JP2022134244A - Manufacturing method of electronic device - Google Patents

Abstract

To provide a manufacturing method of an electronic device, which can be applied to an electronic device having a water-soluble charge transport layer and can suppress deterioration of an organic functional layer.SOLUTION: A manufacturing method of an electronic device having a function portion in which at least a first electrode, an organic functional layer, a water-soluble charge transport layer, and a second electrode are laminated on a substrate in this order, comprises at least the steps of: forming the first electrode on the substrate; forming the organic functional layer on the substrate on which the first electrode is formed; forming a water-soluble charge transport layer on the organic functional layer; forming a patterned protective layer on the water-soluble charge transport layer; removing the organic functional layer and the water-soluble charge transport layer at a position without being coated with a protective layer by performing etching using the patterned protective layer as a mask; removing the patterned protective layer; and forming the second electrode onto the water-soluble charge transport layer.SELECTED DRAWING: Figure 1

Description

The present invention relates to an electronic device manufacturing method.

Organic electronic devices having organic functional layers using organic semiconductors such as light-emitting layers and photoelectric conversion layers are used in organic light-emitting diode (OLED) displays and lighting, organic solar cells (OPV), organic photodetectors (OPD), and the like. are being applied and put to practical use. By using soluble organic semiconductors, these organic electronic devices have the advantage of being able to use coating-type manufacturing processes that are different from conventional inorganic semiconductors.

On the other hand, the manufacture of electronic devices requires patterning of functional layers for electrode connection and the like. Since functional layers made of inorganic semiconductors have poor solubility, patterning methods using photolithography are often used. Since the organic functional layer has high solubility, pattern coating methods such as inkjet printing are being studied. However, in order to pattern each multilayer film by inkjet coating, it is expected that the coating liquid for each layer will be required to have inkjet coatability and that new equipment will be required. On the other hand, when a highly soluble organic functional layer is patterned by conventional photolithography, there is a problem that the organic solvent used in photolithography deteriorates the organic functional layer.

Therefore, as a method for patterning an organic layer by photolithography, a shielding layer and a photoresist layer patterned by photolithography are provided on the organic layer, and the photoresist layer is used as a mask to pattern the shielding layer by dry etching to obtain a shielding layer. A method of patterning an organic layer by dry etching using the layer as a mask and then removing the shielding layer by exposing it to water has been proposed (see, for example, Patent Document 1).

Japanese Patent Publication No. 2016-535413

According to the patterning method disclosed in Patent Document 1, deterioration of the organic layer due to photolithography can be suppressed by forming a water-soluble shielding layer on the organic layer.

On the other hand, in organic electronic devices such as OPVs, a water-soluble charge transport layer such as a salt of polyethylenedioxythiophene and polystyrene sulfonate (PEDOT:PSS) is often used on the organic functional layer. When the patterning method using the water-soluble shielding layer described in Patent Document 1 is applied to an organic electronic device having such a water-soluble charge-transporting layer, the water-soluble charge-transporting layer dissolves during the manufacturing process. There is a need for a patterning method that is also applicable to electronic devices having a charge transport layer.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for manufacturing an electronic device, which can be applied to an electronic device having a water-soluble charge transport layer and can suppress deterioration of the organic functional layer.

As a result of extensive studies, the present inventors have found that in the case of an electronic device in which a water-soluble charge transport layer is formed on an organic functional layer, the water-soluble charge transport layer can function as a protective layer for the organic functional layer. That is, the present invention provides a method for manufacturing an electronic device having a functional portion in which at least a first electrode, an organic functional layer, a water-soluble charge transport layer, and a second electrode are laminated in this order on a substrate, the method comprising at least:
forming a first electrode on the substrate;
forming an organic functional layer on the substrate on which the first electrode is formed;
forming a water-soluble charge transport layer on the organic functional layer;
forming a patterned protective layer on the water-soluble charge transport layer;
removing the organic functional layer and the water-soluble charge transport layer at positions not covered by the protective layer by etching using the patterned protective layer as a mask;
removing the patterned protective layer; and
A method of manufacturing an electronic device, comprising the step of forming a second electrode on the water-soluble charge transport layer.

According to the production method of the present invention, an electronic device having a water-soluble charge transport layer can be efficiently produced while suppressing deterioration of the organic functional layer.

It is a schematic sectional view showing one mode of the electronic device in the present invention. It is a schematic sectional drawing which shows one aspect|mode of the electronic device manufacturing method of this invention. 1 shows the results of optical microscopic observation of a laminated film of an organic functional layer and a water-soluble charge transport layer in Example 1. FIG. 4 shows the results of optical microscopic observation of a laminated film of an organic functional layer and a water-soluble charge transport layer in Example 3. FIG.

<Electronic device>
The electronic device according to the present invention has a functional site in which at least a first electrode, an organic functional layer, a water-soluble charge transport layer, and a second electrode are laminated in this order on a substrate. Here, the term "functional site" refers to a site in which the first electrode, organic functional layer, water-soluble charge transport layer, and second electrode are laminated in this order. It may also have other layers. FIG. 1 shows a schematic cross-sectional view of one embodiment of the electronic device of the present invention. A substrate 1 has a functional portion 6 in which a first electrode 2, an organic functional layer 3, a water-soluble charge transport layer 4, and a second electrode 5 are laminated in this order.

Unnecessary portions of the organic functional layer 3 and the water-soluble charge transport layer 4 are removed (patterned), and by exposing a portion of the first electrode 2, electrical connection can be facilitated. In addition, by removing unnecessary organic layers, moisture absorption and the like can be suppressed, and durability can be improved.

Applications of electronic devices having such a structure include, for example, organic light-emitting diodes (OLEDs), organic solar cells (OPVs), organic photodiodes (OPDs), and the like. An organic semiconductor material and a water-soluble charge transport layer that exhibit desired functions can be appropriately selected and used.

The device configuration of the OLED includes, for example, a configuration of substrate/first electrode/charge transport layer/light-emitting layer/water-soluble charge transport layer/second electrode. In this case, the light-emitting layer corresponds to the organic functional layer in the invention. A charge injection layer may be further provided at the first electrode/charge transport layer interface or the water-soluble charge transport layer/second electrode interface. More specifically,
substrate/first electrode/hole injection layer/hole transport layer/light emitting layer/water-soluble electron transport layer/electron injection layer/second electrode,
substrate/first electrode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/water-soluble electron transport layer/second electrode,
substrate/first electrode/electron injection layer/electron transport layer/light emitting layer/water-soluble hole transport layer/hole injection layer/second electrode,
substrate/first electrode/electron injection layer/electron transport layer/light-emitting layer/hole transport layer/water-soluble hole transport layer/second electrode,
and other configurations.

