in the image sensor block of the eighteenth embodiment. [Figure 79] FIG. 79 is a schematic plan view of a first electrode and a charge storage electrode segment in a solid-state imaging device according to a nineteenth embodiment. [Figure 80] FIG. 80 is a schematic plan view of a first electrode and a charge storage electrode segment in a modified example of the solid-state imaging device of the nineteenth embodiment. [Figure 81] FIG. 81 is a schematic plan view of a first electrode and a charge storage electrode segment in a modified example of the solid-state imaging device of the nineteenth embodiment. [Figure 82] FIG. 82 is a schematic plan view of a first electrode and a charge storage electrode segment in a modified example of the solid-state imaging device of the nineteenth embodiment. [Figure 83] FIG. 83 is a schematic partial cross-sectional view of another modified example of the imaging element of the sixth embodiment, the stack-type imaging element. [Figure 84] FIG. 84 is a schematic partial cross-sectional view of still another modified example of the imaging element of the stacked imaging element according to the sixth embodiment. [Figure 85]85A, 85B, and 85C are enlarged schematic partial cross-sectional views of a portion of a first electrode and the like of the imaging element of Example 6 and still another modified example of the stack-type imaging element. [Figure 86] FIG. 86 is a schematic partial cross-sectional view of still another modified example of the imaging element of the stacked imaging element according to the sixth embodiment. [Figure 87] FIG. 87 is a schematic partial cross-sectional view of still another modified example of the imaging element, the stack-type imaging element, of Example 6. [Figure 88] FIG. 88 is a schematic partial cross-sectional view of still another modified example of the imaging element, the stack-type imaging element, of Example 6. [Figure 89] FIG. 89 is a schematic partial cross-sectional view of another modified example of the imaging element of the tenth embodiment, the stack-type imaging element. [Figure 90] FIG. 90 is a schematic partial cross-sectional view of still another modified example of the imaging element, the stack-type imaging element, of the sixth embodiment. [Figure 91] FIG. 91 is a schematic partial cross-sectional view of still another modified example of the imaging element, the stack-type imaging element, of the sixth embodiment. [Figure 92] FIG. 92 is a schematic partial cross-sectional view enlarging a portion where a charge storage electrode, a photoelectric conversion layer, and a second electrode are laminated in a modified example of the image sensor of Example 12. As shown in FIG. [Figure 93] FIG. 93 is a schematic partial cross-sectional view enlarging a portion where a charge storage electrode, a photoelectric conversion layer, and a second electrode are laminated in a modified example of the image sensor of Example 13. As shown in FIG. [Figure 94] FIG. 94 is a conceptual diagram of an example in which the imaging element of the present disclosure, a solid-state imaging device constituted by a stacked imaging element, is used in an electronic device (camera). [Figure 95] FIG. 95 is a conceptual diagram of a conventional stacked type imaging element (stacked type solid-state imaging device). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, the present disclosure will be described based on examples with reference to the drawings, but the present disclosure is not limited to the examples, and various numerical values ​​and materials in the examples are merely examples. The description will be made in the following order. 1. General Description of the Imaging Element, the Stacked Imaging Element, and the Solid-State Imaging Device According to the First to Third Aspects of the Present Disclosure 2. Example 1 (Image sensor according to the first embodiment of the present disclosure, and image sensor according to the first-A embodiment of the present disclosure) 3. Example 2 (Image sensor according to aspect 1-B of the present disclosure) 4. Example 3 (Image sensor according to aspect 1-C of the present disclosure) 5. Example 4 (Image sensor according to the second aspect of the present disclosure) 6. Example 5 (Image sensor according to the third aspect of the present disclosure) 7. Example 6 (Stacked imaging element of the present disclosure and solid-state imaging device according to the second aspect of the present disclosure) 8. Example 7 (Stacked imaging element of the present disclosure and solid-state imaging device according to the second aspect of the present disclosure) 9. Example 8 (Modification of the image sensor of Examples 6 to 7) 10. Example 9 (Modifications of Examples 6 to 8, Solid-state Imaging Device According to the First Aspect of the Present Disclosure) 11. Example 10 (Modification of Examples 6 to 9, Image Sensor Having Transfer Control Electrodes) 12. Example 11 (Modification of Examples 6 to 10, Imaging device having a plurality of charge storage electrode segments) 13. Example 12 (Image sensor having first and sixth configurations) 14. Example 13 (Image sensor having the second and sixth configurations of the present disclosure) 15. Example 14 (Image sensor having third configuration) 16. Example 15 (Image sensor having fourth configuration) 17. Example 16 (Fifth Configuration Image Sensor) 18. Example 17 (Image sensor having sixth configuration) 19. Example 18 (Solid-state imaging device with first and second configurations) 20. Example 19 (Modification of Example 18) 21.Other

[0016] <General Description of the Imaging Element, the Stacked Imaging Element, and the Solid-State Imaging Device According to the First to Third Aspects of the Present Disclosure> The imaging element according to the first aspect of the present disclosure, the imaging element according to the first aspect of the present disclosure constituting the stacked imaging element, and the imaging element according to the first aspect of the present disclosure constituting the solid-state imaging device according to the first aspect to the second aspect of the present disclosure may be collectively referred to as "the imaging element according to the first aspect of the present disclosure, etc." below. Also, the imaging element according to the second aspect of the present disclosure, the imaging element according to the second aspect of the present disclosure constituting the stacked imaging element, and the imaging element according to the second aspect of the present disclosure constituting the solid-state imaging device according to the first aspect to the second aspect of the present disclosure may be collectively referred to as "the imaging element according to the second aspect of the present disclosure, etc." below. Furthermore, the imaging element according to the third aspect of the present disclosure, the imaging element according to the third aspect of the present disclosure constituting the stacked imaging element, and the imaging element according to the third aspect of the present disclosure constituting the solid-state imaging device according to the first aspect to the second aspect of the present disclosure may be collectively referred to as "the imaging element according to the third aspect of the present disclosure, etc." below.

[0017] In the imaging element according to the first aspect of the present disclosure, The second region is located opposite the first electrode, The first region can be adjacent to the second region. For convenience, an imaging element according to the first aspect of the present disclosure having such a configuration may be referred to as an "imaging element according to aspect 1-A of the present disclosure." In the imaging element according to aspect 1-A of the present disclosure, the material constituting the first insulating layer can have the same polarity as the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode, and further, The carriers sent to the first electrode are electrons, the first insulating layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide; The second insulating layer may be made of silicon oxide. In these cases, a second insulating layer extension portion extending from the second insulating layer may be formed between the first insulating layer and the photoelectric conversion layer. When the carriers sent to the first electrode are holes, the first insulating layer is made of silicon oxynitride or silicon nitride; The second insulating layer may take the form of silicon oxide.

[0018] When the area of ​​the first region is S1 and the area of ​​the second region is S2, in the image sensor according to the first-A aspect of the present disclosure, 0.1≦S2 / (S1+S2)≦0.9 It is preferable to satisfy the following:

[0019] Alternatively, in the imaging element according to the first aspect of the present disclosure, The first region is located opposite the first electrode, The second region may be located adjacent to the first region. For convenience, an imaging element or the like according to the first aspect of the present disclosure in this form may be referred to as "an imaging element or the like according to aspect 1-B of the present disclosure." In the imaging element or the like according to aspect 1-B of the present disclosure, the material constituting the first insulating layer may be configured to have a polarity different from the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode, and further, The carriers sent to the first electrode are electrons, the first insulating layer is made of silicon oxynitride or silicon nitride; The second insulating layer may be made of silicon oxide. In these cases, a second insulating layer extension portion extending from the second insulating layer may be formed between the first insulating layer and the photoelectric conversion layer. When the carriers sent to the first electrode are holes, the first insulating layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide; The second insulating layer may take the form of silicon oxide.

[0020] In the imaging element according to the first-B aspect of the present disclosure, 0.1≦S2 / (S1+S2)≦0.9 It is preferable to satisfy the following:

[0021] Alternatively, in the imaging element according to the first aspect of the present disclosure, The portion of the insulating layer located between the charge storage electrode and the photoelectric conversion layer further includes a third region, The first region is located opposite the first electrode, the third region is located adjacent to the first region, the second region is located between the first region and the photoelectric conversion layer and between the third region and the photoelectric conversion layer; the portion of the insulating layer occupying the third region is made of a third insulating layer; The absolute value of the fixed charge of the material constituting the second insulating layer can be smaller than the absolute value of the fixed charge of the material constituting the third insulating layer. For convenience, the imaging device according to the first aspect of the present disclosure in this form may be referred to as "the imaging device according to the first-C aspect of the present disclosure." In the imaging device according to the first-C aspect of the present disclosure, the material constituting the first insulating layer has a polarity different from the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode; The material constituting the third insulating layer may be in a form having the same polarity as the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode, and further, The carriers sent to the first electrode are electrons, the first insulating layer is made of silicon oxynitride or silicon nitride; the third insulating layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide; The second insulating layer may be in the form of silicon oxide. If the carriers sent to the first electrode are holes, the first insulating layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide; the third insulating layer is made of silicon oxynitride or silicon nitride; The second insulating layer may take the form of silicon oxide.

[0022] When the area of ​​the third region is S3, in the image sensor according to the first-C aspect of the present disclosure, 0.1≦S1 / (S1+S3)≦0.9 It is preferable to satisfy the following:

[0023] In the imaging device according to the first embodiment of the present disclosure, the fixed charge can be measured based on CV measurement using a nano-probe method. That is, the flat band voltage can be obtained from the CV measurement, and the amount of fixed charge can be evaluated.

[0024] Furthermore, in the imaging device according to the first aspect of the present disclosure, including the imaging device according to the first-A aspect of the present disclosure, the imaging device according to the first-B aspect of the present disclosure, and the imaging device according to the first-C aspect of the present disclosure, An insulating material layer (which may be referred to as a "first insulating material layer" for convenience) is provided between the first electrode and the charge storage electrode, The material constituting the insulating material layer (first insulating material layer) may have a polarity different from that of the carriers generated in the photoelectric conversion layer and sent to the first electrode. In other words, such a configuration is a combination of the imaging element etc. according to the first aspect of the present disclosure and the imaging element etc. according to the second aspect of the present disclosure.

[0025] Furthermore, in the above-described preferred embodiment, the imaging device etc. according to aspect 1-A of the present disclosure described above, the imaging device etc. according to aspect 1-B of the present disclosure, and the imaging device etc. according to aspect 1-C of the present disclosure, a second insulating material layer is provided in contact with at least a part of the portion of the charge storage electrode that does not face the first electrode; The material constituting the second insulating material layer may have the same polarity as the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode. That is, such a form is a combination of the imaging element according to the first aspect of the present disclosure and the imaging element according to the third aspect of the present disclosure. Furthermore, the imaging element according to the first aspect of the present disclosure, the imaging element according to the second aspect of the present disclosure, and the imaging element according to the third aspect of the present disclosure may be appropriately combined.

[0026] In the imaging device according to the second aspect of the present disclosure, the insulating layer may extend at least partially between the photoelectric conversion layer and the insulating material layer. a second insulating material layer is provided in contact with at least a part of the portion of the charge storage electrode that does not face the first electrode; The material constituting the second insulating material layer may have the same polarity as the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode, and further, The carriers sent to the first electrode are electrons, the insulating material layer comprises silicon oxynitride or silicon nitride; The second insulating material layer may be in the form of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide. If the carriers sent to the first electrode are holes, the insulating material layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide; The second layer of insulating material may take the form of silicon oxynitride or silicon nitride.

[0027] In the imaging element according to the third aspect of the present disclosure, The carriers sent to the first electrode are electrons, The insulating material layer may be in the form of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide. In addition, when the carriers sent to the first electrode are holes, The layer of insulating material may take the form of silicon oxynitride or silicon nitride.

[0028] In the imaging elements according to the first to third aspects of the present disclosure including the various preferred embodiments described above, the imaging elements according to the first to third aspects of the present disclosure constituting a stacked type imaging element, and the imaging elements according to the first to third aspects of the present disclosure constituting a solid-state imaging device according to the first to second aspects of the present disclosure (hereinafter, these imaging elements may be collectively referred to as "the imaging elements, etc. of the present disclosure"), instead of at least one material selected from the group consisting of aluminum oxide (Al2O3), hafnium oxide (HfO2), zirconium oxide (ZrO2), tantalum oxide (Ta2O5), and titanium oxide (TiO2), Lanthanum oxide (La2O3), praseodymium oxide (Pr2O3), cerium oxide (CeO2), neodymium oxide (Nd2O3), promethium oxide (Pm2O3), samarium oxide (Sm2O3), europium oxide (Eu2O3), gadolinium oxide (Gd2O3), terbium oxide (Tb2O3), dysprosium oxide (Dy2O3), holmium oxide (Ho2O3), thulium oxide (Tm2O3), ytterbium oxide (Yb2O3), lutetium oxide (Lu2O3), yttrium oxide (Y2O3), hafnium nitride, aluminum nitride, hafnium oxynitride, and aluminum oxynitride can also be used.

[0029] In addition, in the imaging element and the like of the present disclosure including the various preferred embodiments described above, silicon oxide may be replaced by a silicon oxide-based material. Examples of silicon oxide-based materials include silicon oxide (SiOX), BPSG, PSG, BSG, AsSG, PbSG, SOG (spin-on glass), and low dielectric constant materials (e.g., polyaryl ether, cycloperfluorocarbon polymer and benzocyclobutene, cyclic fluororesin, polytetrafluoroethylene, fluorinated aryl ether, fluorinated polyimide, amorphous carbon, and organic SOG). Alternatively, instead of silicon oxide, organic insulating materials (organic polymers) exemplified by polymethyl methacrylate (PMMA); polyvinylphenol (PVP); polyvinyl alcohol (PVA); polyimide; polycarbonate (PC); polyethylene terephthalate (PET); polystyrene; silanol derivatives (silane coupling agents) such as N-2(aminoethyl)3-aminopropyltrimethoxysilane (AEAPTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), octadecyltrichlorosilane (OTS), etc.; novolac-type phenolic resins; fluorine-based resins; and straight-chain hydrocarbons having a functional group at one end that can be bonded to a control electrode, such as octadecanethiol and dodecyl isocyanate, can be used, or combinations of these can be used.

[0030] Examples of methods for forming the insulating layer, the first insulating layer, the second insulating layer, and the third insulating layer include various CVD methods, various PVD methods, and ALD methods.

[0031] In the imaging element and the like according to the present disclosure including the preferred embodiments described above, The semiconductor substrate further includes a control unit having a drive circuit. The first electrode and the charge storage electrode are connected to a drive circuit, During the charge accumulation period, the drive circuit applies a potential V 11 is applied to the charge storage electrode, and a potential V 12 is applied, charges are accumulated in the photoelectric conversion layer, During the charge transfer period, the drive circuit applies a potential V 21 is applied to the charge storage electrode, and a potential V 22 When a potential of the first electrode is higher than that of the second electrode, the charge stored in the photoelectric conversion layer is read out to the control unit via the first electrode. V 12 ≧V 11 , and V 22 <V 21 and the potential of the first electrode is lower than the potential of the second electrode, V 12 ≦V 11 , and V 22 >V 21 It is.

[0032] Furthermore, in the imaging element and the like of the present disclosure including the various preferred embodiments described above, a charge transfer control electrode (lower charge transfer control electrode) may be formed in a region facing a region of the photoelectric conversion layer located between adjacent imaging elements via an insulating layer. The semiconductor substrate further includes a control unit having a drive circuit. the first electrode, the second electrode, the charge storage electrode, and the charge transfer control electrode are connected to a drive circuit; During the charge accumulation period, the drive circuit applies a potential V 11 is applied to the charge storage electrode, and a potential V 12 is applied to the charge transfer control electrode, and a potential V 13 is applied, charges are accumulated in the photoelectric conversion layer, During the charge transfer period, the drive circuit applies a potential V 21 is applied to the charge storage electrode, and a potential V 22 is applied to the charge transfer control electrode, and a potential V 23 is applied, and the charges stored in the photoelectric conversion layer are read out to the control unit via the first electrode. However, when the potential of the first electrode is higher than the potential of the second electrode, V 12 ≧V 11 , V 12 >V13 , and V 21 >V 22 >V 23 and the potential of the first electrode is lower than the potential of the second electrode, V 12 ≦V 11 , V 12 <V 13 , and V 21 <V 22 <V 23 The charge transfer control electrode may be formed at the same level as the first electrode or the charge storage electrode, or may be formed at a different level.

[0033] Furthermore, or alternatively, a charge transfer control electrode (upper charge transfer control electrode) may be formed on the region of the photoelectric conversion layer located between the adjacent image pickup elements, instead of the second electrode. The semiconductor substrate further includes a control unit having a drive circuit. the first electrode, the second electrode, the charge storage electrode, and the charge transfer control electrode are connected to a drive circuit; During the charge accumulation period, a potential V2' is applied to the second electrode from the drive circuit, and a potential V 13 ' is applied, charges are accumulated in the photoelectric conversion layer, During the charge transfer period, a potential V2″ is applied to the second electrode from the drive circuit, and a potential V 23 " is applied, and the charges stored in the photoelectric conversion layer are read out to the control unit via the first electrode. However, if the potential of the first electrode is higher than the potential of the second electrode, V2' ≧ V 13 ', and V2" ≧ V 23 " and the potential of the first electrode is lower than the potential of the second electrode, V2'≦V 13 ', and V2"≦V 23 " The charge transfer control electrode is formed at the same level as the second electrode.

[0034] The imaging element and the like of the present disclosure, including the preferred embodiment described above, may further include a semiconductor substrate, and the photoelectric conversion unit may be disposed above the semiconductor substrate. The first electrode, the charge storage electrode, the second electrode, and the various electrodes are connected to a drive circuit, which will be described later.

[0035] Furthermore, the imaging element etc. of the present disclosure, including the various preferred embodiments described above, may be configured to further include a transfer control electrode (charge transfer electrode) that is disposed between the first electrode and the charge storage electrode, spaced apart from the first electrode and the charge storage electrode, and that is disposed opposite the photoelectric conversion layer via an insulating layer in the imaging element etc. according to the first embodiment of the present disclosure, or an insulating material layer in the imaging element etc. according to the second embodiment of the present disclosure. For convenience, the imaging element etc. of the present disclosure having such a configuration may be referred to as "the imaging element etc. of the present disclosure having a transfer control electrode." And, in the imaging element etc. of the present disclosure having a transfer control electrode, The semiconductor substrate further includes a control unit having a drive circuit. the first electrode, the charge storage electrode, and the transfer control electrode are connected to a drive circuit; During the charge accumulation period, the drive circuit applies a potential V 11 is applied to the charge storage electrode, and a potential V 12 is applied to the transfer control electrode, and a potential V 14 is applied, charges are accumulated in the photoelectric conversion layer, During the charge transfer period, the drive circuit applies a potential V 21 is applied to the charge storage electrode, and a potential V 22 is applied to the transfer control electrode, and a potential V 24 is applied, and the charges stored in the photoelectric conversion layer are read out to the control unit via the first electrode. However, when the potential of the first electrode is higher than the potential of the second electrode, V 12 >V 14 , and V 22 ≦V 24 ≦V 21 and the potential of the first electrode is lower than the potential of the second electrode, V 12 <V 14 , and V 22 ≧V 24 ≧V 21 It is.

[0036] Furthermore, the imaging element etc. of the present disclosure, including the various preferred embodiments described above, may further include a charge discharge electrode connected to the photoelectric conversion layer and arranged at a distance from the first electrode and the charge storage electrode. For convenience, such an imaging element etc. of the present disclosure will be referred to as "an imaging element etc. of the present disclosure having a charge discharge electrode." In the imaging element etc. of the present disclosure having a charge discharge electrode, the charge discharge electrode may be arranged so as to surround the first electrode and the charge storage electrode (i.e., in a frame shape). The charge discharge electrode may be shared (common) among a plurality of imaging elements. In this case, the photoelectric conversion layer extends through a second opening provided in the insulating layer and is connected to the charge discharging electrode; The edge of the top surface of the charge discharging electrode is covered with an insulating layer, A charge discharge electrode is exposed on the bottom surface of the second opening, When the surface of the insulating layer in contact with the top surface of the charge discharging electrode is defined as the third surface, and the surface of the insulating layer in contact with the part of the photoelectric conversion layer facing the charge storage electrode is defined as the second surface, the side surface of the second opening can have a slope that widens from the third surface toward the second surface.

[0037] Furthermore, in the imaging element and the like of the present disclosure that are provided with a charge discharging electrode, The semiconductor substrate further includes a control unit having a drive circuit. the first electrode, the charge storage electrode, and the charge discharging electrode are connected to a drive circuit; During the charge accumulation period, the drive circuit applies a potential V 11 is applied to the charge storage electrode, and a potential V 12 is applied to the charge discharge electrode, and a potential V 15 is applied, charges are accumulated in the photoelectric conversion layer, During the charge transfer period, the drive circuit applies a potential V21 is applied to the charge storage electrode, and a potential V 22 is applied to the charge discharge electrode, and a potential V 25 When a potential of the first electrode is higher than that of the second electrode, the charge stored in the photoelectric conversion layer is read out to the control unit via the first electrode. V 15 >V 11 , and V 25 <V 21 and the potential of the first electrode is lower than the potential of the second electrode, V 15 <V 11 , and V 25 >V 21 It is.

[0038] Furthermore, in the imaging element etc. of the present disclosure including the various preferred embodiments described above, the charge storage electrode may be configured to be composed of a plurality of charge storage electrode segments. For convenience, an imaging element etc. of the present disclosure having such a configuration may be referred to as an "imaging element etc. of the present disclosure having a plurality of charge storage electrode segments." The number of charge storage electrode segments may be two or more. In an imaging element etc. of the present disclosure having a plurality of charge storage electrode segments, when a different potential is applied to each of the N charge storage electrode segments, When the potential of the first electrode is higher than the potential of the second electrode, during the charge transfer period, the potential applied to the charge storage electrode segment (the first photoelectric conversion unit segment) located closest to the first electrode is higher than the potential applied to the charge storage electrode segment (the Nth photoelectric conversion unit segment) located farthest from the first electrode, When the potential of the first electrode is lower than the potential of the second electrode, during the charge transfer period, the potential applied to the charge storage electrode segment (the first photoelectric conversion unit segment) located closest to the first electrode can be lower than the potential applied to the charge storage electrode segment (the Nth photoelectric conversion unit segment) located farthest from the first electrode.

[0039] Furthermore, in the imaging element and the like of the present disclosure including the various preferred embodiments described above, the size of the charge storage electrode may be larger than that of the first electrode. When the area of ​​the charge storage electrode is s1' and the area of ​​the first electrode is s1, the following may be adopted, but is not limited thereto: 4≦s1' / s1 It is preferable to satisfy the following:

[0040] The second electrode located on the light incident side may be common to a plurality of imaging elements, except when an upper charge transfer control electrode is formed. That is, the second electrode can be a so-called solid electrode. In the imaging element etc. of the present disclosure, the photoelectric conversion layer can be common to a plurality of imaging elements. That is, a form in which one photoelectric conversion layer is formed in a plurality of imaging elements can be used.

[0041] Furthermore, in the imaging element etc. of the present disclosure including the various preferred embodiments described above, the first electrode can be configured to extend inside an opening provided in the insulating layer (in the imaging element etc. according to the second aspect of the present disclosure, in some cases, a part of the insulating material layer and the insulating layer) and be connected to the photoelectric conversion layer. Alternatively, the photoelectric conversion layer can be configured to extend inside an opening provided in the insulating layer and be connected to the first electrode, in which case, The edge of the top surface of the first electrode is covered with an insulating layer, The first electrode is exposed at the bottom of the opening. When the surface of the insulating layer in contact with the top surface of the first electrode is defined as the first surface, and the surface of the insulating layer in contact with the part of the photoelectric conversion layer facing the charge storage electrode is defined as the second surface, the side of the opening can have a slope that spreads from the first surface toward the second surface, and further, the side of the opening having a slope that spreads from the first surface toward the second surface can be located on the charge storage electrode side. Note that this also includes a form in which another layer is formed between the photoelectric conversion layer and the first electrode (for example, a form in which a material layer suitable for charge storage is formed between the photoelectric conversion layer and the first electrode).

[0042] Furthermore, in the imaging element and the like of the present disclosure including the various preferred embodiments described above, At least a floating diffusion layer and an amplifying transistor that configure a control unit are provided on the semiconductor substrate, The first electrode may be connected to the floating diffusion layer and the gate of the amplification transistor. The semiconductor substrate is further provided with a reset transistor and a selection transistor which constitute a control section, The floating diffusion layer is connected to one of the source / drain regions of the reset transistor, One of the source / drain regions of the amplifying transistor is connected to one of the source / drain regions of the selection transistor, and the other of the source / drain region of the selection transistor is connected to a signal line.

[0043] Alternatively, as modified examples of the imaging element etc. of the present disclosure including the various preferred embodiments described above, imaging elements of the first to sixth configurations described below can be given. That is, in the imaging elements of the first to sixth configurations of the imaging element etc. of the present disclosure including the various preferred embodiments described above, The photoelectric conversion unit is composed of N (N≧2) photoelectric conversion unit segments, The photoelectric conversion layer is composed of N photoelectric conversion layer segments, The insulating layer is composed of N insulating layer segments, In the image pickup devices of the first to third configurations, the charge storage electrode is composed of N charge storage electrode segments, In the image sensor of the fourth or fifth configuration, the charge storage electrode is composed of N charge storage electrode segments arranged to be spaced apart from each other, an n-th (n=1, 2, 3,...,N) photoelectric conversion section segment is composed of an n-th charge storage electrode segment, an n-th insulating layer segment, and an n-th photoelectric conversion layer segment; The larger the value of n, the farther the photoelectric conversion segment is located from the first electrode.

