WO2015076058A1 - Substrat équipé d'une couche fonctionnelle organique et son procédé de production - Google Patents

Substrat équipé d'une couche fonctionnelle organique et son procédé de production Download PDF

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Publication number
WO2015076058A1
WO2015076058A1 PCT/JP2014/078311 JP2014078311W WO2015076058A1 WO 2015076058 A1 WO2015076058 A1 WO 2015076058A1 JP 2014078311 W JP2014078311 W JP 2014078311W WO 2015076058 A1 WO2015076058 A1 WO 2015076058A1
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layer
organic
protective film
substrate
film
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PCT/JP2014/078311
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English (en)
Japanese (ja)
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真二 今井
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富士フイルム株式会社
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a substrate with an organic functional layer having a protective film for protecting the organic functional layer, and a method for producing the same, and more particularly, a substrate with an organic functional layer applicable to a color filter, an imaging device, an organic solar cell, an organic EL, It relates to the manufacturing method.
  • a color imaging device using an organic photoelectric conversion layer includes a pixel electrode formed on a semiconductor substrate on which a signal readout circuit is formed, an organic photoelectric conversion layer formed on the pixel electrode, and a counter electrode ( An upper electrode), a protective film formed on the counter electrode and protecting the counter electrode, a color filter, and the like.
  • the protective film is composed of a SiOxNy film formed by a plasma CVD method.
  • Various types of such protective films have been conventionally proposed (see Patent Documents 1 and 2 and Non-Patent Document 1).
  • Patent Document 1 describes an imaging device having an organic photoelectric conversion layer that uses a silicon oxynitride film (SiOxNy film) formed by a plasma CVD method as a protective film for protecting a counter electrode.
  • SiOxNy film silicon oxynitride film
  • this protective film is a single layer, it is described that the internal stress of the entire protective film is ⁇ 50 MPa to +60 MPa.
  • Patent Document 2 discloses a gas barrier in which a solvent-resistant layer (acrylic cured resin), a cardo polymer layer (epoxy cured resin), and a silicon oxynitride layer are formed in this order on both surfaces of a polyimide film. A film is described. It is described that this silicon oxynitride layer is formed by a plasma CVD method. In addition, a SiOxNy layer is formed as a gas barrier layer by sputtering on a solvent resistant layer (acrylic cured resin), a cardo polymer layer is formed thereon, and a silicon oxynitride layer is formed on the cardo polymer layer. A gas barrier film formed of is described.
  • a preferred range for x is 0.5 to 1.5, a more preferred range is 0.7 to 1.3, a preferred range for y is 0.15 to 1, and a more preferred range is 0.3 to 0.7. ing.
  • Non-Patent Document 1 describes that a SiOxNy film is formed by a plasma CVD method at a substrate temperature of 350 ° C.
  • Non-Patent Document 1 discusses the composition and physical properties of the SiOxNy film, and shows the relationship between the composition of the SiOxNy film and the refractive index and density. In addition to this, the relationship between the refractive index and the density of the SiOxNy film is shown.
  • SiOxNy film used as the protective film As described above, there is a description regarding internal stress, film composition, and film density of the SiOxNy film used as the protective film. However, there is no SiOxNy film used as a protective film that is transparent, has a predetermined refractive index, and has excellent barrier properties, and is transparent and has no excellent film stability.
  • An object of the present invention is to provide a substrate with an organic functional layer having a protective film which is transparent and has excellent film stability, and a method for producing the same, by solving the above-mentioned problems based on the prior art.
  • a first aspect of the present invention includes a base material, an organic functional layer disposed on the base material, and a protective film disposed on the organic functional layer.
  • a substrate with an organic functional layer wherein 2.20 (g / m 3 ) ⁇ ⁇ ⁇ 2.60 (g / m 3 ) where ⁇ is a density of ⁇ (g / m 3 ).
  • the organic functional layer is an organic photoelectric conversion layer that generates charges when irradiated with light, and the organic photoelectric conversion layer is provided with a lower electrode on the substrate side and a transparent upper electrode on the opposite side of the substrate It is preferable that a protective film is disposed on the upper electrode.
  • the organic functional layer is a color filter layer containing an organic substance, and a protective film is disposed on the color filter layer.
  • x and y preferably satisfy 0.5 ⁇ x ⁇ 1.0 and ⁇ 2.2y + 2.1 ⁇ x ⁇ ⁇ 2.2y + 2.32.
  • the density ⁇ (g / m 3 ) of the protective film is preferably 2.30 (g / m 3 ) ⁇ ⁇ ⁇ 2.60 (g / m 3 ).
  • the second aspect of the present invention includes a step of forming a protective film composed of silicon oxynitride represented by SiOxNy on the organic functional layer disposed on the substrate, and x and y of SiOxNy are 0. .5 ⁇ x ⁇ 1.0 and ⁇ 2.2y + 2.1 ⁇ x ⁇ ⁇ 2.2y + 2.41 and when the density of the protective film is ⁇ (g / m 3 ), 2.20 ( g / m 3 ) ⁇ ⁇ ⁇ 2.60 (g / m 3 ) A method for producing a substrate with an organic functional layer is provided.
  • membrane stability can be provided.
  • membrane stability can be manufactured.