As a device configuration of OPV or OPD, for example,
substrate/first electrode/charge transport layer/photoelectric conversion layer/water-soluble charge transport layer/second electrode,
and other configurations. Here, the photoelectric conversion layer corresponds to the organic functional layer in the invention.

<Substrate>
For the substrate, a material on which an electrode material and an organic functional layer can be laminated can be selected according to the type and application of the electronic device. For example, alkali-free glass, quartz glass, aluminum, iron, copper, inorganic materials such as alloys such as stainless steel; polyester, polycarbonate, polyolefin, polyamide, polyimide, polyphenylene sulfide, polyparaxylene polymethyl methacrylate, epoxy resin, fluorine resin films and plates made of organic materials such as Further, when the electronic device is an optical device such as an OLED OPV or OPD, and the substrate side is used to transmit light, the substrate preferably has a light transmittance of about 80%. Here, the wavelength of the transmitted light is the light emission wavelength range for OLED, the visible light to near-infrared range of 400 to 1500 nm for OPV, and the light sensitivity wavelength range for OPD. When a plurality of elements are arranged and functioned, it is preferable to use a substrate combined with a TFT array (TFT array substrate) or to form a TFT array on the substrate.

<First electrode and second electrode>
The first electrode and the second electrode are each composed of a conductive material. Examples of conductive materials include gold, platinum, silver, copper, iron, zinc, tin, aluminum, indium, chromium, nickel, cobalt, scandium, vanadium, yttrium, cerium, samarium, europium, terbium, ytterbium, molybdenum, Metals such as tungsten and titanium, their alloys, metal oxides and composite metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO) ), alkali metals and alkaline earth metals (lithium, magnesium, sodium, potassium, calcium, strontium, barium), graphite, graphite intercalation compounds, carbon nanotubes, graphene, polyaniline and its derivatives, polythiophene and its derivatives. be done. Two or more of these may be used, and a laminated structure of these may be used. Among these, those that form an ohmic contact with a layer adjacent to the electrode, such as the charge transport layer, are preferred.

Since the first electrode is not removed in the subsequent step of removing the protective layer, the organic functional layer and the water-soluble charge transport layer, it is made of metals, metal oxides, composite metal oxides, etc. that have high etching resistance to organic solvents and alkaline aqueous solutions. It is preferably composed of

When the electronic device is an optical device such as OLED, OPV, or OPD, at least one of the first electrode and the second electrode preferably has optical transparency. At least one of them should be light transmissive, but both may be light transmissive. Here, having light transmittance means transmitting light to such an extent that incident light reaches the photoelectric conversion layer and electromotive force is generated. That is, when the light transmittance exceeds 0%, it is said to have light transmittance. This light-transmitting electrode preferably has a light transmittance of 60% to 100% in the entire wavelength range of 400 nm or more and 900 nm or less. ITO, IZO, GZO, and the like are examples of the conductive material that constitutes the light-transmitting electrode. The thickness of the light-transmitting electrode may be sufficient as long as sufficient conductivity is obtained, and is preferably 20 nm to 300 nm although it varies depending on the material. It is sufficient that the non-light-transmitting electrode has conductivity, and the thickness is not particularly limited.

<Organic functional layer>
The organic functional layer in the present invention is a layer that contains an organic material and exhibits a function according to the application of the electronic device. In the case of OLED, it refers to a light-emitting layer, and in the case of OPV and OPD, it refers to a photoelectric conversion layer.

The organic material forming the organic functional layer can be appropriately selected according to the function of the electronic device. Hydrophobic materials are preferred from the viewpoint of laminating the water-soluble charge transport layer on the organic functional layer.

For example, in the case of OLEDs, the organic materials forming the light-emitting layer include hosts and dopants of various colors. More specifically, the following are listed. Two or more kinds of each of these may be used.
Emissive layer host: MCP, TCTA, TATP, CBP, carbazole-based materials, etc. Emissive layer red dopant: DCJTB, Rubrene, Ir(btp)2(acac), PtOEP, Ir(MDQ)2acac, etc. Emissive layer green dopant: C545T, Ir (PPY)3, Ir(PPY)2acac, Ir(3mppy)3, etc. Emitting layer blue dopants: BCzVBi, DPAVBi, FIrPic, 4P-NPD, DBZa, etc.

For example, in the case of OPVs and OPDs, organic materials constituting the photoelectric conversion layer include electron-donating organic semiconductors and electron-accepting organic semiconductors, and more specifically, the following. Two or more kinds of each of these may be used.

Electron-donating organic semiconductor: an organic compound that exhibits p-type semiconductor properties or has hole-transporting properties, such as polythiophene-based polymers, 2,1,3-benzothiadiazole-thiophene-based copolymers, and quinoxaline-thiophene system copolymer, thienothiophene-benzodithiophene-based copolymer, thienopyrroledione-based copolymer, isoindigo-based copolymer, diketopyrrolopyrrole-based copolymer, poly-p-phenylene vinylene-based polymer, poly Conjugated polymers such as p-phenylene polymers, polyfluorene polymers, polypyrrole polymers, polyaniline polymers, polyacetylene polymers, polythienylene vinylene polymers, H ₂ phthalocyanine (H ₂ Pc ), copper phthalocyanine (CuPc), phthalocyanine derivatives such as zinc phthalocyanine (ZnPc), porphyrin derivatives, N,N′-diphenyl-N,N′-di(3-methylphenyl)-4,4′-diphenyl-1, Triarylamine derivatives such as 1′-diamine (TPD), N,N′-dinaphthyl-N,N′-diphenyl-4,4′-diphenyl-1,1′-diamine (NPD), 4,4′- Carbazole derivatives such as di(carbazol-9-yl)biphenyl (CBP), low-molecular-weight organic compounds such as oligothiophene derivatives (terthiophene, quarterthiophene, sexithiophene, octithiophene, etc.), and the like can be mentioned.