[0044] In the imaging element of the first configuration, the thickness of the insulating layer segment gradually changes from the first photoelectric conversion unit segment to the Nth photoelectric conversion unit segment. In the imaging element of the second configuration, the thickness of the photoelectric conversion layer segment gradually changes from the first photoelectric conversion unit segment to the Nth photoelectric conversion unit segment. In the imaging element of the third configuration, the materials constituting the insulating layer segment are different in adjacent photoelectric conversion unit segments. In the imaging element of the fourth configuration, the materials constituting the charge storage electrode segment are different in adjacent photoelectric conversion unit segments. In the imaging element of the fifth configuration, the area of ​​the charge storage electrode segment gradually decreases from the first photoelectric conversion unit segment to the Nth photoelectric conversion unit segment. The area may decrease continuously or stepwise.

[0045] Alternatively, in the imaging element of the sixth configuration in the imaging element etc. of the present disclosure including the various preferred embodiments described above, when the stacking direction of the charge storage electrode, the insulating layer and the photoelectric conversion layer is the Z direction and the direction away from the first electrode is the X direction, the cross-sectional area of ​​the stacked portion when the stacked portion in which the charge storage electrode, the insulating layer and the photoelectric conversion layer are stacked is cut in the YZ imaginary plane changes depending on the distance from the first electrode. Note that the change in the cross-sectional area may be a continuous change or a step-like change.

[0046] In the imaging devices of the first to second configurations, the N photoelectric conversion layer segments are continuously provided, the N insulating layer segments are also continuously provided, and the N charge storage electrode segments are also continuously provided. In the imaging devices of the third to fifth configurations, the N photoelectric conversion layer segments are continuously provided. In the imaging devices of the fourth and fifth configurations, the N insulating layer segments are continuously provided, while in the imaging device of the third configuration, the N insulating layer segments are provided corresponding to each of the photoelectric conversion section segments. Furthermore, in the imaging devices of the fourth to fifth configurations, and in some cases in the imaging device of the third configuration, the N charge storage electrode segments are provided corresponding to each of the photoelectric conversion section segments. And in the imaging devices of the first to sixth configurations, the same potential is applied to all of the charge storage electrode segments. Alternatively, in the imaging devices of the fourth to fifth configurations, and in some cases in the imaging device of the third configuration, different potentials may be applied to each of the N charge storage electrode segments.

[0047] In the imaging elements of the first to sixth configurations, and the stacked imaging elements and solid-state imaging devices of the present disclosure to which such imaging elements are applied, the thickness of the insulating layer segment is specified, or the thickness of the photoelectric conversion layer segment is specified, or the materials constituting the insulating layer segment are different, or the materials constituting the charge storage electrode segment are different, or the area of ​​the charge storage electrode segment is specified, or the cross-sectional area of ​​the stacked portion is specified, so that a kind of charge transfer gradient is formed, and the charge generated by photoelectric conversion can be transferred to the first electrode more easily and reliably. As a result, the occurrence of afterimages and the occurrence of charge transfer residue can be prevented.

[0048] A modified example of the stacked type imaging element of the present disclosure may be a stacked type imaging element having at least one imaging element of the first to sixth configurations described above. A modified example of the solid-state imaging device according to the first aspect of the present disclosure may be a solid-state imaging device having a plurality of imaging elements of the first to sixth configurations described above, and a modified example of the solid-state imaging device according to the second aspect of the present disclosure may be a solid-state imaging device having a plurality of stacked type imaging elements having at least one imaging element of the first to sixth configurations described above.

[0049] In the imaging elements of the first to fifth configurations, the photoelectric conversion unit segment with a larger value of n is located farther from the first electrode, but whether or not it is located farther from the first electrode is determined based on the X direction. In the imaging element of the sixth configuration, the direction away from the first electrode is defined as the X direction, but the "X direction" is defined as follows. That is, a pixel region in which a plurality of imaging elements or stacked imaging elements are arranged is composed of a plurality of pixels arranged regularly in a two-dimensional array, that is, in the X direction and the Y direction. When the planar shape of the pixel is rectangular, the direction in which the side closest to the first electrode extends is defined as the Y direction, and the direction perpendicular to the Y direction is defined as the X direction. Alternatively, when the planar shape of the pixel is an arbitrary shape, the overall direction including the line segment and curve closest to the first electrode is defined as the Y direction, and the direction perpendicular to the Y direction is defined as the X direction.

[0050] Below, for the imaging elements of the first to sixth configurations, we will explain the case where the potential of the first electrode is higher than the potential of the second electrode. However, if the potential of the first electrode is lower than the potential of the second electrode, the potentials can be reversed.

[0051] In the imaging element of the first configuration, the thickness of the insulating layer segments gradually changes from the first photoelectric conversion unit segment to the Nth photoelectric conversion unit segment, and the thickness of the insulating layer segments may gradually become thicker or thinner, thereby forming a kind of charge transfer gradient.

[0052] When the charges to be stored are electrons, the thickness of the insulating layer segments can be gradually increased. When the charges to be stored are holes, the thickness of the insulating layer segments can be gradually decreased. In these cases, during the charge storage period, |V 12 |≧|V 11 In this state, the nth photoelectric conversion segment can store more charge than the (n+1)th photoelectric conversion segment, and a strong electric field is applied, reliably preventing the flow of charge from the first photoelectric conversion segment to the first electrode. Then, during the charge transfer period, |V 22 |<|V 21 |When this state is reached, it is possible to reliably ensure the flow of charge from the first photoelectric conversion segment to the first electrode, and the flow of charge from the (n+1)th photoelectric conversion segment to the nth photoelectric conversion segment.

[0053] In the imaging element of the second configuration, the thickness of the photoelectric conversion layer segments gradually changes from the first photoelectric conversion section segment to the Nth photoelectric conversion section segment, and the thickness of the photoelectric conversion layer segments may gradually become thicker or thinner, thereby forming a kind of charge transfer gradient.

[0054] When the charges to be stored are electrons, a configuration in which the thickness of the photoelectric conversion layer segment gradually increases may be adopted, and when the charges to be stored are holes, a configuration in which the thickness of the photoelectric conversion layer segment gradually decreases may be adopted. When the thickness of the photoelectric conversion layer segment gradually increases, V 12 ≧V 11 In this state, and if the thickness of the photoelectric conversion layer segment gradually becomes thinner, V 12 ≦V 11In this state, a stronger electric field is applied to the nth photoelectric conversion segment than to the (n+1)th photoelectric conversion segment, and it is possible to reliably prevent the flow of charges from the first photoelectric conversion segment to the first electrode. 22 <V 21 When the thickness of the photoelectric conversion layer segment gradually decreases, V 22 >V 21 In this state, the flow of charge from the first photoelectric conversion segment to the first electrode and the flow of charge from the (n+1)th photoelectric conversion segment to the nth photoelectric conversion segment can be reliably ensured.

[0055] In the imaging element of the third configuration, the materials constituting the insulating layer segments are different in adjacent photoelectric conversion unit segments, which forms a kind of charge transfer gradient. However, it is preferable that the relative dielectric constant values ​​of the materials constituting the insulating layer segments gradually decrease from the first photoelectric conversion unit segment to the Nth photoelectric conversion unit segment. By adopting such a configuration, during the charge accumulation period, V 12 ≧V 11 In this state, the nth photoelectric conversion segment can store more charge than the (n+1)th photoelectric conversion segment. During the charge transfer period, V 22 <V 21 In this state, the flow of charge from the first photoelectric conversion segment to the first electrode and the flow of charge from the (n+1)th photoelectric conversion segment to the nth photoelectric conversion segment can be reliably ensured.

[0056] In the image sensor of the fourth configuration, the materials constituting the charge storage electrode segments are different in adjacent photoelectric conversion unit segments, which forms a kind of charge transfer gradient, but it is preferable that the work function values ​​of the materials constituting the insulating layer segments gradually increase from the first photoelectric conversion unit segment to the Nth photoelectric conversion unit segment. By adopting such a configuration, a potential gradient advantageous for signal charge transfer can be formed regardless of the positive or negative voltage.

[0057] In the image sensor of the fifth configuration, the area of ​​the charge storage electrode segments gradually decreases from the first photoelectric conversion unit segment to the Nth photoelectric conversion unit segment, and a kind of charge transfer gradient is formed. 12 ≧V 11 In this state, the nth photoelectric conversion segment can store more charge than the (n+1)th photoelectric conversion segment. Then, during the charge transfer period, V 22 <V 21 In this state, the flow of charge from the first photoelectric conversion segment to the first electrode and the flow of charge from the (n+1)th photoelectric conversion segment to the nth photoelectric conversion segment can be reliably ensured.

[0058] In the image sensor of the sixth configuration, the cross-sectional area of ​​the laminated portion changes depending on the distance from the first electrode, which forms a kind of charge transfer gradient. Specifically, if the thickness of the cross-section of the laminated portion is constant and the width of the cross-section of the laminated portion is narrowed as it moves away from the first electrode, then, as explained in the image sensor of the fifth configuration, during the charge accumulation period, V 12 ≧V 11 In this state, the area closer to the first electrode can store more charge than the area farther away. Therefore, during the charge transfer period, V 22 <V 21In this state, the flow of charges from the region close to the first electrode to the first electrode and from the region farther away to the region close to the first electrode can be reliably ensured. On the other hand, if a configuration is adopted in which the width of the cross section of the laminated portion is constant and the thickness of the cross section of the laminated portion, specifically, the thickness of the insulating layer segment, is gradually increased, then, as explained in the image sensor of the first configuration, during the charge accumulation period, V 12 ≧V 11 In this state, the area closer to the first electrode can store more charge than the area farther away, and a strong electric field is applied, reliably preventing the flow of charge from the area closer to the first electrode to the first electrode. 22 <V 21 In this state, the flow of charges from the region close to the first electrode to the first electrode and from the region farther away to the region close to the first electrode can be reliably ensured. Also, by adopting a configuration in which the thickness of the photoelectric conversion layer segment is gradually increased, as explained in the image sensor of the second configuration, during the charge accumulation period, V 12 ≧V 11 In this state, a stronger electric field is applied to the region closer to the first electrode than to the region farther away, and it is possible to reliably prevent the flow of charges from the region closer to the first electrode to the first electrode. 22 <V 21 In this state, the flow of charges from the region close to the first electrode to the first electrode and the flow of charges from the distant region to the close region can be reliably ensured.

[0059] As another modification of the solid-state imaging device according to the first aspect of the present disclosure, The imaging device has a plurality of imaging elements having the first to sixth configurations, An imaging element block is composed of a plurality of imaging elements, A solid-state imaging device in which the first electrode is shared among a plurality of imaging elements constituting an imaging element block can be used. For convenience, a solid-state imaging device having such a configuration is referred to as a "solid-state imaging device having a first configuration." Alternatively, as another modified example of the solid-state imaging device according to the second aspect of the present disclosure, A plurality of stacked image pickup devices each having at least one image pickup device of the first to sixth configurations are provided, An imaging element block is composed of a plurality of stacked imaging elements, A solid-state imaging device can be configured in such a way that the first electrode is shared among the multiple stacked imaging elements that make up the imaging element block. For convenience, a solid-state imaging device configured in this way is called a "solid-state imaging device of second configuration." By sharing the first electrode among the multiple imaging elements that make up the imaging element block in this way, the configuration and structure of the pixel region in which the multiple imaging elements are arranged can be simplified and miniaturized.

[0060] In the solid-state imaging devices of the first and second configurations, one floating diffusion layer is provided for a plurality of imaging elements (one imaging element block). Here, the plurality of imaging elements provided for one floating diffusion layer may be composed of a plurality of first type imaging elements described later, or may be composed of at least one first type imaging element and one or more second type imaging elements described later. Then, by appropriately controlling the timing of the charge transfer period, it becomes possible for the plurality of imaging elements to share one floating diffusion layer. The plurality of imaging elements are operated in cooperation with each other and are connected to a driving circuit described later as an imaging element block. That is, the plurality of imaging elements constituting the imaging element block are connected to one driving circuit. However, the charge storage electrode is controlled for each imaging element. Also, it is possible for the plurality of imaging elements to share one contact hole portion. The arrangement relationship between the first electrode shared by the plurality of imaging elements and the charge storage electrode of each imaging element may be such that the first electrode is arranged adjacent to the charge storage electrode of each imaging element. Alternatively, the first electrode may be disposed adjacent to some of the charge storage electrodes of the multiple imaging elements, but not adjacent to the charge storage electrodes of the remaining multiple imaging elements, in which case the charge transfer from the remaining multiple imaging elements to the first electrode passes through some of the multiple imaging elements. In order to ensure the transfer of charge from each imaging element to the first electrode, it is preferable that the distance between the charge storage electrode constituting the imaging element and the charge storage electrode constituting the imaging element (for convenience, referred to as "distance A") is longer than the distance between the first electrode and the charge storage electrode in the imaging element adjacent to the first electrode (for convenience, referred to as "distance B"). It is also preferable that the value of distance A is larger for imaging elements located farther away from the first electrode.

[0061] Furthermore, in the imaging element and the like of the present disclosure including the various preferred embodiments described above, a configuration may be adopted in which light is incident from the second electrode side, and a light shielding layer is formed on the light incident side from the second electrode. Alternatively, a configuration may be adopted in which light is incident from the second electrode side, and light is not incident on the first electrode (or the first electrode and the transfer control electrode in some cases). In this case, a configuration may be adopted in which a light shielding layer is formed on the light incident side from the second electrode, and above the first electrode (or the first electrode and the transfer control electrode in some cases), or an on-chip microlens is provided above the charge storage electrode and the second electrode, and light incident on the on-chip microlens is focused on the charge storage electrode. Here, the light shielding layer may be disposed above the light incident side surface of the second electrode, or may be disposed on the light incident side surface of the second electrode. In some cases, a light shielding layer may be formed on the second electrode. Examples of materials that can be used to form the light-shielding layer include chromium (Cr), copper (Cu), aluminum (Al), tungsten (W), and light-opaque resin (eg, polyimide resin).

[0062] Specific examples of the imaging elements disclosed herein include an imaging element sensitive to blue light having a photoelectric conversion layer (for convenience, referred to as a "first type blue photoelectric conversion layer") that absorbs blue light (light of 425 nm to 495 nm), an imaging element sensitive to green light having a photoelectric conversion layer (for convenience, referred to as a "first type green photoelectric conversion layer") that absorbs green light (light of 495 nm to 570 nm) (for convenience, referred to as a "first type green light imaging element"), and an imaging element sensitive to red light having a photoelectric conversion layer (for convenience, referred to as a "first type red photoelectric conversion layer") that absorbs red light (light of 620 nm to 750 nm) (for convenience, referred to as a "first type red light imaging element"). In addition, for convenience, an imaging element that is a conventional imaging element that does not have a charge storage electrode and is sensitive to blue light will be referred to as a ``second type blue light imaging element'', an imaging element that is sensitive to green light will be referred to as a ``second type green light imaging element'', an imaging element that is sensitive to red light will be referred to as a ``second type red light imaging element'', the photoelectric conversion layer that constitutes the second type blue light imaging element will be referred to as a ``second type blue photoelectric conversion layer'', the photoelectric conversion layer that constitutes the second type green light imaging element will be referred to as a ``second type green photoelectric conversion layer'', and the photoelectric conversion layer that constitutes the second type red light imaging element will be referred to as a ``second type red photoelectric conversion layer''.

[0063] The stacked imaging element of the present disclosure includes at least one imaging element (photoelectric conversion element) of the present disclosure. Specifically, for example, [A] A first type blue light photoelectric conversion unit, a first type green light photoelectric conversion unit, and a first type red light photoelectric conversion unit are stacked in a vertical direction, A configuration in which the control units of the first type blue light imaging element, the first type green light imaging element, and the first type red light imaging element are each provided on a semiconductor substrate; structure [B] The first type blue light photoelectric conversion unit and the first type green light photoelectric conversion unit are stacked in a vertical direction; a second type red light photoelectric conversion unit is disposed below these two layers of the first type photoelectric conversion unit; A configuration in which the control units of the first type blue light imaging element, the first type green light imaging element, and the second type red light imaging element are each provided on a semiconductor substrate; structure [C] a second type blue light photoelectric conversion unit and a second type red light photoelectric conversion unit are disposed below the first type green light photoelectric conversion unit; A configuration in which the control units of the first type green light imaging element, the second type blue light imaging element, and the second type red light imaging element are each provided on a semiconductor substrate; structure [D] A second type green light photoelectric conversion unit and a second type red light photoelectric conversion unit are disposed below the first type blue light photoelectric conversion unit; Examples of configurations and structures include a configuration in which the control units of the first type blue light imaging element, the second type green light imaging element, and the second type red light imaging element are provided on a semiconductor substrate. The arrangement order of the photoelectric conversion units of these imaging elements in the vertical direction is preferably the blue light photoelectric conversion unit, the green light photoelectric conversion unit, and the red light photoelectric conversion unit from the light incidence direction, or the green light photoelectric conversion unit, the blue light photoelectric conversion unit, and the red light photoelectric conversion unit from the light incidence direction. This is because light with a shorter wavelength is absorbed more efficiently on the incident surface side. Since red has the longest wavelength among the three colors, it is preferable to position the red light photoelectric conversion unit in the lowest layer as viewed from the light incidence surface. A single pixel is formed by a stacked structure of these imaging elements. In addition, a first type infrared photoelectric conversion unit may be provided. Here, the photoelectric conversion layer of the first type infrared photoelectric conversion unit is preferably made of, for example, an organic material and is the lowest layer in the laminated structure of the first type imaging element and is disposed above the second type imaging element. Alternatively, a second type infrared photoelectric conversion unit may be provided below the first type photoelectric conversion unit.

[0064] In the first type of imaging element, for example, the first electrode is formed on an interlayer insulating layer provided on a semiconductor substrate. The imaging element formed on the semiconductor substrate may be of a back-illuminated type or a front-illuminated type.

[0065] When the photoelectric conversion layer is made of an organic material, the photoelectric conversion layer is (1) It is composed of a p-type organic semiconductor. (2) It is composed of an n-type organic semiconductor. (3) Consists of a laminated structure of a p-type organic semiconductor layer / n-type organic semiconductor layer. Consists of a laminated structure of a p-type organic semiconductor layer / mixed layer of p-type organic semiconductor and n-type organic semiconductor (bulk heterostructure) / n-type organic semiconductor layer. Consists of a laminated structure of a p-type organic semiconductor layer / mixed layer of p-type organic semiconductor and n-type organic semiconductor (bulk heterostructure). Consists of a laminated structure of an n-type organic semiconductor layer / mixed layer of p-type organic semiconductor and n-type organic semiconductor (bulk heterostructure). (4) It is composed of a mixture of p-type and n-type organic semiconductors (bulk heterostructure). However, the order of the layers may be changed as desired.

[0066] Examples of p-type organic semiconductors include naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, perylene derivatives, tetracene derivatives, pentacene derivatives, quinacridone derivatives, thiophene derivatives, thienothiophene derivatives, benzothiophene derivatives, benzothienobenzothiophene derivatives, triallylamine derivatives, carbazole derivatives, perylene derivatives, picene derivatives, chrysene derivatives, fluoranthene derivatives, phthalocyanine derivatives, subphthalocyanine derivatives, subporphyrazine derivatives, metal complexes having a heterocyclic compound as a ligand, polythiophene derivatives, polybenzothiadiazole derivatives, and polyfluorene derivatives. Examples of n-type organic semiconductors include fullerenes and fullerene derivatives (e.g., fullerenes (higher fullerenes) such as C60, C70, and C74, endohedral fullerenes, etc.) or fullerene derivatives (e.g., fullerene fluorides, PCBM fullerene compounds, fullerene polymers, etc.)), organic semiconductors having larger (deeper) HOMO and LUMO than p-type organic semiconductors, and transparent inorganic metal oxides. Specific examples of n-type organic semiconductors include organic molecules, organometallic complexes, and subphthalocyanine derivatives having heterocyclic compounds containing nitrogen atoms, oxygen atoms, or sulfur atoms as part of their molecular skeletons, such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, isoquinoline derivatives, acridine derivatives, phenazine derivatives, phenanthroline derivatives, tetrazole derivatives, pyrazole derivatives, imidazole derivatives, thiazole derivatives, oxazole derivatives, imidazole derivatives, benzimidazole derivatives, benzotriazole derivatives, benzoxazole derivatives, benzoxazole derivatives, carbazole derivatives, benzofuran derivatives, dibenzofuran derivatives, subporphyrazine derivatives, polyphenylenevinylene derivatives, polybenzothiadiazole derivatives, and polyfluorene derivatives.Examples of groups contained in the fullerene derivative include halogen atoms, linear, branched or cyclic alkyl or phenyl groups, groups having linear or condensed aromatic compounds, groups having halides, partial fluoroalkyl groups, perfluoroalkyl groups, silyl alkyl groups, silyl alkoxy groups, aryl silyl groups, aryl sulfanyl groups, alkyl sulfanyl groups, aryl sulfonyl groups, alkyl sulfonyl groups, aryl sulfide groups, alkyl sulfide groups, amino groups, alkyl amino groups, aryl amino groups, hydroxy groups, alkoxy groups, acyl amino groups, acyloxy groups, carbonyl groups, carboxy groups, carboxoamide groups, carboalkoxy groups, acyl groups, sulfonyl groups, cyano groups, nitro groups, groups having chalcogenides, phosphine groups, phosphonic groups, and derivatives thereof. The thickness of the photoelectric conversion layer (sometimes called "organic photoelectric conversion layer") made of organic materials is not limited, but may be, for example, 1×10. -8 m to 5×10 -7 m, preferably 2.5 × 10 -8 m to 3×10 -7 m, more preferably 2.5 × 10 -8 m to 2×10 -7 m, more preferably 1×10 -7 m to 1.8×10 -7 Examples of the organic semiconductor include p-type and n-type. Although organic semiconductors are often classified as p-type and n-type, the p-type means that they easily transport holes, and the n-type means that they easily transport electrons, and are not limited to the interpretation that they have holes or electrons as the majority carriers of thermal excitation like inorganic semiconductors.

[0067] Alternatively, examples of materials constituting an organic photoelectric conversion layer that converts green light into electricity include rhodamine-based dyes, melacyanine-based dyes, quinacridone derivatives, subphthalocyanine-based dyes (subphthalocyanine derivatives), etc., examples of materials constituting an organic photoelectric conversion layer that converts blue light into electricity include coumaric acid dyes, tris-8-hydroxyquinolialuminum (Alq3), melacyanine-based dyes, etc., and examples of materials constituting an organic photoelectric conversion layer that converts red light into electricity include phthalocyanine-based dyes and subphthalocyanine-based dyes (subphthalocyanine derivatives).

[0068] Alternatively, examples of inorganic materials constituting the photoelectric conversion layer include crystalline silicon, amorphous silicon, microcrystalline silicon, crystalline selenium, amorphous selenium, and chalcopallite compounds such as CIGS (CuInGaSe), CIS (CuInSe2), CuInS2, CuAlS2, CuAlSe2, CuGaS2, CuGaSe2, AgAlS2, AgAlSe2, AgInS2, and AgInSe2, as well as III-V group compounds such as GaAs, InP, AlGaAs, InGaP, AlGaInP, and InGaAsP, as well as compound semiconductors such as CdSe, CdS, In2Se3, In2S3, Bi2Se3, Bi2S3, ZnSe, ZnS, PbSe, and PbS. In addition, quantum dots made of these materials can also be used in the photoelectric conversion layer.

[0069] Alternatively, the photoelectric conversion layer can be a laminated structure of a lower semiconductor layer and an upper photoelectric conversion layer. By providing the lower semiconductor layer in this way, for example, recombination during charge accumulation can be prevented. In addition, the charge transfer efficiency of the charge accumulated in the photoelectric conversion layer to the first electrode can be increased. Furthermore, the charge generated in the photoelectric conversion layer can be temporarily held and the timing of transfer can be controlled. In addition, the generation of dark current can be suppressed. The material constituting the upper photoelectric conversion layer may be appropriately selected from the various materials constituting the photoelectric conversion layer described above. On the other hand, as the material constituting the lower semiconductor layer, it is preferable to use a material having a large band gap energy value (for example, a band gap energy value of 3.0 eV or more) and a higher mobility than the material constituting the photoelectric conversion layer. Specifically, examples of the material include oxide semiconductor materials such as IGZO; transition metal dichalcogenides; silicon carbide; diamond; graphene; carbon nanotubes; and organic semiconductor materials such as condensed polycyclic hydrocarbon compounds and condensed heterocyclic compounds. Alternatively, as the material constituting the lower semiconductor layer, when the charge to be stored is an electron, a material having a larger ionization potential than the material constituting the photoelectric conversion layer can be used, and when the charge to be stored is a hole, a material having a smaller electron affinity than the material constituting the photoelectric conversion layer can be used. Alternatively, the impurity concentration in the material constituting the lower semiconductor layer is 1×10 18 cm -3 It is preferable that the lower semiconductor layer is a single-layer structure or a multi-layer structure. The material constituting the lower semiconductor layer located above the charge storage electrode and the material constituting the lower semiconductor layer located above the first electrode may be different.

[0070] A single-chip color solid-state imaging device can be configured by the solid-state imaging devices according to the first and second aspects of the present disclosure and the solid-state imaging devices having the first and second configurations.

[0071] In the solid-state imaging device according to the second aspect of the present disclosure having a stacked imaging element or the solid-state imaging device of the second configuration, unlike a solid-state imaging device having an imaging element in a Bayer array (i.e., instead of using color filters to separate blue, green, and red light), imaging elements having sensitivity to light of a plurality of wavelengths are stacked in the direction of light incidence within the same pixel to form one pixel, so that it is possible to improve sensitivity and pixel density per unit volume. In addition, since organic materials have a high absorption coefficient, the film thickness of the organic photoelectric conversion layer can be made thinner than that of a conventional Si-based photoelectric conversion layer, and light leakage from adjacent pixels and restrictions on the angle of incidence of light are alleviated. Furthermore, in the conventional Si-based imaging element, false colors occur because color signals are created by performing an interpolation process between three color pixels, but the occurrence of false colors is suppressed in the solid-state imaging device according to the second aspect of the present disclosure having a stacked imaging element or the solid-state imaging device of the second configuration. Since the organic photoelectric conversion layer itself also functions as a color filter, color separation is possible without providing a color filter.