  • (A) is a schematic diagram which shows the board
  • (b) is the state before a protective film is formed in the board
  • (A) And (b) is typical sectional drawing which shows the manufacturing method of the image pick-up element of embodiment of this invention in order of a process.
  • (A) And (b) is typical sectional drawing which shows the manufacturing method of the image pick-up element of embodiment of this invention in order of a process, and shows the post process of FIG.3 (b).
  • (A) is typical sectional drawing which shows the organic solar cell of embodiment of this invention
  • (b) is typical sectional drawing which shows the organic EL element of embodiment of this invention.
  • FIG. 1A is a schematic diagram showing a substrate with an organic functional layer according to an embodiment of the present invention
  • FIG. 1B shows a state before a protective film is formed on the substrate with an organic functional layer according to an embodiment of the present invention. It is a schematic diagram which shows a state.
  • the substrate 10 with an organic functional layer has a base material 12, an organic functional layer 14, and a protective film 16.
  • the substrate 12 supports the organic functional layer 14 and the protective film 16.
  • the base material 12 can support the organic functional layer 14 and the protective film 16 and has a predetermined strength against heat and the like applied when the organic functional layer 14 and the protective film 16 are produced.
  • it is composed of a flat plate.
  • a glass base material, a metal base material with an insulating layer, a resin base material, a metal base material, etc. can be used, for example.
  • a conductive or insulating base material can be used suitably.
  • the organic functional layer 14 includes an organic substance and exhibits a predetermined function, and has a heat resistance of 240 ° C. or lower.
  • Examples of the organic functional layer 14 include an organic photoelectric conversion layer used for an image sensor, a photoelectric conversion layer containing an organic substance used for an organic solar cell, an organic EL layer used for an organic EL, and a color filter.
  • the organic functional layer 14 is used in the form of a single element such as a color filter, an organic photoelectric conversion layer used for an image sensor, a photoelectric conversion layer containing an organic substance used for an organic solar cell, and an organic EL layer. Are used.
  • the heat resistance is a temperature at which the function of the organic functional layer 14 can be maintained.
  • the function of the organic functional layer 14 since it is 240 degrees C or less, when temperature exceeds 240 degreeC, the function of the organic functional layer 14 will be impaired. For example, in the case of a color filter, problems such as changes in transmittance and color occur, and the original spectral characteristics change. If it is an organic photoelectric conversion layer, performance degradation, such as a raise of a dark current, will arise. If it is an organic EL layer, light emission intensity will fall.
  • the protective film 16 is for protecting the organic functional layer 14.
  • the protective film 16 has a function of protecting the organic functional layer 14 for a long time in a high temperature and high humidity environment, and functions as a barrier film.
  • the protective film 16 is directly provided on the organic functional layer 14 in FIG. 1A, but the arrangement of the protective film 16 is not limited to this as long as the organic functional layer 14 can be protected. Absent.
  • an electrode, a transparent electrode, another component or structure, etc. may be provided on the organic functional layer 14, and the protective film 16 may be provided on the electrode or other component or structure.
  • the protective film 16 is made of silicon oxynitride represented by SiOxNy.
  • x and y have a composition satisfying 0.5 ⁇ x ⁇ 1.0 and ⁇ 2.2y + 2.1 ⁇ x ⁇ ⁇ 2.2y + 2.41.
  • a composition satisfying 0.5 ⁇ x ⁇ 1.0 and ⁇ 2.2y + 2.1 ⁇ x ⁇ ⁇ 2.2y + 2.32 is preferable.
  • the method for measuring the composition of the protective film 16 is not particularly limited as long as the composition can be specified, and various known measuring methods can be used. An example of the measurement method will be described in detail later.
  • the protective film 16 is 2.20 (g / m 3 ) ⁇ ⁇ ⁇ 2.60 (g / m 3 ), where the density is ⁇ (g / m 3 ).
  • the protective film 16 is a silicon oxynitride film that is transparent and has a stable film quality by being in the above composition range. Moreover, the refractive index is in the range of 1.65 to 1.75.
  • the term “transparent” means that the light absorptance is less than 0.2% in the wavelength range of 400 to 800 nm (visible light range). That is, the term “transparent” means that the light absorptance in the wavelength range of 400 to 800 nm is a maximum value of less than 0.2%. If the light absorption rate in the visible light region is 0.2%, light absorption can be ignored. If the protective film 16 is out of the above composition range, it is not transparent and the refractive index does not fall within the range of 1.65 to 1.75. “Not transparent” means that the light absorption rate in the visible light region is 0.2% or more.
  • the protective film 16 has a predetermined heat resistance and can protect the organic functional layer 14.
  • the density of the protective film 16 is less than 2.20 (g / m 3 )
  • predetermined heat resistance cannot be obtained.
  • the density of the protective film 16 exceeds 2.60 (g / m 3 )
  • the film stress of the protective film 16 increases and adversely affects the lower organic functional layer 14.
  • the protective film 16 preferably has a thickness of 100 nm or more.
  • the protective film 16 represented by SiOxNy is formed by a plasma CVD method at a temperature of 240 ° C. or lower in a reaction chamber such as a process chamber.
  • a plasma CVD method it is possible to form a film at a higher film formation rate than the vapor deposition method or the like.
  • the substrate temperature is 240 ° C. or lower.
  • a silicon oxynitride film having the above composition is formed by a plasma CVD method.