Electron-accepting organic semiconductor: an organic compound that exhibits n-type semiconductor characteristics or has electron-transporting properties. 4,9,10-naphthyltetracarboxydiimide, perylene derivatives (3,4,9,10-perylenetetracarboxylic dianhydride, perylenediimide derivatives, perylenediimide dimers, perylenediimide polymers, etc.), oxazole derivatives (2 -(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, 2,5-di(1-naphthyl)-1,3,4-oxadiazole, etc.) , triazole derivatives (3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole, etc.), phenanthroline derivatives, fullerene derivatives, carbon nanotubes, poly-p- A derivative obtained by introducing a cyano group into a phenylene vinylene polymer (CN-PPV) and the like can be mentioned.

The photoelectric conversion layer preferably contains an electron-donating organic semiconductor and an electron-accepting organic semiconductor, and may be a laminated structure or a mixed layer thereof. Among them, a mixed layer of an electron-donating organic semiconductor and an electron-accepting organic semiconductor is preferable from the viewpoint of improving the photoelectric conversion function. It is preferable to include an electron-donating organic semiconductor and an electron-accepting organic semiconductor in the range of electron-donating organic semiconductor component:electron-accepting organic semiconductor component=1 to 99:99 to 1 (mass ratio), more preferably 20 ~80:80-20.

The thickness of the organic functional layer can be appropriately selected according to the desired function and removability in subsequent steps. From the viewpoint of the charge mobility of the organic material, the thickness is preferably 10 nm or more and 500 nm or less.

<Water-soluble charge transport layer>
The water-soluble charge-transporting layer is a layer having hole-transporting properties or electron-transporting properties and is removable when washed with water. The material forming the charge transport layer does not necessarily have to be completely dissolved in water. More specifically, the water-soluble charge transport layer is a layer that dissolves or disperses in water and is removed within 5 minutes when immersed in water at 25°C.

Examples of materials for forming the water-soluble charge transport layer include polythiophene-based polymers, poly-p-phenylene vinylene-based polymers, polyfluorene-based polymers, polypyrrole polymers, polyaniline polymers, polyfuran polymers, and polypyridine polymers. , salts such as conductive polymers such as polycarbazole polymers, ionic substituted fluorene-based polymers ("Advanced Materials", 2011, vol. 23, pp. 4636-4643; "Organic Electronics )”, 2009, vol. 10, pp. 496-500) and a combination of an ionic substituted fluorene-based polymer and a substituted thiophene-based polymer (“Journal of American Chemical Society”, 2011, 133 Vol., pp. 8416-8419), polyethylene oxide ("Advanced Materials", 2007, Vol. 19, pp. 1835-1838), ammonium salts, amine salts, pyridinium salts, imidazo Lithium salts, phosphonium salts, carboxylates, sulfonates, phosphates, sulfate ester salts, phosphate ester salts, sulfates, nitrates, acetonate salts, compounds having ionic groups such as oxoacid salts, and metal complexes etc.

When the thickness of the water-soluble charge-transporting layer is within the preferred range described later, the material for forming the water-soluble charge-transporting layer is preferably a conductive polymer material because of its high charge-transporting properties, and polyethylenedioxythiophene. Salt is more preferred. Specific examples of salts of polyethylenedioxythiophene include a mixture of polyethylenedioxythiophene and polystyrene sulfonate (PSS) (PEDOT:PSS).

The water-soluble charge transport layer may further contain additives such as surfactants.

The thickness of the water-soluble charge transport layer is preferably 10 nm or more, more preferably 50 nm or more, from the viewpoint of protecting the organic functional layer in the later step of removing the organic functional layer and the water-soluble charge transport layer. On the other hand, the thickness of the water-soluble charge transport layer is preferably 1,000 nm or less, more preferably 200 nm or less, from the viewpoint of charge transport properties.

<Other Charge Transport Layers and Charge Injection Layers>
The electronic device of the present invention may have, in addition to the water-soluble charge transport layer, a charge transport layer and/or a charge injection layer adjacent to the organic functional layer to improve its functionality.

For example, in the case of OLEDs, organic materials constituting the charge transport layer or the charge injection layer include the following. Two or more kinds of each of these may be used.
Hole injection layer (HIL): F4-TCNQ, MeO-TPD, HATCN, etc. Hole transport layer (HTL): MeO-TPD, TPD, spiro-TAD, NPD, NPB, TCTA, CBP, TAPC, amine-based materials, Carbazole-based materials, etc. Electron transport layer (ETL): Alq3, TPBI, Bphen, NBphen, BCP, BAlq, TAZ-based materials, etc. Electron injection layer (EIL): Liq, etc.;

For example, in the case of OPV or OPD, the organic material constituting the charge transport layer includes those exemplified as the organic materials constituting the electron-donating organic semiconductor in the case of the hole transport layer, and in the case of the electron transport layer include those exemplified as the organic material constituting the electron-accepting organic semiconductor.

Inorganic materials may also be used as other materials constituting the charge transport layer. Examples of such inorganic materials include titanium oxide (TiO _x ) such as TiO ₂ , zinc oxide (ZnO _x ) such as ZnO, silicon oxide (SiO _x ) such as SiO ₂ , tin oxide ₍ SnO _x ), tungsten oxide (WOx) such as WO3 _, tantalum oxide (TaOx ₎ such as _{Ta2O3 ,} barium titanate ( _BaTixOy ) such as BaTiO3 _, barium zirconate ( _{BaZrx )} such as _BaZrO3 Oy), zirconium oxide ( _ZrOx ) such as ZrO2, hafnium oxide ( _HfOx ) such as _HfO2 , aluminum oxide ( _{AlOx )} such as _{Al2O3 ,} yttrium oxide _{( YOx )} such as _Y2O3 ), metal oxides such as zirconium silicate ( _ZrSixOy ) such as _ZrSiO4 , nitrides such as silicon nitride ( _{SiNx )} such as _Si3N4 , cadmium sulfide ( _{CdSx )} such as CdS, ZnSe, etc. zinc selenide (ZnS _{x ), zinc sulfide (ZnS x )} such as ZnS, and cadmium telluride ( _CdTex ) such as CdTe. You may use 2 or more types of these. Precursors such as these metal salts and metal alkoxides, and intermediate products by hydrolysis and condensation may also be included.

<Method for manufacturing electronic device>
FIG. 2 shows a schematic cross-sectional view of one mode of the electronic device manufacturing method of the present invention.

First, a transparent electrode made of ITO is formed as the first electrode 2 on the substrate 1 (FIG. 2(a)). Sputtering method etc. are mentioned as a formation method of a 1st electrode. At this time, the first electrode may be patterned using a shadow mask, or may be patterned using a photolithography method.

