WO2007119490A1 - トランジスタ素子及びその製造方法並びに発光素子及びディスプレイ - Google Patents
トランジスタ素子及びその製造方法並びに発光素子及びディスプレイ Download PDFInfo
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- WO2007119490A1 WO2007119490A1 PCT/JP2007/055891 JP2007055891W WO2007119490A1 WO 2007119490 A1 WO2007119490 A1 WO 2007119490A1 JP 2007055891 W JP2007055891 W JP 2007055891W WO 2007119490 A1 WO2007119490 A1 WO 2007119490A1
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- IDISMEQKBNKWJX-UHFFFAOYSA-N phenol;pyridine Chemical compound C1=CC=NC=C1.OC1=CC=CC=C1 IDISMEQKBNKWJX-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical class C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/30—Organic light-emitting transistors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/121—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
- H10K59/1213—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements the pixel elements being TFTs
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/92—TFT applications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/351—Thickness
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/18—Carrier blocking layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
Definitions
- Transistor element manufacturing method thereof, light emitting element, and display
- the present invention relates to a transistor element, a manufacturing method thereof, a light emitting element, and a display, and more specifically, a transistor element capable of modulating a large current at a low voltage between an emitter and a collector, a manufacturing method thereof, and the same
- the present invention relates to a light emitting element having a transistor element and a display.
- organic FETs organic field-effect transistors
- liquid crystal or electrophoretic cells There are few reports on the use of organic EL. This is because it is difficult for the current organic FET to pass a large current enough to switch the organic EL that is the current drive device. Therefore, development of organic FETs that operate at lower voltage and higher current is desired.
- a first transistor element of the present invention includes an emitter electrode, a collector electrode, and a semiconductor layer and a sheet-like base electrode provided between the emitter electrode and the collector electrode. It is.
- the semiconductor layer includes a first semiconductor layer provided between the collector electrode and the base electrode, and between the emitter electrode and the base electrode. And a second semiconductor layer provided on the transistor element.
- the semiconductor layer is provided between the emitter electrode and the collector electrode, and the sheet-like base electrode is provided in the semiconductor layer, so that the gap between the emitter electrode and the collector electrode is provided.
- a collector voltage is applied to the emitter electrode and a base voltage is further applied between the emitter electrode and the base electrode, the electric charge (electrons or holes) injected from the emitter electrode is remarkably accelerated by the action of the base voltage. It passes through the electrode and reaches the collector electrode. That is, the current flowing between the emitter electrode and the collector electrode can be amplified by applying the base voltage.
- the sheet-like base electrode accelerates the electric charge supplied from the emitter electrode with a base voltage to form ballistic electrons or ballistic holes, and collects the ballistic electrons or ballistic holes as a collector. Since it is formed on the entire surface with a thickness that can easily penetrate into the semiconductor layer on the electrode side, the charge is remarkably accelerated on the entire formed surface, In addition, the accelerated charge can easily pass through the base electrode.
- the base electrode is provided in a sheet shape (that is, when the base electrode includes a defective portion such as a hole or a crack)
- the emitter electrode force is also applied to the defective portion.
- the transistor element of the present invention it is possible to stably obtain a current amplification action similar to that of the bipolar transistor.
- a first transistor element of the present invention is a transistor element characterized in that a thickness of the base electrode is 80 nm or less.
- the thickness of the base electrode is 80 nm or less, ballistic electrons or ballistic holes accelerated by the base voltage Vb can be easily transmitted. As a result, the charge is remarkably accelerated on the entire surface of the sheet-like base electrode, and the charge with accelerated force can easily pass through the base electrode.
- the base electrode is only required to be provided in the semiconductor layer without a break (without a defect such as a hole or a crack), so the lower limit of the thickness is not particularly limited, but it is usually about 1 nm. .
- a first transistor element of the present invention is a transistor element characterized in that a surface of the base electrode has an uneven shape.
- the base electrode having an uneven shape (or the surface roughness is rough and can also be referred to as the base electrode) is thin even when a base electrode having a predetermined average thickness is formed.
- the base electrode has an uneven shape, the current amplification operation can be stably obtained.
- a first transistor element of the present invention is a transistor element characterized in that a semiconductor layer provided between the collector electrode and the base electrode is a crystalline semiconductor layer.
- the crystalline semiconductor layer provided between the collector electrode and the base electrode has a concave-convex surface (or can be said to have a rough surface), and thus the crystalline semiconductor layer.
- the base electrode provided on the layer is also formed in an uneven shape. Base battery with uneven shape Even when the base electrode having a predetermined average thickness is formed, the pole is thin and thick. However, according to the present invention, when the base electrode has an uneven shape, the current amplification operation is performed. It can be obtained stably.
- the crystal grain size of the semiconductor layer is not less than or about the thickness of the base electrode, and the surface of the base electrode has an uneven shape.
- the transistor element is characterized in that it can be given.
- the crystal grain size of the crystalline semiconductor layer is not less than or equal to the thickness of the base electrode, and the base electrode can be provided with an uneven shape. Therefore, if a base electrode is formed thereon, a base electrode having a concavo-convex shape can be easily formed.
- a first transistor element of the present invention is a transistor element characterized in that the base electrode also has a metallic force, and an oxide film of the base electrode is formed on one or both surfaces of the base electrode. is there.
- a first transistor element according to the present invention includes a first semiconductor layer provided between the collector electrode and the base electrode, and a second semiconductor element provided between the emitter electrode and the base electrode.
- the transistor element is characterized in that the semiconductor layer is formed of a different semiconductor material.
- a first transistor element of the present invention is a transistor element characterized in that the first semiconductor layer and the second semiconductor layer are formed of a hole transport material or an electron transport material.
- a first transistor element of the present invention includes a first semiconductor layer provided between the collector electrode and the base electrode, or a second semiconductor element provided between the emitter electrode and the base electrode.
- the transistor element is characterized in that the semiconductor layer is formed of an organic compound.
- a first transistor element of the present invention is provided between a thickness T1 of a first semiconductor layer provided between the collector electrode and the base electrode, and between the emitter electrode and the base electrode.
- the transistor element is characterized in that the ratio (T1ZT2) to the thickness T2 of the second semiconductor layer is in the range of 1Z1 to: LOZ1.
- the first transistor element of the present invention is a transistor element characterized by having a charge injection layer between the emitter electrode and a semiconductor layer adjacent to the emitter electrode.
- a first transistor element of the present invention is a transistor element characterized in that the charge injection layer contains an alkali metal such as LiF or Ca or a compound thereof.
- a second transistor element of the present invention includes an emitter electrode, a collector electrode, a semiconductor layer and a sheet-like base electrode provided between the emitter electrode and the collector electrode, and at least the emitter electrode and the base
- the transistor element is characterized in that a dark current suppression layer is provided between the electrodes or between the collector electrode and the base electrode.
- This second transistor element is obtained when a small voltage Vb is applied between the emitter electrode and the base electrode when, for example, a voltage Vc of 5V is applied between the emitter electrode and the collector electrode of the first transistor element.
- Vb voltage
- Vc voltage
- An object of the present invention is to provide a transistor element in which a leakage current necessary for operation is suppressed and an ONZOFF ratio is improved in addition to a transistor element in which a thin sheet-like base electrode is inserted in a layer.
- the dark current suppression layer since the dark current suppression layer is provided at least between the emitter electrode and the base electrode or between the collector electrode and the base electrode, the dark current suppression layer allows the emitter electrode to be When a small voltage Vb is applied between the base electrodes or when no voltage Vb is applied, a leakage current other than the current component necessary for transistor operation between the base electrode and the collector electrode ("dark current" (current that flows when the switch is OFF) ) And U.) can be effectively suppressed, and as a result, the ONZOFF ratio can be improved.