  • the silicon oxynitride film is formed in advance by changing the flow rate of the reaction gas, and the film formation conditions (film formation temperature (substrate temperature), pressure in the reaction chamber during film formation ( (Hereinafter referred to as pressure during film formation), power during film formation, gas type (SiH 4 , NH 3 , N 2 O), gas mixture ratio, etc.) are within the above composition range, and A silicon oxynitride film having a density in the above range can be formed.
  • film formation temperature substrate temperature
  • pressure during film formation pressure in the reaction chamber during film formation
  • gas type SiH 4 , NH 3 , N 2 O
  • gas mixture ratio etc.
  • FIG. 2 is a schematic cross-sectional view showing the image sensor of the embodiment of the present invention.
  • the image sensor 20 shown in FIG. 2 is called an organic CMOS, and converts a visible light image into an electrical signal.
  • the imaging device 20 includes a substrate 30, an insulating layer 32, a pixel electrode (lower electrode) 34, an organic layer 36, a counter electrode (upper electrode) 38, a protective film (sealing layer) 40, and a color filter 42. And a partition wall 44, a light shielding layer 46, and an overcoat layer 48.
  • a reading circuit 60 and a counter electrode voltage supply unit 62 are formed on the substrate 30.
  • substrate 30 is corresponded to the base material 12 (refer Fig.1 (a)) of this invention.
  • the substrate 30 for example, a glass substrate or a semiconductor substrate such as Si is used.
  • An insulating layer 32 made of a known insulating material is formed on the substrate 30.
  • a plurality of pixel electrodes 34 are formed on the surface of the insulating layer 32.
  • the pixel electrodes 34 are arranged in a matrix on the surface 32a of the insulating layer 32, for example.
  • a first connection portion 64 that connects the pixel electrode 34 and the readout circuit 60 is formed in the insulating layer 32.
  • a second connection portion 66 that connects the counter electrode 38 and the counter electrode voltage supply unit 62 is formed.
  • the second connection part 66 is formed at a position not connected to the pixel electrode 34 and the organic layer 36.
  • the first connection part 64 and the second connection part 66 are made of a conductive material.
  • a wiring layer 68 made of a conductive material for connecting the readout circuit 60 and the counter electrode voltage supply unit 62 to, for example, the outside of the imaging element 20 is formed inside the insulating layer 32.
  • the circuit board 35 is formed by forming the pixel electrodes 34 connected to the first connection portions 64 on the surface 32 a of the insulating layer 32 on the substrate 30.
  • the circuit board 35 is also referred to as a CMOS substrate.
  • An organic layer 36 is formed so as to cover the plurality of pixel electrodes 34 and avoid the second connection portion 66, and the organic layer 36 is formed across the plurality of pixel electrodes 34.
  • the organic layer 36 receives incident light L including at least visible light and generates electric charges according to the amount of light, and includes a photoelectric conversion layer 52 and an electron blocking layer 50.
  • the electron blocking layer 50 is formed on the pixel electrode 34 side, and the photoelectric conversion layer 52 is formed on the surface 50 a of the electron blocking layer 50.
  • the organic layer 36 may be a single photoelectric conversion layer 52 without providing the electron blocking layer 50.
  • the electron blocking layer 50 is a layer for suppressing injection of electrons from the pixel electrode 34 to the photoelectric conversion layer 52.
  • the photoelectric conversion layer 52 generates charges according to the amount of incident light L, for example, received light such as visible light.
  • the photoelectric conversion layer 52 is an organic photoelectric conversion layer mainly composed of an organic material, and is formed on the electron blocking layer 50 across the plurality of pixel electrodes 34. As long as the photoelectric conversion layer 52 and the electron blocking layer 50 have a constant film thickness on the pixel electrode 34, the film thickness may not be constant otherwise. In this case, the film thickness is a thickness in a region where the film thickness is constant.
  • the photoelectric conversion layer 52 will be described in detail later.
  • the counter electrode 38 is an electrode facing the pixel electrode 34, and is provided so as to cover the photoelectric conversion layer 52.
  • a photoelectric conversion layer 52 is provided between the pixel electrode 34 and the counter electrode 38.
  • the counter electrode 38 is made of a conductive material that is transparent to the incident light L (light including at least visible light) in order to make light incident on the photoelectric conversion layer 52.
  • the counter electrode 38 is electrically connected to the second connection portion 66 disposed outside the photoelectric conversion layer 52, and is connected to the counter electrode voltage supply portion 62 via the second connection portion 66. Yes.
  • Examples of the material of the counter electrode 38 include metals, metal oxides, metal nitrides, metal borides, organic conductive compounds, and mixtures thereof. Specific examples include tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), conductive metal oxides such as titanium oxide, and metal nitrides such as TiN. Metal, gold (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), aluminum (Al), etc., and a mixture or laminate of these metals and conductive metal oxides Products, organic conductive compounds such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO.
  • Particularly preferable materials for the transparent conductive film are ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), gallium-doped zinc oxide ( GZO).
  • a particularly preferable material among the materials of the counter electrode 38 is ITO.
  • the light transmittance of the counter electrode 38 is preferably 60% or more, more preferably 80% or more, more preferably 90% or more, and more preferably 95% or more in the visible light wavelength.