Next, the organic functional layer 3 is formed on the substrate 1 patterned with the first electrode 2 (FIG. 2(b)). Methods for forming the organic functional layer include, for example, spin coating, blade coating, slit die coating, screen printing coating, bar coating, mold coating, print transfer method, immersion pulling method, inkjet method, spray method, and vacuum deposition. law, etc. It can be selected from among these according to the type of organic material, thickness adjustment, orientation control, and other film properties to be obtained. In the present invention, since the organic functional layer is patterned in a post-process, it is compatible with spin coating, blade coating, and slit die coating, which are not good at pattern formation. When the organic functional layer is formed using a coating method, it is preferable to apply a coating liquid in which an organic material is dissolved in a solvent, and then dry the coating.

Next, a water-soluble charge transport layer 4 is formed on the organic functional layer 3 (FIG. 2(c)). Examples of the method for forming the water-soluble charge transport layer include the methods exemplified as the method for forming the organic functional layer. In the present invention, since the water-soluble charge transport layer is patterned in a post-process, it is particularly compatible with spin coating, blade coating, and slit die coating, which are not good at pattern film formation. When the water-soluble charge transport layer is formed using a coating method, it is preferable to apply a coating solution in which a water-soluble charge transport layer material is dissolved in a solvent, and then dry the coating. A surfactant may be added to the coating liquid to increase affinity with the hydrophobic organic functional layer. As the solvent for the coating liquid, a polar solvent such as water or alcohol is preferable in order to further suppress damage to the organic functional layer.

Next, a patterned protective layer 10 is formed on the water-soluble charge transport layer 4 (FIG. 2(d)). As a method for forming a patterned protective layer, for example, after forming the protective layer on the entire surface, patterning by photolithography, or a film forming method that allows direct pattern film formation (e.g., spray coating using a shadow mask). method, inkjet method, printing transfer method, etc.). From the viewpoint of being frequently used in the manufacturing process of inorganic semiconductors, a method of patterning by photolithography after forming a protective layer on the entire surface is preferable.

Methods for forming the protective layer over the entire surface include, for example, spin coating, blade coating, slit die coating, and the like. Then, a patterned protective layer is formed by exposure through a shadow mask and development using a developer. In the developing step, when an alkaline aqueous solution or the like is used as a developer, the water-soluble charge transport layer may be patterned together with the protective layer.

As the material for the protective layer, an organic material is preferable from the viewpoint of solubility in the subsequent step of removing the patterned protective layer. When the photolithography method is used, the protective layer is preferably a photoresist material, and more preferably a positive photoresist material from the viewpoint of not exposing the functional site. As the positive photoresist material, for example, a commercially available photoresist material such as a material containing a novolak-type phenolic resin can be used. Examples of such a photoresist material include "MICROPOSIT" (registered trademark) SC32A-16 PHOTORESIST manufactured by Rohm and Haas Electronic Materials Co., Ltd., and the like.

When the protective layer is formed on the entire surface by using a coating method, it is preferable to apply a coating liquid in which the protective layer material is dissolved in a solvent, and then dry the coating. As the solvent for the protective layer coating solution, an organic solvent is preferable from the viewpoint of suppressing dissolution of the water-soluble charge transport layer, and an ester-based organic solvent is preferable from the viewpoint of further suppressing damage to the organic functional layer. Examples of ester organic solvents include ethyl acetate, butyl acetate, methyl lactate, γ-butyrolactone, diethylene glycol monobutyl ether acetate, 1-methoxy-2-propyl acetate, methyl 3-methoxypropionate and dimethyl carbonate.

The thickness of the protective layer is preferably 10 nm or more, more preferably 100 nm or more, from the viewpoint of improving the protective function for the organic functional layer and the water-soluble charge transport layer in the subsequent etching step. On the other hand, the film thickness of the protective layer is preferably 10,000 nm or less, more preferably 1,000 nm or less, from the viewpoint of removability in the subsequent step of removing the patterned protective layer.

Next, etching is performed using the patterned protective layer as a mask to remove the organic functional layer and the water-soluble charge transport layer at positions not covered with the protective layer (FIG. 2(e)). The etching treatment method includes, for example, wet etching using a solvent, dry etching using oxygen plasma, and the like. The solvent used for wet etching is preferably a solvent that does not dissolve the protective layer but dissolves the organic functional layer and the water-soluble charge transport layer. can be selected. For example, benzene, toluene, xylene, ethylbenzene, cumene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, styrene, mesitylene, 1,2,4-trimethylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentyl Benzene, dipentylbenzene, dodecylbenzene, ethynylbenzene, tetralin, anisole, phenetole, butylphenyl ether, pentylphenyl ether, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,2,4-trimethoxybenzene, 2 -Methoxytoluene, 2,5-dimethylanisole, o-chlorophenol, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-bromonaphthalene, 1-methylnaphthalene, o-diiodobenzene, acetophenone, 2,3 -benzofuran, 2,3-dihydrobenzofuran, 1,4-benzodioxane, phenyl acetate, methyl benzoate, cresol, aniline, aromatic hydrocarbons such as nitrobenzene, dichloromethane, 1,2-dichloroethylene, trichlorethylene, tetrachlorethylene, chloroform , carbon tetrachloride, dichloroethane, trichloroethane, 1,3-dichloropropane, 1,1,1,2-tetrachloroethane, 1,1,1,3-tetrachloropropane, 1,2,2,3-tetrachloropropane, 1 , 1,2,3-tetrachloropropane, pentachloropropane, hexachloropropane, heptachloropropane, 1-bromopropane, 1,2-dibromopropane, 2,2-dibromopropane, 1,3-dibromopropane, 1,2,3 -tribromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, 1-iodopropane, 1,3-dibromo Organic solvents such as halogenated hydrocarbons such as iodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexane, 1,7-diiodoheptane and 1,8-diiodooctane is mentioned. You may use 2 or more types of these.

Next, the protective layer is removed (FIG. 2(f)). Examples of methods for removing the protective layer include removal with a solvent and dry etching. As the solvent used for removal with a solvent, an organic solvent is preferable from the viewpoint of not dissolving the water-soluble charge transport layer, and an ester-based organic solvent is more preferable from the viewpoint of further suppressing damage to the organic functional layer. Examples of the ester-based organic solvent include those exemplified as the ester-based organic solvent for the protective layer coating solution, methyl 3-methoxypropionate, and the like. When a solvent is used for removing the protective layer, it is preferable to remove the solvent by heating or vacuum treatment as appropriate.