- the dark current suppression layer can effectively suppress the dark current when the voltage Vb is not applied between the emitter electrodes and the base electrode. For example, when the voltage Vb is applied between the emitter electrodes and the base electrode, the dark current is suppressed. It works like a little disturbing.
- a second transistor element of the present invention is a transistor element characterized in that the dark current suppressing layer is provided between the collector electrode and the base electrode.
- the second transistor element of the present invention is a transistor element characterized in that the dark current suppressing layer and the base electrode are provided adjacent to each other.
- the dark current suppression layer is provided between the collector electrode and the base electrode, it is possible to effectively suppress the flow of dark current, and as a result, O
- the NZOFF ratio can be improved.
- a second transistor element of the present invention is a transistor element characterized in that the dark current suppressing layer is an organic insulating layer or an inorganic insulating layer.
- a second transistor element of the present invention is a transistor element characterized in that the dark current suppressing layer is an organic semiconductor layer or an inorganic semiconductor layer.
- a second transistor element of the present invention is a transistor element characterized in that the dark current suppression layer is formed of silicon oxide or aluminum oxide.
- a second transistor element of the present invention is a transistor element characterized in that the dark current suppressing layer is formed by a chemical reaction of the base electrode.
- a second transistor element of the present invention is a transistor element characterized in that the dark current suppressing layer has a thickness of 20 nm or less.
- the semiconductor layer provided between the emitter electrode and the base electrode or between the collector electrode and the base electrode is formed of an organic compound.
- the method for producing a transistor element of the present invention is a method for producing a transistor element comprising an emitter electrode, a collector electrode, and a semiconductor layer and a sheet-like base electrode provided between the emitter electrode and the collector electrode.
- a dark current suppression layer at least between the emitter electrode and the base electrode or between the collector electrode and the base electrode by conducting a chemical reaction between the base electrode and the base electrode.
- the dark current suppressing layer is formed by oxidizing a part of the base electrode after providing the base electrode. It is a manufacturing method.
- the transistor element manufacturing method of the present invention is a transistor element manufacturing method characterized in that after the base electrode is provided, the base electrode is heated to form the dark current suppressing layer. is there.
- the dark current suppressing layer can be easily formed, and a transistor element in which the ONZOFF ratio is improved by suppressing the leakage current can be easily provided.
- the electronic device of the present invention is an electronic device having a transistor element as a switching element.
- the transistor element includes an emitter electrode, a collector electrode, a semiconductor layer and a sheet-like element provided between the emitter electrode and the collector electrode.
- This is an electronic device characterized by comprising a base electrode.
- An electronic device of the present invention is an electronic device having a transistor element as a switching element.
- the transistor includes an emitter electrode, a collector electrode, a semiconductor layer provided between the emitter electrode and the collector electrode, and a semiconductor layer.
- An electronic device comprising a sheet-like base electrode, wherein a dark current suppression layer is provided at least between the emitter electrode and the base electrode or between the collector electrode and the base electrode It is.
- the present invention can be an electronic device in which the first or second transistor element of the present invention is used as a switching element, for example, an organic EL element.
- the first or second transistor element can modulate a large current at a low voltage, for example, it is preferably combined as a drive transistor which is an organic EL switching element.
- An electronic device can be provided.
- a first light-emitting element of the present invention includes an emitter electrode, a collector electrode, a semiconductor layer and a sheet-like base electrode provided between the emitter electrode and the collector electrode, and a base electrode and a collector electrode.
- the organic EL layer is provided with an organic EL layer, and the organic EL layer includes at least one light emitting layer.
- the second light-emitting element of the present invention includes an emitter electrode, a collector electrode, a semiconductor layer and a sheet-like base electrode provided between the emitter electrode and the collector electrode, at least the emitter electrode and the base Dark current provided between the electrodes or between the collector electrode and the base electrode
- a light-emitting element including a suppression layer and an organic EL layer provided between a base electrode and a collector electrode, wherein the organic EL layer includes at least one light-emitting layer.
- the light emitting device of the present invention has an organic EL layer between a base electrode and a collector electrode, and the organic EL layer includes at least one light emitting layer, so that planar light emission by a large current is possible. Become.
- the base electrode does not need to be finely patterned as in the conventional SIT structure, and large current modulation is possible at a low voltage, and the ONZOFF ratio can be further improved.
- a practical light-emitting element having a simple structure can be provided.
- the organic EL layer is one or more selected from a hole transport layer, an electron transport layer, a hole injection layer, and an electron injection layer. It is preferable to have a layer, or (b) the organic EL layer has an exciton blocking layer.
- the display of the present invention includes a substrate and a light-emitting element on the substrate.
- the light-emitting element includes an emitter electrode, a collector electrode, and a semiconductor layer and a sheet-like member provided between the emitter electrode and the collector electrode.
- a display comprising a base electrode and an organic EL layer provided between the base electrode and the collector electrode, wherein the organic EL layer includes at least one light emitting layer.
- the sheet-like base electrode has a thickness within a range in which ballistic electrons or ballistic holes accelerated by the base voltage Vb can be easily transmitted. Since it is formed, the charge is remarkably accelerated on the entire formed surface, and the accelerated charge can easily pass through the base electrode. As a result, the first transistor element of the present invention can stably obtain a current amplification effect similar to that of a bipolar transistor.
- the second transistor element of the present invention all of the emitter electrodes are formed by the dark current suppression layer.
- the negative current can be effectively suppressed, so that the ONZOFF ratio can be improved, and the transistor Contrast can be improved.
- a dark current suppressing layer can be easily formed, and a transistor element having an improved ONZOFF ratio by suppressing leakage current can be easily formed. Can be provided.
- the first or second transistor element can perform a large current modulation at a low voltage, for example, as a driving transistor which is an organic EL switching element.
- An electronic device preferably combined can be provided.
- the organic EL layer is provided between the base electrode and the collector electrode constituting the first or second transistor device, and the organic EL layer is at least one layer. Since the above light emitting layer is included, planar light emission by a large current is possible. In this case, the base electrode does not need to be finely patterned as in the conventional SIT structure, can be modulated with a large current at a low voltage, and the ONZOFF ratio can be improved. A practical light-emitting element having a structure can be provided.
- FIG. 1 is a schematic cross-sectional view showing an example of a first transistor element of the present invention.
- FIG. 2 is a graph showing the change in collector current with respect to the collector voltage.
- FIG. 3 is a graph showing the ratio of change in base current to change in collector current (current amplification factor (hF E)).
- FIGS. 4 (A) and 4 (B) show the modulation current Ic (A) and the case of using the same configuration as the transistor element measured in FIGS. 2 and 3 except for the thickness of the base electrode. It is the graph which showed the film thickness dependence of the current amplification factor hF E (B) of the base electrode.
- FIG. 5 is a graph showing current transmittance a when the thickness of the base electrode is changed.
- FIG. 6 shows the dependence of the base electrode on the injection current (A) from the emitter electrode and the current (B) reached the collector electrode when the base electrode material is changed. It is a graph which shows sex.
- FIG. 7 is an energy diagram of the transistor element of the present invention.
- FIG. 8 is a schematic sectional view showing an example of the second transistor element of the present invention.
- FIG. 9 is a schematic cross-sectional view showing another example of the second transistor element of the present invention.
- FIG. 10 shows a path of ON current and OFF current in the case of the second transistor element of FIG.
- FIG. 11 shows a path of ON current and OFF current in the case of the second transistor element of FIG.
- FIG. 12 is a graph showing the experimental results of ON current and ON / NZOFF ratio when a silicon oxide film is formed as a dark current suppressing layer.
- FIG. 13 shows a graph of the collector current when a dark current suppressing layer is formed.
- FIG. 14 shows a graph of the collector current after the dark current suppressing layer is formed of natural acid.
