TW202218483A - Organic patterned layer and metal patterned method using the same - Google Patents

Abstract

The invention relates to an organic patterned layer and a metal patterning method using the organic patterned layer. An organic patterned layer disposed on the outside of a transparent electrode in an organic semiconductor element, the organic patterned layer being characterized in that: an organic compound constituting the organic patterned layer has the following characteristics; a. A static contact angle (temperature and humidity: 23 DEG C, 50%) with respect to 1 [mu] L of pure water during membrane preparation is 85 DEG C or more; b. The glass transition temperature (Tg) is 100 DEG C or less. And c. A low molecule having a molecular weight of 1000 or less. The metal patterning method is characterized in that the organic patterned layer is disposed on the outside of the transparent electrode in the organic semiconductor element, and a metal film is selectively formed in the wiring region of the non-light-transmitting portion.

Description

Organic pattern forming layer and metal pattern forming method using the same

The present invention relates to an organic pattern forming layer used in producing a metal pattern in an organic semiconductor element, and a metal pattern forming method using the organic pattern forming layer.

In recent years, with the popularization of portable information terminals and the like, there is a strong demand for energy saving, thinning, and weight reduction of displays, sensors, and the like mounted in these terminals. At the same time, organic semiconductors with advantages such as light weight, excellent moldability, flexibility, and ease of molecular design are attracting attention. Up to now, many improvements have been made in order to put an organic semiconductor element into practical use, and the element characteristics have been dramatically improved by providing a layered structure of an organic semiconductor thin film with functional separation.

An organic electroluminescence element (hereinafter, simply referred to as an organic EL (Electroluminescence) element) as a typical example of an organic semiconductor element is a light-emitting element using electroluminescence of an organic compound. For organic EL elements in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially provided on a substrate, the bottom emission structure emits light by extracting light from the bottom. element, achieving high efficiency and durability (for example, see Non-Patent Document 1).

Furthermore, in recent years, an organic EL element with a top-emission structure that emits light from the top has been used, and the cathode of the organic EL element uses a metal thin film including a silver-magnesium alloy or the like as a transparent electrode. In the bottom-emission structure that extracts light from the bottom with pixel circuits, the area of the light-emitting portion that extracts light is limited. On the other hand, in the organic EL element of the top-emission structure, light is extracted from the upper part without being blocked by the pixel circuit, so there is an advantage that the area of the light-emitting portion from which the light is extracted can be enlarged.

However, the cathode wiring in the top emission structure has a thin film thickness and a large resistance value. If the wiring resistance increases, there will be uneven brightness in the display surface, or crosstalk in which the brightness changes in stripes depending on the display content of the display, and the display quality will be significantly impaired. In addition, the larger the number of light-emitting pixels in the light-emitting display portion, the greater the number of wirings, the thinner the wiring width of each wiring, and the increased wiring resistance. At the same time, signal delay or voltage drop increases, making it difficult to drive at a high frame rate.

In order to improve this problem, in Patent Documents 1 and 2, it is proposed to reduce wiring resistance by forming a film of a metal having a low resistivity in the non-light-emitting region of the non-transmissive portion of the wiring portion. However, this proposed method requires a mask with a fine opening pattern matching the wiring, and the position of the mask is shifted when the mask is replaced, or the thermal deformation of the mask caused by the radiant heat from the evaporation source causes the film-forming position to shift. Therefore, ensuring the accuracy becomes a problem.

Recently, a method for forming a metal pattern without a mask using an organic thin film containing a photoresponsive compound or polydimethylsiloxane (PDMS) has been proposed (for example, see Non-Patent Document 2). , 3). However, at present, the production of organic semiconductors is dominated by the vacuum evaporation method, which requires UV (Ultraviolet) irradiation or a wet film-forming device, so there is a problem that the production steps become complicated. Therefore, there is a need for a metal pattern forming method using an organic thin film that can be formed by a vacuum evaporation method and selectively repel metals. [Prior Art Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-91083 [Patent Document 2] Japanese Patent Laid-Open No. 2001-148292 [Patent Document 3] Japanese Patent Laid-Open No. 2017-163075 [Non-patent literature]

[Non-Patent Document 1] Proceedings for the 9th Symposium of the Society of Applied Physics, pp. 55-61 (2001) [Non-Patent Document 2] J. Mater. Chem. C., 2014, 2,221 [Non-Patent Document 3] Mater. Horiz., 2020, 7, 143～148 [Non-Patent Document 4] Appl. Phys. Express, 2012, 5, 041603

(The problem that the invention intends to solve)

An object of the present invention is to provide an organic pattern forming layer containing a specific organic compound and capable of repelling metal vapor, and a metal pattern forming method using the organic pattern forming layer and capable of selectively forming a metal film. (Technical means to solve problems)

Therefore, in order to achieve the above-mentioned object, the inventors of the present application have conducted intensive research, and as a result, found that the following aspects are important as the characteristics of an organic thin film suitable for an organic pattern forming layer: (1) small surface energy, (2) molecular mobility high, (3) the film can be formed by a vacuum evaporation method, and (4) the film quality stability is high.

That is, in order to form an organic thin film with the above-mentioned characteristics, the inventors of the present application found that a compound having the following characteristics can form a stable thin film by a vacuum evaporation method, and can realize an organic thin film with a low surface energy and can repel metal vapor, thereby completing the present invention. invention. (1) The static contact angle (temperature and humidity: 23°C, 50%) relative to 1 μL of pure water during film formation is 85° or more, (2) The glass transition temperature is below 100°C, (3) The molecular weight is 1000 or less.

That is, the present invention includes the following organic pattern forming layers and metal pattern forming methods using the same.

1) An aspect of the present invention is an organic pattern forming layer, characterized in that the organic pattern forming layer is disposed outside a transparent electrode in an organic semiconductor element, and the organic compound constituting the organic pattern forming layer has the following characteristics. a) The static contact angle (temperature and humidity: 23°C, 50%) relative to 1 μL of pure water during film formation is 85° or more, b) The glass transition temperature (Tg) is below 100°C, c) The molecular weight is 1000 or less.

2) The above-mentioned organic compound is preferably a compound containing at least one nitrogen-containing heterocycle represented by the following formula (1) or the following formula (2).

[hua 1]

[hua 2]

In formula (1) or formula (2), X is a single bond, S, O, Si, CR ₉ R ₁₀ , SiR ₁₁ R ₁₂ , or NR ₁₃ , and R ₁ to R ₁₉ may be the same or different from each other, respectively. Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a straight-chain or branched alkyl group with 1 to 8 carbon atoms which may have a substituent, and a group with 5 to 10 carbon atoms which may have a substituent cycloalkyl groups, straight-chain or branched alkenyl groups with 2 to 6 carbon atoms that may have substituents, straight-chain or branched alkoxy groups with 1 to 8 carbon atoms that may have substituents group, cycloalkoxy group with 2 to 10 carbon atoms which may have substituents, linear or branched trialkylsilyl group with 3 to 9 carbon atoms which may have substituents, substituted or unsubstituted Substituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group, or substituted or unsubstituted aryloxy group, R ₁ -R ₁₉ They exist independently of each other, or adjacent groups can also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring. In addition, the dotted-line part in Formula (1) or Formula (2) shows a bond site|part.

3) X in the above formula (1) is preferably a single bond.

4) In addition, another aspect of the present invention is a metal pattern forming method, characterized in that any organic pattern forming layer described in the above 1) to 3) is arranged on the outside of the transparent electrode in the organic semiconductor element, A metal film is selectively formed in the wiring area of the non-transparent portion.

5) The organic pattern forming layer is preferably formed by a vacuum evaporation method.

6) The metal for forming the above metal film is preferably one of Ag, Al, Cu, Au, Ni, Co, Fe, Mg, Mo, Nb, Pd, and Pt, or an alloy containing a plurality of these metals. (Compared to the efficacy of the prior art)

Since the organic pattern forming layer of the present invention can efficiently repel metal vapor, the metal pattern forming method of the present invention using the organic pattern forming layer of the present invention can perform metal pattern forming without a mask. That is, when an organic semiconductor element is produced, by using the metal pattern forming method of the present invention, a metal having a relatively low resistivity can be selectively formed on the wiring portion of the element.