  • the counter electrode 38 preferably has a thickness of 5 to 30 nm. By making the counter electrode 38 have a thickness of 5 nm or more, the lower layer can be sufficiently covered, and uniform performance can be obtained. On the other hand, if the thickness of the counter electrode 38 exceeds 30 nm, the counter electrode 38 and the pixel electrode 34 may be locally short-circuited, resulting in an increase in dark current. By making the counter electrode 38 have a film thickness of 30 nm or less, the occurrence of a local short circuit can be suppressed.
  • the counter electrode voltage supply unit 62 applies a predetermined voltage to the counter electrode 38 via the second connection unit 66.
  • the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.
  • the pixel electrode 34 is an electrode for collecting charges for collecting charges generated in the photoelectric conversion layer 52.
  • the pixel electrode 34 is connected to the readout circuit 60 via the first connection portion 64.
  • the readout circuit 60 is provided on the substrate 30 corresponding to each of the plurality of pixel electrodes 34, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 34.
  • Examples of the material of the pixel electrode 34 include metals, conductive metal oxides, metal nitrides and borides, organic conductive compounds, and mixtures thereof. Specific examples include tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), conductive metal oxides such as titanium oxide, and titanium nitride (TiN).
  • Conductive metal nitrides such as molybdenum nitride, tantalum nitride, tungsten nitride, metals such as gold (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), aluminum (Al), Furthermore, mixtures or laminates of these metals and conductive metal oxides, organic conductive compounds such as polyaniline, polythiophene and polypyrrole, laminates of these with ITO, and the like can be mentioned.
  • Particularly preferable materials for the transparent conductive film are ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), gallium-doped zinc oxide ( GZO).
  • a particularly preferable material is any one of titanium nitride, molybdenum nitride, tantalum nitride, and tungsten nitride.
  • the readout circuit 60 is constituted by, for example, a CCD, a MOS circuit, a TFT circuit, or the like, and is shielded from light by a light shielding layer (not shown) provided in the insulating layer 32.
  • the readout circuit 60 is preferably a CMOS circuit from the viewpoint of noise and high speed.
  • a high-concentration n region surrounded by a p region is formed on the substrate 30, and the first connection portion 64 is connected to the n region.
  • a read circuit 60 is provided in the p region.
  • the n region functions as a charge storage unit that stores the charge of the photoelectric conversion layer 52.
  • the signal charge accumulated in the n region is converted into a signal corresponding to the amount of charge by the readout circuit 60 and output to the outside of the image sensor 20 or the like via the wiring layer 68, for example.
  • the organic layer 36 corresponds to the organic functional layer of the present invention, and the heat resistance is 240 ° C. or lower.
  • the protective film 40 is formed so as to cover the counter electrode 38.
  • the protective film 40 is not directly provided on the organic layer 36.
  • the protective film 40 can protect the organic layer 36 including the photoelectric conversion layer 52 from deterioration factors such as water molecules and oxygen.
  • the protective film 40 protects the organic layer 36 by preventing entry of factors that degrade the organic photoelectric conversion material contained in a solution such as an organic solvent, plasma, or the like in each manufacturing process of the imaging element 20.
  • the intrusion of factors that deteriorate the organic photoelectric conversion material such as water molecules and oxygen is prevented, and the deterioration of the organic layer 36 is prevented during long-term storage and long-term use. .
  • the protective film 40 is formed, the already formed organic layer 36 is not deteriorated. Further, the incident light L reaches the organic layer 36 through the protective film 40. For this reason, the protective film 40 is transparent to light having a wavelength detected by the organic layer 36, for example, visible light.
  • the protective film 40 has a single layer structure.
  • the protective film 40 is a silicon oxynitride film represented by SiOxNy having the same composition and density as the protective film 16 described above.
  • the protective film 40 is formed by a plasma CVD method at a temperature of 240 ° C. or lower.
  • the protective film 40 has a thickness of 30 to 500 nm. If the total film thickness of the protective film 40 is less than 30 nm, the barrier property may be lowered, or the resistance of the color filter to the developer may be lowered. On the other hand, if the thickness of the protective film 40 exceeds 500 nm, it is difficult to suppress color mixing when the pixel size is less than 1 ⁇ m.
  • the imaging device 20 having a pixel size of less than 2 ⁇ m, particularly about 1 ⁇ m, if the distance between the color filter 42 and the photoelectric conversion layer 52, that is, the thickness of the protective film 40 is large, the incident light in the protective film 40 There is a risk that the influence of the oblique incidence component of light (visible light) becomes large and color mixing occurs. For this reason, it is preferable that the protective film 40 is thin.
  • the color filter 42 is formed at a position facing each pixel electrode 34 on the protective film 40.
  • the partition wall 44 is provided between the color filters 42 on the protective film 40 and is for improving the light transmission efficiency of the color filter 42.
  • the light shielding layer 46 is formed in a region other than the region (effective pixel region) where the color filter 42 and the partition wall 44 are provided on the protective film 40, and light is incident on the photoelectric conversion layer 52 formed outside the effective pixel region. Is to prevent.
  • the color filter 42, the partition wall 44, and the light shielding layer 46 are formed by, for example, a photolithography method. Although the color filter 42 is provided, the color filter 42 may not be provided. In this case, since the partition wall 44 and the light shielding layer 46 are not provided in addition to the color filter 42, the protective film 40 is the uppermost layer.