Next, the second electrode 5 is formed. (Fig. 2(g)). Examples of the method for forming the second electrode include a vacuum vapor deposition method.

After forming the second electrode, a sealing base material such as a gas barrier film may be attached in order to impart gas barrier properties.

The electronic device manufacturing method of the present invention is useful for OLEDs, OPVs, OPDs, etc. that require patterning. Among them, high-performance OPVs form a coating type water-soluble charge transport layer on a coating type photoelectric conversion layer. It is particularly useful for photoelectric conversion devices such as OPV and OPD.

EXAMPLES The present invention will now be described more specifically based on examples. In addition, the present invention is not limited to the following examples. Among the compounds used in Examples and the like, those using abbreviations are shown below.
Isc: short-circuit current density Voc: open-circuit voltage FF: fill factor η: photoelectric conversion efficiency ITO: indium tin oxide 60 PCBM: [6,6]-phenyl C61 butyric acid methyl ester.

(Synthesis example 1)
Compound A-1 was synthesized by the method shown in Formula 1. The compound (1-i) described in Synthesis Example 1 is prepared by referring to the method described in "Journal of the American Chemical Society", 2009, Vol. 131, pp. 7792-7799. Compound (1-p) was synthesized with reference to the method described in "Angewandte Chem International Edition", 2011, vol. 50, pp. 9697-9702.

38 g (0.27 mol) of methyl-2-thiophenecarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 108 g (1.34 mol) of chloromethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) are stirred at 0°C. 125 g (0.48 mol) of tin tetrachloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added over 1 hour, followed by stirring at room temperature for 8 hours. After stirring was completed, 100 ml of water was slowly added at 0° C., and extracted with chloroform three times. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting brown solid was recrystallized from methanol to obtain compound (1-b) as a pale yellow solid (24.8 g, yield 39%). The results of ¹ H-NMR measurement of compound (1-b) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.71 (s, 1H), 4.79 (s, 1H), 4.59 (s, 1H), 3.88 (s, 3H) ppm.

24.8 g (0.10 mmol) of the above compound (1-b) was dissolved in 1.2 L of methanol (manufactured by Sasaki Chemical Industry Co., Ltd.), and sodium sulfide (manufactured by Aldrich) 8 was added thereto while stirring at 60°C. A solution of 0.9 g (0.11 mol) in 100 ml of methanol was added dropwise over 1 hour, and the mixture was further stirred at 60° C. for 4 hours. After completion of the reaction, the solvent was removed under reduced pressure, 200 ml of chloroform and 200 ml of water were added, and insoluble matter was filtered off. The organic layer was washed twice with water and once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (eluent, chloroform) to obtain compound (1-c) as a white solid (9.8 g, yield 48%). The results of ¹ H-NMR measurement of compound (1-c) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.48 (s, 1 H), 4.19 (t, J=3.0 Hz, 2 H), 4.05 (t, J=3.0 Hz, 2 H), 3.87 (s, 3H) ppm.

To 9.8 g (49 mmol) of the above compound (1-c), 100 ml of water and then 30 ml of a 3M sodium hydroxide aqueous solution were added, and the mixture was heated with stirring at 80° C. for 4 hours. After completion of the reaction, 15 ml of concentrated hydrochloric acid was added at 0° C., and the precipitated solid was collected by filtration and washed several times with water. The resulting solid was dried to give compound (1-d) as a white solid (8.9 g, yield 98%).
¹ H-NMR (270 MHz, DMSO-d ₆ ): 7.46 (s, 1 H), 4.18 (t, J = 3.2 Hz, 2 H), 4.01 (t, J = 3.2 Hz, 2 H ) ppm.

1.46 g (7.8 mmol) of the above compound (1-d) was dissolved in 60 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred at -78°C. 10.7 ml (17.2 mmol) of 1.6 M, manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise, and the mixture was stirred at -78°C for 1 hour. Then, 20 ml of a dry tetrahydrofuran solution containing 4.91 g (15.6 mmol) of N-fluorobenzenesulfonimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at -78°C over 10 minutes, followed by stirring at room temperature for 12 hours. After completion of the reaction, 50 ml of water was slowly added. After adding 3M hydrochloric acid to acidify the aqueous layer, it was extracted three times with chloroform. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. After removing by-products by silica gel column chromatography (eluent, ethyl acetate), the compound (1-e) was obtained as pale yellow powder (980 mg, yield 61%) by recrystallization from ethyl acetate. The results of ¹ H-NMR measurement of compound (1-e) are shown below.
¹ H-NMR (270 MHz, DMSO-d ₆ ): 13.31 (brs, 1H), 4.20 (t, J = 3.0 Hz, 2H), 4.03 (t, J = 3.0 Hz, 2H ) ppm.

800 mg (3.9 mmol) of the above compound (1-e) in 10 ml of dehydrated dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) solution, 1 ml of oxalyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and then dimethylformamide (Wako Pure Chemical Industries, Ltd.). Kogyo Co., Ltd.) was added, and the mixture was stirred at room temperature for 3 hours. Solvent and excess oxalyl chloride were removed under reduced pressure to obtain compound (1-f) as a yellow oil. The compound (1-f) was directly used in the next reaction.

10 ml of a dichloromethane solution of the above compound (1-f, crude product) was mixed with 1.3 g (10 mmol) of 1-octanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 800 mg (8 mmol) of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.). ) in dichloromethane at room temperature and stirred at room temperature for 6 hours. The reaction solution was washed twice with 1M hydrochloric acid, once with water and once with saturated brine, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to remove the solvent. Purification by silica gel column chromatography (eluent, chloroform) gave compound (1-g) as a pale yellow solid (1.12 g, yield 90%). The results of ¹ H-NMR measurement of compound (1-g) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 4.27 (t, J=6.7 Hz, 2H), 4.16 (t, J=3.0 Hz, 2H), 4.01 (t, J=3 .0 Hz, 2H), 1.72 (m, 2H), 1.5-1.3 (m, 12H), 0.88 (t, J = 7.0 Hz, 3H) ppm.