Hereinafter, embodiments of the present invention will be described in detail. In the present invention, an embodiment will be described with reference to FIGS. 1( a ) to ( c ), but the present invention is not limited to this. In addition, the drawings referred to in the description are only schematic drawings and not restrictive drawings.

In addition, the term "to" in the embodiments and the scope of the claims indicates a range, for example, "5 to 10" means "5 or more and 10 or less", which means that the numerical values before and after "to" are also included.

The metal pattern forming method of the present invention is schematically shown in FIGS. 1( a ) to ( c ). The organic semiconductor element is configured as follows: a lower electrode 12 is formed on the surface of a substrate 11 , an organic layer 13 including a carrier transport layer, a functional layer, etc. is formed thereon, and a semitransparent or transparent organic layer 13 is formed on the organic layer 13 . Upper electrode 14 . A plurality of lower electrodes 12 and upper electrodes 14 are arranged in stripes so as to be orthogonal to each other, and organic semiconductor elements including lower electrodes 12 , organic layers 13 , and upper electrodes 14 are formed at their intersections. The upper electrode 14 includes a transparent conductive film 14A and a metal film 14B, and as shown in FIG. 1( c ), is formed with a wiring pattern composed of a light-transmitting portion 14a and a non-light-transmitting portion 14b. FIG. 1( a ) shows a state in which the organic pattern forming layer 15 is formed on the portion of the transparent conductive film 14A corresponding to the light-transmitting portion 14a before vapor deposition of the metal vapor.

Fig. 1(b) shows the state after vapor deposition of metal vapor. As shown in FIG. 1( b ), in a portion corresponding to the light-transmitting portion 14 a , the metal vapor is repelled by the organic pattern forming layer 15 and a metal film is not formed. On the other hand, in the portion corresponding to the non-transparent portion 14b, since the organic pattern forming layer 15 is not formed, the metal film 14B is formed without repelling the metal vapor. In this way, since the metal wiring can be selectively vapor-deposited using the organic pattern forming layer, even a complex wiring can be patterned simply and efficiently without a mask. Therefore, when the organic semiconductor element is produced, the metal wiring pattern can be formed without a mask, so that the bending of the mask caused by the radiant heat generated during metal vapor deposition and the adhesion of metal vapor in the conventional metal pattern forming method using a mask is eliminated. It is possible to improve the quality and productivity of organic semiconductor devices.

The metal pattern forming method of the present invention will be described in more detail. The formation material of the lower electrode 12 provided on the substrate 11 shown in FIG. 1(a) can be, for example, indium tin oxide (ITO) or tin oxide (SnO ₂ ), zinc oxide (ZnO), indium zinc oxide ( IZO), indium tungsten oxide (IWO); metals such as Au, Pt, Ag, Cr, Ni, Al; and mixtures or laminates of these metals and conductive metal oxides; organic polyaniline, polythiophene, polypyrrole, etc. Conductive compounds; laminates of these organic conductive compounds and ITO, etc. These materials can be formed into a film by a vacuum evaporation method, an electron beam evaporation method, an ion plating method, a laser ablation method, a sputtering method, or the like. As a material for forming the substrate 11 , for example, resin substrates such as glass substrates and plastic films, and semiconductor substrates such as silicon wafers can be used. The material of the substrate 11 is not particularly limited, and can be appropriately selected as required.

(azine)衍生物 ④電子注入層(EIL，Electron Injection Layer)：LiF、CsCO ₃、CsF、Yb、8-羥基喹啉鋰(Liq，8-Hydroxyquinoline lithium) ⑤主體：1,3-二咔唑-9-基苯(MCP，1,3-Bis(N-carbazolyl) benzene)、4,4',4''-三(咔唑-9-基)三苯胺(TCTA，4,4',4"-Tris(carbazol-9-yl)triphenylamine)、三過氧化三丙酮(TATP，Triacetone triperoxide)、4,4'-二(9-咔唑)聯苯(CBP，4,4'-Bis(9-carbazolyl)-1,1'-biphenyl)、蒽衍生物或咔唑衍生物 ⑥紅色摻雜劑：雙(2-(2'-苯并噻吩基)吡啶-N,C3')(乙醯丙酮)合銥(Ir(btp)2(acac)，Bis(2-benzo[b]thiophen-2-yl-pyridine) (acetylacetonate) iridium(III))、八乙基卟啉鉑(PtOEP，Octaethylporphyrin-Pt(II))、(乙醯丙酮)雙(2-甲基二苯并[f,h]喹喏啉)合銥(Ir(MDQ)2acac，Bis(2-methyldibenzo [f,h]quinoxaline) (acetylacetonate)iridium(III)) ⑦綠色摻雜劑：三(2-苯基吡啶)合銥(Ir(PPY)3，Tris[2-(pyridin-2-yl)phenyl]iridium)、乙醯丙酮酸二(2-苯基吡啶)銥(Ir(PPY)2acac，acetylacetonatobis(2-phenylpyridine)iridium)、三[2-(3-甲基-2-吡啶基)苯基]銥(Ir(3mppy)3，Tris(2-phenyl-3-methyl-pyridine)iridium) ⑧藍色摻雜劑：4,4'-雙(9-乙基-3-咔唑乙烯基)-1,1'-聯苯(BCzVBi，4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl)、4,4'-二[2-[4-(N,N-二苯胺基)-苯基]-乙烯基]聯苯(DPAVBi，4,4'-Bis[4-(diphenylamino)styryl]biphenyl)、雙(4,6-二氟苯基吡啶-C2,N)吡啶甲醯合銥(FIrPic，Bis(4,6-difluorophenylpyridinato-N,C2) picolinatoiridium)、N,N'-雙(1-萘基)-N,N'-二苯基-[1,1':4',1'':4'',1'''-對聯四苯]-4,4'-二胺(4P-NPD，N,N'- di-1-naphthalenyl- N,N'-diphenyl- [1,1':4',1'':4'',1'''- quaterphenyl]-4,4'-diamine)、9,10-二[4-(6-甲基苯并噻唑-2-基)苯基]蒽(DBZa，9,10-Bis[4-(6-Methylbenzothiazol-2-yl)phenyl]anthracene)、硼系化合物 ii)有機光伏元件/有機光電轉換元件： ①活性層之供體：亞酞菁、噻吩、硒吩、或其等之衍生物 ②活性層之受體：苝、富勒烯、喹吖酮、或其等之衍生物 ③第一緩衝層(電子阻擋層)：咔唑、苯胺、或其等之衍生物 ④第二緩衝層(電洞阻擋層)：吡啶、喹啉、吖啶、吲哚、咪唑、苯并咪唑、啡啉、苯甲腈、或其等之衍生物 Next, an organic layer 13 serving as a functional layer is provided on the lower electrode 12 . As a material for forming the organic layer 13, for example, the following materials in i) organic EL element and ii) organic photovoltaic element/organic photoelectric conversion element can be mentioned. The type, film thickness, structure, and dye doping form of these materials are not particularly limited. i) Organic EL element: ①Hole Injection Layer (HIL): Poly(3,4-ethylenedioxythiophene)-poly(polystyrene sulfonate) (PEDOT:PSS, poly(3) ,4-ethylenedioxythiophene) polystyrene sulfonate), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanodimethyl-p-benzoquinone (F4TCNQ, 2,3,5,6-Tetrafluoro-7 ,7,8,8-tetracyanoquinodimethane), 1,4,5,8,9,11-hexaazabenzonitrile (HATCN, 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile), MoO ₃ ② Hole Transport Layer (HTL): N,N,N',N'-tetrakis(4-methoxy-phenyl)benzidine (Meo-TPD, N,N,N',N'- tetrakis(4-methoxy-phenyl)benzidine), N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD, N,N'-Bis(3-methylphenyl) -N,N'-diphenylbenzidine), 2,2',7,7'-tetrakis (diphenylamino)-9,9'-spirobifluorene (spiro-TAD, 2,2',7,7' -Tetrakis(N,N-diphenylamino)-9,9-spirobifluorene), N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4 '-Diamine (NPD, N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine), tris(4-carbazole-9- phenyl)amine (TCTA, Tris(4-carbazoyl-9-ylphenyl)amine), 4,4'-bis(9-carbazole)biphenyl (CBP, 4,4'-bis(carbazol-9-yl) biphenyl), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)benzenamine] (TAPC, 4,4'- Cyclohexylidenebis[N,N-bis(4-methylphenyl)benzenamine]) , Aromatic amine derivatives or carbazole derivatives ③ Electron Transport Layer (ETL, Electron Transport Layer): 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBI, 2,2',2-(1 ,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)), 4,7-diphenyl-1,10-phenanthroline (Bphen, 4,7-Diphenyl-1,10-phenanthroline) ), 2,9-Bis(2-naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline (NBphen, 2,9-Bis(naphthalen-2-yl)-4,7-diphenyl- 1,10-phenanthroline), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline/ Bathocuproine), Bis(2-methyl-8-quinolinolate-N1,O8)-(1,1'-biphenyl-4-hydroxy)aluminum (BAlq, Bis(2-methyl-8-quinolinolate)-4 -(phenylphenolato)aluminium), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ, 3 -(Biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole), acridine