  • the overcoat layer 48 is for protecting the color filter 42 from subsequent processes and is formed so as to cover the color filter 42, the partition wall 44 and the light shielding layer 46.
  • one pixel electrode 34, on which the organic layer 36, the counter electrode 38, and the color filter 42 are provided, is a unit pixel Px.
  • the overcoat layer 48 a polymer material such as an acrylic resin, a polysiloxane resin, a polystyrene resin, and a fluorine resin, or an inorganic material such as silicon oxide and silicon nitride can be used as appropriate.
  • a photosensitive resin such as polystyrene
  • the overcoat layer 48 can be patterned by a photolithography method, so that it is used as a photoresist when opening the peripheral light shielding layer, sealing layer, insulating layer, etc. on the bonding pad.
  • the overcoat layer 48 itself is preferably processed as a microlens, which is preferable.
  • the overcoat layer 48 can be used as an antireflection layer, and it is also preferable to form various low refractive index materials used as the partition walls of the color filter 42.
  • the overcoat layer 48 can be configured to have two or more layers combining the above materials.
  • the color filter 42 contains an organic substance and corresponds to the organic functional layer of the present invention.
  • the overcoat layer 48 can also be a silicon oxynitride film having the same composition and density as the protective film 16, similarly to the protective film 40 described above.
  • the imaging device 20 can protect the organic layer 36 by the protective film 40 for a long time even in a severe environment of high temperature and high humidity such as a temperature of 85 ° C. and a relative humidity of 85%. For this reason, the image sensor 20 can be used without degrading performance for a long time even in the above-mentioned severe environment of high temperature and high humidity. For this reason, the image sensor 20 is suitable for applications where the use environment is severe such as a monitoring camera.
  • the pixel electrode 34 is formed on the surface of the insulating layer 32, but is not limited thereto, and may be embedded in the surface portion of the insulating layer 32.
  • the second connection portion 66 and one counter electrode voltage supply portion 62 are provided, but a plurality of the second connection portion 66 and the counter electrode voltage supply portion 62 may be provided.
  • a voltage drop at the counter electrode 38 can be suppressed by supplying a voltage from both ends of the counter electrode 38 to the counter electrode 38.
  • the number of sets of the second connection portion 66 and the counter electrode voltage supply portion 62 may be appropriately increased or decreased in consideration of the chip area of the element.
  • the photoelectric conversion layer 52 includes a p-type organic semiconductor material and an n-type organic semiconductor material.
  • Exciton dissociation efficiency can be increased by joining a p-type organic semiconductor material and an n-type organic semiconductor material to form a donor-acceptor interface.
  • the photoelectric conversion layer of the structure which joined the p-type organic-semiconductor material and the n-type organic-semiconductor material expresses high photoelectric conversion efficiency.
  • a photoelectric conversion layer in which a p-type organic semiconductor material and an n-type organic semiconductor material are mixed is preferable because the junction interface is increased and the photoelectric conversion efficiency is improved.
  • the p-type organic semiconductor material is a donor organic semiconductor material (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound.
  • the metal complex etc. which it has as can be used.
  • the present invention is not limited to this, and any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor) compound as described above may be used as the donor organic semiconductor.
  • the n-type organic semiconductor material is an acceptor organic semiconductor material, and is mainly represented by an electron transporting organic compound and means an organic compound having a property of easily accepting electrons. More specifically, an n-type organic semiconductor refers to an organic compound having a larger electron affinity when two organic compounds are used in contact with each other. Therefore, any organic compound can be used as the acceptor organic compound as long as it is an electron-accepting organic compound.
  • condensed aromatic carbocyclic compounds naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives
  • 5- to 7-membered heterocyclic compounds containing nitrogen atoms, oxygen atoms, and sulfur atoms E.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole , Benzoxazole, benzothiazole, carbazole, purine, triazolopy
  • Any organic dye may be used as the p-type organic semiconductor material or the n-type organic semiconductor material, but preferably a cyanine dye, a styryl dye, a hemicyanine dye, a merocyanine dye (including zero methine merocyanine (simple merocyanine)) 3-nuclear merocyanine dye, 4-nuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye , Triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, perinone dye, phenazine
  • fullerene or a fullerene derivative having excellent electron transport properties.
  • Fullerene C 60 , fullerene C 70 , fullerene C 76 , fullerene C 78 , fullerene C 80 , fullerene C 82 , fullerene C 84 , fullerene C 90 , fullerene C 96 , fullerene C 240 , fullerene C 540 , mixed Fullerene and fullerene nanotube are represented, and a fullerene derivative represents a compound having a substituent added thereto.
  • the substituent for the fullerene derivative is preferably an alkyl group, an aryl group, or a heterocyclic group.
  • the alkyl group is more preferably an alkyl group having 1 to 12 carbon atoms, and the aryl group and the heterocyclic group are preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring.
  • substituents may further have a substituent, and the substituents may be bonded as much as possible to form a ring.
  • substituents may be bonded as much as possible to form a ring.
  • you may have a some substituent and they may be the same or different.
  • a plurality of substituents may be combined as much as possible to form a ring.
  • the photoelectric conversion layer contains fullerene or a fullerene derivative
  • electrons generated by photoelectric conversion can be quickly transported to the pixel electrode 34 or the counter electrode 38 via the fullerene molecule or fullerene derivative molecule.
