# US 9,520,449 B2 · Photoelectric conversion device, solid-state image pickup unit, and electronic apparatuses having work function adjustment layers and diffusion suppression layers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,520,449 B2 - Document ID: US9520449B2 - Status: Granted - Kind: B2 - Application number: 14/437,270 - Filed: 2013-09-25 - Published: 2015-10-08 - Granted: 2016-12-13 - Earliest claimed: 2012-11-06 - Assignees: Sony Corporation - Applicants: Sony Corporation - Inventors: Toru Udaka; Osamu Enoki; Masaki Murata; Rui Morimoto; Ryoji Arai - Web page: https://patentgrep.com/patent/US9520449B2 ## CPC - H10K 30/353: {comprising blocking layers, e.g. exciton blocking layers} - H10K 30/81: Electrodes - H10K 30/82: Transparent electrodes, e.g. indium tin oxide [ITO] electrodes - H10K 39/32: Organic image sensors - H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole} - H10K 2102/00: Constructional details relating to the organic devices covered by this subclass - H10K 2102/101: {comprising transparent conductive oxides [TCO]} - H10K 2102/102: {comprising tin oxides, e.g. fluorine-doped SnO2} - H10K 2102/103: {comprising indium oxides, e.g. ITO} - Y02E 10/549: Organic PV cells - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract A photoelectric conversion device includes an organic photoelectric conversion film; a first electrode and a second electrode provided with the organic photoelectric conversion film in between; and a charge block layer provided between the second electrode and the organic photoelectric conversion film, in which the charge block layer includes a work function adjustment layer including a metal element on the second electrode side of the organic photoelectric conversion film, the metal element being adopted to adjust a work function, and a first diffusion suppression layer provided between the work function adjustment layer and the second electrode and suppressing diffusion of the metal element to the second electrode side. ## Claims ### Claim 1 A photoelectric conversion device comprising: an organic photoelectric conversion film; a first electrode and a second electrode provided with the organic photoelectric conversion film in between; and a charge block layer provided between the second electrode and the organic photoelectric conversion film, wherein the charge block layer includes a work function adjustment layer including a metal element on a side of the organic photoelectric conversion film that is closest to the second electrode, the metal element being adopted to adjust a work function, and a first diffusion suppression layer provided between the work function adjustment layer and the second electrode, wherein the first diffusion suppression layer is capable of suppressing diffusion of the metal element to the side of the organic photoelectric conversion film that is closest to the second electrode, wherein the first diffusion suppression layer is made of at least one oxygen-free organic molecule selected from a phenanthroline derivative, a rubrene derivative, an anthracene derivative, a triazine derivative, a perylene derivative, and a tetracyanoquinodimethane (TCNQ) derivative. ### Claim 2 (depends on 1) The photoelectric conversion device according to claim 1, wherein the charge block layer further includes a second diffusion suppression layer on the organic photoelectric conversion film side of the work function adjustment layer, and wherein the second diffusion suppression layer is made of at least one oxygen-free organic molecule selected from a phenanthroline derivative, a rubrene derivative, an anthracene derivative, a triazine derivative, a perylene derivative, and a tetracyanoquinodimethane (TCNQ) derivative. ### Claim 3 (depends on 1) The photoelectric conversion device according to claim 1, wherein the charge block layer further includes a third diffusion suppression layer between the work function adjustment layer and the first diffusion suppression layer, and wherein the third diffusion suppression layer is made of at least one oxygen-free organic molecule selected from a phenanthroline derivative, a rubrene derivative, an anthracene derivative, a triazine derivative, a perylene derivative, and a tetracyanoquinodimethane (TCNQ) derivative. ### Claim 4 (depends on 1) The photoelectric conversion device according to claim 1, wherein the first electrode is a conductive film having light transparency. ### Claim 5 (depends on 4) The photoelectric conversion device according to claim 4, wherein the first electrode is configured of one kind selected from indium tin oxide (ITO), tin oxide (TO), a tin oxide (SnO2)-based material doped with a dopant, and a zinc oxide-based material doped with a dopant. ### Claim 6 (depends on 1) The photoelectric conversion device according to claim 1, wherein the second electrode includes one or more kinds selected from aluminum (Al), copper (Cu), nickel (Ni), chromium (Cr), vanadium (V), titanium (Ti), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), palladium (Pd), hafnium (Hf), tantalum (Ta), tungsten (W), platinum (Pt), and gold (Au). ### Claim 7 (depends on 1) The photoelectric conversion device according to claim 1, wherein the second electrode is a conductive film having light transparency and a different work function from the first electrode. ### Claim 8 (depends on 7) The photoelectric conversion device according to claim 7, wherein the second electrode is configured of one kind selected from indium tin oxide (ITO), tin oxide (TO), a tin oxide (SnO2)-based material doped with a dopant, and a zinc oxide-based material doped with a dopant. ### Claim 9 (depends on 1) The photoelectric conversion device according to claim 1, wherein the metal element is one of lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), cesium (Cs), and barium (Ba). ### Claim 10 A photoelectric conversion device comprising: an organic photoelectric conversion film; a first electrode and a second electrode provided with the organic photoelectric conversion film in between; and a charge block layer provided between the second electrode and the organic photoelectric conversion film, wherein the charge block layer includes a work function adjustment layer including a metal element on a side of the organic photoelectric conversion film that is closest to the second electrode, the metal element being adopted to adjust a work function, and a first diffusion suppression layer provided between the work function adjustment layer and the organic photoelectric conversion film, wherein the first diffusion suppression layer is capable of suppressing diffusion of the metal element, wherein the first diffusion suppression layer is made of at least one oxygen-free organic molecule selected from a phenanthroline derivative, a rubrene derivative, an anthracene derivative, a triazine derivative, a perylene derivative, and a tetracyanoquinodimethane derivative, wherein the charge block layer further includes a second diffusion suppression layer on the side of the organic photoelectric conversion film that is closest to the second electrode, and wherein the second diffusion suppression layer is made of at least one oxygen-free organic molecule selected from a phenanthroline derivative, a rubrene derivative, an anthracene derivative, a triazine derivative, a perylene derivative, and a tetracyanoquinodimethane derivative. ### Claim 11 A solid-state image pickup unit provided with a plurality of pixels each of which includes a photoelectric conversion device, the photoelectric conversion device comprising: an organic photoelectric conversion film; a first electrode and a second electrode provided with the organic photoelectric conversion film in between; and a charge block layer provided between the second electrode and the organic photoelectric conversion film, wherein the charge block layer includes a work function adjustment layer including a metal element on a side of the organic photoelectric conversion film that is closest to the second electrode, the metal element being adopted to adjust a work function, and a first diffusion suppression layer provided between the work function adjustment layer and the second electrode, wherein the first diffusion suppression layer is capable of suppressing diffusion of the metal element to the side of the organic photoelectric conversion film that is closest to the second electrode, wherein the first diffusion suppression layer is made of at least one oxygen-free organic molecule selected from a phenanthroline derivative, a rubrene derivative, an anthracene derivative, a triazine derivative, a pervlene derivative, and a tetracyanoquinodimethane derivative. ### Claim 12 An electronic apparatus provided with a solid-state image pickup unit, the solid-state image pickup unit being provided with a plurality of pixels each of which includes a photoelectric conversion device, the photoelectric conversion device comprising: an organic photoelectric conversion film; a first electrode and a second electrode provided with the organic photoelectric conversion film in between; and a charge block layer provided between the second electrode and the organic photoelectric conversion film, wherein the charge block layer includes a work function adjustment layer including a metal element on the a side of the organic photoelectric conversion film that is closest to the second electrode, the metal element being adopted to adjust a work function, and a first diffusion suppression layer provided between the work function adjustment layer and the second electrode, wherein the first diffusion suppression layer is capable of suppressing diffusion of the metal element to the side of the organic photoelectric conversion film that is closest to the second electrode, wherein the first diffusion suppression layer is made of at least one oxygen-free organic molecule selected from a phenanthroline derivative, a rubrene derivative, an anthracene derivative, a triazine derivative, a perylene derivative, and a tetracyanoquinodimethane derivative.