(azine) derivatives ④ Electron Injection Layer (EIL): LiF, CsCO ₃ , CsF, Yb, 8-Hydroxyquinoline lithium (Liq, 8-Hydroxyquinoline lithium) ⑤ Host: 1,3-dicarbazole -9-ylbenzene (MCP, 1,3-Bis(N-carbazolyl) benzene), 4,4',4''-tris(carbazol-9-yl)triphenylamine (TCTA, 4,4',4 "-Tris(carbazol-9-yl)triphenylamine), Triacetone triperoxide (TATP, Triacetone triperoxide), 4,4'-bis(9-carbazole)biphenyl (CBP, 4,4'-Bis(9 -carbazolyl)-1,1'-biphenyl), anthracene derivatives or carbazole derivatives ⑥Red dopant: bis(2-(2'-benzothienyl)pyridine-N,C3')(acetylacetone) ) Iridium (Ir(btp)2(acac), Bis(2-benzo[b]thiophen-2-yl-pyridine) (acetylacetonate) iridium(III)), PtOEP, Octaethylporphyrin-Pt (II)), (acetylacetone) bis(2-methyldibenzo[f,h]quinoxaline) iridium (Ir(MDQ)2acac, Bis(2-methyldibenzo[f,h]quinoxaline) ( acetylacetonate)iridium(III)) ⑦Green dopant: Tris(2-phenylpyridine)iridium (Ir(PPY)3, Tris[2-(pyridin-2-yl)phenyl]iridium), acetylpyruvate Bis(2-phenylpyridine)iridium (Ir(PPY)2acac, acetylacetonatobis(2-phenylpyridine)iridium), tris[2-(3-methyl-2-pyridine)phenyl]iridium (Ir(3mppy)3 , Tris(2-phenyl-3-methyl-pyridine)iridium) ⑧Blue dopant: 4,4'-bis(9-ethyl-3-carbazole vinyl)-1,1'-biphenyl ( BCzVBi, 4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl), 4,4'-bis[2-[4-(N,N-diphenylamino)-phenyl ]-Vinyl]biphenyl (DPAVBi, 4,4'-Bis[4-(diphenylamino)styryl]biphenyl), bis(4,6 -Difluorophenylpyridine-C2,N)picolinatoiridium (FIrPic, Bis(4,6-difluorophenylpyridinato-N,C2)picolinatoiridium), N,N'-bis(1-naphthyl)-N,N '-Diphenyl-[1,1':4',1'':4'',1'''-p-tetraphenyl]-4,4'-diamine (4P-NPD, N,N'- di-1-naphthalenyl- N,N'-diphenyl- [1,1':4',1'':4'',1'''- quaterphenyl]-4,4'-diamine), 9,10- Bis[4-(6-Methylbenzothiazol-2-yl)phenyl]anthracene (DBZa, 9,10-Bis[4-(6-Methylbenzothiazol-2-yl)phenyl]anthracene), boron compound ii ) Organic photovoltaic element/organic photoelectric conversion element: ① Donor of active layer: subphthalocyanine, thiophene, selenophene, or derivatives thereof ② Acceptor of active layer: perylene, fullerene, quinacridone, or Derivatives thereof ③ First buffer layer (electron blocking layer): carbazole, aniline, or derivatives thereof ④ Second buffer layer (hole blocking layer): pyridine, quinoline, acridine, indole, Imidazole, benzimidazole, phenanthroline, benzonitrile, or derivatives thereof

These materials used for the organic layer 13 can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet. In addition, these materials may be formed into a film alone, or may be formed by mixing a plurality of them, or may be used as a single layer, respectively. In addition, it is also possible to have a layered structure of layers formed by forming these materials individually, a layered structure of layers formed by mixing them into a film, or a layer formed by forming a film of these materials independently and a film formed by mixing a plurality of types. Layered structure. The total thickness of each layer of the organic layer 13 is preferably about 100 nm to 700 nm, more preferably about 100 nm to 300 nm.

Next, the transparent conductive film 14A is provided on the organic layer 13 . The transparent conductive film 14A is formed of a translucent or transparent conductive material such as indium tin oxide (ITO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and an alloy of magnesium and silver (MgAg alloy). These materials can be formed by vacuum evaporation method, electron beam evaporation method, ion plating method, laser ablation method, sputtering method, etc., more preferably, vacuum evaporation method with less thermal influence on the organic layer 13 Law.

Next, the organic pattern forming layer 15 is provided on the upper part of the part other than the non-transparent part 14b of the transparent conductive film 14A. Since the organic pattern forming layer 15 has the property of repelling metal vapor, as shown in FIGS. 1( a ) and 1 ( b ), metal patterning can be performed without a mask. The metal film 14B is formed on the portion where the organic pattern forming layer 15 does not exist (ie, the non-light-transmitting portion 14b), thereby obtaining the wiring structure shown in FIG. 1(c).

Furthermore, an optical functional layer having light-condensing properties or a sealing layer such as SiN and SiO may be formed on the organic pattern forming layer 15 and/or the metal film 14B shown in FIG. 1( b ). Thereby, the optical properties can be improved and/or the penetration of moisture or oxygen can be suppressed.

As the material of the metal film ^14B shown in FIG. 1(b), it is preferable to use Ag, Al, Cu, Au, Ni, Co, Fe, Mg, Mo, Nb, Pd, Pt, etc. are more preferably Ag from the viewpoint of reducing wiring resistance. In addition, these materials can be formed by vacuum evaporation, electron beam evaporation, ion plating, laser ablation, sputtering, etc., and are more preferably vacuum evaporation with less thermal influence on the organic layer 13. plating method. From the viewpoint of reducing resistance, the thickness of the metal film 14B is preferably 15 nm or more, but the present invention is not particularly limited to this thickness.

In addition, as the material of the metal film 14B, in order to reduce the resistance of the wiring, it is also preferable to include Ag, Al, Cu, Au, Ni, Co, Fe, Mg, Mo, Nb, Pd, Pt, etc. having a relatively low resistivity The alloy is more preferably an alloy containing Ag.

In addition, a plurality of layers of wiring including a single metal film or an alloy film is preferable because a lower resistance can be obtained. For example, two metal films are formed on a glass substrate, one with a magnesium-silver alloy (AgMg) having a film thickness of 10 nm, and the other with silver (Ag) formed on the magnesium-silver alloy film with a film thickness of 15 nm. Using a low-resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation), the surface resistivity of the AgMg film was measured, and the result was that the surface resistivity of the AgMg film was 44.1 Ω/□. The surface resistivity was 2.7 Ω/□. Compared with the AgMg single-layer film, the resistivity of the AgMg/Ag multilayer film is about 1/20 times smaller, so the wiring resistance in the circuit of the organic semiconductor element is also reduced by more than one digit, which means that the consumption can be greatly improved. power loss.

The film forming method of the organic pattern forming layer 15 shown in FIGS. 1( a ) and 1 ( b ) is not particularly limited, for example, it can be formed by a vacuum evaporation method using a vacuum evaporation apparatus or an electron beam evaporation method . In addition, it can also be formed by wet processes such as spin coating, doctor blade, discharge coating, spray coating, inkjet, letterpress printing, gravure printing, screen printing, and microgravure coating. . Among them, the vacuum evaporation method is more preferable from the viewpoint of the production process. In addition, the film thickness of the organic pattern forming layer 15 is preferably about 10 nm to 300 nm, and more preferably about 10 nm to 100 nm.