  • fullerene molecules or fullerene derivative molecules are connected to form an electron path, the electron transport property is improved, and high-speed response of the photoelectric conversion element can be realized.
  • the fullerene or fullerene derivative is preferably contained in the photoelectric conversion layer by 40% (volume ratio) or more. If there are too many fullerenes or fullerene derivatives, the p-type organic semiconductor will decrease, the junction interface will become smaller, and the exciton dissociation efficiency will decrease.
  • the triarylamine compound described in Japanese Patent No. 4213832 is used as a p-type organic semiconductor material mixed with fullerene or a fullerene derivative in the photoelectric conversion layer 52, a high SN ratio of the photoelectric conversion element can be expressed. Is particularly preferred. If the ratio of fullerene or fullerene derivative in the photoelectric conversion layer is too large, the amount of triarylamine compounds decreases and the amount of incident light absorbed decreases. As a result, the photoelectric conversion efficiency is reduced. Therefore, the fullerene or fullerene derivative contained in the photoelectric conversion layer preferably has a composition of 85% (volume ratio) or less.
  • an electron donating organic material can be used.
  • TPD N, N′-bis (3-methylphenyl
  • Porphyrin compounds triazole derivatives, Xadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, annealed amine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, silazane derivatives, carbazole derivatives, bifluorenes Derivatives can be used, and as the polymer material, polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof can be used. It is possible to use any compound that has sufficient hole transport properties, even if it is not a functional compound.
  • an inorganic material can be used as the electron blocking layer 50.
  • an inorganic material has a dielectric constant larger than that of an organic material, when it is used for the electron blocking layer 50, a large voltage is applied to the photoelectric conversion layer, and the photoelectric conversion efficiency can be increased.
  • Materials that can be used as the electron blocking layer 50 include calcium oxide, chromium oxide, chromium oxide copper, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, Examples include indium silver oxide and iridium oxide.
  • the layer adjacent to the photoelectric conversion layer 52 among the plurality of layers is preferably a layer made of the same material as the p-type organic semiconductor contained in the photoelectric conversion layer 52.
  • the layer can be a layer made of an inorganic material, and when it is a plurality of layers, one or more layers can be a layer made of an inorganic material.
  • FIGS. 3A and 3B are schematic cross-sectional views illustrating the manufacturing method of the image sensor according to the embodiment of the present invention in the order of steps
  • FIGS. 4A and 4B are diagrams of the embodiment of the present invention. It is typical sectional drawing which shows the manufacturing method of an image pick-up element in order of a process, and shows the post process of FIG.3 (b).
  • the first circuit is formed on the substrate 30 on which the readout circuit 60 and the counter electrode voltage supply unit 62 are formed.
  • the insulating layer 32 provided with the connecting portion 64, the second connecting portion 66, and the wiring layer 68 is formed, and the pixel electrode 34 connected to each first connecting portion 64 is further formed on the surface 32a of the insulating layer 32.
  • a formed circuit board 35 (CMOS substrate) is prepared. In this case, as described above, the first connection unit 64 and the readout circuit 60 are connected, and the second connection unit 66 and the counter electrode voltage supply unit 62 are connected.
  • the pixel electrode 34 is made of, for example, TiN.
  • the electron blocking layer 50 is transferred to a film forming chamber (not shown) through a predetermined transfer path, and as shown in FIG.
  • the electron blocking material is formed into a film under a predetermined vacuum using, for example, an evaporation method so as to cover 34, thereby forming the electron blocking layer 50.
  • the electron blocking material for example, a carbazole derivative, more preferably a bifluorene derivative is used.
  • the photoelectric conversion layer 52 is transported to a film forming chamber (not shown) by a predetermined transport path, and the photoelectric conversion layer 52 is deposited on the surface 50a of the electron blocking layer 50 by a predetermined vacuum using, for example, a vapor deposition method.
  • a photoelectric conversion material for example, a p-type organic semiconductor material and fullerene or a fullerene derivative are used. Thereby, the photoelectric conversion layer 52 is formed and the organic layer 36 is formed.
  • the organic layer 36 (the photoelectric conversion layer 52 and the electron blocking layer 50) is covered, and the second connection portion 66 is covered.
  • the counter electrode 38 is formed in a predetermined vacuum by using, for example, a sputtering method with the pattern formed in (1).
  • the protective film 40 is transferred to a film forming chamber (not shown) through a predetermined transfer path, and as shown in FIG. 4A, the counter electrode 38 is covered so as to cover the surface 32a of the insulating layer 32.
  • a silicon oxynitride film SiOxNy film
  • a silicon oxynitride film having the above composition and density is formed using a plasma CVD method at a substrate temperature of 240 ° C. or lower.
  • the silicon oxynitride film was formed by changing the flow rate of the reaction gas in advance, and the film formation conditions (film formation temperature (substrate temperature), film formation pressure, film formation)
  • a silicon oxynitride film having a density within the above range and a density within the above range is determined by determining the power and gas type (SiH 4 , NH 3 , N 2 O) and gas mixing ratio, etc.) Can do.
  • the color filter 42, the partition wall 44, and the light shielding layer 46 are formed on the surface 40a of the protective film 40 by using, for example, a photolithography method.
  • a photolithography method As the color filter 42, the partition wall 44, and the light shielding layer 46, known ones used for organic solid-state imaging devices are used.