10 ml of an ethyl acetate solution of 630 mg (3.6 mmol) of metachlorobenzoic acid (manufactured by Nacalai Tesque Co., Ltd.) was added dropwise at 0° C. to 40 ml of an ethyl acetate solution of 1.1 g (3.5 mmol) of the above compound (1-g). , and stirred at room temperature for 5 hours. After removing the solvent under reduced pressure, 30 ml of acetic anhydride was added and the mixture was heated under reflux for 3 hours. After removing the solvent again under reduced pressure, purification by silica gel column chromatography (eluent, dichloromethane:hexane=1:1) gave compound (1-h) as pale yellow oil (1.03 g, yield 94%). rice field. The results of ¹ H-NMR measurement of compound (1-h) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.65 (d, J=2.7 Hz, 1 H), 7.28 (dd, J=2.7 Hz and 5.4 Hz, 1 H), 4.31 (t , J=6.8 Hz, 2H), 1.75 (m, 2H), 1.42-1.29 (m, 12H), 0.89 (t, J=6.8 Hz, 3H) ppm.

1.25 g (7.0 mmol) of N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 20 ml of a dimethylformamide solution of 1.0 g (3.2 mmol) of the above compound (1-h) at room temperature. Stir at room temperature for hours. After completion of the reaction, 10 ml of 5% sodium thiosulfate aqueous solution was added and stirred for 5 minutes. After adding 80 ml of ethyl acetate, the organic layer was washed with water five times and saturated brine once, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (eluent, chloroform:hexane=1:3) gave compound (1-i) as a pale yellow solid (1.2 g, yield 79%). The results of ¹ H-NMR measurement of compound (1-i) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 4.32 (t, J = 6.5 Hz, 2H), 1.75 (m, 2H), 1.42-1.29 (m, 12H), 0. 89 (t, J = 6.8 Hz, 3H) ppm.

100 g (0.68 mol) of 3-thiophenecarbonyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 300 ml of a dichloromethane solution of 110 g (1.5 mol) of diethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) at 0° C. for 1 hour. It was added over time and stirred at room temperature for 3 hours. After stirring was completed, 200 ml of water was added, and the organic layer was washed with water three times and saturated brine once. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain compound (1-k) as a pale orange liquid (102 g, yield 82%). The results of ¹ H-NMR measurement of compound (1-k) are shown below.

¹ H-NMR (270 MHz, CDCl ₃ ): 7.47 (dd, J=3.2 Hz and 1.0 Hz, 1 H), 7.32 (dd, J=5.0 Hz and 3.2 Hz, 1 H), 7 .19 (dd, J=5.0 Hz and 1.0 Hz, 1 H), 3.43 (brs, 4 H), 1.20 (t, J=6.5 Hz, 6 H) ppm.

In 400 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 73.3 g (0.40 mol) of the above compound (1-k), normal butyllithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.) ) 250 ml (0.40 mol) was added dropwise at 0° C. over 30 minutes. After completion of dropping, the mixture was stirred at room temperature for 4 hours. After stirring was completed, 100 ml of water was slowly added, and after stirring for a while, the reaction mixture was poured into 800 ml of water. The precipitated solid was collected by filtration and washed with water, methanol and then hexane in that order to obtain compound (1-l) as a yellow solid (23.8 g, yield 27%). The results of ¹ H-NMR measurement of compound (1-l) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.69 (d, J=4.9 Hz, 2H), 7.64 (d, J=4.9 Hz, 2H) ppm.

To 400 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 42 g (0.50 mol) of thiophene, 250 ml (0.40 mol) of normal butyllithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.) was added. It was added dropwise at -78°C over 30 minutes. After the reaction mixture was stirred at −78° C. for 1 hour, 76.4 g (0.40 mol) of 2-ethylhexyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at −78° C. over 15 minutes. After the reaction solution was stirred at room temperature for 30 minutes, it was heated and stirred at 60° C. for 6 hours. After stirring, the reaction solution was cooled to room temperature, and 200 ml of water and 200 ml of ether were added. The organic layer was washed twice with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain compound (1-n) as a colorless liquid (28.3 g, 36%). The results of ¹ H-NMR measurement of compound (1-n) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.11 (d, 4.9 Hz, 1 H), 6.92 (dd, 4.9 Hz and 3.2 Hz, 1 H), 6.76 (d, J=3 .2Hz, 1H), 2.76 (d, J = 6.8Hz, 2H), 1.62 (m, 1H), 1.4-1.3 (m, 8H), 0.88 (m, 6H) ) ppm.

In 400 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 17.5 g (89 mmol) of the above compound (1-n), 57 ml of normal butyllithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.) (89 mmol) was added dropwise at 0° C. over 30 minutes. After the reaction solution was stirred at 50° C. for 1 hour, 4.9 g (22 mmol) of the above compound (1-l) was added at 50° C. and stirred for 1 hour. After stirring, the reaction solution was cooled to 0° C., and a solution of 39.2 g (175 mmol) of tin chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 80 ml of 10% hydrochloric acid was added. Stirred for an hour. After stirring, 200 ml of water and 200 ml of diethyl ether were added, and the organic layer was washed twice with water and then with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (eluent, hexane) gave compound (1-o) as a yellow oil (7.7 g, yield 59%). The results of ¹ H-NMR measurement of compound (1-o) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.63 (d, J=5.7 Hz, 1 H), 7.45 (d, J=5.7 Hz, 1 H), 7.29 (d, J=3 .6Hz, 1H), 6.88 (d, J = 3.6Hz, 1H), 2.86 (d, J = 7.0Hz, 2H), 1.70-1.61 (m, 1H), 1 .56-1.41 (m, 8H), 0.97-0.89 (m, 6H) ppm.

In 25 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 870 mg (1.5 mmol) of the above compound (1-o), normal butyllithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.) 2 .0 ml (3.3 mmol) was added at −78° C. using a syringe and stirred at −78° C. for 30 minutes and at room temperature for 30 minutes. After cooling the reaction mixture to −78° C., 800 mg (4.0 mmol) of trimethyltin chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at −78° C. and stirred at room temperature for 4 hours. After stirring was completed, 50 ml of diethyl ether and 50 ml of water were added, and the mixture was stirred at room temperature for 5 minutes, and the organic layer was washed twice with water and then with saturated brine. After drying the solvent with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The resulting orange oil was recrystallized from ethanol to obtain compound (1-p) as a pale yellow solid (710 mg, yield 52%). The results of ¹ H-NMR measurement of compound (1-p) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.68 (s, 2H), 7.31 (d, J=3.2 Hz, 2H), 6.90 (d, J=3.2 Hz, 2H), 2.87 (d, J=6.2Hz, 4H), 1.69 (m, 2H), 1.40-1.30 (m, 16H), 1.0-0.9 (m, 12H), 0.39 (s, 18H) ppm.