In order to make the organic pattern forming layer of the present invention have the property of repelling metal vapor, the static contact angle of the organic film formed of the organic compound with respect to 1 μL of pure water is preferably 85° or more. Moreover, it is preferable that the glass transition temperature of the organic compound which forms an organic film is 100 degrees C or less. The reason is that the radiant heat generated when the metal film is evaporated can promote molecular mobility, and can repel metal vapor more. Furthermore, in order to stably form a film by the vacuum evaporation method, the organic compound forming the organic film is preferably a low molecular weight compound having a molecular weight of 1000 or less.

The organic compound that can be used as the material of the organic pattern forming layer of the present invention has a molecular formula including carbon atoms and hydrogen atoms as constituent elements, and may also include oxygen atoms, nitrogen atoms, fluorine atoms, silicon atoms, chlorine atoms, bromine atoms, boron atoms atom, an iodine atom, and a compound which may also have a substituent. From the viewpoint of molecular stability, a compound having a nitrogen-containing heterocycle is preferred.

Furthermore, the organic compound which can be used as the material of the organic pattern forming layer of the present invention is more preferably a compound containing at least one of the nitrogen-containing heterocycles represented by the above formula (1) or (2).

As "a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent", "a may have a substituent" represented by R ₁ to R ₁₉ in the above formulas (1) and (2) "Cycloalkyl group with 5 to 10 carbon atoms" or "linear or branched alkenyl group with 2 to 6 carbon atoms which may have substituents", "linear or branched alkenyl group with 1 to 8 carbon atoms" A branched alkyl group", "a cycloalkyl group having 5 to 10 carbon atoms", or a "straight-chain or branched alkenyl group having 2 to 6 carbon atoms", specifically, a methyl base, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, n-heptyl , isoheptyl, neoheptyl, n-octyl, isooctyl, neooctyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, vinyl, allyl, isopropenyl , 2-butenyl, etc., these groups can also be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

基、噻吩基、硒碸基、呋喃基、吡咯基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、苯并

唑基、苯并噻唑基、喹

啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、咔啉基等芳香族雜環基般之基，該等取代基亦可進而經上述所例示之取代基取代。又，該等取代基彼此亦可經由單鍵、經取代或未經取代之亞甲基、氧原子或硫原子相互鍵結而形成環。 As "a linear or branched alkyl group having 1 to 8 carbon atoms having a substituent", "a carbon atom having a substituent" represented by R ₁ to R ₁₉ in the above formulas (1) and (2) "Substituent" in "cycloalkyl group having 5 to 10 atoms" or "linear or branched alkenyl group having 2 to 6 carbon atoms having substituent", specifically, deuterium can be exemplified Atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; Alkoxy; vinyl, allyl and other alkenyl groups; phenoxy, tolyloxy and other aryloxy groups; benzyloxy, phenethoxy and other aralkoxy groups; phenyl, biphenyl, triphenyl Aromatic hydrocarbon groups such as terphenylyl, naphthyl, anthracenyl, phenanthrenyl, perylene, indenyl, pyrenyl, perylene, allenyl, triphenylenyl or condensed polycyclic aromatic groups base; pyridyl, pyrimidinyl, three

base, thienyl, selenyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoyl

azolyl, benzothiazolyl, quinoline

Aromatic heterocyclic groups such as olinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, carboline, etc., and these substituents may be further substituted by the above-exemplified substitutions base substitution. In addition, these substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

As "a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent", "a optionally substituted alkoxy group" represented by R ₁ to R ₁₉ in the above formulas (1) and (2) "Cycloalkoxy group with 5 to 10 carbon atoms" or "linear or branched trialkylsilyl group with 3 to 9 carbon atoms which may have a substituent" 8 of linear or branched alkoxy", "cycloalkoxy with 5 to 10 carbon atoms", or "linear or branched alkoxy with 3 to 9 carbon atoms which may have substituents"Trialkylsilyl", specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 3-butoxy, n-pentoxy, n-hexyl Oxy, n-heptyloxy, n-octyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, 1-adamantyloxy, 2-adamantyloxy, trimethyl Silyl group, triethylsilyl group, tert-butyldimethylsilyl group, triisopropylsilyl group, etc., these groups can also pass through single bond, substituted or unsubstituted methylene group, oxygen atom Or sulfur atoms are bonded to each other to form a ring.

As "a linear or branched alkoxy group having 1 to 8 carbon atoms having a substituent" represented by R ₁ to R ₁₉ in the above formulas (1) and (2), "a substituent having a substituent The "substituent" in the "cycloalkoxy group having 5 to 10 carbon atoms" or "the linear or branched trialkylsilyl group having 3 to 12 carbon atoms which may have a substituent" can be exemplified. and "a linear or branched alkyl group having a substituent with 1 to 8 carbon atoms" and "a substituent having a carbon number of 5" represented by R ₁ to R ₁₉ in the above general formula (1). The related examples of the "substituent" in the "cycloalkyl group having 10 to 10 carbon atoms" or "the linear or branched alkenyl group having a substituent with 2 to 6 carbon atoms" are the same, and the applicable form may be adopted. Example of the same.

基、呋喃基、吡咯基、噻吩基、硒碸基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、苯并

唑基、苯并噻唑基、喹

啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、

啶基、啡啉基、吖啶基、及咔啉基等，該等基彼此亦可經由單鍵、經取代或未經取代之亞甲基、氧原子或硫原子相互鍵結而形成環。 As "substituted or unsubstituted aromatic hydrocarbon group", "substituted or unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted aromatic heterocyclic group" represented by R ₁ to R ₁₉ in the above formulas (1) and (2) "Aromatic hydrocarbon group", "aromatic heterocyclic group" or "condensed polycyclic aromatic group" in "substituted or unsubstituted condensed polycyclic aromatic group", specifically, phenyl, bicyclic Phenyl, terphenylyl, naphthyl, anthracenyl, phenanthryl, indenyl, indenyl, pyrenyl, perylene, allenyl, triphenylenyl, pyridyl, Pyrimidyl, three

base, furyl, pyrrolyl, thienyl, selenyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoyl

azolyl, benzothiazolyl, quinoline

Linyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl,

The pyridyl group, the phenanthroline group, the acridine group, and the carboline group, etc., these groups can also be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

基、噻吩基、硒碸基、呋喃基、吡咯基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、苯并

唑基、苯并噻唑基、喹

啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、咔啉基等芳香族雜環基；苯乙烯基、萘乙烯基等芳基乙烯基；乙醯基、苯甲醯基等醯基等基，該等取代基亦可進而經上述所例示之取代基取代。又，該等取代基彼此亦可經由單鍵、經取代或未經取代之亞甲基、氧原子或硫原子相互鍵結而形成環。 As one of "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group" or "substituted condensed polycyclic aromatic group" represented by R ₁ to R ₁₉ in the above formulas (1) and (2) Specifically, the "substituent" includes a deuterium atom, a cyano group, and a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and other linear or branched alkyl groups with 1 to 6 carbon atoms; methoxy , ethoxy, propoxy and other linear or branched alkoxy with 1 to 6 carbon atoms; vinyl, allyl and other alkenyl groups; phenoxy, tolyloxy and other aryloxy groups; Aralkoxy groups such as benzyloxy, phenethoxy; phenyl, biphenyl, terphenylyl, naphthyl, anthracenyl, phenanthryl, indenyl, indenyl, pyrenyl, perylene, Allenyl, pyridyl, triphenylenyl and other aromatic hydrocarbon groups or condensed polycyclic aromatic groups; pyridyl, pyrimidinyl, triphenylenyl, etc.

base, thienyl, selenyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoyl

azolyl, benzothiazolyl, quinoline

Aromatic heterocyclic groups such as olinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, and carboline; arylvinyl such as styryl, naphthylvinyl, etc.; acetylene , a benzyl group and the like, and these substituents may be further substituted by the substituents exemplified above. In addition, these substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the "aryloxy group" in the "substituted or unsubstituted aryloxy group" represented by R ₁ to R ₁₉ in the above formulae (1) and (2) include: phenoxy group, biphenyloxy, bis-triphenoxy, naphthyloxy, anthracenyloxy, phenanthreneoxy, indenyloxy, indenyloxy, pyreneoxy, peryleneoxy, etc., these groups can also be separated from each other by a single Bonds, substituted or unsubstituted methylene groups, oxygen atoms or sulfur atoms are bonded to each other to form a ring. In addition, these groups may have a substituent, and examples of the substituent include "substituted aromatic hydrocarbon group" and "substituted aromatic heterocyclic group" represented by R ₁ to R ₁₉ in the above formula (1). "" or the "substituent group" in the "substituted condensed polycyclic aromatic group" is the same, and the applicable aspect may also be the same.