  • the formation process of the color filter 42, the partition wall 44, and the light shielding layer 46 may be under a predetermined vacuum or non-vacuum.
  • an overcoat layer 48 is formed using, for example, a coating method so as to cover the color filter 42, the partition wall 44, and the surface 47 of the light shielding layer 46.
  • the image sensor 20 shown in FIG. 2 can be formed.
  • the overcoat layer 48 a known layer used for an organic solid-state imaging device is used.
  • the overcoat layer 48 may be formed in a predetermined vacuum or non-vacuum.
  • the overcoat layer 48 is formed of a silicon oxynitride film (SiOxNy film)
  • the overcoat layer 48 can be formed by the same method as the protective film 40.
  • substrate with an organic functional layer of this invention can also be called an organic solar cell and an organic EL element, for example.
  • Fig.5 (a) is typical sectional drawing which shows the organic solar cell of embodiment of this invention
  • (b) is typical sectional drawing which shows the organic EL element of embodiment of this invention.
  • An organic solar cell 70 shown in FIG. 5A has an organic photoelectric conversion layer 76. This organic photoelectric conversion layer 76 corresponds to the organic functional layer of the present invention, and the heat resistance is 240 ° C. or lower.
  • the organic solar cell 70 is formed by laminating a lower electrode 74, an organic photoelectric conversion layer 76, a transparent electrode (upper electrode) 78, and a protective film 80 in this order on a substrate 72.
  • Incident light L is incident from the transparent electrode 78 side.
  • the protective film 80 has the same composition and density as the protective film 16 described above, and is formed by the same manufacturing method as the protective film 16. For this reason, the detailed description is abbreviate
  • the substrate 72 corresponds to the base material 12 of the present invention (see FIG. 1 (a)).
  • the lower electrode 74, the organic photoelectric conversion layer 76, and the transparent electrode 78 are configured by general materials used for known organic solar cells. For this reason, the detailed description is abbreviate
  • the current generated in the organic photoelectric conversion layer 76 by the irradiation of the incident light L is taken out by the lower electrode 74 and the transparent electrode 78.
  • the organic photoelectric conversion layer 76 can be protected over a long period of time in a high temperature and high humidity environment by providing the same protective film 80 as the protective film 16 described above. Thereby, durability of the organic solar cell 70 can be improved.
  • the protective film 80 is transparent as described above, and does not prevent the incident light L from entering the organic photoelectric conversion layer 76.
  • An organic EL element 70a shown in FIG. 5B is a light emitting element using the organic EL layer 86, and is called a top emission method.
  • symbol is attached
  • the organic EL layer 86 corresponds to the organic functional layer of the present invention, and the heat resistance is 240 ° C. or lower.
  • a TFT 82, a cathode 84, an organic EL layer 86, a transparent electrode (upper electrode) 78, and a protective film 80 are laminated on a substrate 72 in this order.
  • a power source 88 is connected to the TFT 82, the cathode 84 and the transparent electrode 78.
  • the protective film 80 is the same as the organic solar cell 70 shown in FIG.
  • the organic EL layer 86 is a portion that emits light, and is a layer in which a hole injection layer, a hole transport layer, a light emitting layer, an electron injection / transport layer, and the like are sequentially stacked.
  • the cathode 84 and the transparent electrode 78 are for applying a voltage necessary for causing the organic EL layer 86 to emit light, and the TFT 82 is for controlling the light emission of the organic EL element 70a.
  • the power supply 88 generates a voltage necessary for causing the organic EL layer 86 to emit light, and drives the TFT 82.
  • the TFT 82, the cathode 84, the organic EL layer 86, and the transparent electrode 78 are appropriately configured with general materials used for known organic EL elements. For this reason, the detailed description is abbreviate
  • the organic EL element 70a having such a configuration, by providing the same protective film 80 as the above-described protective film 16, the organic EL layer 86 can be protected for a long time in a high temperature and high humidity environment. Thereby, durability of the organic EL element 70a can be improved.
  • the protective film 80 is transparent as described above, and does not affect the light emitted from the organic EL layer 86.
  • the protective film of the present invention is not limited to any of the above-described examples, and the organic functional layer having a heat resistance of 240 ° C. or lower is protected for a long time in a high-temperature and high-humidity environment. It can be suitably used for those requiring transparency that does not hinder the incidence of light and the emission of light from the organic functional layer.
  • the present invention is basically configured as described above. As mentioned above, although the board
  • a pixel electrode is formed on a part of the surface of the base material on the base material, and an organic functional layer is formed on the base material as a photoelectric conversion layer so as to cover the pixel electrode.
  • a photoelectric conversion element main body having a simplified structure in which a counter electrode is formed on the organic functional layer and a protective film covering the counter electrode is formed was used.
  • the protective film a silicon oxynitride film represented by SiOxNy was used.
  • element units described later having the same configuration were used except for the configuration of the protective film.
  • an element unit formed as follows was prepared.
  • a non-alkali glass substrate having a thickness of 0.7 mm was prepared as a substrate, and an indium tin oxide (ITO) film having a thickness of 100 nm was formed as a pixel electrode on the substrate by a sputtering method.
  • ITO indium tin oxide
  • a material represented by the following chemical formula 1 was deposited as an electron blocking layer on the substrate so as to have a thickness of 100 nm at a deposition rate of 10 to 20 nm / s as an electron blocking layer so as to cover the image electrode. .