- FIG. 15 shows the relationship between the time of leaving in the atmospheric environment and the ONZOFF ratio.
- FIG. 16 is a schematic diagram showing an example of a light-emitting element having an organic EL layer between the base electrode and the collector electrode of the first transistor element, the organic EL layer including at least one light-emitting layer. It is sectional drawing.
- FIG. 17 is a schematic diagram showing an example of a light-emitting element having an organic EL layer between the base electrode and the collector electrode of the second transistor element, and the organic EL layer including at least one light-emitting layer. It is sectional drawing.
- FIG. 18 is an experimental example of the light emitting device having the configuration shown in FIG. 16, and is a graph showing changes in EL luminance when the base voltage Vb is changed while applying a constant voltage as the collector voltage Vc. It is.
- FIG. 19 is a schematic cross-sectional view showing a switching structure of an organic EL using the transistor element of the present invention.
- FIG. 20 is a schematic diagram showing a current path when the base voltage Vb is applied to the cobraner type device while applying the total voltage VDD.
- FIG. 21 is a graph showing luminance modulation characteristics in the cobraner type serial device shown in FIG.
- FIG. 1 is a schematic cross-sectional view showing an example of the first transistor element of the present invention.
- the first transistor element 10 of the present invention includes an emitter electrode 3, a collector electrode 2, and a semiconductor layer 5 (5A, 5B) disposed between the emitter electrode 3 and the collector electrode 2. ) And a sheet-like base electrode 4.
- the semiconductor layer 5 includes a first semiconductor layer 5A provided between the collector electrode 2 and the base electrode 4, and a second semiconductor layer 5B provided between the emitter electrode 3 and the base electrode 4. And have.
- Reference numeral 1 represents a substrate.
- the first transistor element 10 having such morphological power is a vertical transistor element, but has an advantage that it requires patterning of fine electrodes such as grids and stripes.
- the first transistor element for example, a transparent ITO electrode having a thickness of lOOnm is used as the collector electrode 2, and a perylene pigment (Me-PTC, average thickness) which is an n-type organic semiconductor is formed thereon.
- a perylene pigment Me-PTC, average thickness
- a second semiconductor layer 5B having an average thickness (lOOnm) and an emitter electrode 3 having an average thickness of 3 Onm made of silver were laminated in that order by a film forming means such as vacuum evaporation.
- the ON current and OFF current are the collector current Ic and the base when the collector voltage Vc is applied between the emitter electrode and the collector electrode, and when the base voltage Vb is applied between the emitter electrode and the base electrode, and when not applied. The change in the current lb was measured.
- the base electrode 4 is in direct contact with the semiconductor layer 5, almost no current flows into the base electrode 4.
- the ratio of the change in the base current to the change in the collector current that is, the current amplification factor (hFE) exceeded 1, reaching a maximum of 170.
- the first transistor element of the present invention apparently functions effectively as a current amplification type transistor element similar to the bipolar transistor.
- the semiconductor layer 5 (5A, 5B) is provided between the emitter electrode 3 and the collector electrode 2, and the sheet-like base electrode 4 is provided in the semiconductor layer 5.
- the transistor performance of the first transistor element 10 according to the present invention is that a collector voltage Vc is applied between the emitter electrode 3 and the collector electrode 2, and If a base voltage Vb is applied between the emitter electrode 3 and the base electrode 4, charges (electrons or holes) injected from the emitter electrode 3 are remarkably accelerated by the action of the base voltage Vb, and the base electrode 4 is This is based on the principle of transmitting and reaching the collector electrode 2. In other words, the current flowing between the emitter electrode and the collector electrode can be amplified by applying the base voltage Vb.
- the sheet-like base electrode 4 has a thickness within a range in which ballistic electrons or ballistic holes accelerated by the base voltage Vb can be easily transmitted (in FIG. 1). Is a predetermined effective width W.), the charge is remarkably accelerated on the entire formed surface, and the accelerated charge can easily pass through the base electrode 4. Therefore, according to the first transistor element 10 of the present invention, a current amplifying action similar to that of the bipolar transistor can be stably obtained.
- the force by which the first transistor element of the present invention is formed on the substrate The type and structure of the substrate 1 are not particularly limited, and can be appropriately determined depending on the material of each layer to be laminated. For example, a material having various material strengths such as a metal such as A1, glass, quartz, or resin can be used.
- a material having various material strengths such as a metal such as A1, glass, quartz, or resin can be used.
- the substrate is preferably formed of a material that becomes transparent or translucent.
- an organic light-emitting device with a top emission structure that emits light from the emitter electrode 3 side force is produced, it is not always necessary to use a material that becomes transparent or translucent.
- one that is generally used as a substrate for an organic EL element that is, one that strongly supports the organic EL element can be preferably used.
- a flexible material or a hard material is selected according to the application. Specific examples of materials that can be used include glass, quartz, polyethylene, polypropylene, polyethylene terephthalate, polymethacrylate, polymethylmethacrylate, polymethylacrylate, polyester, and polycarbonate.
- the shape of the substrate 1 may be a single wafer shape or a continuous shape, and examples thereof include a card shape, a film shape, a disk shape, and a chip shape.
- the electrodes constituting the first transistor element of the present invention there are a collector electrode 2, an emitter electrode 3 and a base electrode 4.
- the collector electrode 2 is usually provided on a substrate 1 and is formed on a base.
- the electrode 4 is provided so as to be embedded in the semiconductor layer 5 (the first semiconductor layer 5A and the second semiconductor layer 5B), and the emitter electrode 3 has the semiconductor layer 5 and the base electrode 4 at positions facing the collector electrode 2. It is provided so that it may be pinched.
- the electrode material a thin film made of metal, conductive oxide, conductive polymer or the like is used. Note that a barrier layer, a smooth layer, or the like may be provided between the substrate 1 and the collector electrode 2.
- a material for forming the collector electrode 2 is, for example, ITO (indium tin Oxide), indium oxide, IZO (indium zinc oxide), SnO, ZnO
- ITO indium tin Oxide
- IZO indium zinc oxide
- SnO zinc oxide
- ZnO ZnO
- transparent conductive films such as gold, metals having a high work function such as gold and chromium
- conductive polymers such as polyaline, polyacetylene, polyalkylthiophene derivatives, and polysilane derivatives.
- the material for forming the emitter electrode 3 includes simple metals such as aluminum and silver, magnesium alloys such as MgAg, aluminum alloys such as AlLi, AlCa and AlMg, alkali metals such as Li and Ca, and alkali metals thereof.
- Metal having a small work function such as an alloy of the same kind.
- the semiconductor layer 5 constituting the first transistor element of the present invention is a hole transport layer having an organic compound power
- the material for forming the collector electrode 2 and the emitter electrode 3 are used. This is the opposite of the forming material.
- the base electrode 4 forms a Schottky contact with the constituent material of the semiconductor layer 5
- the base electrode 4 is formed of the same material as the electrode used for the collector electrode 2 and the emitter electrode 3 described above. Can be mentioned. Since the base electrode 4 acts to forcibly supply the charge supplied from the emitter electrode 3 into the first semiconductor layer 5A on the collector electrode 2 side, the base electrode 4 is not necessarily formed as the first semiconductor. The material does not have to be easily injected into layer 5A. However, when the first semiconductor layer 5A on the collector electrode 2 side is a hole injection layer or a layer having a hole injection material, the work function is small, and it is preferable to form the base electrode 4 with a material.
- the base electrode 4 is preferably formed of a material having a large work function.
- the material for forming the base electrode 4 include simple metals such as aluminum and silver, magnesium alloys such as MgAg, aluminum alloys such as AlLi, AlCa, and AlMg, alkaline metals such as Li and Ca, and LiF.