As X in the above formula (1), a single bond is particularly preferred from the viewpoint of thermal stability.

As R ₁ to R ₈ in the above formula (1), a hydrogen atom, a fluorine atom, or a trimethylsilyl group is preferable, and from the viewpoint of synthesis, a hydrogen atom is more preferable.

As R ₉ to R ₁₂ in the above formula (1), a methyl group or a phenyl group is preferable, and a methyl group is more preferable from the viewpoint of synthesis.

As R ₁₃ in the above formula (1), a methyl group or a phenyl group is preferable, and a phenyl group is preferable from the viewpoint of the thermal stability of the molecule.

As R ₁₄ to R ₁₉ in the above formula (2), a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group is preferable, and a hydrogen atom is more preferable from the viewpoint of synthesis.

The compound represented by the following formula (3) can be exemplified as a compound containing at least one of the nitrogen-containing heterocycles represented by the above formula (1) or (2) suitable for use in the organic pattern forming layer of the present invention.

[hua 3]

In formula (3), X, R ₁ to R ₈ , and R ₁₄ to R ₁₉ are the same as X, R ₁ to R ₈ , and R ₁₄ to R ₁₉ defined in formula (1) or formula (2). n and m each represent an integer of 0 or more. However, n+m is 1 or more. The upper limit value of n+m is not particularly limited, but is, for example, 5 or less, preferably 3 or less, and more preferably 2 or less. A represents an optionally substituted cycloalkane having 5 to 10 carbon atoms, an optionally substituted cycloalkene having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted Aromatic heterocycle, or a group derived from a substituted or unsubstituted condensed polycyclic aromatic, or -SiR ₁₁ R ₁₂ -O-SiR ₁₁ R ₁₂ -. R ₁₁ and R ₁₂ are the same as R _{11 and R 12 defined in formula (1) or formula (2), and a plurality of R 11 and R 12 may be} the same or different, respectively.

、呋喃、吡咯、噻吩、硒碸、喹啉、異喹啉、苯并呋喃、苯并噻吩、吲哚啉、咔唑、苯并

唑、苯并噻唑、喹

啉、苯并咪唑、吡唑、二苯并呋喃、二苯并噻吩、

啶、啡啉、吖啶、及咔啉等，該等基彼此亦可經由單鍵、經取代或未經取代之亞甲基、氧原子或硫原子相互鍵結而形成環。 As the "optionally substituted cycloalkane having 5 to 10 carbon atoms", the "optionally substituted cycloalkene having 5 to 10 carbon atoms", the "substituted or unsubstituted cycloalkene" of the formula (3) derived Substituted aromatic hydrocarbons", "substituted or unsubstituted aromatic heterocycles", or "substituted or unsubstituted condensed polycyclic aromatics""cycloalkanes with 5 to 10 carbon atoms", "Cycloolefin having 5 to 10 carbon atoms", "aromatic hydrocarbon", "aromatic heterocycle", or "condensed polycyclic aromatic", specifically, cyclopentane, cyclohexane, Adamantane, cyclopentene, cyclohexene, benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, perylene, indene, pyrene, perylene, fluoranthene, triphenylene, pyridine, pyrimidine, tris

, furan, pyrrole, thiophene, selenide, quinoline, isoquinoline, benzofuran, benzothiophene, indoline, carbazole, benzo

azole, benzothiazole, quinoline

Linen, benzimidazole, pyrazole, dibenzofuran, dibenzothiophene,

pyridine, phenanthroline, acridine, and carboline, etc., these groups can also be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

基、噻吩基、硒碸基、呋喃基、吡咯基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、苯并

唑基、苯并噻唑基、喹

啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、咔啉基等芳香族雜環基；苯乙烯基、萘乙烯基等芳基乙烯基；乙醯基、苯甲醯基等醯基；碳數1～10之烷基矽基；碳數1～10之烷氧基矽基等基，該等取代基亦可進而經上述所例示之取代基(尤其是氟原子等鹵素原子)取代。又，該等取代基彼此亦可經由單鍵、經取代或未經取代之亞甲基、氧原子或硫原子相互鍵結而形成環。 The "substituted cycloalkane having 5 to 10 carbon atoms", "the substituted cycloalkene having 5 to 10 carbon atoms", "substituted aromatic hydrocarbons", The "substituent" in the "substituted aromatic heterocycle" or "substituted condensed polycyclic aromatic" specifically includes a deuterium atom, a cyano group, a nitro group; a fluorine atom, a chlorine atom, a bromine atom Atoms, iodine atoms and other halogen atoms; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, etc. Linear or branched alkyl groups with 1 to 6 carbon atoms; linear or branched alkoxy groups with 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy; ethylene alkenyl groups such as phenyl, allyl, etc.; aryloxy groups such as phenoxy and tolyloxy; aralkoxy groups such as benzyloxy and phenethoxy; phenyl, biphenyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, indenyl, pyrenyl, perylene, allenyl, triphenylenyl and other aromatic hydrocarbon groups or condensed polycyclic aromatic groups; pyridyl, Pyrimidyl, three

base, thienyl, selenyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoyl

azolyl, benzothiazolyl, quinoline

Aromatic heterocyclic groups such as olinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, and carboline; arylvinyl such as styryl, naphthylvinyl, etc.; acetylene , benzyl and other acyl groups; alkylsilyl groups with 1 to 10 carbon atoms; alkoxysilyl groups with 1 to 10 carbon atoms, and these substituents can also be further exemplified by the above-mentioned substituents (especially substituted by halogen atoms such as fluorine atoms. In addition, these substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

As the compound containing at least one of the nitrogen-containing heterocycles represented by the above formula (1) or (2) suitable for use in the organic pattern forming layer of the present invention, specific examples of preferred compounds are shown below, but are not limited to in these compounds.

[hua 4]

[hua 5]

[hua 6]

[hua 7]

[hua 8]

[Chemical 9]

[Chemical 10]

In the present invention, the above-mentioned compound (1-4) or compound (1-9) is particularly preferred from the viewpoint of surface energy.

The compound itself containing at least one of the nitrogen-containing heterocycles represented by the above formula (1) or (2) can be synthesized according to a known method (for example, Patent Document 3).

The compound containing at least one of the nitrogen-containing heterocycles represented by the above formulas (1) and (2) can be purified by the following methods: purification by column chromatography; silica gel, activated carbon, activated clay, etc. Adsorption purification; recrystallization using solvent; or crystallization method, sublimation purification method, etc. Compounds can be identified by NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) analysis. Important physical property values include glass transition point (Tg) and contact angle. The glass transition point (Tg) is an indicator of the thermal motion of molecules in the film state, and the contact angle is an indicator of the surface energy of the film. In addition, the metal film thickness measurement is an index of the ratio of the metal vapor repelling.

The compound used in the organic semiconductor element of the present invention is preferably prepared by using a method of purification by column chromatography, adsorption and purification by silica gel, activated carbon, activated clay, or the like, and purification by solvent. After purification by recrystallization or crystallization, it is finally purified by a sublimation purification method.

The glass transition point (Tg) can be measured with a high-sensitivity differential scanning calorimeter (manufactured by Bruker AXS, DSC3100S) using powder.

The contact angle can be measured by the following method: an organic thin film of 50 nm is formed on a silicon substrate, and a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., PCA-1) is used at a temperature of 23°C and a humidity of 50%. ) to measure the static contact angle relative to 1 μL of pure water.

The molecular weight of the compound was calculated by identifying the structure of the compound by NMR analysis based on ¹ H-NMR (CDCl ₃ ).

For the measurement of the film thickness, the thickness of the metal film was measured using a stylus type film thickness meter (manufactured by KLA-Tencor, Alpha-step), and the ratio of the metal vapor repellency of the organic pattern forming layer was calculated.