[0072] On the other hand, in the solid-state imaging device according to the first aspect of the present disclosure or the solid-state imaging device of the first configuration, the requirements for the spectral characteristics of blue, green, and red can be relaxed by using color filters, and the solid-state imaging device of the first configuration has high mass productivity. In addition to the Bayer array, the array of imaging elements in the solid-state imaging device according to the first aspect of the present disclosure or the solid-state imaging device of the first configuration can be an interline array, a G-stripe RB checkered array, a G-stripe RB complete checkered array, a checkered complementary color array, a stripe array, a diagonal stripe array, a primary color color difference array, a field color difference sequential array, a frame color difference sequential array, a MOS type array, an improved MOS type array, a frame interleaved array, and a field interleaved array. Here, one pixel (or subpixel) is formed by one imaging element.

[0073] A pixel region in which a plurality of the imaging elements or stacked imaging elements of the present disclosure are arranged is composed of a plurality of pixels arranged regularly in a two-dimensional array. The pixel region is usually composed of an effective pixel region that actually receives light, amplifies the signal charge generated by photoelectric conversion, and reads it out to a drive circuit, and a black reference pixel region that outputs optical black that serves as a reference for the black level. The black reference pixel region is usually arranged on the outer periphery of the effective pixel region.

[0074] In the imaging element and the like of the present disclosure including the various preferred forms and configurations described above, light is irradiated, photoelectric conversion occurs in the photoelectric conversion layer, and holes and electrons are separated as carriers. The electrode from which the holes are extracted is the anode, and the electrode from which the electrons are extracted is the cathode. There are forms in which the first electrode constitutes the anode and the second electrode constitutes the cathode, and conversely, there are forms in which the first electrode constitutes the cathode and the second electrode constitutes the anode.

[0075] When a stacked imaging element is constructed, the first electrode, the charge storage electrode, the charge transfer control electrode, the transfer control electrode, and the second electrode may be made of a transparent conductive material. The first electrode, the charge storage electrode, the charge transfer control electrode, and the transfer control electrode may be collectively referred to as the "first electrode, etc." Alternatively, when the imaging element, etc. of the present disclosure is arranged on a plane, for example, in a Bayer arrangement, the second electrode may be made of a transparent conductive material, and the first electrode, etc. may be made of a metal material. In this case, specifically, the second electrode located on the light incident side may be made of a transparent conductive material, and the first electrode, etc. may be made of, for example, Al-Nd (alloy of aluminum and neodymium) or ASC (alloy of aluminum, samarium, and copper). An electrode made of a transparent conductive material may be called a "transparent electrode." Here, it is desirable that the band gap energy of the transparent conductive material is 2.5 eV or more, preferably 3.1 eV or more. Examples of the transparent conductive material constituting the transparent electrode include conductive metal oxides. Specifically, examples of the transparent conductive material include indium oxide, indium tin oxide (ITO, Indium Tin Oxide, including Sn-doped In2O3, crystalline ITO, and amorphous ITO), and indium zinc oxide (IZO, Indium Zinc Oxide) in which indium is added as a dopant to zinc oxide. Examples of the oxide include indium-gallium oxide (IGO) in which indium is added as a dopant to gallium oxide, indium-gallium-zinc oxide (IGZO, In-GaZnO4) in which indium and gallium are added as dopants to zinc oxide, indium-tin-zinc oxide (ITZO) in which indium and tin are added as dopants to zinc oxide, IFO (F-doped In2O3), tin oxide (SnO2), ATO (Sb-doped SnO2), FTO (F-doped SnO2), zinc oxide (including ZnO doped with other elements), aluminum-zinc oxide (AZO) in which aluminum is added as a dopant to zinc oxide, gallium-zinc oxide (GZO) in which gallium is added as a dopant to zinc oxide, titanium oxide (TiO2), niobium-titanium oxide (TNO) in which niobium is added as a dopant to titanium oxide, antimony oxide, spinel-type oxide, and oxides having a YbFe2O4 structure.Alternatively, a transparent electrode having a base layer of gallium oxide, titanium oxide, niobium oxide, nickel oxide, etc. may be used. The thickness of the transparent electrode is 2×10. -8 m to 2×10 -7 m, preferably 3 × 10 -8 m to 1×10 -7 When the first electrode is required to be transparent, it is preferable that the other electrodes are also made of a transparent conductive material from the viewpoint of simplifying the manufacturing process.

[0076] Alternatively, when transparency is not required, the conductive material constituting the anode having the function as an electrode for extracting holes is preferably composed of a conductive material having a high work function (for example, φ=4.5 eV to 5.5 eV). Specific examples of such a conductive material include gold (Au), silver (Ag), chromium (Cr), nickel (Ni), palladium (Pd), platinum (Pt), iron (Fe), iridium (Ir), germanium (Ge), osmium (Os), rhenium (Re), and tellurium (Te). On the other hand, the conductive material constituting the cathode having the function as an electrode for extracting electrons is preferably composed of a conductive material having a low work function (for example, φ=3.5 eV to 4.5 eV). Specific examples of the conductive material include alkali metals (for example, Li, Na, K, etc.) and their fluorides or oxides, alkaline earth metals (for example, Mg, Ca, etc.) and their fluorides or oxides, aluminum (Al), zinc (Zn), tin (Sn), thallium (Tl), sodium-potassium alloys, aluminum-lithium alloys, magnesium-silver alloys, indium, ytterbium, and other rare earth metals, and alloys thereof. Alternatively, the materials constituting the anode and cathode may include metals such as platinum (Pt), gold (Au), palladium (Pd), chromium (Cr), nickel (Ni), aluminum (Al), silver (Ag), tantalum (Ta), tungsten (W), copper (Cu), titanium (Ti), indium (In), tin (Sn), iron (Fe), cobalt (Co), and molybdenum (Mo), or alloys containing these metal elements, conductive particles made of these metals, conductive particles of alloys containing these metals, polysilicon containing impurities, carbon-based materials, oxide semiconductors, carbon nanotubes, graphene, and other conductive materials, or may have a laminated structure of layers containing these elements. Furthermore, the materials constituting the anode and cathode may include organic materials (conductive polymers) such as poly(3,4-ethylenedioxythiophene) / polystyrenesulfonic acid [PEDOT / PSS]. Moreover, these conductive materials may be mixed with a binder (polymer) to form a paste or ink, which may then be hardened and used as an electrode.

[0077] As a method for forming a film of the first electrode or the second electrode (anode or cathode), a dry method or a wet method can be used. Examples of the dry method include physical vapor deposition (PVD) and chemical vapor deposition (CVD). Examples of the film formation method using the principle of the PVD method include vacuum deposition using resistance heating or high-frequency heating, EB (electron beam) deposition, various sputtering methods (magnetron sputtering, RF-DC coupled bias sputtering, ECR sputtering, facing target sputtering, high-frequency sputtering), ion plating, laser ablation, molecular beam epitaxy, and laser transfer. Examples of the CVD method include plasma CVD, thermal CVD, metal organic (MO) CVD, and photo CVD. On the other hand, examples of the wet method include electrolytic plating, electroless plating, spin coating, inkjet printing, spray coating, stamping, microcontact printing, flexographic printing, offset printing, gravure printing, and dip printing. Examples of the patterning method include chemical etching such as shadow mask, laser transfer, and photolithography, and physical etching using ultraviolet light, laser, etc. Examples of the planarization technique for the first electrode, etc. and the second electrode include laser planarization, reflow, and CMP (Chemical Mechanical Polishing).

[0078] Silicon oxide-based materials, such as silicon nitride (SiN Y); metal oxide high dielectric insulating materials such as aluminum oxide (Al2O3) and the like. In addition, organic insulating materials (organic polymers) such as polymethyl methacrylate (PMMA); polyvinylphenol (PVP); polyvinyl alcohol (PVA); polyimide; polycarbonate (PC); polyethylene terephthalate (PET); polystyrene; silanol derivatives (silane coupling agents) such as N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (AEAPTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), octadecyltrichlorosilane (OTS), and the like; novolac-type phenolic resins; fluorine-based resins; and linear hydrocarbons having a functional group at one end capable of bonding to a control electrode, such as octadecanethiol and dodecyl isocyanate, can be used. In addition, silicon oxide materials include silicon oxide (SiO X ), BPSG, PSG, BSG, AsSG, PbSG, silicon oxynitride (SiON), SOG (spin-on glass), and low dielectric constant materials (e.g., polyaryl ether, cycloperfluorocarbon polymer and benzocyclobutene, cyclic fluororesin, polytetrafluoroethylene, fluorinated aryl ether, fluorinated polyimide, amorphous carbon, and organic SOG).

[0079] The configurations and structures of the floating diffusion layer, amplifying transistor, reset transistor, and selection transistor constituting the control section may be the same as those of the conventional floating diffusion layer, amplifying transistor, reset transistor, and selection transistor. The driving circuit may also have a known configuration and structure.

[0080] The first electrode is connected to the floating diffusion layer and the gate of the amplifying transistor, and a contact hole may be formed to connect the first electrode to the floating diffusion layer and the gate of the amplifying transistor. Examples of materials that form the contact hole include polysilicon doped with impurities, tungsten, high-melting point metals such as Ti, Pt, Pd, Cu, TiW, TiN, TiNW, WSi2, and MoSi2, metal silicides, and stacked layers of these materials (e.g., Ti / TiN / W).

[0081] A first carrier blocking layer may be provided between the organic photoelectric conversion layer and the first electrode, and a second carrier blocking layer may be provided between the organic photoelectric conversion layer and the second electrode. A first charge injection layer may be provided between the first carrier blocking layer and the first electrode, and a second charge injection layer may be provided between the second carrier blocking layer and the second electrode. For example, materials constituting the electron injection layer include alkali metals such as lithium (Li), sodium (Na), and potassium (K) and their fluorides and oxides, and alkaline earth metals such as magnesium (Mg) and calcium (Ca) and their fluorides and oxides.

[0082] Examples of the film-forming method for various organic layers include dry film-forming methods and wet film-forming methods. Examples of the dry film-forming methods include vacuum deposition using resistance heating, high-frequency heating, and electron beam heating, flash deposition, plasma deposition, EB deposition, various sputtering methods (two-pole sputtering, direct current sputtering, direct current magnetron sputtering, high-frequency sputtering, magnetron sputtering, RF-DC combined bias sputtering, ECR sputtering, facing target sputtering, high-frequency sputtering, and ion beam sputtering), DC (Direct Current) method, RF method, multi-cathode method, activation reaction method, field deposition method, various ion plating methods such as high-frequency ion plating and reactive ion plating, laser ablation method, molecular beam epitaxy method, laser transfer method, and molecular beam epitaxy method (MBE method). Examples of the CVD method include plasma CVD method, thermal CVD method, MOCVD method, and photo-CVD method. On the other hand, examples of wet methods include spin coating, immersion, casting, microcontact printing, drop casting, various printing methods such as screen printing, inkjet printing, offset printing, gravure printing, and flexographic printing, stamping, spraying, and various coating methods such as air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater, transfer roll coater, gravure coater, kiss coater, cast coater, spray coater, slit orifice coater, and calendar coater. In addition, in the coating method, examples of the solvent include non-polar or low polar organic solvents such as toluene, chloroform, hexane, and ethanol. Examples of patterning methods include chemical etching such as shadow mask, laser transfer, and photolithography, and physical etching using ultraviolet light or laser. As a planarization technique for various organic layers, a laser planarization method, a reflow method, and the like can be used.

[0083] Two or more types of imaging elements having the first to sixth configurations, such as the imaging elements according to the first to third aspects of the present disclosure including the preferred forms and configurations described above, can be combined as desired.

[0084] As described above, the imaging element or solid-state imaging device may be provided with an on-chip microlens or a light-shielding layer, and may be provided with a driving circuit and wiring for driving the imaging element, as necessary. If necessary, a shutter may be provided for controlling the incidence of light on the imaging element, and an optical cut filter may be provided depending on the purpose of the solid-state imaging device.

[0085] In addition, in the solid-state imaging devices of the first and second configurations, a configuration can be adopted in which one on-chip microlens is disposed above one imaging element, or a configuration can be adopted in which an imaging element block is formed from two imaging elements, and one on-chip microlens is disposed above the imaging element block.

[0086] For example, when stacking a solid-state imaging device with a readout integrated circuit (ROIC), the readout integrated circuit and a driving substrate having a connection part made of copper (Cu) are stacked on top of the imaging element having a connection part so that the connection parts are in contact with each other, and the stacking can be performed by joining the connection parts, or the connection parts can be joined using solder bumps or the like.

[0087] In addition, in the driving method for driving the solid-state imaging device according to the first and second aspects of the present disclosure, In all the imaging elements, charges are simultaneously accumulated in the photoelectric conversion layer while the charges in the first electrodes are discharged to the outside of the system, and then, In all of the image pickup elements, the electric charges accumulated in the photoelectric conversion layers are transferred to the first electrodes at the same time, and after the transfer is completed, the electric charges transferred to the first electrodes are read out in sequence in each of the image pickup elements. A method for driving a solid-state imaging device can be achieved by repeating each step.

[0088] In such a driving method for a solid-state imaging device, each imaging element has a structure in which light incident from the second electrode side does not enter the first electrode, and in all imaging elements, charges are simultaneously accumulated in the photoelectric conversion layer while the charges in the first electrode are discharged to the outside of the system, so that the first electrodes can be reliably reset simultaneously in all imaging elements. Then, in all imaging elements, the charges accumulated in the photoelectric conversion layer are simultaneously transferred to the first electrode, and after the transfer is completed, the charges transferred to the first electrode in each imaging element are read out in sequence. Therefore, a so-called global shutter function can be easily realized. EXAMPLES

[0089] Example 1 relates to an imaging element according to the first aspect of the present disclosure. The imaging element will be described in detail in Example 6 and thereafter. FIG. 1A shows a schematic partial cross-sectional view of the imaging element of Example 1, and FIG. 2 shows a schematic arrangement of a first electrode, an insulating layer, and the like in the imaging element of Example 1. In order to simplify the drawings, various imaging element components located below an interlayer insulating layer described later may be collectively indicated by reference number 91. Reference numbers 63, 64, 65, 66, and 81 will also be described in Example 6.

[0090] The image sensor of the first embodiment is first electrode 11, a charge storage electrode 14 disposed apart from the first electrode 11; a photoelectric conversion layer 13 that is in contact with the first electrode 11 and is formed above the charge storage electrode 14 with an insulating layer 82 interposed therebetween; and A second electrode 12 formed on the photoelectric conversion layer 13; It is equipped with:

[0091] and, A portion of the insulating layer 82 located between the charge storage electrode 14 and the photoelectric conversion layer 13 has a first region 82a1 and a second region 82a2, The portion of the insulating layer occupying the first region 82a1 is made of the first insulating layer 82A1, The portion of the insulating layer occupying the second region 82a2 is made of the second insulating layer 82A2, The absolute value of the fixed charge of the material constituting the second insulating layer 82A2 is smaller than the absolute value of the fixed charge of the material constituting the first insulating layer 82A1.

[0092] Here, in the imaging element of the first embodiment, the second region 82a2 is located opposite to the first electrode 11, and the first region 82a1 is located adjacent to the second region 82a2. That is, the first region 82a1 and the second region 82a2 are located at the same level. In FIG. 2, the first insulating layer 82A1 is indicated by diagonal lines from the upper right to the lower left, and the second insulating layer 82A2 is indicated by diagonal lines from the upper left to the lower right, in only one of the imaging elements. The first electrode 11 and the charge storage electrode 14 are also illustrated. In the example shown in FIG. 2, one common first electrode 11 is provided corresponding to the four charge storage electrodes 14 in the four imaging elements, but the present invention is not limited to such a form. For example, one first electrode 11 may be provided corresponding to one charge storage electrode 14, or one common first electrode 11 may be provided corresponding to two charge storage electrodes 14. That is, it is sufficient that one (common) first electrode 11 is provided corresponding to one or more charge storage electrodes 14. The same applies below. A second insulating layer 82A2 is provided between the imaging elements. A second insulating layer 82A2 is also provided between the first electrode 11 and the charge storage electrode 14.

[0093] The material constituting the first insulating layer 82A1 has the same polarity as the polarity of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. Specifically, the carriers sent to the first electrode 11 are electrons, the first insulating layer 82A1 is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide (more specifically, for example, aluminum oxide, Al2O3), and the second insulating layer 82A2 is made of silicon oxide (SiO2).

[0094] When the area of ​​the first region 82a1 is S1 and the area of ​​the second region 82a2 is S2, in the image sensor of the first embodiment, 0.1≦S2 / (S1+S2)≦0.9 It is preferable to satisfy the following, specifically, for example: S2 / (S1+S2)=0.5 The value of the fixed charge of aluminum oxide (Al2O3) is as follows:

[0095] In the imaging device of the first embodiment, the absolute value of the fixed charge of the material constituting the second insulating layer is smaller than the absolute value of the fixed charge of the material constituting the first insulating layer. Therefore, during charge transfer, a difference occurs between the transfer state of the charge stored in the portion of the photoelectric conversion layer on the first insulating layer and the transfer state of the charge stored in the portion of the photoelectric conversion layer on the second insulating layer, and as a result, during charge transfer, the charge stored in the photoelectric conversion layer can be more reliably transferred to the first electrode.

[0096] That is, in the imaging element of Example 1, during charge accumulation, carriers (electrons) generated in the photoelectric conversion layer 13 are attracted to the charge accumulation electrode 14, but since the first region 82a1 (first insulating layer 82A1) has the same polarity (specifically, negative polarity) as the polarity (specifically, negative polarity) of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11, the carriers (electrons) in the portion of the photoelectric conversion layer 13 located above the first region 82a1 tend to move to the portion of the photoelectric conversion layer 13 located above the second region 82a2 (first insulating layer 82A2), and the carriers are accumulated in large amounts in the portion of the photoelectric conversion layer 13 located above the second region 82a2 (the portion closer to the first electrode 11). As a result, during charge transfer, the charge accumulated in the photoelectric conversion layer 13 can be transferred more reliably to the first electrode 11.

[0097] In addition, in the imaging element of Example 1 or Examples 2 to 5 described later, a charge storage electrode is provided that is disposed apart from the first electrode and faces the photoelectric conversion layer via an insulating layer, so that when light is irradiated onto the photoelectric conversion section and photoelectric conversion is performed in the photoelectric conversion section, charges can be stored in the photoelectric conversion layer. Therefore, at the start of exposure, it is possible to completely deplete the charge storage section and erase the charges. As a result, it is possible to suppress the occurrence of phenomena such as increased kTC noise, worsening random noise, and reduced image quality.

[0098] FIG. 1B shows a schematic partial cross-sectional view of a modified image sensor of the first embodiment. Between the first insulating layer 82A1 and the photoelectric conversion layer 13, a second insulating layer extension portion 82A2' extending from the second insulating layer 82A2 is formed. The first region 82a1 and the second region 82a2 are located at the same level. That is, the area directly below the photoelectric conversion layer 13 is occupied by the second insulating layer 82A2 (specifically, SiO2) having an absolute value of fixed charge smaller than the absolute value of the fixed charge of the material constituting the first insulating layer 82A1. Therefore, the area between the photoelectric conversion layer 13 and the charge storage electrode 14 can be occupied by an insulating layer having excellent characteristics as a whole. EXAMPLES

[0099] Example 2 is a modification of Example 1, and relates to an imaging element according to aspect 1-B of the present disclosure. A schematic partial cross-sectional view of the imaging element of Example 2 is shown in Fig. 3A. Also, the arrangement relationship of the first electrode, the insulating layer, and the like in the imaging element of Example 2 is shown in Fig. 4.

[0100] In the imaging element of the second embodiment, the first region 82b1 is located opposite the first electrode 11, and the second region 82b2 is located adjacent to the first region 82b1. The first region 82b1 and the second region 82b2 are located at the same level. In FIG. 4, the first insulating layer 82B1 is indicated by diagonal lines from the upper right to the lower left, and the second insulating layer 82B2 is indicated by diagonal lines from the upper left to the lower right, in only one of the imaging elements. The second insulating layer 82B2 is provided between the imaging elements. The second insulating layer 82B2 is also provided between the first electrode 11 and the charge storage electrode 14. The material constituting the first insulating layer 82B1 has a polarity (specifically, a positive polarity) different from the polarity (specifically, a negative polarity) of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. Specifically, the carriers sent to the first electrode 11 are electrons, the first insulating layer 82B1 is made of silicon oxynitride or silicon nitride (more specifically, silicon nitride, SiN), and the second insulating layer 82B2 is made of silicon oxide (SiO2).

[0101] When the area of ​​the first region 82b1 is S1 and the area of ​​the second region 82b2 is S2, in the image sensor of the second embodiment, 0.1≦S2 / (S1+S2)≦0.9 It is preferable to satisfy the following, specifically, for example: S2 / (S1+S2)=0.5 It can be said that:

[0102] In the imaging element of the second embodiment, during charge accumulation, carriers (electrons) generated in the photoelectric conversion layer 13 are attracted to the charge accumulation electrode 14, but the first region 82b1 (first insulating layer 82B1) has a polarity different from the polarity of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. Therefore, carriers (electrons) in the portion of the photoelectric conversion layer 13 located on the first region 82b1 (first insulating layer 82B1) tend to move to the portion of the photoelectric conversion layer 13 located on the second region 82b2, and carriers are accumulated in a large amount in the portion of the photoelectric conversion layer 13 located on the first region 82b1 (first insulating layer 82B1) (the portion closer to the first electrode 11). As a result, during charge transfer, the charge accumulated in the photoelectric conversion layer 13 can be transferred more reliably to the first electrode 11.

[0103] FIG. 3B shows a schematic partial cross-sectional view of a modified image sensor of the second embodiment. Between the first insulating layer 82B1 and the photoelectric conversion layer 13, a second insulating layer extension portion 82B2' extending from the second insulating layer 82B2 is formed. The first region 82b1 and the second region 82b2 are located at the same level. That is, the second insulating layer 82B2 (specifically, SiO2) having an absolute value of fixed charge smaller than the absolute value of the fixed charge of the material constituting the first insulating layer 82B1 is occupied directly below the photoelectric conversion layer 13. Therefore, an insulating layer having excellent characteristics as a whole can be occupied between the photoelectric conversion layer 13 and the charge storage electrode 14. EXAMPLES

[0104] Example 3 is also a modification of Example 1, and relates to an imaging element according to aspect 1-C of the present disclosure. A schematic partial cross-sectional view of the imaging element of Example 3 is shown in Fig. 3C. Moreover, the arrangement relationship of the first electrode, the insulating layer, and the like in the imaging element of Example 3 is shown in Fig. 5.

[0105] In the image sensor of the third embodiment, The portion of the insulating layer located between the charge storage electrode 14 and the photoelectric conversion layer 13 further includes a third region 82c3, The first region 82c1 is located opposite the first electrode 11, The third region 82c3 is located adjacent to the first region 82c1, The second region 82c2 is located between the first region 82c1 and the photoelectric conversion layer 13 and between the third region 82c3 and the photoelectric conversion layer 13. The portion of the insulating layer occupying the third region 82c3 is made of a third insulating layer 82C3, The absolute value of the fixed charge of the material constituting the second insulating layer 82C2 is smaller than the absolute value of the fixed charge of the material constituting the third insulating layer 82C3.

[0106] The first region 82c1 and the third region 82c3 are located at the same level. In FIG. 5, the first insulating layer 82C1 is indicated by oblique lines extending from the upper right to the lower left, and the third insulating layer 82C3 is indicated by oblique lines extending from the upper left to the lower right, in only one of the imaging elements. A second insulating layer 82C2 is provided between the imaging elements. A second insulating layer 82C2 is also provided between the first electrode 11 and the charge storage electrode 14. The material constituting the first insulating layer 82C1 has a polarity (specifically, a positive polarity) different from the polarity (specifically, a negative polarity) of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11, and the material constituting the third insulating layer 82C3 has a polarity (specifically, a negative polarity) the same as the polarity of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. Specifically, the carriers sent to the first electrode 11 are electrons, the first insulating layer 82C1 is made of silicon oxynitride or silicon nitride (specifically, silicon nitride, SiN), the third insulating layer 82C3 is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide and titanium oxide (specifically, aluminum oxide, Al2O3), and the second insulating layer 82C2 is made of silicon oxide (SiO2).

[0107] When the area of ​​the first region 82c1 is S1 and the area of ​​the third region 82c3 is S3, in the image sensor of the third embodiment, 0.1≦S1 / (S1+S3)≦0.9 It is preferable to satisfy the following, specifically, for example: S1 / (S1+S3)=0.5 It can be said that:

[0108] In the imaging element of the third embodiment, during charge accumulation, carriers (electrons) generated in the photoelectric conversion layer 13 are attracted to the charge accumulation electrode 14, but the first region 82c1 (first insulating layer 82C1) has a polarity different from that of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11, and the third region 82c3 (first insulating layer 82C3) has a polarity the same as that of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. Therefore, carriers (electrons) in a portion of the photoelectric conversion layer 13 located on the third region 82c3 (third insulating layer 82C3) tend to move to a portion of the photoelectric conversion layer 13 located on the first region 82c1 (first insulating layer 82C1), and carriers are accumulated in large amounts in a portion of the photoelectric conversion layer 13 located on the first region 82c1 (first insulating layer 82C1) (a portion closer to the first electrode 11). As a result, during charge transfer, the charges stored in the photoelectric conversion layer 13 can be transferred to the first electrode 11 more reliably. EXAMPLES

[0109] Example 4 relates to an imaging element according to the second aspect of the present disclosure. Fig. 6A shows a schematic partial cross-sectional view of the imaging element of Example 4. Fig. 7 shows a schematic arrangement of the first electrode, insulating layer, and the like in the imaging element of Example 4. In Fig. 7, the insulating material layer is shaded to clearly show the insulating material layer.