- a metal having a small work function such as an alloy of alkali metals can be preferably used, but if it is possible to form a Schottky contact with the charge (hole, electron) injection layer, ITO (indium tin Oxide), indium oxide, IZO (indium zinc oxide), SnO, ZnO and other transparent conductive films,
- Metals having a high work function such as gold and chromium, conductive polymers such as polyarine, polyacetylene, polyalkylthiophene derivatives, and polysilane derivatives can also be used.
- the bottom that emits light from the substrate 1 side force In the case of an organic light emitting device with an emission structure, it is preferable to form at least the collector electrode 2 with a transparent or translucent material, while the organic light emission with a top emission structure in which light is emitted from the emitter electrode 3 side.
- the base electrode 4 and the emitter electrode 3 When manufacturing an element, it is preferable to form the base electrode 4 and the emitter electrode 3 with a transparent or translucent material. With this configuration, the light extraction efficiency can be improved.
- Transparent or translucent electrode materials include ITO (indium tin oxide), indium oxide, IZO (indium zinc oxide), SnO, ZnO
- a transparent conductive film such as 2 is preferably used.
- the collector electrode 2 and the emitter electrode 3 are formed by a vacuum process or coating such as vacuum deposition, sputtering, CVD, etc., and the film thickness varies depending on the material used, for example. ⁇ ! It is preferably about ⁇ lOOOnm. These film thicknesses were obtained by measuring the average value at five locations on the sample cross section in the thickness direction using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- FIG. 4 shows the amount of modulation current Ic (FIG. 4 (A)) when the same configuration as the transistor element measured in FIGS. 2 and 3 is used except for the thickness of the base electrode 4.
- the current amplification factor h FE (FIG. 4B) are graphs showing the film thickness dependence of the base electrode 4.
- FIG. 5 is a graph showing the current transmittance a when the thickness of the base electrode 4 is changed.
- the current transmittance ⁇ shown in FIG. 5 is expressed by [Ic (charge reaching the collector electrode)] Z [Ic + Ib (charge injected from the emitter electrode)].
- the modulation current amount Ic and the current gain hFE are V, and the deviations are drastically reduced as the base electrode 4 becomes thicker, so that sufficient transistor performance can be obtained. It can be seen that a thin base electrode 4 is essential.
- the current transmittance ⁇ which is the ratio of the charge injected from the emitter electrode 3 to the charge reaching the collector electrode 2
- the thickness of the base electrode 4 is 40 nm or less as shown in FIG. Then, it was found that it showed a very high value of about 99%. This means that almost all the charge from the emitter electrode 3 is transmitted through the base electrode 4, and as a result, it is considered that the current amplification effect similar to that of the bipolar transistor is obtained.
- the base electrode 4 has a thickness of 40 nm or less! / Repulsive force As shown in FIG. 4, it can be used even when the thickness is less than 80 nm. It is. 40nm or less Is a thickness that allows the ballistic electrons or ballistic holes accelerated by the base voltage Vb to easily pass through the semiconductor layer, so that the charge (electrons or holes) is remarkably formed on the entire surface of the sheet-like base electrode 4. The accelerated and accelerated charges can easily pass through the base electrode 4.
- the base electrode 4 only needs to be provided in the semiconductor layer 5 without any breaks (without a defect such as a hole or a crack), so the lower limit of the thickness is not particularly limited, but is usually about 1 nm. Good.
- the thickness of the base electrode 4 was measured with a transmission electron microscope at the sample cross section in the thickness direction.
- FIG. 6 shows an injection current from the emitter electrode 3 when the material for forming the base electrode 4 is changed.
- FIG. 6 is a graph showing the base voltage dependence on (FIG. 6 (A)) and the current reached the collector electrode 2 (FIG. 6 (B)). This graph was measured using the same configuration as the transistor element measured in FIGS. 2 and 3 except that the thickness of the base electrode 4 was 40 nm. As shown in FIG. 6, even when the base voltage Vb is changed, the injection current from the emitter electrode 3 and the current reaching the collector electrode 2 are almost the same, and the current transmittance ⁇ [IcZ (Ic + Ib)] was found to pass through the base electrode 4 with a high probability of 0.99 in each sample in which the material of the base electrode 4 was LiFZAl, Au, Ag.
- the base electrode 4 is made of LiF (thickness 0.5 nm), ZAl (thickness ⁇ m), Au (thickness 30 nm), and Ag (thickness 30 nm).
- LiFZAl being the highest in order of Ag and Au. From this result, it was proved that the material dependence on the current transmissivity ⁇ was small, depending on the material of the base electrode 4.
- the base electrode 4 is provided in the form of a sheet and the thickness thereof is equal to or less than a predetermined thickness, the mechanism showing the high and current transmittance a is not necessarily clear! / A mechanism is conceivable.
- the emitter electrode 4 when the base electrode 4 is provided in the form of a sheet (that is, when the base electrode 4 does not include a defective portion such as a hole or a crack), the emitter electrode It is considered that the charge injected from 3 is accelerated on the entire surface of the sheet-like base electrode 4 and almost all of the charge injected from the emitter electrode 3 becomes ballistic electrons or ballistic holes and passes through the base electrode 4. As a result, the amount of charge that has reached the collector electrode is charged by the electron injected from the emitter electrode. It becomes almost the same as the amount of the load, and it is considered that the current amplification effect is remarkable as a whole.
- the current transmission rate a is high. This is because the charge injected from the emitter electrode 3 causes the base electrode 4 to move into ballistic electrons or ballistic positive. Permeation as a hole is considered to be due to this.
- the energy diagram shown in Fig. 7 is considered to be responsible for the same action as the base layer of the thin base electrode 4 force bipolar transistor (that is, it only causes an increase in the emitter current while preventing carriers from flowing into the base). Propose. As can be seen from FIG.
- the base voltage Vb applied between the emitter electrode and the base electrode increases the charge injection current from the emitter electrode 3 to the second semiconductor layer 5B composed of C60, and the charge is As a result of reaching the conduction band of the first semiconductor layer 5A made of MePCT that does not fall into the electrode 4 with a high probability and being collected in the collector electrode 2, it is considered that a large collector current modulation was obtained.
- the distance through which the charge can pass ballistically through the base electrode 4 (mean free path of electrons or holes) is generally said to be several nanometers and several tens of nanometers! The following thickness is preferred V, which is almost in agreement with the experimental results of the present invention.
- the surface of the base electrode 4 can have an uneven shape.
- the base electrode 4 having the concavo-convex shape can be called a base electrode having a rough surface.
- Such a base electrode 4 is thin and thick even when a base electrode having a predetermined average thickness is formed. I have a place.
- a base electrode having such a constituent force is preferable in that a current amplification effect can be stably obtained.
- the surface shape that has uneven shape force was evaluated with a contact surface shape measuring device (manufacturer: SLOAN THECHNOLOGY, model number: DEKTAK3) or AFM (Seiko Instruments, SPI3800).
- the base electrode 4 when the first semiconductor layer 5A provided between the collector electrode 2 and the base electrode 4 is vacuum-deposited with a crystalline organic compound, the first semiconductor layer 5A on the side where the base electrode 4 is formed.
- the surface of the semiconductor layer 5A has an uneven shape. Therefore, the base electrode 4 provided on the crystalline first semiconductor layer 5A is also formed in an uneven shape.
- the base electrode 4 having a concavo-convex shape is thin even if the base electrode 4 having a predetermined average thickness is formed.
- the base electrode 4 has a concavo-convex shape. When it has, it can obtain the current amplification effect stably.
- a perylene pigment which is an n-type organic semiconductor, which is a constituent material of the transistor element showing the result of FIG. 2 or FIG. 3 is preferable.
- a perylene pigment (Me—PTC), which is an n-type organic semiconductor, which is a constituent material of the transistor element showing the result of FIG. 2 or FIG. 3 is preferable.
- examples of other materials include C60, NTC DA, PTCDA, and Ph-Et-PTC represented by the chemical formula described below.