  • a material represented by the following chemical formula 2 fullerene C 60
  • a material represented by the following chemical formula 3 are deposited at a deposition rate of 16 to 18 nm / s and 25 to 28 nm / s, respectively. Co-evaporated so that the volume ratio of the material shown in 2 and the material shown in chemical formula 3 below was 1: 3, and formed to a thickness of 400 nm.
  • an indium tin oxide (ITO) film having a thickness of 10 nm was formed on the organic layer and the substrate so as to cover the organic layer by sputtering.
  • the sample of Example 1 was produced as follows. A silicon oxynitride film (SiOxNy film) having a thickness of 300 nm is formed as a protective film on the counter electrode and the base material by plasma CVD so as to cover the counter electrode of the element unit thus prepared. Formed. Thus, the sample of Example 1 was produced.
  • SiOxNy film silicon oxynitride film having a thickness of 300 nm
  • the composition of the protective film of each sample of Examples 1 to 9 and Comparative Examples 1 to 7 is as shown in Table 1 below. It should be noted that the protective film is formed in advance so as to have a predetermined composition and density (film formation temperature (substrate temperature), film formation pressure, film formation power, gas type (SiH 4 , NH 3 , N 2 O) and the mixture ratio of the gas, etc.) to previously obtain was formed at the production conditions. In Examples 1 to 9 and Comparative Examples 1 and 6, the substrate temperature was 154 ° C.
  • the film density and film composition of the protective films of the samples of Examples 1 to 9 and Comparative Examples 1 to 7 were measured, and the refractive index at a wavelength of 550 nm was measured using an ellipsometer.
  • the results are shown in Table 1 below.
  • the samples of Examples 1 to 9 and Comparative Examples 1 to 7 were left in an environment having a temperature of 85 ° C. and a relative humidity of 85%, and the dark current after being left in the above environment was not left in the above environment. The time required to reach twice the value was measured. This measurement time was defined as the life.
  • Table 1 The results are shown in Table 1 below.
  • the film density was measured as follows. Rigaku ATX-G was used as the film density measuring instrument. A Cu target was used as the X-ray source, and X-rays were generated at 50 keV-300 mA.
  • the S1 slit is 0.5 mm wide and 5 mm high.
  • the incident side optical element is a Ge (220) crystal.
  • the S2 slit has a width of 0.05 mm and a height of 10 mm.
  • the receiving slit has a width of 0.1 mm and a height of 10 mm. No light receiving side optical element.
  • the Gurard slit is 0.2 mm wide and 20 mm high.
  • the scan axis is 2 ⁇ / ⁇ , the scan range is 0 to 2 °, the sampling range is 0.001 °, and the scan speed is 0.1 ° / min.
  • the film density was calculated by fitting simulation of the measured profile.
  • the composition of the film was measured (XPS) as follows.
  • the pass energy was 112 eV
  • the step was 0.2 eV.
  • There was charging correction both electron gun and low-speed ion gun), and each intensity of C1s, O1s, N1s, and Si2p was corrected with a sensitivity coefficient, and converted to an atomic ratio.
  • Comparative Example 1 As shown in Table 1 above, in Examples 1 to 9, even in an environment where the temperature is 85 ° C. and the relative humidity is 85%, the time until the dark current doubles is at least 100 hours as long as Example 1, and the durability is long. It was possible to improve the performance. On the other hand, in Comparative Example 1, the value of x exceeded the upper limit value of the present invention, the expression of y was not satisfied, and the density was also less than the lower limit value of the present invention. Comparative Example 1 has a low refractive index and a low temperature of 85 ° C. and a relative humidity of 85%, which is as low as 10 hours. In Comparative Example 6, the film density of the protective film is less than the lower limit of the present invention, the refractive index is low, and the temperature 85 ° C. and relative humidity 85% resistance is also low, 50 hours.
  • the protective film does not satisfy the equation of y, and the density exceeds the upper limit of the present invention.
  • the value of x is less than the lower limit of the present invention, and the formula of y is not satisfied also for the protective film.
  • the protective film does not satisfy the expression y, and the density exceeds the upper limit of the present invention.
  • Comparative Example 5 does not satisfy the formula of y for the protective film.
  • the density of the protective film also exceeds the upper limit of the present invention.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Solid State Image Pick-Up Elements (AREA)
  • Light Receiving Elements (AREA)
  • Optical Filters (AREA)
  • Electroluminescent Light Sources (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un substrat équipé d'une couche fonctionnelle organique qui comporte un substrat, une couche fonctionnelle organique disposée sur le substrat, et une pellicule protectrice disposée sur la couche fonctionnelle organique. La pellicule protectrice est constituée d'un oxynitrure de silicium représenté par la formule SiOxNy, x et y satisfaisant aux expressions 0,5 ≤ x ≤ 1,0 et −2,2y + 2,1 ≤ x ≤ −2,2y + 2,41. Étant donné que la densité de la pellicule protectrice est ρ (g/m3), 2,20 (g/m3) ≤ ρ ≤ 2,60 (g/m3).
PCT/JP2014/078311 2013-11-22 2014-10-24 Substrat équipé d'une couche fonctionnelle organique et son procédé de production WO2015076058A1 (fr)

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