[0110] The image sensor of the fourth embodiment is first electrode 11, a charge storage electrode 14 disposed apart from the first electrode 11; a photoelectric conversion layer 13 that is in contact with the first electrode 11 and is formed above the charge storage electrode 14 with an insulating layer 82 interposed therebetween; and A second electrode 12 formed on the photoelectric conversion layer 13; Equipped with Between the first electrode 11 and the charge storage electrode 14, an insulating material layer (first insulating material layer) 82D is provided. The material constituting the insulating material layer (first insulating material layer) 82D has a polarity (specifically, positive polarity) different from the polarity (specifically, negative polarity) of carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. Here, in Example 4, the carriers sent to the first electrode 11 are electrons, the insulating material layer 82D is made of silicon oxynitride or silicon nitride (specifically, silicon nitride, SiN), and the insulating layer 82 is made of silicon oxide (SiO2).

[0111] In the illustrated example, the thickness of the insulating material layer 82D is the same as that of the charge storage electrode 14, but it may be thinner or thicker than the charge storage electrode 14. An insulating layer 82 is preferably formed on the insulating material layer 82D. That is, the insulating layer 82 is also provided between the image pickup elements and between the first electrode 11 and the charge storage electrode 14.

[0112] In the image sensor of Example 4, the material constituting the insulating material layer has a polarity different from that of the carriers generated in the photoelectric conversion layer and sent to the first electrode, so that during charge transfer, the charges stored in the photoelectric conversion layer are transferred to the first electrode via the photoelectric conversion layer located above the insulating material layer, and this transfer can be made more reliable.

[0113] The insulating layer 82 extends at least partially between the photoelectric conversion layer 13 and the insulating material layer 82D. In the example shown in FIG. 6A, the insulating layer 82 is provided between the first electrode 11 and the charge storage electrode 14. On the other hand, in a modified example of the imaging element of Example 4, the schematic partial cross-sectional view of which is shown in FIG. 6B, the insulating layer 82 is provided partially between the first electrode 11 and the charge storage electrode 14. That is, the photoelectric conversion layer 13 is not only in contact with the first electrode 11, but also in contact with a part of the insulating material layer 82D. As a result, during charge transfer, the charge stored in the photoelectric conversion layer 13 is transferred to the first electrode 11 via the photoelectric conversion layer 13 located above the insulating material layer 82D and also via the insulating material layer 82D, so that this transfer can be made more reliable.

[0114] Also, a configuration may be adopted in which an insulating material layer 82D is provided adjacent to at least a part of the portion of the charge accumulation electrode 14 that does not face the first electrode 11. That is, a configuration may be adopted in which an insulating material layer 82D and an insulating layer 82 are laminated and formed between the imaging elements.

[0115] The imaging elements of Examples 1 to 3 or their modified examples can be combined with the imaging element of Example 4 or its modified example. That is, in the imaging elements of Examples 1 to 3 or their modified examples, an insulating material layer 82D is provided between the first electrode 11 and the charge storage electrode 14, and the material constituting the insulating material layer 82D can be configured to have a polarity different from the polarity of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. EXAMPLES

[0116] Example 5 relates to an imaging element according to the third aspect of the present disclosure. Fig. 8A shows a schematic partial cross-sectional view of the imaging element of Example 4. Fig. 9 shows a schematic arrangement of the first electrode, insulating layer, and the like in the imaging element of Example 4. In Fig. 9, the insulating material layer is shaded to clearly show the insulating material layer.

[0117] The image sensor of the fifth embodiment is first electrode 11, a charge storage electrode 14 disposed apart from the first electrode 11; a photoelectric conversion layer 13 that is in contact with the first electrode 11 and is formed above the charge storage electrode 14 with an insulating layer 82 interposed therebetween; and A second electrode 12 formed on the photoelectric conversion layer 13; Equipped with An insulating material layer 82E (which may be referred to as a “second insulating material layer” for convenience in order to clearly distinguish it from the insulating material layer (first insulating material layer) 82D in the fourth embodiment) is provided in contact with at least a part of the portion of the charge-storage electrode 14 that does not face the first electrode 11, The material constituting the second insulating material layer 82E has the same polarity (specifically, negative polarity) as the polarity (specifically, negative polarity) of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. The carriers sent to the first electrode 11 are electrons, and the second insulating material layer 82E is made of at least one material (specifically, aluminum oxide, Al2O3) selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide.

[0118] In the imaging element of Example 5, the material constituting the insulating material layer (second insulating material layer) has the same polarity as the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode. Therefore, during charge accumulation or charge transfer, it is possible to suppress the flow of charges toward the insulating material layer (second insulating material layer), and during charge transfer, it is possible to more reliably transfer the charges accumulated in the photoelectric conversion layer to the first electrode.

[0119] The imaging elements of Examples 1 to 3 or their modifications can be combined with the imaging element of Example 5 or its modifications. That is, in the imaging elements of Examples 1 to 3 or their modifications, An insulating material layer 82E (second insulating material layer 82E) is provided in contact with at least a part of the portion of the charge storage electrode 14 that does not face the first electrode 11, The material constituting the insulating material layer 82E (second insulating material layer 82E) can be in a form having the same polarity as the polarity of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11.

[0120] Alternatively, the imaging element of Example 4 or its modified example can be combined with the imaging element of Example 5 or its modified example. That is, in the imaging element of Example 4 or its modified example, a schematic partial cross-sectional view is shown in FIG. 8B, and the arrangement relationship of the first electrode, the insulating layer, etc. is shown in FIG. 10. A second insulating material layer 82E is provided in contact with at least a part of the portion of the charge-storage electrode 14 that does not face the first electrode 11, The material constituting the second insulating material layer 82E can be configured to have the same polarity as the polarity of the carriers generated in the photoelectric conversion layer 13 and sent to the first electrode 11. In FIG. 10, the insulating material layer 82D and the second insulating material layer 82E are indicated with diagonal lines in order to clearly show the insulating material layer 82D and the second insulating material layer 82E. Furthermore, The carriers sent to the first electrode 11 are electrons, The insulating material layer 82D is made of silicon oxynitride or silicon nitride. The second layer of insulating material 82E may be in the form of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide. EXAMPLES

[0121] Example 6 relates to a stacked type imaging element of the present disclosure and a solid-state imaging device according to the second aspect of the present disclosure. That is, the stacked type imaging element in Example 6 includes at least one of the imaging elements of Examples 1 to 5 or their modified examples, and the solid-state imaging device of Example 6 includes a plurality of stacked type imaging elements of Example 6.

[0122] A schematic cross-sectional view of a part of the imaging element (two imaging elements arranged side by side) of Example 6 is shown in Fig. 11. Also, a schematic partial cross-sectional view of one of the imaging element and stacked imaging element of Example 6 is shown in Fig. 12, equivalent circuit diagrams of the imaging element and stacked imaging element of Example 6 are shown in Figs. 13 and 14, and a schematic layout diagram of the first electrode and charge storage electrode constituting the imaging element of Example 6 and the transistor constituting the control unit is shown in Fig. 15. Furthermore, schematic layout diagrams of the first electrode and charge storage electrode constituting the imaging element of Example 6 are shown in Figs. 16 and 17, the state of electric potential at each part during operation of the imaging element of Example 6 is shown in Fig. 18, an equivalent circuit diagram of the imaging element and stacked imaging element of Example 6 for explaining each part of Fig. 18 is shown in Fig. 19A, and a conceptual diagram of the solid-state imaging device of Example 6 is shown in Fig. 20.

[0123] As described in Examples 1 to 5, the imaging element of Example 6 (for example, the green light imaging element described later) or the imaging element of Example 7 described later has a photoelectric conversion section formed by stacking a first electrode 11, a photoelectric conversion layer 13 and a second electrode 12, and the photoelectric conversion section further has a charge storage electrode 14 arranged at a distance from the first electrode 11 and facing the photoelectric conversion layer 13 with an insulating layer 82 interposed therebetween.

[0124] 16, one image sensor is provided with one charge storage electrode 14 corresponding to one first electrode 11. On the other hand, in the example shown in Fig. 17 (Modification 1 of Example 6), two image sensors are provided with one common first electrode 11 corresponding to two charge storage electrodes 14. The schematic cross-sectional view of a portion of the image sensor of Example 6 (two juxtaposed image sensors) shown in Fig. 11 corresponds to Fig. 17.

[0125] The second electrode 12 located on the light incident side is common to the plurality of imaging elements, except for the imaging element of Example 7 described later. That is, the second electrode 12 is a so-called solid electrode. The photoelectric conversion layer 13 is common to the plurality of imaging elements. That is, one layer of the photoelectric conversion layer 13 is formed in the plurality of imaging elements.

[0126] The stacked type imaging element of the sixth embodiment has at least one imaging element of the sixth embodiment or one imaging element of the seventh embodiment described later, and the sixth embodiment has one imaging element of the sixth embodiment or one imaging element of the seventh embodiment described later.

[0127] Furthermore, the solid-state imaging device of the sixth embodiment includes a plurality of stacked imaging elements, which are the imaging elements of the sixth embodiment or the seventh embodiment described later.

[0128] Alternatively, in the imaging element of Example 6, the region (region-B of the photoelectric conversion layer) 13 of the photoelectric conversion layer 13 located between the adjacent imaging elements BThe charge transfer control electrode 21 is formed in a region facing the charge storage electrodes 14 of the adjacent image pickup elements via the insulating layer 82. In other words, the portion 82 of the insulating layer 82 in the region (region-b) sandwiched between the charge storage electrodes 14 of the adjacent image pickup elements (region-B of the insulating layer 82) B The charge transfer control electrode 21 is formed under the charge storage electrode 14. The charge transfer control electrode 21 is provided at a distance from the charge storage electrode 14. In other words, the charge transfer control electrode 21 surrounds the charge storage electrode 14 and is provided at a distance from the charge storage electrode 14. The charge transfer control electrode 21 is connected to the region-B (13) of the photoelectric conversion layer via an insulating layer 82. B 15. Although the charge transfer control electrode 21 is omitted in Fig. 12, the charge transfer control electrode 21 is formed in the direction of the arrow "A". The charge transfer control electrode 21 is shared by the imaging elements arranged in the left-right direction of the paper surface of Fig. 15, and is also shared by a pair of imaging elements arranged in the up-down direction of the paper surface of Fig. 15.

[0129] The first region 82a1, 82b1, 82c1, the second region 82a2, 82b2, 82c2, the third region 82c3, the first insulating layers 82A1, 82B1, 82C1, the second insulating layers 82A2, 82B2, 82C2, the second insulating layer extensions 82A2', 82B2', the third insulating layer 82C3, the insulating material layer (first insulating material layer) 82D, the insulating material layer (second insulating material layer) 82E, the charge transfer control electrode 21, as well as the connection hole 23, the pad portion 22, and the wiring V, which will be described later. OBFor convenience, an imaging element not provided with the first region 82a1, 82b2, 82c3, 82d4, 82e5, 82f6, 82f7, 82f8, 82f9, 82f10, 82f11, 82f12, 82f13, 82f14, 82f15, 82f16, 82f17, 82f18, 82f19, 83f20, 84f21, 86f22, 87f23, 88f24, 89f25, 90f26, 91f27, 92f28, 93f4, 93f5, 94f6, 95f7, 96f8, 97f9, 98f10, 99f11, 100f12, 130f13, 140f14, 150f15, 160f16, 170f17, 182f29, 190f28, 191f29, 183f30, 191f31, 191f32, 192f33, 192f40, 192f55, 193f61, 193f7, 193f82, 193f9, 194f18, 195f19, 196f19, 197f19, 198f19, 199f10, 199f11, 199f20, 199f12, 199f13, 199f21, 199f32, 199f41, 199f56, 2b1, 82c1, the second region 82a2, 82b2, 82c2, the third region, 82c3, the first insulating layer 82A1, 82B1, 82C1, the second insulating layer 82A2, 82B2, 82C2, the second insulating layer extensions 82A2', 82B2', the third insulating layer 82C3, the insulating material layer (first insulating material layer) 82D, the insulating material layer (second insulating material layer) 82E, the charge transfer control electrode 21, etc. are omitted from the illustration and are collectively indicated by the reference number 82.

[0130] The device further includes a semiconductor substrate (more specifically, a silicon semiconductor layer) 70, and the photoelectric conversion unit is disposed above the semiconductor substrate 70. The device further includes a control unit provided on the semiconductor substrate 70 and having a drive circuit to which the first electrode 11 and the second electrode 12 are connected. Here, the light incident surface of the semiconductor substrate 70 is referred to as the upper side, and the opposite side of the semiconductor substrate 70 is referred to as the lower side. A wiring layer 62 made up of a plurality of wirings is provided below the semiconductor substrate 70.

[0131] The semiconductor substrate 70 includes at least a floating diffusion layer FD1 and an amplifying transistor TR1 which constitute the control unit. amp The first electrode 11 is provided on the floating diffusion layer FD1 and the amplification transistor TR1. amp The semiconductor substrate 70 further includes a reset transistor TR1 which constitutes a control section. rst and selection transistor TR1 sel The floating diffusion layer FD1 is connected to the reset transistor TR1. rst and the amplifier transistor TR1 is connected to one of the source / drain regions of the amplifier transistor TR1. amp The other source / drain region of the select transistor TR1sel and a select transistor TR1 is connected to one of the source / drain regions of the select transistor TR1. sel The other source / drain region of each of these amplifying transistors TR1 is connected to a signal line VSL1. amp , reset transistor TR1 rst and selection transistor TR1 sel constitutes the drive circuit.

[0132] Specifically, the imaging element and stacked imaging element of Example 6 are back-illuminated imaging elements and stacked imaging elements, and have a structure in which three imaging elements are stacked: a green light imaging element of Example 6 of a first type having sensitivity to green light and including a first type green photoelectric conversion layer that absorbs green light (hereinafter referred to as a "first imaging element"), a conventional blue light imaging element of a second type having sensitivity to blue light and including a second type blue photoelectric conversion layer that absorbs blue light (hereinafter referred to as a "second imaging element"), and a conventional red light imaging element of a second type having sensitivity to red light and including a second type red photoelectric conversion layer that absorbs red light (hereinafter referred to as a "third imaging element"). Here, the red light imaging element (third imaging element) and the blue light imaging element (second imaging element) are provided in a semiconductor substrate 70, and the second imaging element is located closer to the light incident side than the third imaging element. Also, the green light imaging element (first imaging element) is provided above the blue light imaging element (second imaging element). The stacked structure of the first imaging element, the second imaging element, and the third imaging element constitutes one pixel. No color filter is provided.

[0133] In the first imaging element, the first electrode 11 and the charge storage electrode 14 are formed on an interlayer insulating layer 81 at a distance from each other. Also, the charge transfer control electrode 21 is formed on the interlayer insulating layer 81 at a distance from the charge storage electrode 14. The interlayer insulating layer 81, the charge storage electrode 14, and the charge transfer control electrode 21 are covered with an insulating layer 82. A photoelectric conversion layer 13 is formed on the insulating layer 82, and a second electrode 12 is formed on the photoelectric conversion layer 13. A protective layer 83 is formed on the entire surface including the second electrode 12, and an on-chip microlens 90 is provided on the protective layer 83. The first electrode 11, the charge storage electrode 14, the charge transfer control electrode 21, and the second electrode 12 are composed of transparent electrodes made of, for example, ITO (work function: about 4.4 eV). The photoelectric conversion layer 13 is composed of a layer including a well-known organic photoelectric conversion material (e.g., organic materials such as rhodamine-based dyes, melacyanine-based dyes, and quinacridone) having sensitivity to at least green light. The photoelectric conversion layer 13 may further include a material layer suitable for charge storage. That is, a material layer suitable for charge storage may be further formed between the photoelectric conversion layer 13 and the first electrode 11 (e.g., in the connection portion 67). The interlayer insulating layer 81, the insulating layer 82, and the protective layer 83 are composed of well-known insulating materials (e.g., SiO2 and SiN). The photoelectric conversion layer 13 and the first electrode 11 are connected by the connection portion 67 provided in the insulating layer 82. The photoelectric conversion layer 13 extends in the connection portion 67. That is, the photoelectric conversion layer 13 extends in the opening 84 provided in the insulating layer 82 and is connected to the first electrode 11.

[0134] The charge storage electrode 14 is connected to a drive circuit. Specifically, the charge storage electrode 14 is connected to a connection hole 66, a pad portion 64, and a wiring V, which are provided in the interlayer insulating layer 81. OA 1, which is connected to a vertical drive circuit 112 constituting a drive circuit.

[0135] The charge transfer control electrode 21 is also connected to the drive circuit. Specifically, the charge transfer control electrode 21 is connected to a connection hole 23, a pad portion 22, and a wiring V, which are provided in the interlayer insulating layer 81. OBMore specifically, the charge transfer control electrode 21 is connected to the region-B (13 B ) facing the insulating layer 82 (area-B (82) of the insulating layer). B In other words, the portion 82 of the insulating layer 82 in the region (region-b) between the charge storage electrodes 14 constituting the adjacent image pickup elements is B The charge transfer control electrode 21 is formed under the charge storage electrode 14. The charge transfer control electrode 21 is provided at a distance from the charge storage electrode 14. In other words, the charge transfer control electrode 21 surrounds the charge storage electrode 14 and is provided at a distance from the charge storage electrode 14. The charge transfer control electrode 21 is connected to the region-B (13 B ) is placed opposite.

[0136] The size of the charge storage electrode 14 is larger than that of the first electrode 11. When the area of ​​the charge storage electrode 14 is s1' and the area of ​​the first electrode 11 is s1, the following is not limited thereto. 4≦s1' / s1 It is preferable that the following is satisfied. In the image sensor of the sixth embodiment or the seventh embodiment described later, for example, but not limited to, s1' / s1=8 In Examples 12 to 15 described later, the three photoelectric conversion segments 101, 102, and 103 were all the same size and had the same planar shape.

[0137] An element isolation region 71 is formed on the first surface (front surface) 70A of the semiconductor substrate 70, and an oxide film 72 is formed on the first surface 70A of the semiconductor substrate 70. Furthermore, on the first surface side of the semiconductor substrate 70, a reset transistor TR1 constituting a control unit of the first imaging element is formed. rst , amplifying transistor TR1 amp and selection transistor TR1 sel is provided, and further, a first floating diffusion layer FD1 is provided.

[0138] Reset transistor TR1 rst The reset transistor TR1 is composed of a gate portion 51, a channel forming region 51A, and source / drain regions 51B and 51C. rst The gate 51 of the reset transistor TR1 is connected to the reset line RST1. rst One of the source / drain regions 51C also serves as the first floating diffusion layer FD1, and the other source / drain region 51B is connected to a power supply V DD is connected to

[0139] The first electrode 11 is connected to the reset transistor TR1 via a connection hole 65 provided in the interlayer insulating layer 81, a pad portion 63, a contact hole portion 61 formed in the semiconductor substrate 70 and the interlayer insulating layer 76, and a wiring layer 62 formed in the interlayer insulating layer 76. rst The first floating diffusion layer FD1 is connected to one of the source / drain regions 51C.

[0140] Amplification transistor TR1 amp The gate portion 52 is composed of a gate section 52, a channel forming region 52A, and source / drain regions 52B, 52C. The gate portion 52 is connected to the first electrode 11 and the reset transistor TR1 via a wiring layer 62. rst One of the source / drain regions 51C (first floating diffusion layer FD1) is connected to the power supply VDD. The other of the source / drain regions 52B is connected to the power supply VDD.

[0141] Selection transistor TR1 sel The amplifier transistor TR1 includes a gate portion 53, a channel forming region 53A, and source / drain regions 53B and 53C. The gate portion 53 is connected to a selection line SEL1. The source / drain region 53B is connected to the amplifier transistor TR1. amp The other source / drain region 53C is connected to a signal line (data output line) VSL1 (117).

[0142] The second imaging element includes an n-type semiconductor region 41 provided on a semiconductor substrate 70 as a photoelectric conversion layer. trs The gate portion 45 of the transfer transistor TR2 extends to the n-type semiconductor region 41 and is connected to the transfer gate line TG2. trs A second floating diffusion layer FD2 is provided in a region 45C of the semiconductor substrate 70 near the gate portion 45. The charges stored in the n-type semiconductor region 41 are read out to the second floating diffusion layer FD2 via a transfer channel formed along the gate portion 45.

[0143] In the second imaging element, a reset transistor TR2 constituting a control unit of the second imaging element is further provided on the first surface side of the semiconductor substrate 70. rst , amplifying transistor TR2 amp and selection transistor TR2 sel is provided.

[0144] Reset transistor TR2 rst The reset transistor TR2 is composed of a gate portion, a channel forming region, and a source / drain region. rst The gate of the reset transistor TR2 is connected to the reset line RST2. rst One of the source / drain regions is connected to the power supply V DD , and the other source / drain region also serves as the second floating diffusion layer FD2.

[0145] Amplification transistor TR2 amp The reset transistor TR2 is composed of a gate portion, a channel forming region, and a source / drain region. rst The other source / drain region (second floating diffusion layer FD2) of the second floating diffusion layer FD1 is connected to the power supply V DD is connected to

[0146] Selection transistor TR2 selThe amplifier transistor TR2 is composed of a gate portion, a channel forming region, and a source / drain region. The gate portion is connected to a selection line SEL2. One of the source / drain regions is connected to the amplifier transistor TR2. amp The other source / drain region is connected to a signal line (data output line) VSL2.

[0147] The third imaging element includes an n-type semiconductor region 43 provided on a semiconductor substrate 70 as a photoelectric conversion layer. trs The gate portion 46 of the transfer transistor TR3 is connected to the transfer gate line TG3. trs A third floating diffusion layer FD3 is provided in a region 46C of the semiconductor substrate 70 near the gate portion 46. The charges stored in the n-type semiconductor region 43 are read out to the third floating diffusion layer FD3 via a transfer channel 46A formed along the gate portion 46.

[0148] In the third imaging element, a reset transistor TR3 constituting a control unit of the third imaging element is further provided on the first surface side of the semiconductor substrate 70. rst , amplifying transistor TR3 amp and selection transistor TR3 sel is provided.

[0149] Reset transistor TR3 rst The reset transistor TR3 consists of a gate portion, a channel forming region, and a source / drain region. rst The gate of the reset transistor TR3 is connected to the reset line RST3. rst One of the source / drain regions is connected to the power supply V DD , and the other source / drain region also serves as the third floating diffusion layer FD3.

[0150] Amplification transistor TR3 amp The reset transistor TR3 is composed of a gate portion, a channel forming region, and a source / drain region. rstThe other source / drain region (third floating diffusion layer FD3) of the first transistor is connected to the power supply V DD is connected to

[0151] Selection transistor TR3 sel The amplifier transistor TR3 is composed of a gate portion, a channel forming region, and a source / drain region. The gate portion is connected to a selection line SEL3. One of the source / drain regions is connected to the amplifier transistor TR3. amp The other source / drain region is connected to a signal line (data output line) VSL3.

[0152] The reset lines RST1, RST2, and RST3, the selection lines SEL1, SEL2, and SEL3, and the transfer gate lines TG2 and TG3 are connected to a vertical drive circuit 112 that constitutes a drive circuit, and the signal lines (data output lines) VSL1, VSL2, and VSL3 are connected to a column signal processing circuit 113 that constitutes a drive circuit.

[0153] Between the n-type semiconductor region 43 and the surface 70A of the semiconductor substrate 70, + A p-type semiconductor layer 44 is provided between the n-type semiconductor region 41 and the n-type semiconductor region 43 to suppress the generation of dark current. + The layer 42 is formed, and further, a part of the side surface of the n-type semiconductor region 43 is p + The semiconductor substrate 70 is surrounded by a layer 42. The back surface 70B of the semiconductor substrate 70 is + A layer 73 is formed, and p + An HfO2 film 74 and an insulating film 75 are formed in a portion of the layer 73 where the contact hole portion 61 is to be formed inside the semiconductor substrate 70. In the interlayer insulating layer 76, wiring is formed across a plurality of layers, but is not shown in the figure.

[0154] The HfO2 film 74 is a film having a negative fixed charge, and by providing such a film, the generation of dark current can be suppressed. Note that, instead of the HfO2 film, an aluminum oxide (Al2O3) film, a zirconium oxide (ZrO2) film, a tantalum oxide (Ta2O5) film, a titanium oxide (TiO2) film, a lanthanum oxide (La2O3) film, a praseodymium oxide (Pr2O3) film, a cerium oxide (CeO2) film, a neodymium oxide (Nd2O3) film, a promethium oxide (Pm2O3) film, a samarium oxide (Sm2O3) film, a europium oxide (Eu2O3) film, a gadolinium oxide (Gd2O3) film, an oxide Terbium (Tb2O3) film, dysprosium oxide (Dy2O3) film, holmium oxide (Ho2O3) film, thulium oxide (Tm2O3) film, ytterbium oxide (Yb2O3) film, lutetium oxide (Lu2O3) film, yttrium oxide (Y2O3) film, hafnium nitride film, aluminum nitride film, hafnium oxynitride film, and aluminum oxynitride film can also be used. Methods for forming these films include, for example, CVD, PVD, and ALD.