In the metal pattern forming method of the present invention, since the light-transmitting part of the transparent or semi-transparent electrode has an organic thin film with a small surface energy as the organic pattern forming layer, metal vapor can be repelled, and the resistivity can be selectively reduced. The metal is formed into a film on the wiring portion.

One advantage of the metal pattern forming method of the present invention is that the metal pattern can be formed without a mask. In the conventional metal pattern forming method using a mask, the worry of the mask bending due to the radiant heat generated during metal vapor deposition and the adhesion of metal vapor is eliminated, and the quality and productivity of the organic semiconductor device can be improved.

Another advantage of the metal pattern forming method of the present invention is that the method can be interchanged with conventional semiconductor step production lines. Therefore, there is no problem that the production steps become complicated. [Example]

Hereinafter, the embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

(Example 1) <Synthesis of 9,9'-(1,4-phenylene)bis-9H-carbazole (Compound 1-1)> In a reaction vessel substituted with nitrogen, 6.01 g of p-dibromobiphenyl, 9.38 g of carbazole, 499 mg of copper iodide, 479 mg of 1,10-phenanthroline, 8.85 g of potassium carbonate, and 10 mL of dodecylbenzene were added. , heated and stirred at 175°C for 16 hours. After standing to cool, 20 mL of toluene was added, followed by filtration. After 150 mL of toluene was used to dissolve the organic matter from the solid separated by filtration, the organic layers were combined, 15 g of silica and 15 g of activated clay were added, and the mixture was stirred. Inorganic matter was removed by filtration, concentrated, and the precipitated solid was washed with 100 mL of methanol. The solid was collected by filtration, whereby 9.0 g (yield 86%) of white powder of 9,9'-(1,4-phenylene)bis-9H-carbazole was obtained.

The structure of the obtained white powder was identified by NMR, and its molecular weight was deduced. The following 20 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.18(4H), 7.81(4H), 7.57(4H), 7.48(4H), 7.34(4H). Therefore, it is estimated that the obtained white powder system compound (1-1) has a molecular weight of 408.49.

化合物(1-1) [Chemical 11]

Compound (1-1)

(Example 2) <Synthesis of 3,5-bis(carbazol-9-yl)-1-trifluoromethylbenzene (Compound 1-4)> 5.07 g of 3,5-dibromotrifluorotoluene, 6.15 g of carbazole, 108 mg of copper powder, 304 mg of 1,10-phenanthroline, 5.77 g of potassium carbonate, and dodecyl were added to a reaction vessel substituted with nitrogen. Benzene 10 mL was heated and stirred at 190°C for 7 hours. After standing to cool, 20 mL of toluene was added, followed by filtration. To the solid separated by filtration, 60 mL of chloroform was added, and after stirring, it was filtered to remove inorganic substances. After combining the organic layers, 9 g of silica was added and stirred. The silica was removed by filtration, concentrated, and the precipitated solid was washed with 100 mL of methanol. The obtained solid was dissolved in 20 mL of toluene, 60 mL of methanol was added thereto, and the precipitated solid was collected to obtain 3,5-bis(carbazol-9-yl)-1-trifluoromethylbenzene. 4.5 g of white powder (yield 57%).

The structure of the obtained white powder was identified by NMR, and its molecular weight was deduced. The following 19 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.17(4H), 8.05(1H), 7.98(2H), 7.54(4H), 7.47(4H), 7.36(4H). Therefore, it is estimated that the obtained white powder system compound (1-4 ) with a molecular weight of 476.49.

化合物(1-4) [Chemical 12]

Compound (1-4)

(Example 3) <Synthesis of α,α'-bis(carbazol-9-yl)-m-xylene (Compound 1-5)> 4.38 g of α,α'-dichloro-m-xylene, 8.48 g of carbazole, 5.85 g of sodium tert-butoxide, and 100 mL of tetrahydrofuran were added to the reaction vessel substituted with nitrogen, heated, and stirred under reflux for 4 Hour. After standing to cool, 100 mL of water was added, followed by filtration. The obtained solid was transferred to a reaction vessel, 100 mL of methanol and 20 mL of tetrahydrofuran were added, and the mixture was refluxed, allowed to cool, and then filtered. After heating and dissolving the obtained white powder in 50 mL of toluene, 50 mL of methanol was added after cooling, and the precipitated solid was collected to obtain α,α'-bis(carbazol-9-yl)-m-xylene. 9.1 g of white powder (83% yield).

The structure of the obtained white powder was identified by NMR, and its molecular weight was deduced. The following 24 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.13(4H), 7.40(4H), 7.28-7.24(8H), 7.11(1H), 7.01(1H), 6.94(2H), 5.40(4H). Therefore, it is estimated that the obtained white The powder system compound (1-5) has a molecular weight of 436.54.

化合物(1-5) [Chemical 13]

Compound (1-5)

(Example 4) <Synthesis of 9-(9-phenyl-9H-carbazol-3-yl)phenyl-9H-carbazole (Compound 1-8)> 10.0 g of 1-bromo-3-(9-phenyl-9H-carbazol-3-yl)benzene, 5.0 g of carbazole, 0.2 g of copper powder, and 0.4 g of sodium bisulfite were added to a reaction vessel substituted with nitrogen. , 0.5 g of 1,10-phenanthroline, 5.2 g of potassium carbonate, and 15 mL of dodecylbenzene, and stirred at 190° C. for 5 hours. After cooling to room temperature, 0.2 g of copper powder, 0.4 g of sodium hydrogen sulfite, 0.5 g of 1,10-phenanthroline, and 5.2 g of potassium carbonate were added, and the mixture was further stirred at 190° C. for 4 hours. After cooling to 100°C, 100 mL of toluene was added, and the mixture was stirred at 100°C for 30 minutes. Hot filtration was performed, and the obtained filtrate was dried and hardened. The obtained solid was washed with 50 mL of ethanol, and dried under reduced pressure at 50° C. for 15 h to obtain 9-(9-phenyl-9H-carbazol-3-yl)phenyl-9H-carbazol 11.5 g of white powder of azole (yield 99.4%).

The structure of the obtained white powder was identified by NMR, and its molecular weight was deduced. The following 24 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.41(1H), 8.18(3H), 8.93(1H), 7.83(2H), 7.80(2H), 7.65-7.43(12H), 7.31(3H). Therefore, it is estimated that the obtained white The powder system compound (1-8) has a molecular weight of 484.59.

化合物(1-8) [Chemical 14]

Compound (1-8)

(Example 5) <Synthesis of 3,5-bis(carbazol-9-yl)-1-hexylbenzene (compound 1-9)> In a reaction vessel replaced with nitrogen, 7.00 g of 3,5-dibromo-1-hexylbenzene, 8.08 g of carbazole, 141 mg of copper powder, 394 mg of 1,10-phenanthroline, 7.64 g of potassium carbonate, and dodecane were added. Alkylbenzene 20 mL was heated and stirred at 200°C for 16 hours. After standing to cool, 20 mL of toluene was added, followed by filtration. After concentration, 100 mL of toluene, 12 g of silica, and 13 g of activated clay were added, and the mixture was stirred at 80° C. for 30 minutes. After removing inorganic substances by filtration, it was concentrated, and the crude product was purified by silica gel chromatography (eluent: hexane/toluene) to obtain the target 3,5-bis(carbazole-9- 8.18 g (yield 76%) of white powder of phenyl)-1-hexylbenzene.

The structure of the obtained white powder was identified by NMR, and its molecular weight was deduced. The following 32 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.15(4H), 7.63(1H), 7.55-7.51(6H), 7.42(4H), 7.30(4H), 2.83(2H), 1.76(2H), 1.50-1.30(6H), 0.92 (3H). Therefore, the obtained white powder system compound (1-9) was estimated to have a molecular weight of 492.65.