- organic compounds other than these may be used.
- the crystal grain size of the crystalline semiconductor layer can be measured with a transmission electron microscope, and the crystal grain size was not less than or equal to the thickness of the base electrode 4 and about 50 nm or more. . In this way, if the crystal grain size of the crystalline first semiconductor layer 5A is set to be equal to or greater than the thickness of the base electrode 4, the base electrode 4 is formed on the first semiconductor layer 5A, thereby forming an uneven shape. Can easily form a base electrode.
- the surface roughness Rz of the crystalline semiconductor layer was evaluated by AFM (Seiko Instruments, SPI3800), Me-PTC was about 200 nm to 400 nm, NTCDA was 300 nm to 500 nm, and C60 was 50 nm to 100 nm.
- the base electrode 4 may be made of a metal, and an oxide thin film of the base electrode 5 may be formed on one side or both sides of the base electrode 4.
- a protective layer (not shown) for reducing damage applied to the semiconductor layer 5 at the time of electrode formation is formed on the semiconductor layer 5. It may be provided.
- a semi-transparent film such as Au, Ag, A1, or a deposited film such as an inorganic semiconductor film such as ZnS or ZnSe, or a sputtered film, which is difficult to damage at the time of film formation, is about l to 500 nm It is preferable to form a film with a thickness of
- the semiconductor layer 5 constituting the first transistor element of the present invention various semiconductor materials can be exemplified, and usually a charge transport material having good charge transport characteristics can be exemplified.
- the forms are (0 first semiconductor layer 5A provided between collector electrode 2 and base electrode 4, and second semiconductor layer 5B provided between emitter electrode 3 and base electrode 4).
- the GO first semiconductor layer 5A and the second semiconductor layer 5B are formed of a hole transport material or an electron transport material, and (m) the emitter electrode 3 and the base.
- the semiconductor layers 5A and 5B provided between the electrode 4 or between the collector electrode 2 and the base electrode 4 are both formed of a strong organic compound.
- TCDA TCDA
- PTCDA Me-PTC
- Ph—Et— PTC anthraquinodimethane
- fluorenylidene methane tetracyanethylene
- fluorenone diphenoquinone oxadiazonole
- Anthrone thiopyran dioxide
- diphenoquinone benzoquinone
- malono-tolyl -ditrobenzene
- nitroanthraquinone maleic anhydride or perylenetetracarboxylic acid, or their derivatives, etc.
- the light emitting layer forming materials listed in the description section of the light emitting element of the present invention to be described later may be used.
- the charge mobility of the semiconductor layer 5 is preferably at least as high as possible.
- the thickness of the first semiconductor layer 5A on the collector electrode 2 side is usually 300 ⁇ ! ⁇ A force capable of increasing about lOOOnm, preferably about 400 ⁇ m to 700nm. Note that if the thickness is less than 300 nm or exceeds lOOOnm, transistor operation may not occur. On the other hand, it is desirable that the thickness of the second semiconductor layer 5B on the emitter electrode 3 side is basically thinner than that of the second semiconductor layer 5B. 50 ⁇ ! About 150nm. If the thickness is less than 50 nm, a conduction problem may occur and the yield may decrease.
- a transistor element was used in which an emitter electrode 3 having an average thickness of 30 nm and also having silver strength was stacked in that order by a film forming means such as vacuum evaporation.
- the thickness of the first semiconductor layer 5A is lOOnm for Alq and C60, and 10 for NTCDA, PTCDA, and Me-PTC.
- the collector voltage Vc was set to 5V, and the base voltage Vb was modulated in the range of OV to 3V.
- the output modulation characteristics are measured when the collector voltage Vc is applied between the emitter electrode and the collector electrode, and when the base voltage Vb is applied between the emitter electrode and the base electrode.
- the change in current Ic and base current lb was measured.
- the ratio of the base current change to the collector current change that is, the current amplification factor (hFE) was calculated. Table 1 shows the results.
- the semiconductor layer 5 (5A, 5B) constituting the first transistor element of the present invention has a force capable of using a charge transport material. Specifically, a high current amplification effect is produced by a combination of materials. be able to. At present, these combinations are considered to be related to the LUMO position of the semiconductor material, as shown in Fig. 7, so it is desirable to combine them in consideration of this point.
- Table 1 also shows the measurement results of the ONZOFF ratio when the collector voltage Vc is 5 V, the base voltage Vb is 3 V, and the OFF voltage is 0 V. ON as shown in Table 1.
- the OFF ratio was large when the first semiconductor layer 5A made of NTCDA or PTCDA was formed, and was 40 or 20, respectively.
- the ONZOFF ratio was 100, which was extremely high.
- the first transistor element of the present invention apparently functions effectively as a current amplification type transistor element similar to a bipolar transistor.
- FIG. 8 is a schematic sectional view showing an example of the second transistor element of the present invention
- FIG. 9 is a schematic sectional view showing another example of the second transistor element of the present invention.
- the second transistor elements 20 and 30 of the present invention include an emitter electrode 3 and a collector electrode 2.
- a semiconductor layer 5 and a sheet-like base electrode 4 are provided between the emitter electrode 3 and the collector electrode 2, and at least between the emitter electrode 3 and the base electrode 4 or between the collector electrode 2 and the base electrode 4.
- Dark current suppression layers 6 and 7 are provided.
- the dark current suppression layer 6 is provided between the collector electrode 2 and the base electrode 4
- FIG. 9 the dark current suppression layer 6 is provided between the collector electrode 2 and the base electrode 4.
- a negative current suppression layer 7 is provided between the emitter electrode 3 and the base electrode 4.
- the second transistor element is different from the first transistor element in that a dark current suppression layer is provided, and is otherwise the same as the first transistor element.
- a dark current suppression layer is provided, and is otherwise the same as the first transistor element.
- the same reference numerals are used and description thereof is omitted.
- the substrate is omitted.
- FIG. 10 shows a path of ON current and OFF current in the case of the second transistor element 20 in FIG. 8, and FIG. 11 shows a case in the case of the second transistor element 30 in FIG.
- the path of ON current and OFF current is shown.
- a transistor element that improves the ONZOFF ratio by suppressing the leakage current required for operation by forming a dark current suppression layer (6, 7) on one or both sides of the thin sheet-like base electrode 4 formed on is there.
- the second transistor elements 20 and 30 of the present invention at least between the emitter electrode 3 and the base electrode 4 or between the collector electrode 2 and the base electrode 4 Since a dark current suppression layer (6, 7) is provided between them, when the dark voltage suppression layer applies a small voltage Vb between the emitter electrode and the base electrode, or when no voltage Vb is applied, It is possible to effectively suppress the dark current from flowing between the base electrode and the collector electrode in the transistor operation, and as a result, the ONZOFF ratio can be improved.
- the negative current suppression layers 6 and 7 can effectively suppress the dark current when the voltage Vb is not applied between the emitter electrode base electrodes, for example, when the voltage Vb is applied between the emitter electrode base electrodes. It is desirable to use something that does not hinder the so-called ON current.
- the dark current suppression layers 6 and 7 function so that the emitter current generated by the collector voltage Vc does not pass through the base electrode 4 when the base voltage Vb is turned off. Therefore, as shown in FIG. Provided between the collector electrode 2 and the base electrode 4. If necessary, the dark current suppressing layer 7 can be provided on both surfaces of the base electrode 4.
- the dark current suppression layer to be formed is preferably provided adjacent to the base electrode 4 (that is, in contact with the base electrode 4).
- the dark current suppressing layer is preferably formed uniformly on the base electrode 4.
- uniformly means that it is formed on the entire surface without holes or cuts. If the dark current suppression layer is too thin, it is difficult to form a uniform dark current suppression layer. If the dark current suppression layer is too thick, the base voltage Vb is turned on. Current may be significantly suppressed.