[0155] Hereinafter, the operation of the imaging element (first imaging element) of Example 6 will be described with reference to FIG. 18 and FIG. 19A. The imaging element of Example 6 is provided on a semiconductor substrate 70 and further includes a control unit having a drive circuit, and the first electrode 11, the second electrode 12, the charge storage electrode 14, and the charge transfer control electrode 21 are connected to the drive circuit. Here, the potential of the first electrode 11 is made higher than the potential of the second electrode 12. That is, for example, the first electrode 11 is made to have a positive potential, the second electrode 12 is made to have a negative potential, and electrons generated by photoelectric conversion in the photoelectric conversion layer 13 are read out to the floating diffusion layer. The same applies to other examples. Note that, in a form in which the first electrode 11 is made to have a negative potential, the second electrode 12 is made to have a positive potential, and holes generated based on photoelectric conversion in the photoelectric conversion layer 13 are read out to the floating diffusion layer, the high and low potentials described below may be reversed.

[0156] The symbols used in Fig. 18, Fig. 46 and Fig. 47 in Example 10 described later, and Fig. 53 and Fig. 54 in Example 11 are as follows: Fig. 19A, Fig. 19B, and Fig. 19C are equivalent circuit diagrams of the image sensor and stacked image sensor of Examples 6, 10, and 11 for explaining the respective parts of Fig. 18 (Example 6), Fig. 46 (Example 10), and Fig. 53 (Example 11).

[0157] P A Point P in the region of the photoelectric conversion layer 13 facing the region located between the charge storage electrode 14 or the transfer control electrode (charge transfer electrode) 15 and the first electrode 11 A Electric potential at P B Point P in the region of the photoelectric conversion layer 13 facing the charge transfer control electrode 21 B Electric potential at P C Point P in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 C Electric potential at P C1 Point P in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 14A C1 Electric potential at P C2 Point P in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 14B C2 Electric potential at P C3 Point P in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 14C C3 Electric potential at P D Point P in the region of the photoelectric conversion layer 13 facing the transfer control electrode (charge transfer electrode) 15 D Electric potential at FD: Electric potential at the first floating diffusion layer FD1 V OA Potential at the charge storage electrode 14 V OA-A Potential at the charge storage electrode segment 14A V OA-B Potential at the charge storage electrode segment 14B V OA-C Potential at the charge storage electrode segment 14C V OT Potential at the transfer control electrode (charge transfer electrode) 15 RST Reset transistor TR1 rst The potential at the gate portion 51 V DD ...Power supply potential VSL1 Signal line (data output line) VSL1 TR1 rst Reset transistor TR1 rst TR1 amp Amplification transistor TR1 amp TR1 sel Selection transistor TR1 sel

[0158] During the charge accumulation period, the drive circuit applies a potential V 11 is applied to the charge storage electrode 14, and a potential V 12 is applied to the charge transfer control electrode 21, and a potential V 13 A voltage V V is applied to the second electrode 12. Photoelectric conversion occurs in the photoelectric conversion layer 13 due to the light incident on the photoelectric conversion layer 13. Holes generated by the photoelectric conversion are guided from the second electrode 12 to the wiring V OU On the other hand, since the potential of the first electrode 11 is made higher than the potential of the second electrode 12, that is, for example, a positive potential is applied to the first electrode 11 and a negative potential is applied to the second electrode 12, V 12 ≧V 11 , preferably V 12 >V 11 And V 12 >V 13 As a result, electrons generated by photoelectric conversion are attracted to the charge storage electrode 14 and are stored in the region 13 of the photoelectric conversion layer 13 facing the charge storage electrode 14. C That is, charges are accumulated in the photoelectric conversion layer 13. 12 >V 11Therefore, the electrons generated inside the photoelectric conversion layer 13 do not move toward the first electrode 11. 12 >V 13 Therefore, the electrons generated inside the photoelectric conversion layer 13 do not move toward the charge transfer control electrode 21. That is, it is possible to prevent the charge generated by the photoelectric conversion from flowing into the adjacent image sensor. As the photoelectric conversion progresses, the potential in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 becomes more negative.

[0159] In the latter part of the charge accumulation period, a reset operation is performed. This resets the potential of the first floating diffusion layer FD1, and the potential of the first floating diffusion layer FD1 becomes equal to the power supply potential V DD It becomes.

[0160] After the reset operation is completed, the electric charge is read out. That is, during the electric charge transfer period, the driving circuit applies a potential V 21 is applied to the charge storage electrode 14, and a potential V 22 is applied to the charge transfer control electrode 21, and a potential V 23 is applied, where V 21 >V 22 >V 23 As a result, the electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 are read out to the first electrode 11 and further to the first floating diffusion layer FD1. That is, the charges stored in the photoelectric conversion layer 13 are read out to the control unit. Also, V 22 >V 23 For this reason, the electrons generated inside the photoelectric conversion layer 13 do not move toward the charge transfer control electrode 21. That is, it is possible to prevent the charges generated by photoelectric conversion from flowing into the adjacent imaging element.

[0161] This completes a series of operations including charge accumulation, reset operation, and charge transfer.

[0162] The amplifier transistor TR1 after electrons are read out to the first floating diffusion layer FD1 amp , selection transistor TR1 selThe operation of the second imaging element is the same as that of the conventional transistors. Also, the series of operations of the second imaging element and the third imaging element, such as charge accumulation, reset operation, and charge transfer, are the same as the series of operations of the conventional charge accumulation, reset operation, and charge transfer. Also, the reset noise of the first floating diffusion layer FD1 can be removed by correlated double sampling (CDS) processing, as in the conventional case.

[0163] As described above, in the imaging element of Example 6 or Example 7 described later, the charge storage electrode is disposed apart from the first electrode and opposed to the photoelectric conversion layer via the insulating layer. Therefore, when light is irradiated to the photoelectric conversion unit and photoelectric conversion is performed in the photoelectric conversion unit, a kind of capacitor is formed by the photoelectric conversion layer, the insulating layer, and the charge storage electrode, and charge can be stored in the photoelectric conversion layer. Therefore, at the start of exposure, it is possible to completely deplete the charge storage unit and erase the charge. As a result, it is possible to suppress the occurrence of phenomena such as increased kTC noise, worsening random noise, and a decrease in image quality. In addition, since all pixels can be reset simultaneously, a so-called global shutter function can be realized.

[0164] Moreover, in the imaging element of the sixth embodiment, when light is incident on the photoelectric conversion layer and photoelectric conversion occurs in the photoelectric conversion layer, the absolute value of the potential applied to the portion of the photoelectric conversion layer facing the charge storage electrode is greater than the absolute value of the potential applied to the region-B of the photoelectric conversion layer, so that the charge generated by the photoelectric conversion is strongly attracted to the portion of the photoelectric conversion layer facing the charge storage electrode. As a result, the charge generated by the photoelectric conversion can be prevented from flowing into an adjacent imaging element, so that the quality of the captured image does not deteriorate. Alternatively, since a charge transfer control electrode is formed in the region facing the region-B of the photoelectric conversion layer via an insulating layer, the electric field and potential of the region-B of the photoelectric conversion layer located above the charge transfer control electrode can be controlled. As a result, the charge generated by the photoelectric conversion can be prevented from flowing into an adjacent imaging element by the charge transfer control electrode, so that the quality of the captured image does not deteriorate.

[0165] Fig. 20 shows a conceptual diagram of a solid-state imaging device of Example 6. The solid-state imaging device 100 of Example 6 is composed of an imaging region 111 in which stacked imaging elements 101 are arranged in a two-dimensional array, and a vertical driving circuit 112, a column signal processing circuit 113, a horizontal driving circuit 114, an output circuit 115, a driving control circuit 116, and the like as driving circuits (peripheral circuits) thereof. It goes without saying that these circuits can be composed of well-known circuits, and can also be composed using other circuit configurations (for example, various circuits used in conventional CCD-type solid-state imaging devices and CMOS-type solid-state imaging devices). In Fig. 20, the reference number "101" for the stacked imaging element 101 is displayed in only one line.

[0166] The drive control circuit 116 generates clock signals and control signals that serve as references for the operations of the vertical drive circuit 112, the column signal processing circuit 113, and the horizontal drive circuit 114, based on the vertical synchronizing signal, the horizontal synchronizing signal, and the master clock. The generated clock signals and control signals are then input to the vertical drive circuit 112, the column signal processing circuit 113, and the horizontal drive circuit 114.

[0167] The vertical drive circuit 112 is configured with, for example, a shift register, and sequentially selects and scans each stack-type imaging element 101 in the imaging region 111 in the vertical direction on a row-by-row basis. Then, pixel signals (image signals) based on currents (signals) generated according to the amount of light received in each stack-type imaging element 101 are sent to a column signal processing circuit 113 via signal lines (data output lines) 117 and VSL.

[0168] The column signal processing circuit 113 is arranged, for example, for each column of the stacked imaging element 101, and performs signal processing such as noise removal and signal amplification on the image signals output from one row of the stacked imaging element 101 using signals from black reference pixels (not shown, but formed around the effective pixel area) for each imaging element. A horizontal selection switch (not shown) is provided at the output stage of the column signal processing circuit 113 and connected between the horizontal signal line 118.

[0169] The horizontal drive circuit 114 is configured by, for example, a shift register, and sequentially outputs horizontal scanning pulses to sequentially select each of the column signal processing circuits 113 and output signals from each of the column signal processing circuits 113 to a horizontal signal line 118.

[0170] The output circuit 115 processes the signals sequentially supplied from each of the column signal processing circuits 113 via a horizontal signal line 118 and outputs the processed signals.

[0171] FIG. 21 shows an equivalent circuit diagram of the imaging element of Example 6 and a modified example (modified example 2 of Example 6) of the stacked imaging element. FIG. 22 shows a schematic layout diagram of the first electrode and the charge storage electrode constituting the modified example (modified example 2 of Example 6) of the imaging element of Example 6 and the transistors constituting the control unit. rst The other source / drain region 51B is connected to a power supply V DD Instead of connecting to ground,

[0172] The imaging element and stacked type imaging element of the sixth embodiment can be fabricated, for example, by the following method. That is, first, an SOI substrate is prepared. Then, a first silicon layer is formed on the surface of the SOI substrate by epitaxial growth. + Next, a second silicon layer is formed on the first silicon layer by epitaxial growth, and an element isolation region 71, an oxide film 72, a p + layer 42, n-type semiconductor region 43, p + A layer 44 is formed on the second silicon layer. Various transistors constituting the control section of the image sensor are formed on the second silicon layer, and a wiring layer 62, an interlayer insulating layer 76, and various wirings are formed thereon, and then the interlayer insulating layer 76 and a support substrate (not shown) are bonded together. Thereafter, the SOI substrate is removed to expose the first silicon layer. The surface of the second silicon layer corresponds to the surface 70A of the semiconductor substrate 70, and the surface of the first silicon layer corresponds to the back surface 70B of the semiconductor substrate 70. The first silicon layer and the second silicon layer are collectively referred to as the semiconductor substrate 70. Next, an opening for forming a contact hole portion 61 is formed on the rear surface 70B side of the semiconductor substrate 70, and an HfO2 film 74, an insulating film 75 and the contact hole portion 61 are formed. Furthermore, pad portions 63, 64, 22, an interlayer insulating layer 81, connection holes 65, 66, 23, a first electrode 11, a charge storage electrode 14, a charge transfer control electrode 21, and an insulating layer 82 (including a first region 82a1, 82b1, 82c1, a second region 82a2, 82b2, 82c2, a third region 82c3, a first insulating layer 82A1, 82B1, 82C1, a second insulating layer 82A2, 82B2, 82C2, a second insulating layer extension portion 82A2', 82B2', a third insulating layer 82C3, an insulating material layer (first insulating material layer) 82D, and an insulating material layer (second insulating material layer) 82E) are formed. Next, the connection portion 67 is opened, and the photoelectric conversion layer 13, the second electrode 12, the protective layer 83, and the on-chip microlens 90 are formed. Through the above steps, the imaging element and the stacked type imaging element of Example 6 can be obtained.

[0173] 23 (Modification 3 of Example 6), 24 (Modification 4 of Example 6), and 25 (Modification 5 of Example 6) are schematic layout diagrams of other modifications of the first electrodes and charge storage electrodes constituting the imaging element of Example 6. In the examples shown in these drawings, one common first electrode 11 is provided in correspondence with the four charge storage electrodes 14 in the four imaging elements. In the example shown in FIG. 23, a portion 82 of an insulating layer 82 in a region (region-b) sandwiched between the charge storage electrodes 14 and the charge storage electrodes 14 is B 24, the charge transfer control electrode 21 is formed under the insulating layer 82 in the region surrounded by the four charge storage electrodes 14. The example shown in Fig. 25 is a combination of the examples shown in Fig. 23 and Fig. 24. The examples shown in Fig. 23, Fig. 24 and Fig. 25 also correspond to solid-state imaging devices of the first and second configurations.

[0174] Alternatively, a schematic cross-sectional view of a part of a modified example (modification 6 of embodiment 6) of the imaging element of embodiment 6 (two imaging elements arranged side by side) is shown in FIG. 26. DN and the upper photoelectric conversion layer 13 UP The upper photoelectric conversion layer 13 may have a laminated structure. UP and the lower semiconductor layer 13 DN is shared among a plurality of imaging elements. That is, in a plurality of imaging elements, one upper photoelectric conversion layer 13 UP and the lower semiconductor layer 13 DN In this way, the lower semiconductor layer 13 DN By providing the upper photoelectric conversion layer 13, for example, recombination during charge accumulation can be prevented. Also, the charge transfer efficiency of the charge accumulated in the photoelectric conversion layer 13 to the first electrode 11 can be increased. Furthermore, the charge generated in the photoelectric conversion layer 13 can be temporarily held, and the timing of transfer can be controlled. Also, the generation of dark current can be suppressed. Upper photoelectric conversion layer 13 UP The material for the lower semiconductor layer 13 may be appropriately selected from various materials for forming the photoelectric conversion layer 13. DNIt is preferable to use a material having a large band gap energy (for example, a band gap energy of 3.0 eV or more) and a higher mobility than the material constituting the photoelectric conversion layer, and specifically, for example, an oxide semiconductor material such as IGZO can be used. DN When the charge to be stored is an electron, the material constituting the lower semiconductor layer may have an ionization potential greater than that of the material constituting the photoelectric conversion layer. Alternatively, the impurity concentration in the material constituting the lower semiconductor layer may be 1×10 18 cm -3 It is preferable that the following is true: The configuration and structure of the sixth modified example of the sixth embodiment can be applied to the other embodiments.

[0175] In the above description of Example 6, the description has been given based on a form in which the charge transfer control electrode 21 is formed, but the formation of the charge transfer control electrode 21 is not essential, and in some cases, the formation of the charge transfer control electrode 21 can be omitted. EXAMPLES

[0176] Example 7 also relates to the stacked imaging element of the present disclosure and the solid-state imaging device according to the second aspect of the present disclosure. That is, the stacked imaging element in Example 7 includes at least one of the imaging elements of Examples 1 to 5 or their modified examples, and the solid-state imaging device of Example 7 includes a plurality of the stacked imaging elements of Example 6.

[0177] A schematic cross-sectional view of a portion of the imaging element (two imaging elements arranged side by side) of Example 7 is shown in Fig. 27, and schematic plan views of a portion of the imaging element (2 x 2 imaging elements arranged side by side) of Example 7 are shown in Figs. 28 and 29. In the imaging element of Example 7, a region 13 of a photoelectric conversion layer 13 located between adjacent imaging elements is BInstead of forming the second electrode 12, a charge transfer control electrode 24 is formed on the photoelectric conversion layer 13. The charge transfer control electrode 24 is provided spaced apart from the second electrode 12. In other words, the second electrode 12 is provided for each imaging element, and the charge transfer control electrode 24 surrounds at least a portion of the second electrode 12 and is provided on the region-B of the photoelectric conversion layer 13 spaced apart from the second electrode 12. The charge transfer control electrode 24 is formed at the same level as the second electrode 12.

[0178] 28, one image sensor has one charge storage electrode 14 corresponding to one first electrode 11. On the other hand, in the example shown in Fig. 29 (Modification 1 of Example 7), two image sensors have one common first electrode 11 corresponding to two charge storage electrodes 14. The schematic cross-sectional view of a portion of the image sensor of Example 7 (two juxtaposed image sensors) shown in Fig. 27 corresponds to Fig. 29.

[0179] In the seventh embodiment, the second electrode 12 located on the light incident side is shared among the imaging elements arranged in the horizontal direction of the paper of FIG. 28, and is shared among a pair of imaging elements arranged in the vertical direction of the paper of FIG. 28. The charge transfer control electrode 24 is also shared among the imaging elements arranged in the horizontal direction of the paper of FIG. 28, and is also shared among a pair of imaging elements arranged in the vertical direction of the paper of FIG. 28. The second electrode 12 and the charge transfer control electrode 24 can be obtained by forming a material layer constituting the second electrode 12 and the charge transfer control electrode 24 on the photoelectric conversion layer 13, and then patterning the material layer. The second electrode 12 and the charge transfer control electrode 24 are each connected to a separate wiring (not shown), and these wirings are connected to a driving circuit. The wiring connected to the second electrode 12 is shared among a plurality of imaging elements. The wiring connected to the charge transfer control electrode 24 is also shared among a plurality of imaging elements.

[0180] In the image sensor of the seventh embodiment, during the charge accumulation period, the driving circuit applies a potential V2' to the second electrode 12 and a potential V 13During the charge transfer period, a potential V2″ is applied to the second electrode 12 from the drive circuit, and a potential V 23 " is applied, and the charge accumulated in the photoelectric conversion layer 13 is read out to the control unit via the first electrode 11. Here, since the potential of the first electrode 11 is higher than the potential of the second electrode 12, V2' ≧ V 13 ', and V2" ≧ V 23 " It is.

[0181] As described above, in the imaging element of Example 7, instead of a second electrode being formed on the region of the photoelectric conversion layer located between adjacent imaging elements, a charge transfer control electrode is formed. Therefore, the charge transfer control electrode can prevent the charge generated by photoelectric conversion from flowing into the adjacent imaging element, and therefore no degradation in quality occurs in the captured video (image).

[0182] 30A and 30B are schematic plan views of a part of a modified example (modified example 2 of the seventh embodiment) of the imaging element of the seventh embodiment. In addition, in FIG. 30A, FIG. 31A, FIG. 33A, FIG. 34A, FIG. 35A, and FIG. 36A, an example is shown in which one common first electrode 11 is provided in correspondence with four charge storage electrodes 14 in four imaging elements. Then, as shown in FIG. 30B, the second electrode 12 is provided above the charge storage electrode 14 and has approximately the same size as the charge storage electrode 14. The second electrode 12 is surrounded by the charge transfer control electrode 24. The charge transfer control electrode 24 is provided in common in each imaging element. An insulating film (not shown) is formed on the photoelectric conversion layer 13 including the second electrode 12 and the charge transfer control electrode 24, and a contact hole (not shown) connected to the second electrode 12 is formed in the insulating film above the second electrode 12, and a wiring V connected to the contact hole is formed on the insulating film. OU (not shown) are provided. The second electrode 12, the insulating film, the contact hole, the wiring V OUThe configurations and structures are the same in the following modified examples. Also, the examples shown in Figures 30A, 30B, 31A, 31B, 33A, 33B, 34A, 34B, 35A, 35B, 36A, and 36 are also solid-state imaging devices of the first and second configurations.

[0183] 31A and 31B are schematic plan views of a portion of Modification 3 of Example 7. As shown in FIG. 31B, the second electrode 12 is provided above the charge storage electrode 14 and has approximately the same size as the charge storage electrode 14. The second electrode 12 is surrounded by a charge transfer control electrode 24. The charge transfer control electrode 24 is provided in common to the four imaging elements. The common portion is formed on the photoelectric conversion layer 13.

[0184] A schematic cross-sectional view of a portion of a modified example (Modification 4A of Example 7) of the imaging element (two imaging elements arranged side by side) of Example 7 is shown in Fig. 32A, and schematic plan views of the portion are shown in Fig. 33A and Fig. 33B. In Modification 4A of Example 7, the second electrode 12 is provided for each imaging element, the charge transfer control electrode 24 is provided so as to surround at least a portion of the second electrode 12 and be spaced apart from the second electrode 12, and a portion of the charge storage electrode 14 exists below the charge transfer control electrode 24. The second electrode 12 is provided above the charge storage electrode 14 and has a size smaller than that of the charge storage electrode 14.

[0185] FIG. 32B shows a schematic cross-sectional view of a part of a modified example (modified example 4B of embodiment 7) of the imaging element (two imaging elements arranged side by side) of embodiment 7, and FIG. 34A and FIG. 34B show schematic plan views of the part. In modified example 4B, the second electrode 12 is provided for each imaging element, the charge transfer control electrode 24 is provided to surround at least a part of the second electrode 12 and spaced apart from the second electrode 12, a part of the charge storage electrode 14 exists below the charge transfer control electrode 24, and the charge transfer control electrode (lower charge transfer control electrode) 21 is provided below the charge transfer control electrode (upper charge transfer control electrode) 24. The size of the second electrode 12 is smaller than that of modified example 4A. That is, the area of ​​the second electrode 12 facing the charge transfer control electrode 24 is located closer to the first electrode 11 than the area of ​​the second electrode 12 facing the charge transfer control electrode 24 in modified example 4A. The charge storage electrode 14 is surrounded by a charge transfer control electrode 21 .

[0186] 35A and 35B are schematic plan views of a part of a modified example (modified example 4C of the embodiment 7) of the imaging element of the embodiment 7. In the modified example 4C, a part of the charge storage electrode 14 exists below the charge transfer control electrode 24, as in the modified example 4B of the embodiment 7. The size of the second electrode 12 is smaller than that of the modified example 4A. That is, the area of ​​the second electrode 12 facing the charge transfer control electrode 24 is located closer to the first electrode 11 than the area of ​​the second electrode 12 facing the charge transfer control electrode 24 in the modified example 4A. In addition, the charge transfer control electrode 24 is composed of an outer charge transfer control electrode 241 and an inner charge transfer control electrode 242 provided between the outer charge transfer control electrode 241 and the second electrode 12. The charge storage electrode 14 is surrounded by the charge transfer control electrode 21. During the charge transfer period, by satisfying the relationship (potential applied to the outer charge transfer control electrode 241)<(potential applied to the inner charge transfer control electrode 242)<(potential applied to the second electrode 11), charge transfer can be performed more effectively.

[0187] 36A and 36B are schematic plan views of a part of a modified example (modified example 4D of embodiment 7) of the imaging element of embodiment 7. In modified example 4D, a charge transfer control electrode (lower charge transfer control electrode) 21 is provided below the charge transfer control electrode (upper charge transfer control electrode) 24, as in modified example 4B of embodiment 7. The size of the second electrode 12 is smaller than that of modified example 4B. That is, the region of the second electrode 12 facing the charge transfer control electrode 24 is located closer to the first electrode 11 than the region of the second electrode 12 facing the charge transfer control electrode 24 in modified example 4B. In addition, the distance between the charge transfer control electrode 24 and the second electrode 12 is wider than that of modified example 4B. The charge storage electrode 14 is surrounded by the charge transfer control electrode 21. A potential generated by coupling between the charge transfer control electrode 24 and the second electrode 12 is applied to the region of the photoelectric conversion layer 13 located below the region between the charge transfer control electrode 24 and the second electrode 12. EXAMPLES

[0188] Example 8 is a modification of Examples 6 to 7. The imaging element and stacked imaging element of Example 8, the schematic partial cross-sectional view of which is shown in FIG. 37, are front-illuminated imaging elements and stacked imaging elements, and have a structure in which three imaging elements are stacked: a first-type green light imaging element (first imaging element) of Example 6 having sensitivity to green light and including a first-type green photoelectric conversion layer that absorbs green light, a second-type conventional blue light imaging element (second imaging element) having sensitivity to blue light and including a second-type blue photoelectric conversion layer that absorbs blue light, and a second-type conventional red light imaging element (third imaging element) having sensitivity to red light and including a second-type red photoelectric conversion layer that absorbs red light. Here, the red light imaging element (third imaging element) and the blue light imaging element (second imaging element) are provided in a semiconductor substrate 70, and the second imaging element is located closer to the light incident side than the third imaging element. Moreover, the green light imaging element (first imaging element) is provided above the blue light imaging element (second imaging element).

[0189] Various transistors constituting a control unit are provided on the front surface 70A side of the semiconductor substrate 70 in the same manner as in Example 6. These transistors can be substantially similar in configuration and structure to the transistors described in Example 6. In addition, the semiconductor substrate 70 is provided with a second imaging element and a third imaging element, and these imaging elements can also be substantially similar in configuration and structure to the second imaging element and the third imaging element described in Example 6.

[0190] Interlayer insulating layers 77, 78 are formed on the surface 70A of the semiconductor substrate 70, and a photoelectric conversion section (first electrode 11, photoelectric conversion layer 13, and second electrode 12) constituting the imaging element of Example 6, as well as a charge storage electrode 14, etc. are provided on the interlayer insulating layer 78.

[0191] In this way, except for being a front-illuminated type, the configurations and structures of the imaging element and stack-type imaging element of Example 8 can be similar to the configurations and structures of the imaging element and stack-type imaging element of Example 6, so detailed description thereof will be omitted. EXAMPLES

[0192] The ninth embodiment is a modification of the sixth to eighth embodiments.

[0193] The imaging element and stacked imaging element of Example 9, the schematic partial cross-sectional view of which is shown in FIG. 38, are back-illuminated imaging elements and stacked imaging elements, and have a structure in which two imaging elements, the first imaging element of Example 6 of the first type and the second imaging element of the second type, are stacked. Also, the imaging element and the modified example of the stacked imaging element of Example 9, the schematic partial cross-sectional view of which is shown in FIG. 39, are front-illuminated imaging elements and stacked imaging elements, and have a structure in which two imaging elements, the first imaging element of Example 6 of the first type and the second imaging element of the second type, are stacked. Here, the first imaging element absorbs primary color light, and the second imaging element absorbs complementary color light. Alternatively, the first imaging element absorbs white light, and the second imaging element absorbs infrared light.