化合物(1-9) [Chemical 15]

Compound (1-9)

(Example 6) <Synthesis of 1,4-dihexyl-2,5-bis(carbazol-9-yl)benzene (Compound 1-11)> 5.12 g of 1,4-dibromo-2,5-dihexylbenzene, 4.47 g of carbazole, 82.2 mg of copper powder, 241 mg of 1,10-phenanthroline, 4.41 g of potassium carbonate, and 14 mL of dodecylbenzene, heated, and stirred at 190° C. for 42 hours. After standing to cool, 20 mL of toluene was added, followed by filtration. To the solid separated by filtration, 100 mL of chloroform was added, and after stirring, inorganic substances were removed by filtration, and the organic layers were combined and concentrated. To the obtained crude product, 100 mL of toluene, 12 g of silica, and 12 g of activated clay were added, followed by stirring. Inorganic substances were removed by filtration and concentrated. 30 mL of hexane was added to the precipitated solid, followed by stirring, and the solid obtained by filtration was collected to obtain 1,4-dihexyl-2,5-bis(carbazol-9-yl)benzene as a brownish white color Powder 3.0 g (yield 41%).

The structure of the obtained tea-white powder was identified by NMR, and its molecular weight was deduced. The following 44 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.20(4H), 7.48-7.45(6H), 7.33(4H), 7.20(4H), 2.35(4H), 1.30(4H), 1.01-0.90(12H), 0.68(6H). Therefore , the obtained compound (1-11) of the above-mentioned tea-white powder system was estimated to have a molecular weight of 576.81.

化合物(1-11) [Chemical 16]

Compound (1-11)

(Example 7) <Synthesis of 9-(2-biphenyl)-9H-carbazole (Compound 1-29)> 5.7 g of carbazole, 8.0 g of 2-bromobiphenyl, 0.2 g of copper powder, 0.5 g of sodium hydrogen sulfite, 0.6 g of 1,10-phenanthroline, 7.1 g of potassium carbonate, and ten Dialkylbenzene 20 mL was heated and stirred at 190° C. for 8.5 hours. After cooling to room temperature, 0.2 g of copper powder, 0.4 g of sodium hydrogen sulfite, 0.5 g of 1,10-phenanthroline, and 3.5 g of potassium carbonate were added, and the mixture was further stirred at 190° C. for 9 hours. After cooling to room temperature, 0.8 g of 2-bromobiphenyl, 0.2 g of copper powder, 0.4 g of sodium hydrogen sulfite, 0.5 g of 1,10-phenanthroline, and 3.5 g of potassium carbonate were added, and the mixture was stirred at 190° C. for 9 hours. . After cooling to room temperature, 0.2 g of copper powder, 0.4 g of sodium hydrogen sulfite, 0.5 g of 1,10-phenanthroline, and 3.5 g of potassium carbonate were added, and the mixture was further stirred at 190° C. for 4 hours. After cooling to 100°C, 100 mL of toluene was added, and the mixture was stirred at 100°C for 30 minutes. Hot filtration was performed, and the obtained filtrate was dried and hardened. The obtained solid was purified by silica gel column chromatography using toluene as a developing solvent. The second fraction was recovered, and the obtained solid was further purified by silica gel column chromatography using toluene/hexane=2:3 (v/v) as a developing solvent. The third fraction was recovered, the obtained solid was washed with 10 mL of hexane, and dried under reduced pressure at 50° C. for 15 h to obtain (9-(2-biphenyl)-9H-carbazole). 3.2 g of white powder (yield 28.4%).

The structure of the obtained white powder was identified by NMR, and its molecular weight was deduced. The following 17 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.03(2H), 7.67(1H), 7.60(1H), 7.54(1H), 7.49(1H), 7.27(2H), 7.18(2H), 7.07(2H), 7.04-6.96(5H) ). Therefore, the obtained white powder system compound (1-29) was calculated to have a molecular weight of 319.40.

化合物(1-29) [Chemical 17]

Compound (1-29)

(Example 8) <Synthesis of 9-(3-biphenyl)-9H-carbazole (Compound 1-30)> 5.7 g of carbazole, 8.0 g of 3-bromobiphenyl, 0.2 g of copper powder, 0.5 g of sodium hydrogen sulfite, 0.6 g of 1,10-phenanthroline, 7.1 g of potassium carbonate, and ten Dialkylbenzene 20 mL was heated and stirred at 190° C. for 6 hours. After cooling to 100°C, 100 mL of toluene was added, and the mixture was stirred at 100°C for 30 minutes. Hot filtration was performed, and the obtained filtrate was dried and hardened. The obtained solid was washed with 50 mL of hexane, and dried under reduced pressure at 60° C. for 6 h to obtain 11.0 g of white powder of 9-(3-biphenyl)-9H-carbazole (yield 100%).

The structure of the obtained white powder was identified by NMR, and its molecular weight was deduced. The following 17 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.14(2H), 7.79(1H), 7.68-7.62(4H), 7.53(1H), 7.48-7.36(7H), 7.29(2H). Therefore, it is estimated that the above white powder system compounds obtained (1-30) with a molecular weight of 319.40.

化合物(1-30) [Chemical 18]

Compound (1-30)

(Example 9) <Synthesis of 5,7-dihydro-7,7-dimethyl-5-phenyl-indeno[2,1-b]carbazole (Compound 1-32)> Into a reaction vessel substituted with nitrogen, 4.95 g of 5,7-dihydro-7,7-dimethyl-indeno[2,1-b]carbazole, 4.47 g of carbazole, 7.20 g of iodobenzene, and iodine were added. 352 mg of copper, 445 mg of 3,5-di-tert-butylsalicylic acid, 3.94 g of potassium carbonate, and 10 mL of dodecylbenzene were heated and stirred at 175° C. for 6 hours. 20 mL of toluene was added, followed by filtration. After inorganic matter was removed by filtration, it was concentrated to obtain a yellow liquid. To this, 50 mL of methanol was added, and the precipitated solid was collected to obtain a yellow powder of 5,7-dihydro-7,7-dimethyl-5-phenyl-indeno[2,1-b]carbazole 5.36 g (85% yield).

The structure of the obtained yellow powder was identified by NMR, and its molecular weight was deduced. The following 21 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 8.44(1H), 8.19(1H), 7.85(1H), 7.66-7.59(4H), 7.50(1H), 7.42(1H), 7.38-7.35(4H), 7.31-7.23(2H) , 1.51(6H). Therefore, the obtained compound (1-32) of the yellow powder system was calculated to have a molecular weight of 359.46.

化合物(1-32) [Chemical 19]

Compound (1-32)

(Example 10) <Synthesis of 3,5-bis(indol-1-yl)-benzene (compound 2-1)> 4.04 g of 1,3-difluorobenzene, 9.12 g of indole, 8.62 g of sodium tertbutoxide, and DMF (N,N-dimethylformamide, N,N-dimethylformamide) were added to a reaction vessel substituted with nitrogen. amine) 110 mL, heated and stirred at 95°C to 110°C for 30 hours. After standing to cool, 200 mL of water was added, followed by filtration. To the obtained solid were added 200 mL of chloroform, magnesium sulfate, and 10 g of silica, and after stirring, the mixture was filtered, and the filtrate was concentrated. Hexane was added to the concentrate, and the precipitated solid was collected by filtration. 100 mL of methanol was added to the obtained orange powder, and the mixture was stirred under reflux. The solid was collected by filtration to obtain 5.59 g of the target 3,5-bis(indol-1-yl)-benzene as a beige powder (yield: 51%).

The structure of the obtained beige powder was identified by NMR, and its molecular weight was deduced. The following 16 hydrogen signals were detected in ¹ H-NMR (CDCl ₃ ). δ(ppm)= 7.70(2H), 7.67-7.62(4H), 7.51(2H), 7.39(2H), 7.26(2H), 7.20(2H), 6.72(2H). Therefore, it is estimated that the above beige obtained The toner system compound (2-1) has a molecular weight of 308.38.

化合物(2-1) [hua 20]

Compound (2-1)

(Example 11) <Measurement of glass transition point (Tg)> For the compounds synthesized in Examples 1 to 10, the comparative compound 1 (Alq3 (Tris (8-hydroxyquinolinato)aluminum, tris (8-hydroxyquinolinato)aluminum)) and the comparative compound 2 (NPB (N,N'-Di- [(1-naphthalenyl)-N,N'-diphenyl]-1,1'-biphenyl)-4,4'-diamine，N,N'-diphenyl-N,N'-(1-naphthyl) -1,1'-biphenyl-4,4'-diamine)), and the glass transition point was measured with a high-sensitivity differential scanning calorimeter (manufactured by Bruker AXS, DSC3100SA). The results are shown in Table 1.