- Examples of the material for forming the dark current suppressing layer include an organic insulating layer and an inorganic insulating layer, provided that the film can be formed with the above-described thickness and that the dark current suppressing layer has an operational effect.
- inorganic materials such as Si02, SiNx, A1203, polychloropyrene, polyethylene terephthalate, polyoxymethylene, polyvinyl chloride, polyvinylidene fluoride, cyanoethyl pullulan, polymethyl methacrylate
- examples thereof include organic materials such as polyvinyl phenol, polysulfone, polycarbonate, and polyimide. These forming materials may be used alone or in combination of two or more kinds.
- an organic semiconductor material may be used, or an inorganic semiconductor material may be used. From these materials, an optimum material is selected on the condition that the film can be formed with the above-mentioned thickness and that an effect as a negative current suppressing layer can be obtained. These forming materials may also be used alone, or two or more materials may be used as described above.
- FIG. 12 is a graph showing an ON current and an ON / OFF ratio experimental result in the case where an oxide layer is formed as the dark current suppression layer.
- a transparent ITO electrode having a thickness of lOOnm was used as the collector electrode 2, and a first semiconductor layer 5A (thickness 400 nm) having Me-PTC force and an average thickness of 20 nm consisting of aluminum were also formed thereon.
- the base electrode 4, the second semiconductor layer 5B made of fullerene (C60, average thickness 100 nm), and the emitter electrode 3 with an average thickness of 30 nm, which also has silver strength, are stacked in that order by a film deposition method such as vacuum evaporation.
- the transistor element prepared was used.
- a comparative sample a transistor element without an oxygen substrate was fabricated.
- the ON current and OFF current of the sample were measured. Measurement is performed when the collector voltage Vc is applied between the emitter electrode and the collector electrode, 5V, and the collector current measured when the base voltage Vb is applied between the emitter electrode and the base electrode is set to the ON current.
- the collected collector current was defined as the OFF current.
- the ONZOFF ratio was about 250 when the thickness of the silicon oxide that is the dark current suppression layer was 5 nm. Note that the ON current at this time was lower than when no acid key film was provided, but was much less than that when a 2.5 nm thick oxide film was provided. The power was strong. This is preferable because ONZOFF can be improved without significantly reducing the ON current.
- Fig. 13 and Fig. 14 show the change over time of the collector current when the dark current suppression layer is formed of natural acid, and Fig. 13 shows the case where the dark current suppression layer is not formed. Fig. 14 shows a graph of the collector current after forming the dark current suppression layer with natural acid.
- a transparent ITO electrode having a thickness of lOOnm was used as the collector electrode 2, and a first semiconductor layer 5A having an average thickness of 400 nm made of Me-PTC and a base electrode 4 having an average thickness of 20 nm made of aluminum were formed thereon.
- C6 A transistor element was used in which a second semiconductor layer 5B having an average thickness of lOOnm) and an emitter electrode 3 having an average thickness of 30nm made of silver were stacked in that order by a film forming means such as vacuum evaporation.
- the collector voltage Vc was applied between the emitter electrode and the collector electrode from OV to 5V, and the collector voltage was measured when the base voltage Vb was applied between the emitter electrode and the base electrode at 3V and when 4V was applied.
- the current was the ON current, and the collector current measured when no current was applied was the OFF current.
- the results shown in FIG. 13 are measured immediately after the transistor element is formed, and the dark current suppression layers 6 and 7 are not formed on both surfaces of the base electrode 4.
- the results shown in FIG. 14 were measured after the above-mentioned transistor element was formed and left in an indoor air environment at a temperature of 20 to 25 ° C. and a humidity of 30 to 70% for 37 minutes. Dark current suppression layers 6 and 7 made of aluminum oxide were formed on both sides of the film.
- the aluminum oxide at this time is a natural oxide film of the base electrode 4 made of aluminum, and was confirmed by measuring the thickness with a TEM.
- the thickness of the acid aluminum film increases with the passage of time, and the thickness of the acid aluminum film after 37 minutes is longer than the thickness of the acid aluminum film when the exposure time is 20 minutes.
- the thickness of aluminum was strong. Considering this result together with the experiment in FIG. 12, it is considered that this result is mainly due to the action effect of the acid film formed on the collector electrode 2 side.
- the method for producing a transistor element according to the present invention relates to the above-described second method for producing a transistor element, and comprises a semiconductor layer 5 (5A, 5B) and a sheet-like material between the emitter electrode 3 and the collector electrode 2.
- a base electrode 4 is provided, and a dark current suppression layer (6, 7) is formed at least between the emitter electrode 3 and the base electrode 4 or between the collector electrode 2 and the base electrode 4.
- a dark current suppressing layer is formed by conducting a chemical reaction of the base electrode 4. As shown in the experimental results in FIG. 12 to FIG. 14, such chemical reaction is performed by oxidizing a part of the base electrode 4 (the surface on the side in contact with the semiconductor layer side) after forming the base electrode 4.
- the dark current suppressing layer (6, 7) can be easily formed, and a transistor element in which the ONZOFF ratio is improved by suppressing the leakage current can be easily provided.
- the dark current suppressing layer is provided only on the collector electrode 2 side, after the base electrode 4 is formed on the first semiconductor layer 5A, a chemical reaction such as oxidation is prevented on the base electrode 4. If the protective layer intended to be provided is provided, the natural acid film or the heated acid film of the base electrode 4 can be provided only on the collector electrode 2 side of the upper dark current suppressing layer.
- the electronic device of the present invention is preferably one having the first transistor element of the present invention as a switching element or one having the second transistor element of the present invention as a switching element.
- the present invention can be an electronic device in which the first or second transistor element is used as a switching element, for example, in combination with an organic EL element. Since the first or second transistor element can modulate a large current at a low voltage, an electronic device preferably combined as a drive transistor that is a switching element of an organic EL, for example, can be provided.
- an organic EL layer is provided between the base electrode 4 and the collector electrode 2 and an electronic device is configured using the base electrode 4 as a cathode. Easily inject electrons like Even if it is not used as a cathode, there is an excellent effect that charges can be effectively injected into the charge transport layer constituting the organic EL layer.
- FIG. 16 shows an example of a light-emitting element 40 having an organic EL layer 41 between the base electrode 4 and the collector electrode 2 of the first transistor element, and the organic EL layer 41 includes at least one light-emitting layer 42. It is a schematic cross section shown.
- the first light emitting element 40 has, for example, a transparent ITO electrode having a thickness of lOOnm as a collector electrode 2 and a hole injection layer 44 having a thickness of 2 nm made of CuPc, and an NPD.
- FIG. 17 also shows an organic EL layer 41 between the base electrode 4 and the collector electrode 2 of the second transistor element, and the organic EL layer 41 includes at least one light emitting layer 42.
- 3 is a schematic cross-sectional view showing an example of an element 50.
- FIGS. 16 and 17 The configuration of the light emitting elements 40 and 50 of the present invention shown in FIGS. 16 and 17 as the transistor is the same as the basic configuration of the first and second transistor elements, and thus has already been described. Detailed description of the same configuration will be omitted using the same reference numerals.
- the chemical formulas of the constituent materials of the organic EL layer constituting the light emitting elements 40 and 50 shown in FIGS. 16 and 17 are shown below.
- FIG. 18 is an experimental example of the light emitting device having the configuration shown in FIG. 16, and is a diagram showing a change in EL luminance when the base voltage Vb is changed while a constant voltage is applied as the collector voltage Vc. is there.
- the light emitting device of the present invention has the organic EL layer 41 between the first semiconductor layer 5A and the collector electrode 2 of the transistor device, and is similar to the organic EL layer 41 as a whole. Since it has a planar laminated structure, the planar current can be modulated.