[0194] A modified example of the imaging element of Example 9, the schematic partial cross-sectional view of which is shown in Fig. 40, is a back-illuminated imaging element, and is composed of the first imaging element of Example 6 of the first type. Also, a modified example of the imaging element of Example 9, the schematic partial cross-sectional view of which is shown in Fig. 41, is a front-illuminated imaging element, and is composed of the first imaging element of Example 6 of the first type. Here, the first imaging element is composed of three types of imaging elements, an imaging element that absorbs red light, an imaging element that absorbs green light, and an imaging element that absorbs blue light.

[0195] Furthermore, a solid-state imaging device according to the first aspect of the present disclosure is configured from a plurality of these imaging elements. The plurality of imaging elements may be arranged in a Bayer array. A color filter for separating blue, green, and red light is disposed on the light incident side of each imaging element as necessary.

[0196] Instead of providing one image sensor of the first type according to the sixth embodiment, two may be stacked (i.e., two photoelectric conversion units are stacked and a control unit for the two image sensors is provided on the semiconductor substrate), or three may be stacked (i.e., three photoelectric conversion units are stacked and a control unit for the three image sensors is provided on the semiconductor substrate). Examples of stacked structures of the first type image sensor and the second type image sensor are shown in the following table.

[0197] JPEG0007605880000001.jpg155128 EXAMPLES

[0198] Example 10 is a modification of Examples 6 to 9, and relates to an imaging element and the like of the present disclosure that includes a transfer control electrode (charge transfer electrode). A schematic partial cross-sectional view of a part of the imaging element and stacked imaging element of Example 10 is shown in FIG. 42, equivalent circuit diagrams of the imaging element and stacked imaging element of Example 10 are shown in FIG. 43 and FIG. 44, a schematic layout diagram of the first electrode, transfer control electrode, and charge storage electrode constituting the imaging element of Example 10, and transistors constituting the control unit is shown in FIG. 45, and the state of electric potential at each part during operation of the imaging element of Example 10 is shown in FIG. 46 and FIG. 47. Also, a schematic layout diagram of the first electrode, transfer control electrode, and charge storage electrode constituting the imaging element of Example 10 is shown in FIG. 48, and an equivalent circuit diagram of the imaging element and stacked imaging element of Example 10 for explaining each part of FIG. 46 and FIG. 47 is shown in FIG. 19B.

[0199] The imaging element and stacked type imaging element of Example 10 further include a transfer control electrode (charge transfer electrode) 15 disposed between the first electrode 11 and the charge storage electrode 14, spaced apart from the first electrode 11 and the charge storage electrode 14, and opposed to the photoelectric conversion layer 13 via an insulating layer 82. The transfer control electrode 15 is connected to a pixel driving circuit constituting a driving circuit via a connection hole 68B, a pad portion 68A, and a wiring VOT provided in the interlayer insulating layer 81.

[0200] Hereinafter, the operation of the imaging element (first imaging element) of the tenth embodiment will be described with reference to Fig. 46 and Fig. 47. In Fig. 46 and Fig. 47, in particular, the potential applied to the charge accumulation electrode 14 and the point P D The values ​​of the potential at are different.

[0201] During the charge accumulation period, the driving circuit applies a potential V 11 is applied to the charge storage electrode 14, and a potential V 12 is applied to the transfer control electrode 15, and a potential V 14 A voltage V V is applied to the second electrode 12. Photoelectric conversion occurs in the photoelectric conversion layer 13 due to the light incident on the photoelectric conversion layer 13. Holes generated by the photoelectric conversion are guided from the second electrode 12 to the wiring V OUOn the other hand, since the potential of the first electrode 11 is made higher than the potential of the second electrode 12, that is, for example, a positive potential is applied to the first electrode 11 and a negative potential is applied to the second electrode 12, V 12 >V 14 (For example, V 12 >V 11 >V 14 , or V 11 >V 12 >V 14 ) As a result, electrons generated by photoelectric conversion are attracted to the charge storage electrode 14 and stay in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14. That is, charges are stored in the photoelectric conversion layer 13. 12 >V 14 Therefore, it is possible to reliably prevent electrons generated inside the photoelectric conversion layer 13 from moving toward the first electrode 11. As the photoelectric conversion progresses, the potential in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 becomes more negative.

[0202] In the latter part of the charge accumulation period, a reset operation is performed. This resets the potential of the first floating diffusion layer FD1, and the potential of the first floating diffusion layer FD1 becomes equal to the power supply potential V DD It becomes.

[0203] After the reset operation is completed, the electric charge is read out. That is, during the electric charge transfer period, the driving circuit applies a potential V 21 is applied to the charge storage electrode 14, and a potential V 22 is applied to the transfer control electrode 15, and a potential V 24 is applied, where V 22 ≦V 24 ≦V 21 As a result, the electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 are reliably read out to the first electrode 11 and further to the first floating diffusion layer FD1. That is, the charges stored in the photoelectric conversion layer 13 are read out to the control unit.

[0204] This completes a series of operations including charge accumulation, reset operation, and charge transfer.

[0205] The amplifier transistor TR1 after electrons are read out to the first floating diffusion layer FD1 amp , selection transistor TR1 sel The operations of the second and third imaging elements are the same as those of the conventional transistors. Also, for example, a series of operations such as charge accumulation, reset operation, and charge transfer of the second and third imaging elements are the same as the series of operations such as charge accumulation, reset operation, and charge transfer of the conventional transistors.

[0206] FIG. 48 shows a schematic layout diagram of the first electrode and the charge storage electrode constituting the modified example of the image sensor of the tenth embodiment, and the transistors constituting the control section. The reset transistor TR1 rst The other source / drain region 51B is connected to a power supply V DD Instead of connecting to ground, EXAMPLES

[0207] Example 11 is a modification of Examples 6 to 10, and relates to an imaging element etc. of the present disclosure that includes a plurality of charge storage electrode segments.

[0208] A schematic partial cross-sectional view of a part of the imaging element of Example 11 is shown in Fig. 49, equivalent circuit diagrams of the imaging element of Example 11 and the stacked imaging element are shown in Fig. 50 and Fig. 51, a schematic layout diagram of the first electrode and the charge storage electrode constituting the imaging element of Example 11 and the transistor constituting the control unit is shown in Fig. 52, and the state of electric potential at each part during operation of the imaging element of Example 11 is shown in Fig. 53 and Fig. 54. Also, an equivalent circuit diagram of the imaging element of Example 11 and the stacked imaging element for explaining each part of Fig. 53 is shown in Fig. 19C.

[0209] In Example 11, the charge storage electrode 14 is composed of a plurality of charge storage electrode segments 14A, 14B, and 14C. The number of the charge storage electrode segments may be two or more, and is set to "3" in Example 11. In the imaging element and stacked imaging element of Example 11, different potentials are applied to the N charge storage electrode segments, but since the potential of the first electrode 11 is higher than the potential of the second electrode 12, that is, for example, a positive potential is applied to the first electrode 11 and a negative potential is applied to the second electrode 12, during the charge transfer period, the potential applied to the charge storage electrode segment (first photoelectric conversion unit segment) 14A located closest to the first electrode 11 is higher than the potential applied to the charge storage electrode segment (Nth photoelectric conversion unit segment) 14C located farthest from the first electrode 11. In this way, by applying a potential gradient to the charge storage electrode 14, the electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 are more reliably read out to the first electrode 11 and further to the first floating diffusion layer FD1. That is, the charges stored in the photoelectric conversion layer 13 are read out to the control unit.

[0210] In the example shown in Figure 53, during the charge transfer period, the potential of the charge storage electrode segment 14C < the potential of the charge storage electrode segment 14B < the potential of the charge storage electrode segment 14A is set, so that the electrons that have remained in the photoelectric conversion layer 13 area are read out all at once to the first floating diffusion layer FD1. On the other hand, in the example shown in Figure 54, during the charge transfer period, the potential of the charge storage electrode segment 14C, the potential of the charge storage electrode segment 14B, and the potential of the charge storage electrode segment 14A are gradually changed (i.e., changed in a stepped or sloped manner), so that electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 14C are moved to the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 14B, and then the electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 14B are moved to the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 14A, and then the electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 14A are reliably read out to the first floating diffusion layer FD1.

[0211] FIG. 55 shows a schematic layout diagram of the first electrode and the charge storage electrode constituting the modified example of the image sensor of the eleventh embodiment, and the transistors constituting the control section. The reset transistor TR1 rst The other source / drain region 51B is connected to a power supply V DD Instead of connecting to ground, EXAMPLES

[0212] Example 12 is a modification of Examples 6 to 11, and relates to the image sensor of the first and sixth configurations.

[0213] A schematic partial cross-sectional view of the imaging element and stacked type imaging element of Example 12 is shown in Fig. 56, and a schematic partial cross-sectional view of an enlarged portion where the charge storage electrode, the photoelectric conversion layer, and the second electrode are stacked is shown in Fig. 57. An equivalent circuit diagram of the imaging element and stacked type imaging element of Example 12 is similar to the equivalent circuit diagram of the imaging element of Example 6 described in Figs. 13 and 14, and a schematic layout diagram of the first electrode and charge storage electrode constituting the imaging element of Example 12 and the transistor constituting the control unit is similar to the imaging element of Example 6 described in Fig. 15. Furthermore, the operation of the imaging element (first imaging element) of Example 12 is substantially similar to the operation of the imaging element of Example 6.

[0214] Here, in the image sensor of Example 12 or the image sensors of Examples 13 to 17 described below, The photoelectric conversion unit is composed of N (N≧2) photoelectric conversion unit segments (specifically, three photoelectric conversion unit segments 101, 102, and 103), The photoelectric conversion layer 13 is composed of N photoelectric conversion layer segments (specifically, three photoelectric conversion layer segments 131, 132, and 133), The insulating layer 82 is composed of N insulating layer segments (specifically, three insulating layer segments 821, 822, and 823). In the twelfth to fourteenth embodiments, the charge-storage electrode 14 is composed of N charge-storage electrode segments (specifically, in each embodiment, three charge-storage electrode segments 141, 142, and 143). In Examples 15 to 16, or in some cases in Example 14, the charge-storage electrode 14 is configured with N charge-storage electrode segments (specifically, three charge-storage electrode segments 141, 142, and 143) that are spaced apart from each other, nth (n=1, 2, 3, . . . N) photoelectric conversion segment 10 n represents the n-th charge storage electrode segment 14 n , the nth insulating layer segment 82 n and the n-th photoelectric conversion layer segment 13 n It is composed of The larger the value of n, the farther the photoelectric conversion segment is located from the first electrode 11 .

[0215] Alternatively, the image sensor of the twelfth embodiment or the image sensors of the thirteenth and sixteenth embodiments described later may be The photoelectric conversion section is formed by stacking a first electrode 11, a photoelectric conversion layer 13, and a second electrode 12. The photoelectric conversion unit further includes a charge storage electrode 14 arranged apart from the first electrode 11 and facing the photoelectric conversion layer 13 with an insulating layer 82 interposed therebetween, When the stacking direction of the charge storage electrode 14, the insulating layer 82, and the photoelectric conversion layer 13 is defined as the Z direction and the direction away from the first electrode 11 is defined as the X direction, the cross-sectional area of ​​the stacked portion when the stacked portion in which the charge storage electrode 14, the insulating layer 82, and the photoelectric conversion layer 13 are stacked is cut in the YZ imaginary plane varies depending on the distance from the first electrode.

[0216] Furthermore, in the image sensor of the twelfth embodiment, the first photoelectric conversion unit segment 101 to the Nth photoelectric conversion unit segment 10 NThe thickness of the insulating layer segment gradually changes over the n-th photoelectric conversion section segment 10. Specifically, the thickness of the insulating layer segment gradually increases. Alternatively, in the imaging element of Example 12, the width of the cross section of the laminated portion is constant, and the thickness of the cross section of the laminated portion, specifically, the thickness of the insulating layer segment, gradually increases depending on the distance from the first electrode 11. The thickness of the insulating layer segment increases in a stepped manner. n Insulation layer segment 82 n The thickness of the nth photoelectric conversion segment 10 was constant. n Insulation layer segment 82 n When the thickness of the (n+1)th photoelectric conversion segment 10 is taken as “1”, (n+1) Insulation layer segment 82 (n+1) The thickness of the insulating layer segments 821, 822, and 823 is gradually increased by gradually decreasing the thickness of the charge storage electrode segments 141, 142, and 143. The thickness of the photoelectric conversion layer segments 131, 132, and 133 is constant.

[0217] The operation of the image pickup device of the twelfth embodiment will be described below.

[0218] During the charge accumulation period, the drive circuit applies a potential V 11 is applied to the charge storage electrode 14, and a potential V 12 A voltage V V is applied to the second electrode 12. Photoelectric conversion occurs in the photoelectric conversion layer 13 due to the light incident on the photoelectric conversion layer 13. Holes generated by the photoelectric conversion are guided from the second electrode 12 to the wiring V OU On the other hand, since the potential of the first electrode 11 is made higher than the potential of the second electrode 12, that is, for example, a positive potential is applied to the first electrode 11 and a negative potential is applied to the second electrode 12, V 12 ≧V 11 , preferably V 12 >V 11As a result, electrons generated by photoelectric conversion are attracted to the charge storage electrode 14 and stay in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14. That is, charges are stored in the photoelectric conversion layer 13. 12 >V 11 For this reason, electrons generated inside the photoelectric conversion layer 13 do not move toward the first electrode 11. As the photoelectric conversion progresses, the potential in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 becomes more negative.

[0219] In the image sensor of the twelfth embodiment, the thickness of the insulating layer segment is gradually increased. Therefore, during the charge accumulation period, V 12 ≧V 11 In this state, the n-th photoelectric conversion unit segment 10 n The (n+1)th photoelectric conversion segment 10 (n+1) In this case, a larger amount of charge can be stored than in the conventional method, and a stronger electric field can be applied, so that the flow of charge from the first photoelectric conversion portion segment 101 to the first electrode 11 can be reliably prevented.

[0220] In the latter part of the charge accumulation period, a reset operation is performed. This resets the potential of the first floating diffusion layer FD1, and the potential of the first floating diffusion layer FD1 becomes equal to the power supply potential V DD It becomes.

[0221] After the reset operation is completed, the electric charge is read out. That is, during the electric charge transfer period, the driving circuit applies a potential V 21 is applied to the charge storage electrode 14, and a potential V 22 is applied, where V 21 >V 22 As a result, the electrons that had remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 are read out to the first electrode 11 and further to the first floating diffusion layer FD1. That is, the charges stored in the photoelectric conversion layer 13 are read out to the control unit.

[0222] More specifically, during the charge transfer period, V 21 >V22 In this state, the flow of charges from the first photoelectric conversion segment 101 to the first electrode 11 and the flow of charges from the (n+1)th photoelectric conversion segment 10 (n+1) to the n-th photoelectric conversion unit segment 10 n Therefore, the flow of charge to the substrate can be reliably ensured.

[0223] This completes a series of operations including charge accumulation, reset operation, and charge transfer.

[0224] In the imaging element of Example 12, the thickness of the insulating layer segments gradually changes from the first photoelectric conversion unit segment to the Nth photoelectric conversion unit segment, or the cross-sectional area of ​​the laminated portion in which the charge storage electrode, insulating layer, and photoelectric conversion layer are stacked when cut in the YZ virtual plane changes depending on the distance from the first electrode, so that a kind of charge transfer gradient is formed, making it possible to transfer the charges generated by photoelectric conversion more easily and reliably.

[0225] The imaging element and stacked type imaging element of Example 12 can be fabricated in substantially the same manner as the imaging element of Example 6, and therefore detailed description thereof will be omitted.

[0226] In the imaging element of Example 12, in forming the first electrode 11, the charge storage electrode 14, and the insulating layer 82, first, a conductive material layer for forming the charge storage electrode 143 is formed on the interlayer insulating layer 81, and the conductive material layer is patterned to leave the conductive material layer in the region where the photoelectric conversion unit segments 101, 102, and 103 and the first electrode 11 are to be formed, thereby obtaining a part of the first electrode 11 and the charge storage electrode 143. Next, an insulating layer for forming the insulating layer segment 823 is formed on the entire surface, and the insulating layer is patterned and a planarization process is performed to obtain the insulating layer segment 823. Next, a conductive material layer for forming the charge storage electrode 142 is formed on the entire surface, and the conductive material layer is patterned to leave the conductive material layer in the region where the photoelectric conversion unit segments 101, 102, and the first electrode 11 are to be formed, thereby obtaining a part of the first electrode 11 and the charge storage electrode 142. Next, an insulating layer for forming the insulating layer segment 822 is formed on the entire surface, the insulating layer is patterned, and a planarization process is performed to obtain the insulating layer segment 822. Next, a conductive material layer for forming the charge storage electrode 141 is formed on the entire surface, and the conductive material layer is patterned to leave the conductive material layer in the region where the photoelectric conversion unit segment 101 and the first electrode 11 are to be formed, thereby obtaining the first electrode 11 and the charge storage electrode 141. Next, an insulating layer is formed on the entire surface, and a planarization process is performed to obtain the insulating layer segment 821 (insulating layer 82). Then, the photoelectric conversion layer 13 is formed on the insulating layer 82. In this manner, the photoelectric conversion unit segments 101, 102, and 103 are obtained.

[0227] FIG. 58 shows a schematic layout diagram of the first electrode and the charge storage electrode constituting the modified example of the image sensor of the twelfth embodiment, as well as the transistors constituting the control section. The reset transistor TR1 rst The other source / drain region 51B is connected to a power supply V DD Instead of connecting to ground, EXAMPLES

[0228] The imaging element of Example 13 relates to the imaging elements of the second and sixth configurations of the present disclosure. As shown in Fig. 59, which is a schematic partial cross-sectional view enlarging a portion where a charge storage electrode, a photoelectric conversion layer, and a second electrode are laminated, in the imaging element of Example 13, the first photoelectric conversion unit segment 101 to the Nth photoelectric conversion unit segment 10 N The thickness of the photoelectric conversion layer segment gradually changes over the n-th photoelectric conversion segment 10. Alternatively, in the imaging element of Example 13, the width of the cross section of the laminated portion is constant, and the thickness of the cross section of the laminated portion, specifically, the thickness of the photoelectric conversion layer segment, gradually increases depending on the distance from the first electrode 11. More specifically, the thickness of the photoelectric conversion layer segment gradually increases. The thickness of the photoelectric conversion layer segment increases in a stepped manner. n Photoelectric conversion layer segment 13 n The thickness of the nth photoelectric conversion segment 10 was constant. n Photoelectric conversion layer segment 13 in n When the thickness of the (n+1)th photoelectric conversion segment 10 is taken as “1”, (n+1) Photoelectric conversion layer segment 13 in (n+1) The thickness of the photoelectric conversion layer segments 131, 132, and 133 is gradually increased by gradually decreasing the thickness of the charge storage electrode segments 141, 142, and 143. The thickness of the insulating layer segments 821, 822, and 823 is constant.

[0229] In the image sensor of Example 13, the thickness of the photoelectric conversion layer segment gradually increases, so that during the charge accumulation period, V 12 ≧V 11 In this state, the n-th photoelectric conversion unit segment 10 n The (n+1)th photoelectric conversion segment 10 (n+1) This ensures that charges are prevented from flowing from the first photoelectric conversion portion segment 101 to the first electrode 11. During the charge transfer period, an electric field stronger than V 22 <V 21In this state, the flow of charges from the first photoelectric conversion segment 101 to the first electrode 11 and the flow of charges from the (n+1)th photoelectric conversion segment 10 (n+1) to the n-th photoelectric conversion unit segment 10 n Therefore, the flow of charge to the substrate can be reliably ensured.

[0230] In this way, in the imaging element of Example 13, the thickness of the photoelectric conversion layer segment gradually changes from the first photoelectric conversion segment to the Nth photoelectric conversion segment, or the cross-sectional area of ​​the laminated portion in which the charge storage electrode, insulating layer, and photoelectric conversion layer are stacked when cut in the YZ virtual plane changes depending on the distance from the first electrode, so that a kind of charge transfer gradient is formed, making it possible to transfer the charges generated by photoelectric conversion more easily and reliably.

[0231] In the imaging element of Example 13, in forming the first electrode 11, the charge storage electrode 14, the insulating layer 82, and the photoelectric conversion layer 13, first, a conductive material layer for forming the charge storage electrode 143 is formed on the interlayer insulating layer 81, and the conductive material layer is patterned to leave the conductive material layer in the region where the photoelectric conversion unit segments 101, 102, and 103 and the first electrode 11 are to be formed, thereby obtaining a part of the first electrode 11 and the charge storage electrode 143. Next, a conductive material layer for forming the charge storage electrode 142 is formed on the entire surface, and the conductive material layer is patterned to leave the conductive material layer in the region where the photoelectric conversion unit segments 101, 102, and the first electrode 11 are to be formed, thereby obtaining a part of the first electrode 11 and the charge storage electrode 142. Next, a conductive material layer for forming the charge storage electrode 141 is formed on the entire surface, and the conductive material layer is patterned to leave the conductive material layer in the areas where the photoelectric conversion unit segment 101 and the first electrode 11 are to be formed, thereby obtaining the first electrode 11 and the charge storage electrode 141. Next, an insulating layer 82 is conformally formed on the entire surface. Then, the photoelectric conversion layer 13 is formed on the insulating layer 82, and a planarization process is performed on the photoelectric conversion layer 13. In this manner, the photoelectric conversion unit segments 101, 102, and 103 are obtained. EXAMPLES

[0232] Example 14 relates to an imaging element having a third configuration. A schematic partial cross-sectional view of an imaging element, a stacked imaging element, of Example 14 is shown in Fig. 60. In the imaging element of Example 14, the materials constituting the insulating layer segments are different in adjacent photoelectric conversion unit segments. Here, the first photoelectric conversion unit segment 101 to the Nth photoelectric conversion unit segment 10 N The dielectric constant of the material constituting the insulating layer segment is gradually decreased over the entire length of the imaging element according to the fourteenth embodiment. In the imaging element according to the fourteenth embodiment, the same potential may be applied to all of the N charge-storage electrode segments, or different potentials may be applied to each of the N charge-storage electrode segments. In the latter case, as in the case of the fifteenth embodiment, the charge-storage electrode segments 141, 142, and 143 spaced apart from one another may be connected to the vertical drive circuit 112 constituting the drive circuit via pad portions 641, 642, and 643.

[0233] By adopting such a configuration, a kind of charge transfer gradient is formed, and during the charge accumulation period, V 12 ≧V 11 In this state, the nth photoelectric conversion segment can store more charge than the (n+1)th photoelectric conversion segment. Then, during the charge transfer period, V 22 <V 21 In this state, the flow of charge from the first photoelectric conversion segment to the first electrode and the flow of charge from the (n+1)th photoelectric conversion segment to the nth photoelectric conversion segment can be reliably ensured. EXAMPLES

[0234] Example 15 relates to an imaging element having a fourth configuration. A schematic partial cross-sectional view of an imaging element, a stacked imaging element, of Example 15 is shown in Fig. 61. In the imaging element of Example 15, the materials constituting the charge storage electrode segments are different in adjacent photoelectric conversion unit segments. Here, the first photoelectric conversion unit segment 101 to the Nth photoelectric conversion unit segment 10N The work function value of the material constituting the insulating layer segment is gradually increased over the entire length of the imaging element according to the fifteenth embodiment. In the imaging element according to the fifteenth embodiment, the same potential may be applied to all of the N charge storage electrode segments, or different potentials may be applied to each of the N charge storage electrode segments. In the latter case, the charge storage electrode segments 141, 142, and 143 are connected to a vertical drive circuit 112 constituting a drive circuit via pad portions 641, 642, and 643. EXAMPLES

[0235] The imaging element of Example 16 relates to an imaging element having the fifth configuration. Schematic plan views of the charge storage electrode segments in Example 16 are shown in Figs. 62A, 62B, 63A and 63B, and a schematic layout diagram of the first electrode and charge storage electrode constituting the imaging element of Example 16 and the transistor constituting the control unit is shown in Fig. 64. A schematic partial cross-sectional view of the imaging element and stacked imaging element of Example 16 is similar to that shown in Fig. 61 or 66. In the imaging element of Example 16, the first photoelectric conversion unit segment 101 to the Nth photoelectric conversion unit segment 10 N The area of ​​the charge storage electrode segment gradually decreases over the entire length of the image sensor according to the sixteenth embodiment. In the image sensor according to the sixteenth embodiment, the same potential may be applied to all of the N charge storage electrode segments, or different potentials may be applied to each of the N charge storage electrode segments. Specifically, as in the case of the fifteenth embodiment, the charge storage electrode segments 141, 142, and 143 spaced apart from one another may be connected to the vertical drive circuit 112 constituting the drive circuit via pad portions 641, 642, and 643.

[0236] In the sixteenth embodiment, the charge storage electrode 14 is composed of a plurality of charge storage electrode segments 141, 142, and 143. The number of the charge storage electrode segments may be two or more, and is set to "3" in the sixteenth embodiment. In the imaging element and stacked imaging element of the sixteenth embodiment, the potential of the first electrode 11 is higher than the potential of the second electrode 12, that is, for example, a positive potential is applied to the first electrode 11 and a negative potential is applied to the second electrode 12, so that the potential applied to the charge storage electrode segment 141 located closest to the first electrode 11 during the charge transfer period is higher than the potential applied to the charge storage electrode segment 143 located farthest from the first electrode 11. In this way, by applying a potential gradient to the charge storage electrode 14, the electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 are more reliably read out to the first electrode 11 and further to the first floating diffusion layer FD1. That is, the charge stored in the photoelectric conversion layer 13 is read out to the control unit.

[0237] During the charge transfer period, the potential of the charge storage electrode segment 143 is set to be less than the potential of the charge storage electrode segment 142 and less than the potential of the charge storage electrode segment 141, so that the electrons that have remained in the photoelectric conversion layer 13 region can be read out all at once to the first floating diffusion layer FD1. Alternatively, during the charge transfer period, by gradually changing the potential of the charge storage electrode segment 143, the potential of the charge storage electrode segment 142, and the potential of the charge storage electrode segment 141 (i.e., by changing in a stepped or sloped manner), electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 143 can be moved to the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 142, and then electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 142 can be moved to the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 141, and then electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode segment 141 can be reliably read out to the first floating diffusion layer FD1.