71 mg (0.15 mmol) of compound (1-i) and 136 mg (0.15 mmol) of compound (1-p) were mixed with 4 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.). ), 5 mg of tetrakistriphenylphosphine palladium (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the mixture was stirred at 100° C. for 15 hours under a nitrogen atmosphere. Then, 15 mg of bromobenzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the mixture was stirred at 100° C. for 1 hour. Then, 40 mg of tributyl(2-thienyl)tin (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the mixture was stirred at 100° C. for an additional hour. After stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was collected by filtration and washed with methanol, water and acetone in that order. Then, it was washed with acetone and hexane in that order using a Soxhlet extractor. Next, the resulting solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque, Inc.) and then through a silica gel column (free liquid, chloroform), and then the solvent was distilled off under reduced pressure. The resulting solid was dissolved again in chloroform and then reprecipitated in methanol to obtain compound A-1 (85 mg).

Using a GPC device (manufactured by TOSOH, high-speed GPC device HLC-8320GPC), the average molecular weight (number average molecular weight, weight average molecular weight) of the obtained compound A-1 was calculated by the absolute calibration curve method. was 25,000, the number average molecular weight was 16,000, and the degree of polymerization n calculated by the following formula was 37.
Degree of polymerization n=[(weight average molecular weight)/(molecular weight of repeating unit)].

Evaluation methods in each example and comparative example are shown below.

(film thickness)
The film thickness of the photoelectric conversion layer and the water-soluble charge transport layer formed in each example and comparative example was measured using a spectroscopic film thickness meter (OPTM manufactured by Otsuka Electronics Co., Ltd.).

(Photoelectric conversion efficiency)
The anode and cathode of the photovoltaic element obtained in each example and comparative example were connected to a 2400 series source meter manufactured by Keithley Co., Ltd., and simulated sunlight (OTENTO-SUNIII manufactured by Spectroscopy Instruments Co., Ltd.) was applied from the ITO layer side in the atmosphere. , spectrum shape: AM1.5, intensity: 100 mW/cm ² ), and the current value was measured when the applied voltage was changed from -1V to +2V. From the obtained current value, the photoelectric conversion efficiency was determined by the following equation. It can be said that deterioration of the photoelectric conversion layer is suppressed as the photoelectric conversion efficiency and the short-circuit current density increase.
η (%)=Isc (mA/cm ² )×Voc (V)×FF/irradiation light intensity (mW/cm ² )×100
FF = JVmax/(Isc (mA/ ^cm2 ) x Voc (V))
JVmax (mW/cm ² ) is the value of the product of the current density and the applied voltage at the point where the product of the current density and the applied voltage is maximum between the applied voltage of 0 V and the open circuit voltage.

(Enlarged observation of photoelectric conversion layer)
Water was added dropwise to a portion of the laminated film of the photoelectric conversion layer and the hole transport layer formed in Examples 1 and 3, the hole transport layer was removed, and the exposed photoelectric conversion layer was examined using an optical microscope. Observed magnified. It can be said that deterioration of the photoelectric conversion layer is suppressed to the extent that no black spots are observed in the photoelectric conversion layer.

(Example 1)
2.7 mg of the compound (A-1) obtained in Synthesis Example 1, [6,6]-phenyl C61 butyric acid methyl ester (PCBM) (manufactured by Frontier Carbon) 3.3 mg, 3,4,5-tri 20 mg of methoxytoluene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.38 mL of o-dichlorobenzene are placed in a sample bottle, and the sample bottle is subjected to an ultrasonic cleaning machine (US-2 (trade name) manufactured by Iuchi Seieido Co., Ltd.). By applying ultrasonic waves for 30 minutes at an output of 120 W), a coating liquid A for forming a photoelectric conversion layer, which is an organic functional layer, was obtained.

0.5 mL of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) is added to a sample bottle containing 10 mg of zinc acetate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.), heated and dissolved, and 3-amino Propyltriethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.) was added at a rate of 1% by volume to obtain a precursor coating liquid B for forming an electron transport layer.

PEDOT:PSS solution (CLEVIOS PVP AI4083) 4.0 mL, water 3.5 mL, isopropyl alcohol 2.5 mL and surfactant (Kao Chemical Emulgen 103) 0.1 mg were placed in a sample bottle and stirred to dissolve water. A coating solution C for forming a hole transport layer, which is a positive charge transport layer, was obtained.

A glass substrate on which an ITO transparent conductive layer serving as a cathode was deposited by sputtering to a thickness of 125 nm was cut into a size of 38 mm×46 mm, and the ITO was patterned into a rectangular shape of 38 mm×13 mm by photolithography. As a result of measuring the light transmittance of the obtained substrate using a Hitachi spectrophotometer U-3010, it was 85% or more in the entire wavelength range from 400 nm to 900 nm. This substrate was ultrasonically cleaned for 10 minutes using an alkaline cleaning solution (“Semico Clean” (registered trademark) EL56, manufactured by Furuuchi Chemical Co., Ltd.), and then cleaned with ultrapure water.

After the substrate was treated with UV/ozone for 30 minutes, the above coating solution B was dropped onto the ITO layer, applied by spin coating at 3000 rpm, and heat-treated on a hot plate at 100° C. for 30 minutes to obtain a film thickness. An electron transport layer of about 30 nm was formed.

Next, the above coating solution A is dropped onto the electron transport layer, applied by spin coating, and vacuum-dried by heating at 100° C. for 2 minutes to form a photoelectric conversion layer (organic functional layer) having a thickness of 250 nm on the entire surface of the substrate. formed to

Furthermore, the coating liquid C was dropped onto the photoelectric conversion layer, applied at 2000 rpm by a spin coating method, and heat-treated on a hot plate at 80° C. for 1 minute to form a water-soluble charge transport layer (hole transport layer) having a thickness of 30 nm. layer) was formed over the entire surface of the substrate.