- a light-emitting element with such a structure has the advantage that the aperture ratio can be increased because the area occupied by the drive transistor, which is a drive element, and the organic EL element can be fabricated at a time is substantially zero. In recent years, light emission has been observed even in organic FET structures, but the performance is still low, and organic light-emitting transistors that exhibit practical performance are known to use vertical organic SIT. Yes.
- the light-emitting device of the present invention can realize a light-emitting device capable of current modulation simply by laminating an organic EL layer on the collector electrode 2 side.
- the light emitting device of the present invention does not require fine patterning such as an intermediate electrode and is extremely practical.
- the organic EL layer 41 includes at least one light-emitting layer 42, and further includes a positive layer. It is preferable to have one or more layers selected from the hole injection layer 44, the hole transport layer 43, the electron transport layer, and the electron injection layer.
- a hole transport layer 43 and a hole injection layer 44 are provided on the collector electrode 2 side of the light emitting layer 42.
- An exciton blocking layer 45 is provided on the base electrode 4 side of the light emitting layer 42. In the light emitting elements 40 and 50, a large amount of charge is accelerated by the transistor element and reaches the light emitting layer 42 of the organic EL layer 41, so that the charge injection from the base electrode 4 is easy.
- the organic EL layer 41 does not necessarily have a charge injection layer. For this reason, it is easy to inject electrons as in the conventional case, and it is easy to oxidize, and there is a great effect even if an alkali metal is not used as a cathode.
- the material for forming the light-emitting layer 42 is not particularly limited as long as it is a material generally used as a light-emitting layer of an organic EL element.
- a dye-based light-emitting material, a metal complex-based light-emitting material, a polymer-based material Light emitting materials and the like can be given.
- Examples of the dye-based luminescent material include cyclopentagen derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoguchi quinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives. And thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, pyrazoline dimers, and the like.
- metal complex-based light emitting materials include aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazole zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, and europium complexes.
- Al, Zn, Be, etc., or a metal complex having a rare earth metal such as Tb, Eu, Dy, etc., and having a ligand such as oxadiazole, thiadiazole, phenol pyridine, phenol benzimidazole or quinoline structure Can be mentioned.
- polymer-based light-emitting material examples include polyparaphenylene-lenylene derivatives, polythiophene derivatives, polybaraphene-lene derivatives, polysilane derivatives, polyacetylene derivatives, polybulucarbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, And copolymers thereof.
- An additive such as a doping agent may be added to the light emitting layer 42 for the purpose of improving the light emission efficiency or changing the light emission wavelength.
- doping agents examples include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacitrane, funoxazone, quinoxaline derivatives, force rubazole derivatives, fluorene derivatives, etc. Can be mentioned.
- phthalocyanine As a material for forming the hole transport layer 43, phthalocyanine, naphthalocyanine, porphyrin, oxadiazole, triphenylamine, triazole, imidazole, imidazolone, virazoline, tetrahydroimidazole, hydrazone, stilbene, pentacene, polythiophene or butadiene, or Those derivatives and the like that are usually used as hole transport materials can be used.
- hole transport layer 43 commercially available as a material for forming the hole transport layer 43, for example, poly (3,4) ethylenedioxythiophene Z polystyrene sulfonate (abbreviated as PEDO TZPSS, manufactured by Bayer, trade name: Baytron P AI4083, aqueous solution Can be used as well.
- PEDO TZPSS poly (3,4) ethylenedioxythiophene Z polystyrene sulfonate
- Baytron P AI4083 aqueous solution
- the hole transport layer 43 is formed using a coating liquid for forming a hole transport layer containing such a compound.
- These hole transport materials may be mixed in the light emitting layer 42 described above, or may be mixed in the hole injection layer 44.
- the first semiconductor layer 5A which also has Me-PTC force, is an electron transporting layer and is not provided as a separate electron transporting layer. It may be provided on the base electrode 4 side.
- As the material for forming the electron transport layer anthraquinodimethane, fluorenylidenemethane, tetracyanethylene, fluorenone, diphenoquinoneoxadiazole, anthrone, thiopyran dioxide, diphenoquinone, benzoquinone, malononitrile, -Ditrobenzene, nitroanthraquinone, maleic anhydride or perylenetetracarboxylic acid, or derivatives thereof, which are usually used as electron transport materials, can be used.
- the electron transport layer is formed using a coating liquid for forming an electron transport layer containing such a compound. These electron transport materials may be mixed in the light emitting layer 42 or in the electron injection layer.
- phenolamine starburst-type amine, phthalocyanine, and vanadium oxide are used.
- examples thereof include oxides such as zinc, molybdenum oxide, ruthenium oxide, and aluminum oxide, derivatives such as amorphous carbon, polyarine, and polythiophene.
- an electron injection layer may be provided if necessary.
- a material for forming the electron injection layer aluminum, lithium fluoride, strontium, magnesium oxide, magnesium fluoride, strontium fluoride, calcium fluoride, fluoride, in addition to the compounds exemplified as the light emitting material of the light emitting layer.
- the organic layer such as the light-emitting layer or the charge transport layer described above may contain an oligomer material or a dendrimer light-emitting material or a charge transport injection material as necessary.
- Each of the above-described layers is formed by a vacuum deposition method, or the coating liquid is prepared by dissolving or dispersing each forming material in a solvent such as toluene, black-form, dichloromethane, tetrahydrofuran, dioxane, or the like.
- the coating liquid is formed by coating or printing using a coating apparatus or the like.
- the exciton blocking layer 45 is a layer that functions as a hole blocking layer, an electron blocking layer, or the like, and prevents the removal of carriers (holes, electrons) and efficiently recombines carriers. Block layer.
- the collector electrode 2 since the transistor element is made of an n-type semiconductor material, the collector electrode 2 functions as an anode. As a result, since the collector electrode 2 force holes are injected, it is preferable to form an exciton blocking layer 45 as a hole blocking layer on the adjacent surface of the light emitting layer 42 on the base electrode 4 side.
- BCP (1-bromo-3-chloropropane) was used as a material for forming the exciton blocking layer 45.
- the exciton blocking layer 45 made of BCP shown in Fig. 16 and Fig. 17 does not block electrons from Me-PTC because LUMO is almost the same as Me-PTC in the energy diagram. Since HOMO is higher than Alq3, holes from Alq3 block.
- the collector electrode 2 acts as a cathode, and as a result, electrons are injected from the collector electrode 2.
- An exciton block layer 45 as an electron block layer is preferably formed on the adjacent surface on the base electrode 4 side.
- FIG. 19 is a schematic cross-sectional view showing a switching structure of an organic EL using the transistor element of the present invention.
- Me—PTC thinness 500 nm
- A1 thinness 2 Onm
- LiF thickness 0.5 nm
- ZAl thickness lOOnm
- a 7 nm-thick hole injection layer 44 made of CuPc, a 40 nm-thick hole transport layer 43 made of NPD, and a 70 nm-thickness made of Alq3 As an organic EL device, on the same ITO electrode glass substrate, a 7 nm-thick hole injection layer 44 made of CuPc, a 40 nm-thick hole transport layer 43 made of NPD, and a 70 nm-thickness made of Alq3
- the light emitting layer 42 is laminated in that order.
- FIG. 20 is a schematic diagram showing a current path when the base voltage Vb is applied to the cobraner type device while applying the total voltage VDD.
- FIG. 21 is a graph showing luminance modulation characteristics in the coplanar type serial device shown in FIG. This is the OLED output light intensity when the base voltage Vb is applied while applying the total voltage VDD. The modulation was measured with a luminance meter.
- the transistor element of the present invention has a high performance as a driving transistor for organic EL due to its low voltage and large current modulation characteristics.
- the fact that large current modulation is possible means that the area occupied by transistors in one pixel can be reduced, leading to an improvement in the aperture ratio of the display.