[0238] FIG. 65 shows a schematic layout diagram of the first electrode and the charge storage electrode constituting the modified example of the image sensor of the sixteenth embodiment, and the transistors constituting the control section. The reset transistor TR3 rst The other source / drain region 51B may be grounded instead of being connected to the power supply VDD.

[0239] In the image sensor of the sixteenth embodiment, by adopting such a configuration, a kind of charge transfer gradient is formed. N Since the area of ​​the charge storage electrode segment is gradually reduced over the charge storage period, V 12 ≧V 11 In this state, the nth photoelectric conversion segment can store more charge than the (n+1)th photoelectric conversion segment. Then, during the charge transfer period, V 22 <V 21 In this state, the flow of charge from the first photoelectric conversion segment to the first electrode and the flow of charge from the (n+1)th photoelectric conversion segment to the nth photoelectric conversion segment can be reliably ensured. EXAMPLES

[0240] Example 17 relates to an imaging element having a sixth configuration. FIG. 66 shows a schematic partial cross-sectional view of the imaging element and stacked imaging element of Example 17. FIG. 67A and FIG. 67B show schematic plan views of the charge storage electrode segment in Example 17. The imaging element of Example 17 includes a photoelectric conversion unit including a first electrode 11, a photoelectric conversion layer 13, and a second electrode 12 stacked together, and the photoelectric conversion unit further includes a charge storage electrode 14 that is spaced apart from the first electrode 11 and faces the photoelectric conversion layer 13 via an insulating layer 82. When the stacking direction of the charge storage electrode 14, the insulating layer 82, and the photoelectric conversion layer 13 is defined as the Z direction and the direction away from the first electrode 11 is defined as the X direction, the cross-sectional area of ​​the stacked portion in which the charge storage electrode 14, the insulating layer 82, and the photoelectric conversion layer 13 are stacked in the YZ virtual plane changes depending on the distance from the first electrode 11.

[0241] Specifically, in the image sensor of Example 17, the thickness of the cross section of the laminated portion is constant, and the width of the cross section of the laminated portion becomes narrower as it is farther from the first electrode 11. The width may be narrowed continuously (see FIG. 67A) or may be narrowed in a stepwise manner (see FIG. 67B).

[0242] Thus, in the imaging element of Example 16, the cross-sectional area of ​​the laminated portion in which the charge storage electrode 14, the insulating layer 82, and the photoelectric conversion layer 13 are stacked when cut in the YZ virtual plane changes depending on the distance from the first electrode, so that a kind of charge transfer gradient is formed, making it possible to transfer the charges generated by photoelectric conversion more easily and reliably. EXAMPLES

[0243] The eighteenth embodiment relates to the solid-state imaging device of the first and second configurations.

[0244] The solid-state imaging device of Example 18 is The photoelectric conversion section is formed by stacking a first electrode 11, a photoelectric conversion layer 13, and a second electrode 12. The photoelectric conversion unit further includes a plurality of image pickup elements each including a charge storage electrode 14 disposed apart from the first electrode 11 and facing the photoelectric conversion layer 13 with an insulating layer 82 interposed therebetween, An imaging element block is composed of a plurality of imaging elements, The first electrode 11 is shared by a plurality of imaging elements that form an imaging element block.

[0245] Alternatively, the solid-state imaging device of the eighteenth embodiment includes a plurality of imaging elements described in the sixth to seventeenth embodiments.

[0246] In the eighteenth embodiment, one floating diffusion layer is provided for a plurality of image sensors. By appropriately controlling the timing of the charge transfer period, the plurality of image sensors can share one floating diffusion layer. In this case, the plurality of image sensors can share one contact hole.

[0247] Incidentally, except for the fact that the first electrode 11 is shared by the multiple imaging elements that constitute the imaging element block, the solid-state imaging device of Example 18 has substantially the same configuration and structure as the solid-state imaging devices described in Examples 6 to 17.

[0248] The arrangement of the first electrode 11 and the charge storage electrode 14 in the solid-state imaging device of Example 18 is shown in FIG. 68 (Example 18), FIG. 69 (first modified example of Example 18), FIG. 70 (second modified example of Example 18), FIG. 71 (third modified example of Example 18), and FIG. 72 (fourth modified example of Example 18). Sixteen imaging elements are shown in FIG. 68, FIG. 69, FIG. 72, and FIG. 73, and twelve imaging elements are shown in FIG. 70 and FIG. 71. An imaging element block is composed of two imaging elements. The imaging element block is shown surrounded by a dotted line. The subscripts attached to the first electrode 11 and the charge storage electrode 14 are for distinguishing the first electrode 11 and the charge storage electrode 14. The same applies to the following description. In addition, one on-chip microlens (not shown in FIG. 68 to FIG. 77) is arranged above one imaging element. In one imaging element block, two charge storage electrodes 14 are arranged with the first electrode 11 interposed therebetween (see Figs. 68 and 69). Alternatively, one first electrode 11 is arranged facing two juxtaposed charge storage electrodes 14 (see Figs. 72 and 73). That is, the first electrode is arranged adjacent to the charge storage electrodes of each imaging element. Alternatively, the first electrode is arranged adjacent to some of the charge storage electrodes of the multiple imaging elements, but not adjacent to the remaining charge storage electrodes of the multiple imaging elements (see Figs. 70 and 71). In this case, the movement of charges from the remaining multiple imaging elements to the first electrode passes through some of the multiple imaging elements. It is preferable that the distance A between the charge storage electrode constituting the imaging element and the charge storage electrode constituting the imaging element is longer than the distance B between the first electrode and the charge storage electrode of the imaging element adjacent to the first electrode in order to ensure the movement of charges from each imaging element to the first electrode. It is also preferable to increase the value of the distance A for an imaging element located farther from the first electrode. In the examples shown in Figs. 69, 71 and 73, a charge transfer control electrode 21 is disposed between a plurality of imaging elements constituting an imaging element block. By disposing the charge transfer control electrode 21, it is possible to reliably suppress the transfer of charges in imaging element blocks located on either side of the charge transfer control electrode 21. The potential applied to the charge transfer control electrode 21 is V 13Then, V 12 >V 13 (For example, V 12-2 >V 13 ) can be used.

[0249] The charge transfer control electrode 21 may be formed on the first electrode side at the same level as the first electrode 11 or the charge storage electrode 14, or may be formed at a different level (specifically, at a level lower than the first electrode 11 or the charge storage electrode 14). In the former case, the distance between the charge transfer control electrode 21 and the photoelectric conversion layer can be shortened, making it easier to control the potential. On the other hand, in the latter case, the distance between the charge transfer control electrode 21 and the charge storage electrode 14 can be shortened, which is advantageous for miniaturization.

[0250] Hereinafter, the first electrode 112 and the two charge storage electrodes 14 21 ,14 22 The operation of the imaging element block constructed as above will be described.

[0251] During the charge accumulation period, the driving circuit applies a potential V a is applied to the charge storage electrode 14 21 ,14 22 potential V A A voltage V V is applied to the second electrode 12. Photoelectric conversion occurs in the photoelectric conversion layer 13 due to the light incident on the photoelectric conversion layer 13. Holes generated by the photoelectric conversion are guided from the second electrode 12 to the wiring V OU On the other hand, since the potential of the first electrode 112 is made higher than the potential of the second electrode 12, that is, for example, a positive potential is applied to the first electrode 112 and a negative potential is applied to the second electrode 12, V A ≧V a , preferably V A >V a As a result, the electrons generated by photoelectric conversion are transferred to the charge storage electrode 14 21 ,14 22 is attracted to the charge storage electrode 14 21 ,14 22 That is, charges are accumulated in the photoelectric conversion layer 13.A ≧V a Therefore, the electrons generated inside the photoelectric conversion layer 13 do not move toward the first electrode 112. 21 ,14 22 The potential in the region of the photoelectric conversion layer 13 facing the positive electrode 14 becomes a more negative value.

[0252] In the latter part of the charge accumulation period, a reset operation is performed. This resets the potential of the first floating diffusion layer, and the potential of the first floating diffusion layer becomes equal to the power supply potential V DD It becomes.

[0253] After the reset operation is completed, the electric charge is read out. That is, during the electric charge transfer period, the driving circuit applies a potential V b is applied to the charge storage electrode 14 21 potential V 21-B is applied to the charge storage electrode 14 22 potential V 22-B is applied, where V 21-B <V b <V 22-B As a result, the charge storage electrode 14 21 The electrons that have remained in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 are read out to the first electrode 112 and further to the first floating diffusion layer. 21 The charge stored in the region of the photoelectric conversion layer 13 facing the V 22-B ≦V 21-B <V b In the examples shown in Figures 72 and 73, V 22-B <V b <V 21-B As a result, the charge storage electrode 14 22 The electrons that have stayed in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 are read out to the first electrode 112 and further to the first floating diffusion layer. 22 The electrons that were stopped in the area of ​​the photoelectric conversion layer 13 facing the charge storage electrode 14 are transferred to the charge storage electrode 14. 22The charge accumulation electrode 14 may be read out to the first floating diffusion layer via the adjacent first electrode 113. 22 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 is read out to the control unit. 21 When the readout of the charges accumulated in the region of the photoelectric conversion layer 13 facing the first floating diffusion layer 11 to the control unit is completed, the potential of the first floating diffusion layer 11 may be reset.

[0254] FIG. 78A shows an example of readout driving in the image sensor block of the eighteenth embodiment. [Step-A] Autozero signal input to comparator [Step B] Reset operation of a shared floating diffusion layer [Step-C] Charge storage electrode 14 21 P-phase readout in the imaging element corresponding to the above and transfer of charge to the first electrode 112 [Step-D] Charge storage electrode 14 21 D-phase readout in the imaging element corresponding to the above and transfer of charge to the first electrode 112 [Step-E] Reset operation of a shared floating diffusion layer [Step-F] Autozero signal input to comparator [Step-G] Charge storage electrode 14 22 P-phase readout in the imaging element corresponding to the above and transfer of charge to the first electrode 112 [Step-H] Charge storage electrode 14 22 D-phase readout in the imaging element corresponding to the above and transfer of charge to the first electrode 112 In this way, the charge storage electrode 14 21 and charge storage electrode 14 22 Based on the correlated double sampling (CDS) process, the difference between the P-phase readout in [Step-C] and the D-phase readout in [Step-D] is input to the charge storage electrode 1421 The difference between the P-phase readout in [Step-G] and the D-phase readout in [Step-H] is the signal from the image sensor corresponding to the charge storage electrode 14 22 This is a signal from the imaging element corresponding to

[0255] The operation of [Step-E] may be omitted (see FIG. 78B). Also, the operation of [Step-F] may be omitted. In this case, [Step-G] can be omitted (see FIG. 78C). The difference between the P-phase readout in [Step-C] and the D-phase readout in [Step-D] is calculated by dividing the charge accumulation electrode 14 by the charge accumulation electrode 14. 21 The difference between the D-phase readout in [Step-D] and the D-phase readout in [Step-H] is the signal from the image sensor corresponding to 22 The signal from the imaging element corresponds to the

[0256] In the modifications in which the arrangement of the first electrodes 11 and the charge storage electrodes 14 is typically shown in Fig. 74 (sixth modification of the eighteenth embodiment) and Fig. 75 (seventh modification of the eighteenth embodiment), an imaging element block is made up of four imaging elements. The operation of these solid-state imaging devices can be substantially the same as that of the solid-state imaging devices shown in Figs. 68 to 73.

[0257] In the eighth and ninth modified examples, in which the arrangement of the first electrodes 11 and the charge storage electrodes 14 is shown in schematic form in Figs. 76 and 77, an imaging element block is made up of 16 imaging elements. As shown in Figs. 76 and 77, 11 and charge storage electrode 14 12 Between the charge storage electrode 14 12 and charge storage electrode 14 13 Between the charge storage electrode 14 13 and charge storage electrode 14 14 Charge transfer control electrodes 21A1, 21A2, and 21A3 are disposed between the charge storage electrode 14 and the charge transfer control electrode 21A1. 21 ,14 31 ,14 41 and charge storage electrode 14 22 ,1432 ,14 42 Between the charge storage electrode 14 22 ,14 32 ,14 42 and charge storage electrode 14 23 ,14 33 ,14 43 Between the charge storage electrode 14 23 ,14 33 ,14 43 and charge storage electrode 14 24 ,14 34 ,14 44 Charge transfer control electrodes 21B1, 21B2, and 21B3 are disposed between the image sensor blocks. Furthermore, a charge transfer control electrode 21C is disposed between the image sensor blocks. In these solid-state imaging devices, the charges stored in the photoelectric conversion layer 13 can be read out from the first electrode 11 by controlling the 16 charge storage electrodes 14.

[0258] [STEP-10] Specifically, first, the charge storage electrode 14 11 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 is read out from the first electrode 11. 12 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 11 The charge is read from the first electrode 11 via the area of ​​the photoelectric conversion layer 13 facing the charge storage electrode 14. 13 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 12 and charge storage electrode 14 11 The signal is read out from the first electrode 11 via a region of the photoelectric conversion layer 13 facing the first electrode 11 .

[0259] [Step-20] Then, the charge storage electrode 14 21 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 11 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 22 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 12The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 23 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 13 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 24 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 14 The photoelectric conversion layer 13 is moved to a region thereof facing the photoelectric conversion layer 13.

[0260] [STEP-21] Charge storage electrode 14 31 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 21 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 32 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 22 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 33 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 23 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 34 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 24 The photoelectric conversion layer 13 is moved to a region thereof facing the photoelectric conversion layer 13.

[0261] [Step-22] Charge storage electrode 14 41 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 31 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 42 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 32 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 43 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 33 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 44The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 34 The photoelectric conversion layer 13 is moved to a region thereof facing the photoelectric conversion layer 13.

[0262] [Step-30] Then, by executing [Step-10] again, the charge storage electrode 14 21 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 22 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 23 The charges stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 24 The charges stored in the region of the photoelectric conversion layer 13 facing the first electrode 11 can be read out via the first electrode 11.

[0263] [Step-40] Then, the charge storage electrode 14 21 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 11 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 22 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 12 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 23 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 13 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 24 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 14 The photoelectric conversion layer 13 is moved to a region thereof facing the photoelectric conversion layer 13.

[0264] [Step-41] Charge storage electrode 14 31 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 21 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 32 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 1422 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 33 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 23 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 34 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 24 The photoelectric conversion layer 13 is moved to a region thereof facing the photoelectric conversion layer 13.

[0265] [Step-50] Then, by executing [Step-10] again, the charge storage electrode 14 31 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 32 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 33 The charges stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 34 The charges stored in the region of the photoelectric conversion layer 13 facing the first electrode 11 can be read out via the first electrode 11.

[0266] [Step-60] Then, the charge storage electrode 14 21 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 11 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 22 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 12 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 23 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 13 The charge storage electrode 14 is moved to a region of the photoelectric conversion layer 13 facing the charge storage electrode 14. 24 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 14 The photoelectric conversion layer 13 is moved to a region thereof facing the photoelectric conversion layer 13.

[0267] [Step-70] Then, by executing [Step-10] again, the charge storage electrode 14 41 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 42 The charge stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 43 The charges stored in the region of the photoelectric conversion layer 13 facing the charge storage electrode 14 44 The charges stored in the region of the photoelectric conversion layer 13 facing the first electrode 11 can be read out via the first electrode 11.

[0268] In the solid-state imaging device of Example 18, the first electrode is shared by the multiple imaging elements constituting the imaging element block, so that the configuration and structure of the pixel region in which the multiple imaging elements are arranged can be simplified and miniaturized. Note that the multiple imaging elements provided for one floating diffusion layer may be composed of multiple first type imaging elements, or may be composed of at least one first type imaging element and one or more second type imaging elements. EXAMPLES

[0269] Example 19 is a modification of Example 18. In the solid-state imaging device of Example 19, in which the arrangement of the first electrodes 11 and the charge storage electrodes 14 is shown in Figs. 79, 80, 81 and 82, an imaging element block is composed of two imaging elements. An on-chip microlens 90 is disposed above the imaging element block. In the example shown in Figs. 80 and 82, a charge transfer control electrode 21 is disposed between the imaging elements constituting the imaging element block.

[0270] For example, the charge storage electrode 14 constituting the image sensor block 11 ,14 21 ,14 31 ,14 41 The photoelectric conversion layer corresponding to has high sensitivity to incident light from the diagonal upper right of the drawing. 12 ,14 22 ,14 32 ,1442 The photoelectric conversion layer corresponding to the charge storage electrode 14 has high sensitivity to incident light from the upper left in the drawing. 11 An image pickup element having a charge storage electrode 14 12 By combining it with an image sensor having a charge storage electrode 14, it is possible to obtain an image plane phase difference signal. 11 A signal from an imaging element and a charge storage electrode 14 12 In the example shown in FIG. 79, if signals from an image sensor having a charge storage electrode 14 are added, a single image sensor can be formed by combining these image sensors. 11 and charge storage electrode 14 12 81, the first electrode 111 is disposed between the first and second charge storage electrodes 14. 11 ,14 12 By disposing one first electrode 111 opposite to the other, it is possible to further improve the sensitivity.

[0271] Although the present disclosure has been described above based on preferred embodiments, the present disclosure is not limited to these embodiments. The structures and configurations, manufacturing conditions, manufacturing methods, and materials used of the imaging element, stacked imaging element, and solid-state imaging device described in the embodiments are examples and can be changed as appropriate. The imaging elements of each embodiment can be combined as appropriate. For example, the imaging element of Example 12, the imaging element of Example 13, the imaging element of Example 14, the imaging element of Example 15, and the imaging element of Example 16 can be combined arbitrarily, and the imaging element of Example 12, the imaging element of Example 13, the imaging element of Example 14, the imaging element of Example 15, and the imaging element of Example 17 can be combined arbitrarily.

[0272] In some cases, floating diffusion layers FD1, FD 21 ,FD3,51C,45C,46C can also be shared.

[0273] As shown in Figure 83, for example, as a modified example of the imaging element and stacked imaging element described in Example 6, the first electrode 11 can be configured to extend within an opening 84A provided in an insulating layer 82 and be connected to the photoelectric conversion layer 13.

[0274] Alternatively, Fig. 84 shows a modified example of the imaging element and stacked imaging element described in Example 6, for example, and Fig. 85A shows an enlarged schematic partial cross-sectional view of a portion of the first electrode, etc., in which the edge of the top surface of the first electrode 11 is covered with an insulating layer 82, the first electrode 11 is exposed at the bottom surface of the opening 84B, and when the surface of the insulating layer 82 in contact with the top surface of the first electrode 11 is the first surface 82p and the surface of the insulating layer 82 in contact with the portion of the photoelectric conversion layer 13 facing the charge storage electrode 14 is the second surface 82q, the side surface of the opening 84B has a slope that widens from the first surface 82p toward the second surface 82q. In this way, by providing a slope to the side surface of the opening 84B, the movement of charges from the photoelectric conversion layer 13 to the first electrode 11 becomes smoother. In the example shown in FIG. 85A, the side of the opening 84B is rotationally symmetrical about the axis of the opening 84B, but as shown in FIG. 85B, the opening 84C may be provided so that the side of the opening 84C having an inclination expanding from the first surface 82p to the second surface 82q is located on the charge storage electrode 14 side. This makes it difficult for charges to move from the part of the photoelectric conversion layer 13 on the opposite side of the opening 84C to the charge storage electrode 14. In addition, the side of the opening 84B has an inclination expanding from the first surface 82p to the second surface 82q, but the edge of the side of the opening 84B on the second surface 82q may be located outside the edge of the first electrode 11 as shown in FIG. 85A, or may be located inside the edge of the first electrode 11 as shown in FIG. 85C. By adopting the former configuration, the charge transfer becomes easier, and by adopting the latter configuration, the shape variation during the formation of the opening can be reduced.

[0275] These openings 84B, 84C can be formed by reflowing an etching mask made of a resist material that is formed when forming openings in an insulating layer by an etching method, thereby giving a slope to the opening side of the etching mask, and then etching insulating layer 82 using this etching mask.

[0276] 86 shows, for example, a modified example of the imaging element and stacked imaging element described in Example 6, in which light is incident from the second electrode 12 side and a light shielding layer 92 is formed on the light incident side of the second electrode 12. Note that various wirings provided on the light incident side of the photoelectric conversion layer can also function as the light shielding layer.

[0277] In the example shown in Fig. 86, the light-shielding layer 92 is formed above the second electrode 12, i.e., the light-shielding layer 92 is formed above the first electrode 11 on the light-incident side of the second electrode 12, but it may be disposed on the light-incident surface of the second electrode 12 as shown in Fig. 87. In some cases, the light-shielding layer 92 may be formed on the second electrode 12 as shown in Fig. 88.

[0278] Alternatively, a structure may be used in which light is incident from the second electrode 12 side and light is not incident on the first electrode 11. Specifically, as shown in FIG. 86, a light shielding layer 92 is formed above the first electrode 11 on the light incident side from the second electrode 12. Alternatively, as shown in FIG. 90, a structure may be used in which an on-chip microlens 90 is provided above the charge storage electrode 14 and the second electrode 12, and light incident on the on-chip microlens 90 is focused on the charge storage electrode 14 and does not reach the first electrode 11. As described in the tenth embodiment, when the transfer control electrode 15 is provided, a form in which light is not incident on the first electrode 11 and the transfer control electrode 15 may be used. Specifically, as shown in FIG. 89, a structure in which a light shielding layer 92 is formed above the first electrode 11 and the transfer control electrode 15 may be used. Alternatively, a structure may be used in which the light incident on the on-chip microlens 90 does not reach the first electrode 11 or the first electrode 11 and the transfer control electrode 15 .

[0279] By adopting these configurations and structures, or by providing a light-shielding layer 92 so that light is incident only on the portion of the photoelectric conversion layer 13 located above the charge storage electrode 14, or by designing the on-chip microlens 90, the portion of the photoelectric conversion layer 13 located above the first electrode 11 (or above the first electrode 11 and the transfer control electrode 15) does not contribute to photoelectric conversion, so that all pixels can be reset simultaneously more reliably, and the global shutter function can be realized more easily. That is, in a method for driving a solid-state imaging device having a plurality of imaging elements having these configurations and structures, In all the imaging elements, charges are stored in the photoelectric conversion layer 13 at the same time, while the charges in the first electrodes 11 are discharged to the outside of the system, and then, In all the imaging elements, the electric charges accumulated in the photoelectric conversion layer 13 are transferred to the first electrode 11 at the same time, and after the transfer is completed, the electric charges transferred to the first electrode 11 in each imaging element are read out in sequence. These steps are repeated.

[0280] In such a driving method for a solid-state imaging device, each imaging element has a structure in which light incident from the second electrode side does not enter the first electrode, and in all imaging elements, charges are simultaneously accumulated in the photoelectric conversion layer while the charges in the first electrode are discharged to the outside of the system, so that the first electrodes can be reliably reset simultaneously in all imaging elements. Then, in all imaging elements, the charges accumulated in the photoelectric conversion layer are simultaneously transferred to the first electrode, and after the transfer is completed, the charges transferred to the first electrode in each imaging element are read out in sequence. Therefore, a so-called global shutter function can be easily realized.

[0281] As a modification of the tenth embodiment, as shown in Fig. 90, a plurality of transfer control electrodes may be provided from the position closest to the first electrode 11 toward the charge storage electrode 14. Fig. 91 shows an example in which two transfer control electrodes 15A and 15B are provided. An on-chip microlens 90 is provided above the charge storage electrode 14 and the second electrode 12, and a structure in which light incident on the on-chip microlens 90 is focused on the charge storage electrode 14 and does not reach the first electrode 11 and the transfer control electrodes 15A and 15B may also be used.

[0282] In the twelfth embodiment shown in Fig. 56 and Fig. 57, the thickness of the charge storage electrode segments 141, 142, 143 is gradually reduced, and the thickness of the insulating layer segments 821, 822, 823 is gradually increased. On the other hand, as shown in Fig. 92, which is a schematic partial cross-sectional view enlarging a portion where the charge storage electrode, the photoelectric conversion layer, and the second electrode are stacked in a modification of the twelfth embodiment, the thickness of the charge storage electrode segments 141, 142, 143 may be constant, and the thickness of the insulating layer segments 821, 822, 823 may be gradually increased. The thickness of the photoelectric conversion layer segments 131, 132, 133 is constant.

[0283] In the embodiment 13 shown in Fig. 59, the thickness of the charge storage electrode segments 141, 142, 143 is gradually reduced to gradually increase the thickness of the photoelectric conversion layer segments 131, 132, 133. On the other hand, as shown in Fig. 93, which is a schematic partial cross-sectional view enlarging a portion where the charge storage electrode, the photoelectric conversion layer, and the second electrode are stacked in a modification of the embodiment 13, the thickness of the charge storage electrode segments 141, 142, 143 may be constant, and the thickness of the insulating layer segments 821, 822, 823 may be gradually reduced to gradually increase the thickness of the photoelectric conversion layer segments 131, 132, 133.

[0284] It goes without saying that the various modifications described above can be applied to embodiments other than the sixth embodiment.

[0285] In the embodiment, electrons are used as signal charges, and the conductivity type of the photoelectric conversion layer formed on the semiconductor substrate is n-type, but the present invention can also be applied to a solid-state imaging device in which holes are used as signal charges. In this case, each semiconductor region is made of a semiconductor region of the opposite conductivity type, and the conductivity type of the photoelectric conversion layer formed on the semiconductor substrate is p-type.