[Chemical 21]

[Chemical 22]

[Table 1] compound glass transfer point Compound (1-1) of Example 1 55℃ Compound (1-4) of Example 2 71℃ Compound (1-5) of Example 3 55℃ Compound (1-8) of Example 4 99℃ Compound (1-9) of Example 5 27℃ Compound (1-11) of Example 6 not observed Compound (1-29) of Example 7 30℃ Compound (1-30) of Example 8 30℃ Compound (1-32) of Example 9 50℃ Compound (2-1) of Example 10 19℃ Comparative Compound 1 (Alq3) 180℃ Comparative Compound 2 (NPB) 88℃

It can be seen that the compounds synthesized in Examples 1 to 10 have a glass transition point of 100° C. or lower, and the thermal mobility of the molecules is high.

(Example 12) <Measurement of Contact Angle> Compound (1-4) of Example 2, Compound (1-8) of Example 4, Compound (1-9) of Example 5, Compound (1-29) of Example 7, Compound (1-30) of Example 8, Compound (1-32) of Example 9, Compound (2-1) of Example 10, Comparative Compound 1 (Alq3), and Comparative Compound 2 (NPB), etc. The thickness became 50 nm, and an organic thin film was obtained. Using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., PCA-1), in a constant temperature and humidity environment with a temperature of 23°C and a humidity of 50%, drop 1 drop of 1 on the surface of the organic film from the tip of the injection needle of the contact angle meter. μL of pure water droplets, observe the droplets formed on the surface of the sample from the side, and measure the contact angle. The measurement is performed at several locations on the surface of the organic thin film, and the average value is calculated. The results are shown in Table 2.

[Table 2] compound Contact angle Compound (1-4) of Example 2 93.3° Compound (1-8) of Example 4 89.5° Compound (1-9) of Example 5 91.5° Compound (1-29) of Example 7 87.0° Compound (1-30) of Example 8 86.6° Compound (1-32) of Example 9 88.7° Compound (2-1) of Example 10 90.1° Comparative Compound 1 (Alq3) 74.0° Comparative Compound 2 (NPB) 83.2°

It can be seen that the compounds synthesized in Examples 2, 4, 5, 7-10 have a contact angle of 85° or more, and the surface energy is lower than that of Alq3 and NPB, which are comparative compounds.

(Example 13) <Measurement of Metal Film Thickness-Evaluation of the Ratio of Metal Vapor Repellent by the Organic Pattern Forming Layer> The temperature of the glass substrate was set to 25°C, and the compound (1-4) of Example 2, the compound (1-9) of Example 5, the compound (2-1) of Example 10, and the comparative compound were vapor-deposited on the glass substrate. 1 (Alq3) and the comparative compound (NPB) were made to have a thickness of 50 nm and the like to prepare an organic layer as an organic pattern forming layer. Ag is vapor-deposited on the organic layer under the condition that the film thickness of Ag on the glass substrate without the organic layer becomes 15 nm to obtain a laminated film of organic layer/Ag layer. In addition, for comparison, Ag was vapor-deposited on a glass substrate without an organic layer under the same conditions to obtain a single film of an Ag layer. The film thickness of the Ag layer was measured using a stylus-type film thickness measuring device (manufactured by KLAA-Tencor, Alpha-step), and the ratio of the organic layer to repel Ag vapor was calculated as follows. The results are shown in Table 3. The ratio of repelling Ag vapor (%)=(15-measured Ag film thickness (nm))/15×100

[table 3] lower level Thickness of Ag layer (nm) Ratio of Ag rejection (%) grass Compound (1-4) 4.5 70.0 Compound (1-9) 5.5 63.3 Compound (2-1) 7.3 51.3 Comparative Compound 1 (Alq3) 15.0 0.0 Comparative Compound 2 (NPB) 14.2 5.3 none 15.0 0.0

It can be seen that compared with the comparative compound and the sample without organic layer, the ratio of Ag repelling of the compound synthesized in the example is as high as 51.3%-70.0%, especially the compound (1-4) effectively repels Ag vapor. The reason for this result is that the glass transition temperature of the compounds synthesized in the examples is as low as 100° C. or lower, the contact angle is 85° or higher, and the surface energy is low. In addition, in Non-Patent Document 4, by changing the substrate temperature from 24°C to 40°C, an organic thin film formed of a compound having a low glass transition temperature completely repels metal vapors. Therefore, when the substrate temperature of 25° C. in this embodiment is set to 40° C. or higher, the organic thin film using the compound of the present invention can completely repel Ag vapor.

As mentioned above, although this invention was demonstrated in detail with reference to the specific embodiment, it is clear that a person skilled in the art of this invention can make various changes or correction without deviating from the mind and range of this invention. This application is based on Japanese Patent Application No. 2020-116851 filed on Jul. 7, 2020, the contents of which are incorporated herein by reference. (Industrial Availability)

The metal pattern forming method of the present invention using the organic pattern forming layer of the present invention can be advantageously used, for example, in an organic photodetector (OPD, Organic Photodetector), an organic thin film transistor (OTFT, Organic Thin Film Transistor) or an organic EL In the process of manufacturing organic semiconductor devices or circuits such as elements. The method of the present invention can be used, for example, in the manufacturing process of an organic EL display, and can reduce wiring resistance compared with conventional wiring, and can be used to improve the responsiveness of uneven brightness. For example, the method of the present invention can be used in the manufacturing steps of an organic CMOS (Complementary Metal Oxide Semiconductor) sensor, and can also be used to reduce electrical noise.

11: Substrate 12: Lower electrode 13: Organic layer 14: Upper electrode 14A: Transparent Conductive Film 14a: Translucent part 14B: Metal Film 14b: non-transparent part 15: Organic pattern forming layer

1(a) to (c) schematically show the pattern forming method of the present invention.

11: Substrate

12: Lower electrode

13: Organic layer

14: Upper electrode

14A: Transparent Conductive Film

14a: Translucent part

14B: Metal Film

14b: non-transparent part

15: Organic pattern forming layer

Claims (6)

An organic pattern forming layer, characterized in that the organic pattern forming layer is disposed on the outer side of a transparent electrode in an organic semiconductor element, and the organic compound constituting the organic pattern forming layer has the following characteristics: a. The static contact angle (temperature and humidity: 23°C, 50%) relative to 1 μL of pure water during film formation is 85° or more, b. The glass transition temperature (Tg) is below 100°C, c. The molecular weight is 1000 or less. The organic pattern forming layer according to claim 1, wherein the organic compound comprises at least one nitrogen-containing heterocyclic compound represented by the following formula (1) or the following formula (2):

[hua 2]

(In formula (1) or formula (2), X is a single bond, S, O, Si, CR ₉ R ₁₀ , SiR ₁₁ R ₁₂ , or NR ₁₃ , and R ₁ to R ₁₉ may be the same or different from each other, Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a straight-chain or branched alkyl group with 1 to 8 carbon atoms which may have a substituent, and a group with 5 to 10 carbon atoms which may have a substituent cycloalkyl groups, straight-chain or branched alkenyl groups with 2 to 6 carbon atoms that may have substituents, straight-chain or branched alkoxy groups with 1 to 8 carbon atoms that may have substituents group, cycloalkoxy group with 2 to 10 carbon atoms which may have substituents, linear or branched trialkylsilyl group with 3 to 9 carbon atoms which may have substituents, substituted or unsubstituted Substituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group, or substituted or unsubstituted aryloxy group, R ₁ -R ₁₉ Exist independently of each other, or adjacent groups can also be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring; the dashed line in formula (1) or formula (2) The part indicates the bonding part). The organic pattern forming layer according to claim 2, wherein X in the above formula (1) is a single bond. A metal pattern forming method, characterized in that the organic pattern forming layer of any one of the above claims 1 to 3 is arranged on the outer side of a transparent electrode in an organic semiconductor element, and is selectively arranged in a wiring area of a non-transparent portion A metal film is formed. The metal pattern forming method according to claim 4, wherein the organic pattern forming layer is formed using a vacuum evaporation method. The metal pattern forming method according to claim 4 or 5, wherein the metal film forming the metal film is one of Ag, Al, Cu, Au, Ni, Co, Fe, Mg, Mo, Nb, Pd, and Pt, or Alloys containing multiple metals.

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