- the transistor element of the present invention can be expected as a transistor for driving a flexible display.
- the light-emitting device of the present invention enables large current planar light emission by the organic EL layer provided between the base electrode and the collector electrode. Practical light emission that does not require fine patterning of the base electrode as in the structure, can be modulated with a large current at a low voltage, and can further improve the ONZOFF ratio. An element can be provided.
- the display of the present invention can be a display with high brightness by forming the light emitting element of the present invention on a substrate.
- the substrate any of the various substrates described for the first transistor element can be used.
- the flexible substrate include flexible substrates made of glass, quartz, polyethylene, polypropylene, polyethylene terephthalate, polymethacrylate, polymethylmethacrylate, polymethylacrylate, polyester, polycarbonate, and the like.
- specific shapes that may be a single wafer shape or a continuous shape may include, for example, a card shape, a film shape, a disk shape, and a chip shape.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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US12/293,649 US8120242B2 (en) | 2006-03-22 | 2007-03-22 | Transistor and process of producing the same, light-emitting device, and display |
EP07739334A EP2009700A4 (en) | 2006-03-22 | 2007-03-22 | TRANSISTOR ELEMENT, MANUFACTURING METHOD, LIGHT ELEMENT AND DISPLAY |
CN200780010021XA CN101432883B (zh) | 2006-03-22 | 2007-03-22 | 晶体管元件及其制造方法以及发光元件和显示器 |
KR1020087025659A KR101255407B1 (ko) | 2006-03-22 | 2007-03-22 | 트랜지스터 소자 및 그 제조 방법 및 발광 소자 및 디스플레이 |
US13/351,661 US20120112318A1 (en) | 2006-03-22 | 2012-01-17 | Transistor and process of producing the same, light-emitting device, and display |
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JP2006-078237 | 2006-03-22 | ||
JP2006078237A JP5182775B2 (ja) | 2006-03-22 | 2006-03-22 | トランジスタ素子及びその製造方法、電子デバイス、発光素子並びにディスプレイ |
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US13/351,661 Division US20120112318A1 (en) | 2006-03-22 | 2012-01-17 | Transistor and process of producing the same, light-emitting device, and display |
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US (2) | US8120242B2 (ja) |
EP (1) | EP2009700A4 (ja) |
JP (1) | JP5182775B2 (ja) |
KR (1) | KR101255407B1 (ja) |
CN (2) | CN101432883B (ja) |
TW (1) | TW200810111A (ja) |
WO (1) | WO2007119490A1 (ja) |
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WO2013161078A1 (ja) * | 2012-04-27 | 2013-10-31 | 大日精化工業株式会社 | トランジスタ素子 |
WO2022024239A1 (ja) * | 2020-07-29 | 2022-02-03 | シャープ株式会社 | 発光素子及び当該発光素子の駆動方法 |
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JP5352118B2 (ja) * | 2008-05-07 | 2013-11-27 | 独立行政法人科学技術振興機構 | 有機トランジスタ素子と電子・電気機器 |
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KR101045264B1 (ko) * | 2008-09-09 | 2011-06-29 | 네오뷰코오롱 주식회사 | 디스플레이 장치, 이를 구비하는 모바일 기기 및 디스플레이 제어 방법 |
JP5370810B2 (ja) * | 2008-09-19 | 2013-12-18 | 富士電機株式会社 | トランジスタ素子およびその製造方法 |
JP5534702B2 (ja) * | 2009-04-14 | 2014-07-02 | 日本放送協会 | 有機縦型トランジスタ |
JP5477841B2 (ja) * | 2009-05-11 | 2014-04-23 | 健一 中山 | トランジスタ素子 |
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CN102339955A (zh) * | 2011-10-09 | 2012-02-01 | 北京理工大学 | 一种共振隧穿有机发光二极管及其制备方法 |
DE102012102910B4 (de) * | 2012-04-03 | 2016-09-22 | Novaled Ag | Vertikaler organischer Transistor und Verfahren zum Herstellen |
JP6092679B2 (ja) * | 2013-03-26 | 2017-03-08 | 中山 健一 | トランジスタ素子 |
US9929365B2 (en) * | 2014-05-28 | 2018-03-27 | The Regents Of The University Of Michigan | Excited state management |
US10290816B2 (en) | 2015-11-16 | 2019-05-14 | The Regents Of The University Of Michigan | Organic electroluminescent materials and devices |
KR20170129983A (ko) | 2016-05-17 | 2017-11-28 | 삼성전자주식회사 | 발광소자 패키지, 이를 이용한 디스플레이 장치 및 그 제조방법 |
KR102571946B1 (ko) * | 2022-12-29 | 2023-08-30 | 한국표준과학연구원 | 수직형 유기 박막 트랜지스터 및 제조방법 |
KR102569796B1 (ko) * | 2022-12-29 | 2023-08-25 | 한국표준과학연구원 | 역 구조의 수직형 발광 트랜지스터 및 그 제조방법 |
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WO2009077935A1 (en) * | 2007-12-14 | 2009-06-25 | Philips Intellectual Property & Standards Gmbh | Organic light-emitting device with adjustable charge carrier injection |
KR20100106478A (ko) * | 2007-12-14 | 2010-10-01 | 코닌클리즈케 필립스 일렉트로닉스 엔.브이. | 전하 캐리어 주입을 조정할 수 있는 유기 발광 디바이스 |
RU2472255C2 (ru) * | 2007-12-14 | 2013-01-10 | Конинклейке Филипс Электроникс Н.В. | Органическое светоизлучающее устройство с регулируемой инжекцией носителей заряда |
US8629865B2 (en) | 2007-12-14 | 2014-01-14 | Koninklijke Philips N.V. | Organic light-emitting device with adjustable charge carrier injection |
CN101897052B (zh) * | 2007-12-14 | 2014-05-28 | 皇家飞利浦电子股份有限公司 | 具有可调节电荷载流子注入的有机发光装置 |
TWI499355B (zh) * | 2007-12-14 | 2015-09-01 | Koninkl Philips Electronics Nv | 具有可調電荷載體注入的有機發光裝置 |
KR101588030B1 (ko) | 2007-12-14 | 2016-02-12 | 코닌클리케 필립스 엔.브이. | 전하 캐리어 주입을 조정할 수 있는 유기 발광 디바이스 |
US20120146011A1 (en) * | 2009-09-04 | 2012-06-14 | Ken-Ichi Nakayama | Current-Amplifying Transistor Device and Current-Amplifying, Light-Emitting Transistor Device |
US8927972B2 (en) * | 2009-09-04 | 2015-01-06 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Current-amplifying transistor device and current-amplifying, light-emitting transistor device |
WO2013161078A1 (ja) * | 2012-04-27 | 2013-10-31 | 大日精化工業株式会社 | トランジスタ素子 |
US9608217B2 (en) | 2012-04-27 | 2017-03-28 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Transistor element |
WO2022024239A1 (ja) * | 2020-07-29 | 2022-02-03 | シャープ株式会社 | 発光素子及び当該発光素子の駆動方法 |
Also Published As
Publication number | Publication date |
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CN101432883A (zh) | 2009-05-13 |
EP2009700A1 (en) | 2008-12-31 |
JP2007258308A (ja) | 2007-10-04 |
CN102130299A (zh) | 2011-07-20 |
EP2009700A4 (en) | 2011-09-07 |
US20090108749A1 (en) | 2009-04-30 |
US8120242B2 (en) | 2012-02-21 |
KR20090009818A (ko) | 2009-01-23 |
US20120112318A1 (en) | 2012-05-10 |
KR101255407B1 (ko) | 2013-04-17 |
TW200810111A (en) | 2008-02-16 |
CN101432883B (zh) | 2011-08-10 |
JP5182775B2 (ja) | 2013-04-17 |
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