Next, a positive photoresist material (“MICROPOSIT” SC32A-16 PHOTORESIST manufactured by Rohm and Haas Electronic Materials Co., Ltd.) is applied by spin coating at 1500 rpm, and heat-treated on a hot plate at 80° C. for 1 minute. , a protective layer having a thickness of 500 nm was formed over the entire surface of the substrate. After that, a 20 mm×20 mm area at the center of the substrate was covered with a shadow mask, and UV exposure was performed. Next, an alkaline development treatment is performed using an aqueous tetramethylammonium hydroxide solution having a concentration of 2% by weight to remove the protective layer and the water-soluble charge transport layer (hole transport layer) of the exposed portion, leaving the protective layer and the water-soluble charges. Patterning of the transport layer was performed. Thereafter, the photoelectric conversion layer (organic functional layer) is removed by etching using o-xylene, and then the protective layer is removed by dissolving using 1-methoxy-2-propyl acetate, followed by heating and vacuum drying at 100° C. for 2 minutes. Thus, a substrate-1 having a patterned photoelectric conversion layer (organic functional layer) and a water-soluble charge transport layer (hole transport layer) was obtained.

FIG. 3 shows the results of optical microscopic observation of the photoelectric conversion layer of the substrate-1 thus obtained, which was magnified and observed by the method described above. It was confirmed that the water-soluble charge transport layer had been removed in the water drop portion, and black spots were observed in part of the organic functional layer.

On the other hand, the substrate-1 obtained by the above method and the vapor deposition mask are placed in a vacuum vapor deposition apparatus, and the inside of the apparatus is evacuated again until the degree of vacuum in the apparatus reaches 1×10 ⁻³ Pa or less. A silver layer to be an electrode was vapor-deposited to a film thickness of 200 nm.

After that, the substrate was transferred to a glove box under a nitrogen atmosphere. A photocurable resin (XNR5570 manufactured by Nagase ChemteX Corp.) was applied to a glass (gas barrier substrate) having a size of 20 mm×20 mm and attached to the center of the substrate. Next, after irradiation with ultraviolet light (wavelength 365 nm, intensity 100 mWcm ⁻² ) for 1 minute, heat treatment was performed on a hot plate at 100° C. for 30 minutes to cure the photocurable resin, followed by sealing. As described above, a photovoltaic element having a crossing area of the striped ITO layer and the silver layer of 5 mm×5 mm was produced.

The photoelectric conversion efficiency (η) evaluated by the above method was 3.6%, the short-circuit current density was 14.9 mAcm ⁻² , and no deterioration of the photoelectric conversion layer was observed.

(Example 2)
9.0 mL of PEDOT:PSS solution (CLEVIOS PVP AI4083), 1.0 mL of isopropyl alcohol, and 0.1 mg of a surfactant (EMULGEN 103 manufactured by Kao Chemical) were placed in a sample bottle and stirred to obtain a water-soluble charge transport layer. A coating liquid D for forming a certain hole transport layer was obtained.

A photovoltaic device was produced in exactly the same manner as in Example 1 except that coating solution D was used instead of coating solution C and a water-soluble charge transport layer (hole transport layer) having a thickness of 60 nm was formed over the entire surface of the substrate. . The photoelectric conversion efficiency (η) evaluated by the method described above was 8.0%, the short-circuit current density was 20.6 mAcm ⁻² , and no deterioration of the photoelectric conversion layer was observed.

(Example 3)
Example 1 except that a water-soluble charge transport layer (hole transport layer) having a thickness of 100 nm was formed on the entire surface of the substrate by using the coating solution D instead of the coating solution C and changing the spin coating conditions from 2000 rpm to 600 rpm. A photovoltaic element was produced in exactly the same manner as above. The photoelectric conversion efficiency (η) evaluated by the method described above was 7.6%, the short-circuit current density was 19.7 mAcm ⁻² , and no deterioration of the photoelectric conversion layer was observed. FIG. 4 shows the result of optical microscopic observation of a substrate on which an organic functional layer (photoelectric conversion layer) and a water-soluble charge transport layer (hole transport layer) are patterned. It was confirmed that the water-soluble charge transport layer had been removed in the water-dropped portion, and no black spots were observed in the organic functional layer.

(Comparative example 1)
Example 3 except that patterning of the organic functional layer (photoelectric conversion layer) and water-soluble charge transport layer (hole transport layer) was performed by wiping with a waste cloth instead of forming the protective layer, exposing, developing, and solvent etching. A photovoltaic element was produced in exactly the same manner as above. The photoelectric conversion efficiency (η) evaluated by the method described above was 8.0%, and the short-circuit current density was 19.7 mAcm ⁻² . No deterioration of the photoelectric conversion layer was observed, but manual patterning was insufficient in manufacturing efficiency.

(Comparative example 2)
A photovoltaic element was produced in exactly the same manner as in Example 1 except that the water-soluble charge transport layer was not formed, but it did not exhibit a photoelectric conversion function due to deterioration of the organic functional layer.

(Comparative Example 3)
The steps up to the formation of the water-soluble charge transport layer were carried out in exactly the same manner as in Example 1. After coating an aqueous solution of polyvinyl alcohol as a water-soluble shielding layer before forming the protective layer, formation of the protective layer, exposure, development, solvent etching, and removal of the protective layer were carried out. gone. The resulting substrate was then exposed to water to remove the water-soluble shielding layer, resulting in the removal of the water-soluble charge transport layer as well.

Table 1 summarizes the results of Examples and Comparative Examples.

Reference Signs List 1 substrate 2 first electrode 3 organic functional layer 4 water-soluble charge transport layer 5 second electrode 6 functional site 10 protective layer

Claims (6)

A method for producing an electronic device having a functional portion in which at least a first electrode, an organic functional layer, a water-soluble charge transport layer, and a second electrode are laminated in this order on a substrate, the method comprising:
forming a first electrode on the substrate;
forming an organic functional layer on the substrate on which the first electrode is formed;
forming a water-soluble charge transport layer on the organic functional layer;
forming a patterned protective layer on the water-soluble charge transport layer;
removing the organic functional layer and the water-soluble charge transport layer at positions not covered by the protective layer by etching using the patterned protective layer as a mask;
removing the patterned protective layer; and
A method of manufacturing an electronic device, comprising forming a second electrode on the water-soluble charge transport layer. 2. The method of manufacturing an electronic device according to claim 1, wherein the patterned protective layer is formed by photolithography. 3. The method of manufacturing an electronic device according to claim 1, wherein the film thickness of the water-soluble charge transport layer is 50 nm or more. 4. The method for manufacturing an electronic device according to claim 1, wherein the water-soluble charge transport layer contains a conductive polymer material. 5. The method for manufacturing an electronic device according to claim 1, wherein the water-soluble charge transport layer contains a polyethylenedioxythiophene salt. 6. The method for manufacturing an electronic device according to claim 1, wherein the electronic device is a photoelectric conversion device.

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