[0286] In the embodiment, the present invention is applied to a CMOS type solid-state imaging device in which unit pixels that detect a signal charge corresponding to the amount of incident light as a physical quantity are arranged in a matrix, but the present invention is not limited to the application to a CMOS type solid-state imaging device, and can also be applied to a CCD type solid-state imaging device. In the latter case, the signal charge is transferred vertically by a vertical transfer register of a CCD type structure, transferred horizontally by a horizontal transfer register, and amplified to output a pixel signal (image signal). In addition, the present invention is not limited to all column-type solid-state imaging devices in which pixels are formed in a two-dimensional matrix and a column signal processing circuit is arranged for each pixel column. Furthermore, in some cases, the selection transistor can be omitted.

[0287] Furthermore, the imaging element and stacked imaging element of the present disclosure are not limited to application to solid-state imaging devices that detect the distribution of the amount of incident visible light and capture it as an image, but can also be applied to solid-state imaging devices that capture the distribution of the amount of incident infrared rays, X-rays, particles, etc. In a broader sense, they can be applied to all solid-state imaging devices (physical quantity distribution detection devices) such as fingerprint detection sensors that detect the distribution of other physical quantities such as pressure and capacitance and capture them as an image.

[0288] Furthermore, the present invention is not limited to a solid-state imaging device that scans each unit pixel of an imaging region in sequence by row and reads out pixel signals from each unit pixel. It can also be applied to an XY address type solid-state imaging device that selects an arbitrary pixel by pixel and reads out pixel signals from the selected pixel by pixel. The solid-state imaging device may be formed as a one-chip, or may be a module having an imaging function in which the imaging region and a driving circuit or an optical system are packaged together.

[0289] In addition, the present invention is not limited to application to solid-state imaging devices, but can also be applied to imaging devices. Here, imaging devices refer to camera systems such as digital still cameras and video cameras, and electronic devices with imaging functions such as mobile phones. In some cases, a modular form mounted on an electronic device, i.e., a camera module, is used as the imaging device.

[0290] FIG. 94 is a conceptual diagram showing an example in which a solid-state imaging device 201 constituted by the imaging element and stacked imaging element of the present disclosure is used in an electronic device (camera) 200. The electronic device 200 has a solid-state imaging device 201, an optical lens 210, a shutter device 211, a driving circuit 212, and a signal processing circuit 213. The optical lens 210 forms an image of image light (incident light) from a subject on the imaging surface of the solid-state imaging device 201. As a result, signal charges are accumulated in the solid-state imaging device 201 for a certain period of time. The shutter device 211 controls the light irradiation period and the light blocking period to the solid-state imaging device 201. The driving circuit 212 supplies a driving signal that controls the transfer operation of the solid-state imaging device 201 and the shutter operation of the shutter device 211. Signal transfer of the solid-state imaging device 201 is performed by the driving signal (timing signal) supplied from the driving circuit 212. The signal processing circuit 213 performs various signal processing. The video signal that has undergone signal processing is stored in a storage medium such as a memory, or is output to a monitor. In such an electronic device 200, it is possible to achieve a reduction in pixel size and an improvement in transfer efficiency in the solid-state imaging device 201, and therefore it is possible to obtain an electronic device 200 with improved pixel characteristics. The electronic device 200 to which the solid-state imaging device 201 can be applied is not limited to a camera, and can be applied to imaging devices such as digital still cameras, camera modules for mobile devices such as mobile phones, etc.

[0291] The present disclosure may also be configured as follows. [A01] Imaging device: First aspect first electrode, a charge storage electrode disposed spaced apart from the first electrode; a photoelectric conversion layer in contact with the first electrode and formed above the charge storage electrode with an insulating layer interposed therebetween; and A second electrode formed on the photoelectric conversion layer; Equipped with a portion of the insulating layer located between the charge storage electrode and the photoelectric conversion layer has a first region and a second region; the portion of the insulating layer occupying the first region comprises a first insulating layer; the portion of the insulating layer occupying the second region comprises a second insulating layer; An imaging element in which the absolute value of the fixed charge of the material constituting the second insulating layer is smaller than the absolute value of the fixed charge of the material constituting the first insulating layer. [A02] The second region is located opposite the first electrode, The imaging element according to [A01], wherein the first region is located adjacent to the second region. [A03] The imaging element according to [A02], wherein the material constituting the first insulating layer has the same polarity as the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode. [A04] The carriers sent to the first electrode are electrons, the first insulating layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide; The imaging element according to [A03], wherein the second insulating layer is made of silicon oxide. [A05] The image sensor according to any one of [A02] to [A04], wherein a second insulating layer extension portion extending from the second insulating layer is formed between the first insulating layer and the photoelectric conversion layer. [A06] The first region is located opposite the first electrode, The imaging element according to [A01], wherein the second region is located adjacent to the first region. [A07] The imaging element according to [A06], wherein the material constituting the first insulating layer has a polarity different from the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode. [A08] The carriers sent to the first electrode are electrons, the first insulating layer is made of silicon oxynitride or silicon nitride; The imaging element according to [A07], wherein the second insulating layer is made of silicon oxide. [A09] The image sensor according to any one of [A06] to [A08], wherein a second insulating layer extension portion extending from the second insulating layer is formed between the first insulating layer and the photoelectric conversion layer. [A10] The portion of the insulating layer located between the charge storage electrode and the photoelectric conversion layer further has a third region, The first region is located opposite the first electrode, the third region is located adjacent to the first region, the second region is located between the first region and the photoelectric conversion layer and between the third region and the photoelectric conversion layer; the portion of the insulating layer occupying the third region is made of a third insulating layer; The imaging element according to [A01], wherein the absolute value of the fixed charge of the material constituting the second insulating layer is smaller than the absolute value of the fixed charge of the material constituting the third insulating layer. [A11] The material constituting the first insulating layer has a polarity different from the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode, The imaging element according to [A10], wherein a material constituting the third insulating layer has the same polarity as that of carriers generated in the photoelectric conversion layer and sent to the first electrode. [A12] The carriers sent to the first electrode are electrons, the first insulating layer is made of silicon oxynitride or silicon nitride; the third insulating layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide; The imaging element according to [A11], wherein the second insulating layer is made of silicon oxide. [A13] An insulating material layer is provided between the first electrode and the charge storage electrode, The imaging element according to any one of [A01] to [A12], wherein the material constituting the insulating material layer has a polarity different from the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode. [A14] A second insulating material layer is provided in contact with at least a part of a portion of the charge storage electrode that does not face the first electrode, An imaging element described in any one of [A01] to [A13], wherein the material constituting the second insulating material layer has the same polarity as the polarity of the carriers generated in the photoelectric conversion layer and sent to the first electrode. [A15] 《Imaging element: second aspect》 first electrode, a charge storage electrode disposed spaced apart from the first electrode; a photoelectric conversion layer in contact with the first electrode and formed above the charge storage electrode with an insulating layer interposed therebetween; and A second electrode formed on the photoelectric conversion layer; Equipped with an insulating material layer is provided between the first electrode and the charge storage electrode; An imaging element in which the material constituting the insulating material layer has a polarity different from the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode. [A16] The imaging element according to [A15], wherein the insulating layer extends at least partially between the photoelectric conversion layer and the insulating material layer. [A17] A second insulating material layer is provided in contact with at least a part of a portion of the charge storage electrode that does not face the first electrode, The imaging element according to [A15] or [A16], wherein the material constituting the second insulating material layer has the same polarity as the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode. [A18] The carriers sent to the first electrode are electrons, the insulating material layer comprises silicon oxynitride or silicon nitride; The imaging element according to [A17], wherein the second insulating material layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide. [A19] 《Imaging element: third aspect》 first electrode, a charge storage electrode disposed spaced apart from the first electrode; a photoelectric conversion layer in contact with the first electrode and formed above the charge storage electrode with an insulating layer interposed therebetween; and A second electrode formed on the photoelectric conversion layer; Equipped with an insulating material layer is provided in contact with at least a part of a portion of the charge storage electrode that does not face the first electrode; An imaging element in which the material constituting the insulating material layer has the same polarity as the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode. [A20] The carriers sent to the first electrode are electrons, The imaging element according to [A19], wherein the insulating material layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide. [B01] An imaging element described in any one of [A01] to [A20], in which a charge transfer control electrode is formed in a region facing a region of the photoelectric conversion layer located between an adjacent imaging element via an insulating layer. [B02] An imaging element described in any one of [A01] to [A20], in which a charge transfer control electrode is formed on a region of the photoelectric conversion layer located between an adjacent imaging element, instead of a second electrode being formed on the region of the photoelectric conversion layer located between the adjacent imaging elements. [B03] The semiconductor device further includes a control unit provided on the semiconductor substrate and having a drive circuit, the first electrode, the second electrode, the charge storage electrode, and the charge transfer control electrode are connected to a drive circuit; During the charge accumulation period, the drive circuit applies a potential V 11 is applied to the charge storage electrode, and a potential V 12 is applied to the charge transfer control electrode, and a potential V 13 is applied, charges are accumulated in the photoelectric conversion layer, During the charge transfer period, the drive circuit applies a potential V 21 is applied to the charge storage electrode, and a potential V 22 is applied to the charge transfer control electrode, and a potential V 23 The imaging element according to [B01], wherein a voltage is applied to the photoelectric conversion layer, and charges accumulated in the photoelectric conversion layer are read out to a control unit via the first electrode. However, when the potential of the first electrode is higher than the potential of the second electrode, V 12 ≧V 11 , V 12 >V 13 , and V 21 >V 22 >V 23 and the potential of the first electrode is lower than the potential of the second electrode, V 12 ≦V 11 , V 12 <V 13 , and V 21 <V 22<V 23 It is. [B04] The semiconductor device further includes a control unit provided on the semiconductor substrate and having a drive circuit, the first electrode, the second electrode, the charge storage electrode, and the charge transfer control electrode are connected to a drive circuit; During the charge accumulation period, a potential V2' is applied to the second electrode from the drive circuit, and a potential V 13 ' is applied, charges are accumulated in the photoelectric conversion layer, During the charge transfer period, a potential V2″ is applied to the second electrode from the drive circuit, and a potential V 23 " is applied, and charges accumulated in the photoelectric conversion layer are read out to the control unit via the first electrode. However, when the potential of the first electrode is higher than the potential of the second electrode, V2' ≧ V 13 ', and V2" ≧ V 23 " and the potential of the first electrode is lower than the potential of the second electrode, V2'≦V 13 ', and V2"≦V 23 " It is. [B05] Further comprising a semiconductor substrate, The image sensor according to any one of [A01] to [B04], wherein the photoelectric conversion section is disposed above a semiconductor substrate. [B06] An imaging element described in any one of [A01] to [B05], further comprising a transfer control electrode arranged between the first electrode and the charge storage electrode, spaced apart from the first electrode and the charge storage electrode, and facing the photoelectric conversion layer via an insulating layer. [B07] The image sensor according to any one of [A01] to [B06], wherein the charge storage electrode is composed of a plurality of charge storage electrode segments. [B08] The image sensor according to any one of [A01] to [B07], wherein the charge storage electrode is larger than the first electrode. [B09] The image sensor according to any one of [A01] to [B08], wherein the first electrode extends within an opening provided in the insulating layer and is connected to the photoelectric conversion layer. [B10] The image sensor according to any one of [A01] to [B08], wherein the photoelectric conversion layer extends within an opening provided in the insulating layer and is connected to the first electrode. [B11] The edge of the top surface of the first electrode is covered with an insulating layer, The first electrode is exposed at the bottom of the opening. An imaging element described in [B10], wherein when a surface of the insulating layer in contact with the top surface of the first electrode is defined as a first surface, and a surface of the insulating layer in contact with a portion of the photoelectric conversion layer facing the charge storage electrode is defined as a second surface, the side of the opening has a slope that widens from the first surface toward the second surface. [B12] The image sensor according to [B11], wherein a side surface of the opening having an inclination expanding from the first surface toward the second surface is located on the charge accumulation electrode side. [B13] Control of potential of first electrode and charge storage electrode The semiconductor substrate further includes a control unit having a drive circuit. The first electrode and the charge storage electrode are connected to a drive circuit, During the charge accumulation period, a potential V11 is applied to the first electrode from the drive circuit, and a potential V 12 is applied, charges are accumulated in the photoelectric conversion layer, During the charge transfer period, the drive circuit applies a potential V 21 is applied to the charge storage electrode, and a potential V 22 The imaging element according to any one of [A01] to [B12], wherein a voltage is applied to the photoelectric conversion layer, and charges accumulated in the photoelectric conversion layer are read out to a control unit via the first electrode. However, if the potential of the first electrode is higher than that of the second electrode, V 12 ≧V 11 , and V 22 <V 21 and if the potential of the first electrode is lower than that of the second electrode, V 12 ≦V 11 , and V 22 >V 21 It is. [B14] 《Electrode segment for charge storage》 The image sensor according to any one of [A01] to [B06], wherein the charge storage electrode is composed of a plurality of charge storage electrode segments. [B15] When the potential of the first electrode is higher than that of the second electrode, during the charge transfer period, the potential applied to the charge-storage electrode segment located closest to the first electrode is higher than the potential applied to the charge-storage electrode segment located farthest from the first electrode; An imaging element according to [B14], wherein when the potential of the first electrode is lower than that of the second electrode, during a charge transfer period, the potential applied to the charge storage electrode segment located closest to the first electrode is lower than the potential applied to the charge storage electrode segment located farthest from the first electrode. [B16] At least a floating diffusion layer and an amplifying transistor constituting a control unit are provided on the semiconductor substrate, The image sensor according to any one of [A01] to [B15], wherein the first electrode is connected to the floating diffusion layer and the gate portion of the amplifying transistor. [B17] The semiconductor substrate further includes a reset transistor and a selection transistor that constitute a control unit, The floating diffusion layer is connected to one of the source / drain regions of the reset transistor, The imaging element according to [B16], wherein one source / drain region of the amplifying transistor is connected to one source / drain region of the selection transistor, and the other source / drain region of the selection transistor is connected to a signal line. [B18] The image sensor according to any one of [A01] to [B17], wherein light is incident from the second electrode side, and a light-shielding layer is formed on the light incident side of the second electrode. [B19] The imaging element according to any one of [A01] to [B17], in which light is incident from the second electrode side and no light is incident on the first electrode. [B20] The imaging element according to [B19], further comprising a light-shielding layer formed above the first electrode on the light incident side from the second electrode. [B21] An on-chip microlens is provided above the charge storage electrode and the second electrode; The imaging element according to [B19], wherein light incident on the on-chip microlens is focused on the charge storage electrode. [C01] 《Imaging element: first configuration》 The photoelectric conversion unit is composed of N (N≧2) photoelectric conversion unit segments, The photoelectric conversion layer is composed of N photoelectric conversion layer segments, The insulating layer is composed of N insulating layer segments, The charge storage electrode is composed of N charge storage electrode segments, an n-th (n=1, 2, 3,...,N) photoelectric conversion section segment is composed of an n-th charge storage electrode segment, an n-th insulating layer segment, and an n-th photoelectric conversion layer segment; The larger the value of n, the farther the photoelectric conversion segment is located from the first electrode. The imaging element according to any one of [A01] to [B21], wherein the thickness of the insulating layer segments gradually changes from the first photoelectric conversion portion segment to the Nth photoelectric conversion portion segment. [C02] 《Imaging element: second configuration》 The photoelectric conversion unit is composed of N (N≧2) photoelectric conversion unit segments, The photoelectric conversion layer is composed of N photoelectric conversion layer segments, The insulating layer is composed of N insulating layer segments, The charge storage electrode is composed of N charge storage electrode segments, an n-th (n=1, 2, 3,...,N) photoelectric conversion section segment is composed of an n-th charge storage electrode segment, an n-th insulating layer segment, and an n-th photoelectric conversion layer segment; The larger the value of n, the farther the photoelectric conversion segment is located from the first electrode. The imaging element according to any one of [A01] to [B21], wherein the thickness of the photoelectric conversion layer segments gradually changes from the first photoelectric conversion portion segment to the Nth photoelectric conversion portion segment. [C03] 《Imaging element: 3rd configuration》 The photoelectric conversion unit is composed of N (N≧2) photoelectric conversion unit segments, The photoelectric conversion layer is composed of N photoelectric conversion layer segments, The insulating layer is composed of N insulating layer segments, The charge storage electrode is composed of N charge storage electrode segments, an n-th (n=1, 2, 3,...,N) photoelectric conversion section segment is composed of an n-th charge storage electrode segment, an n-th insulating layer segment, and an n-th photoelectric conversion layer segment; The larger the value of n, the farther the photoelectric conversion segment is located from the first electrode. The imaging element according to any one of [A01] to [B21], wherein adjacent photoelectric conversion unit segments have insulating layer segments made of different materials. [C04] 《Imaging element: 4th configuration》 The photoelectric conversion unit is composed of N (N≧2) photoelectric conversion unit segments, The photoelectric conversion layer is composed of N photoelectric conversion layer segments, The insulating layer is composed of N insulating layer segments, The charge storage electrode is composed of N charge storage electrode segments arranged spaced apart from each other, an n-th (n=1, 2, 3,...,N) photoelectric conversion section segment is composed of an n-th charge storage electrode segment, an n-th insulating layer segment, and an n-th photoelectric conversion layer segment; The larger the value of n, the farther the photoelectric conversion segment is located from the first electrode. The imaging element according to any one of [A01] to [B21], wherein the charge storage electrode segments of adjacent photoelectric conversion units are made of different materials. [C05] 《Imaging element: 5th configuration》 The photoelectric conversion unit is composed of N (N≧2) photoelectric conversion unit segments, The photoelectric conversion layer is composed of N photoelectric conversion layer segments, The insulating layer is composed of N insulating layer segments, The charge storage electrode is composed of N charge storage electrode segments arranged spaced apart from each other, an n-th (n=1, 2, 3,...,N) photoelectric conversion section segment is composed of an n-th charge storage electrode segment, an n-th insulating layer segment, and an n-th photoelectric conversion layer segment; The larger the value of n, the farther the photoelectric conversion segment is located from the first electrode. The imaging element according to any one of [A01] to [B21], wherein the areas of the charge storage electrode segments gradually decrease from the first photoelectric conversion portion segment to the Nth photoelectric conversion portion segment. [C06] 《Imaging element: 6th configuration》 The imaging element described in any one of [A01] to [B21], wherein when the stacking direction of the charge storage electrode, the insulating layer, and the photoelectric conversion layer is the Z direction and the direction away from the first electrode is the X direction, the cross-sectional area of ​​the stacked portion when the stacked portion in which the charge storage electrode, the insulating layer, and the photoelectric conversion layer are stacked is cut in a YZ virtual plane changes depending on the distance from the first electrode. [D01]《Stacked image sensor》 A stacked imaging element having at least one imaging element according to any one of [A01] to [C06]. [E01] Solid-state imaging device: First aspect A solid-state imaging device comprising a plurality of imaging elements according to any one of [A01] to [C06]. [E02] Solid-state imaging device: Second aspect A solid-state imaging device comprising a plurality of the stacked imaging elements according to [D01]. [E03] <<Solid-state imaging device: First configuration>> The imaging device according to any one of [A01] to [B06] includes a plurality of imaging elements, An imaging element block is composed of a plurality of imaging elements, A solid-state imaging device in which a first electrode is shared by a plurality of imaging elements that constitute an imaging element block. [E04] <<Solid-state imaging device: second configuration>> A stacked type imaging element including at least one imaging element according to any one of [A01] to [C06], An imaging element block is composed of a plurality of stacked imaging elements, A solid-state imaging device in which a first electrode is shared by a plurality of stack-type imaging elements that form an imaging element block. [E05] The solid-state imaging device according to any one of [E01] to [E04], wherein one on-chip microlens is disposed above one imaging element. [E06] An image sensor block is composed of two image sensors. The solid-state imaging device according to any one of [E01] to [E04], wherein one on-chip microlens is disposed above the imaging element block. [E07] The solid-state imaging device according to any one of [E01] to [E06], in which one floating diffusion layer is provided for a plurality of imaging elements. [E08] The solid-state imaging device according to any one of [E01] to [E07], wherein the first electrode is disposed adjacent to the charge storage electrode of each imaging element. [E09] A solid-state imaging device according to any one of [E01] to [E08], wherein the first electrode is arranged adjacent to some of the charge storage electrodes of the multiple imaging elements, and is not arranged adjacent to the remaining charge storage electrodes of the multiple imaging elements. [E10] A solid-state imaging device according to [E09], wherein the distance between a charge storage electrode constituting an imaging element and another charge storage electrode constituting an imaging element is longer than the distance between a first electrode and a charge storage electrode in an imaging element adjacent to the first electrode. [F01] <<Method of driving a solid-state imaging device>> The photoelectric conversion unit includes a first electrode, a photoelectric conversion layer, and a second electrode. the photoelectric conversion unit further includes a charge storage electrode disposed apart from the first electrode and facing the photoelectric conversion layer with an insulating layer interposed therebetween; A method for driving a solid-state imaging device including a plurality of imaging elements each having a structure in which light is incident from a second electrode side and light is not incident on a first electrode, comprising: In all the imaging elements, charges are simultaneously accumulated in the photoelectric conversion layer while the charges in the first electrodes are discharged to the outside of the system, and then, A method for driving a solid-state imaging device, which simultaneously transfers electric charges accumulated in a photoelectric conversion layer to a first electrode in all imaging elements, and then, after the transfer is completed, sequentially reads out the electric charges transferred to the first electrode in each imaging element, repeating each step. [Explanation of symbols]

[0292] 101, 102, 103... photoelectric conversion segment, 11... first electrode, 12... second electrode, 13... photoelectric conversion layer, 13 A A region of the photoelectric conversion layer located between the first electrode and the charge storage electrode (region-A of the photoelectric conversion layer), 13 B A region of the photoelectric conversion layer located between adjacent image sensors (region-B of the photoelectric conversion layer), 13 C A portion of the photoelectric conversion layer facing the charge storage electrode, 13 DN ,13 DN '...Lower layer of photoelectric conversion layer, 13 UP ,13 UP '···upper layer of photoelectric conversion layer, 14···electrode for charge storage, 14A, 14B, 14C···electrode segment for charge storage, 15, 15A, 15B···electrode for transfer control (charge transfer electrode), 21···electrode for charge transfer control, 22···pad portion, 23···connection hole, 24, 241, 242···electrode for charge transfer control, 41···n-type semiconductor region constituting second imaging element, 43···n-type semiconductor region constituting third imaging element, 42, 44, 73···p + layer, FD1, FD2, FD3, 45C, 46C... floating diffusion layer, TR1 amp Amplifying transistor, TR1 rst Reset transistor, TR1 sel···Select transistor, 51···Reset transistor TR1 rst Gate of 51A reset transistor TR1 rst The channel forming region of the reset transistor TR1, 51B, 51C rst 52, the source / drain region of amplifying transistor TR1 amp Gate of 52A amplifier transistor TR1 amp Channel formation region, 52B, 52C...amplifying transistor TR1 amp 53, the source / drain region of select transistor TR1 sel Gate section of 53A···Selection transistor TR1 sel The channel forming region of the selection transistor TR1 sel The source / drain region of TR2 trs 45. Gate portion of transfer transistor, TR2 rst Reset transistor, TR2 amp Amplifying transistor, TR2 sel Select transistor, TR3 trs 46: Gate of transfer transistor, TR3 rst Reset transistor, TR3 amp Amplifying transistor, TR3 sel Select transistor, V DD Power supply, RST1, RST2, RST3, reset lines, SEL1, SEL2, SEL3, selection lines, 117, VSL1, VSL2, VSL3, signal lines, TG2, TG3, transfer gate lines, V OA ,V OB ,V OT ,V OU6. Wiring, 61. Contact hole portion, 62. Wiring layer, 63, 64, 68A. Pad port...

Claims

1. a first electrode; a charge storage electrode disposed spaced apart from the first electrode; a photoelectric conversion layer in contact with the first electrode and formed above the charge storage electrode with an insulating layer interposed therebetween; and A second electrode formed on the photoelectric conversion layer; Equipped with a portion of the insulating layer located between the charge storage electrode and the photoelectric conversion layer has a first region and a third region; The first region is located opposite the first electrode, the third region is located adjacent to the first region; the portion of the insulating layer occupying the first region is made of a first insulating layer; the portion of the insulating layer occupying the third region is made of a third insulating layer; the material constituting the first insulating layer has a polarity different from the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode; An imaging element in which the material constituting the third insulating layer has the same polarity as the polarity of carriers generated in the photoelectric conversion layer and sent to the first electrode.

2. The carriers sent to the first electrode are electrons, The image sensor according to claim 1 , wherein the first insulating layer is made of silicon oxynitride or silicon nitride.

3. The carriers sent to the first electrode are electrons, 2. The image sensor according to claim 1, wherein the third insulating layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide.

4. The image sensor according to claim 1 , further comprising a second insulating layer formed between the first insulating layer and the photoelectric conversion layer.

5. 2. The image sensor according to claim 1, further comprising a second insulating layer formed between the third insulating layer and the photoelectric conversion layer.

6. the second region is located between the first region and the photoelectric conversion layer and between the third region and the photoelectric conversion layer; a second insulating layer is provided between the first electrode and the charge storage electrode; the portion of the insulating layer occupying the third region is made of a third insulating layer; 2. The image sensor according to claim 1, wherein the absolute value of the fixed charge of the material constituting the second insulating layer is smaller than the absolute value of the fixed charge of the material constituting the third insulating layer.

7. The carriers sent to the first electrode are electrons, the first insulating layer is made of silicon oxynitride or silicon nitride; the third insulating layer is made of at least one material selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, tantalum oxide, and titanium oxide; The image sensor according to claim 6 , wherein the second insulating layer is made of silicon oxide.

8. A stacked type imaging element comprising at least one imaging element according to claim 1 .

9. A solid-state imaging device comprising a plurality of the imaging elements according to claim 1 .

10. A solid-state imaging device comprising a plurality of the stack-type imaging elements according to claim 8.

Images