WO2011034206A1 - 液体有機半導体材料 - Google Patents
液体有機半導体材料 Download PDFInfo
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- WO2011034206A1 WO2011034206A1 PCT/JP2010/066475 JP2010066475W WO2011034206A1 WO 2011034206 A1 WO2011034206 A1 WO 2011034206A1 JP 2010066475 W JP2010066475 W JP 2010066475W WO 2011034206 A1 WO2011034206 A1 WO 2011034206A1
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- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- 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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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]
- H10K50/14—Carrier transporting 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to an organic material exhibiting electronic conduction.
- the liquid organic semiconductor material of the present invention can be applied to a very wide range of fields. For example, new manufacturing methods and new forms of organic electronic devices such as optical sensors, organic EL, organic transistors, organic solar cells, and organic semiconductor memories. Can be realized.
- Organic semiconductor materials are materials that can be used for optical sensors, organic photosensitivity, organic EL, organic transistors, organic solar cells, organic semiconductor memories, and the like.
- organic semiconductor materials are formed on a substrate by dispersing the organic semiconductor material in an amorphous thin film, a polycrystalline thin film, or a polymer material prepared on the substrate by vacuum deposition or application by a solution.
- a thin film material or a material such as a single crystal of an organic semiconductor substance that is, a material that is solid in the driving temperature range of the device
- This is because in order to produce an organic electronic device, it is necessary to realize the function as an element by utilizing the electronic conductivity exhibited by the organic semiconductor. From this point of view, it has been considered necessary to use amorphous, polycrystalline, single crystal, or the like, which is a material that has hitherto been considered to be able to realize electronic conductivity.
- the conduction in the isotropic phase (liquid phase) of low-molecular non-liquid crystalline organic substances has been considered to be ionic conductivity because of its generally low viscosity. Reported only in special systems.
- One example is the confirmation of the conduction of high-energy electrons generated by irradiation of hydrocarbons such as methane and ethane with high-energy electron beams, X-rays, and short-wavelength light using the time-of-flight method (IEEE Transaction on Electrical Insulation vol.EI-19, No. 5, 390-418).
- This conduction is considered to be a conduction close to a free electron in which the generated high-energy electrons themselves are weakly constrained by molecules, and the mobility is extremely larger than that in a general organic solid, and is several tens of cm 2. Those exceeding / Vs are also known. Further, among the liquid crystal substances, in the isotropic phase of phthalocyanine liquid crystal, which is one of highly viscous discotic liquid crystals, conduction of electron conductivity has been confirmed by a time-of-flight method. (The 54th Joint Conference on Applied Physics (2007) Preliminary Proceedings, p.
- the present inventor has found a material that exhibits an isotropic phase and exhibits fluidity and electron and / or hole conduction.
- the organic semiconductor material of the present invention has been completed based on the above findings.
- an organic semiconductor material that exhibits a liquid state at an operating temperature is provided.
- the organic semiconductor material of the present invention is not particularly limited in the fields where organic semiconductor materials can be used conventionally (for example, photosensors, organic photoreceptors, organic EL, organic transistors, organic solar cells, organic semiconductor memories, etc.). It is possible to apply.
- an organic electronic device using electronic conduction in a liquid state which was difficult in the prior art, can be realized.
- New element structures, configurations, and functions can be realized.
- fabrication process technology that is not confined to conventional methods can be applied and selected, and is particularly effective for devices that require a large area. This is effective in expanding the application range of the device and reducing the manufacturing cost of the device.
- FIG. 1 It is a schematic cross section which shows the apparatus structure of the time of flight (Time-of-flight) type
- Example 6 is a graph showing an example of a transient photocurrent waveform obtained in Example 4; 10 is a graph showing an example of a transient photocurrent waveform obtained in Example 5. 10 is a graph showing an example of a transient photocurrent waveform obtained in Example 6.
- Example 7 it is a graph which shows an example of the result obtained by performing the dilution experiment by n-Hexane similar to Example 2.
- FIG. 8 it is a graph which shows an example of the result obtained by adding polystyrene to toluene and measuring a transient photocurrent.
- the present inventors have not only an ionic substance in which ionic conduction often observed is contained as an impurity, but also an impurity molecule that electrically forms a trap level, that is, a HOMO of a substance generally serving as a base. It has been clarified that ion conduction is induced by ionization of a material having LUMO or HOMO level between the level and the LUMO level. Based on these achievements, “general organic substances”, which are substances that have been considered to be ionic conduction, have been conventionally considered as the electrical conduction of liquids (isotropic liquids) of organic substances. It has been found that a conduction mechanism that satisfies the requirements described later can be confirmed, and that electronic conductivity can be utilized as an organic semiconductor.
- the present invention basically has three aspects. These are the selection of the substance, the purification of the substance, and the confirmation of the conduction mechanism.
- Substance selection In the selection of a substance, it is necessary to select an energy level at a level related to the transport of electric charges in the material from the viewpoints of device function, device driving conditions, selection of electrode material, device usage environment, and the like. For this reason, it is necessary to use an organic substance having at least one aromatic conjugated ⁇ -electron structure in the substance used as the semiconductor of the present invention.
- the “organic substance having at least one aromatic conjugated ⁇ -electron structure” that can be used in the present invention is not particularly limited. From the viewpoint of optical characteristics, for example, a substance having a light absorption peak ( ⁇ Max) in a wavelength region of 260 nm or more can be suitably used.
- a so-called aprotic substance can be suitably used.
- the semiconductor material of the present invention is in the form of a mixture, it is usually preferable that each component constituting the mixture is an aprotic.
- aprotic means, for example, a substance having no hydrogen atom in its chemical structural formula that reacts with metal Na to generate hydrogen gas. More practically, it refers to a substance that does not give stoichiometric hydrogen generation to metal Na in its “dry state” at the lower limit temperature of the operating temperature region of the semiconductor material (in the present invention, for example, ethanol Is not aprotic).
- the organic semiconductor material may be a single substance (for example, a compound) or may be in the form of a “mixture”.
- the form of the mixture is not particularly limited, but it is preferable that the mixture is uniform and does not undergo phase separation at the lower limit temperature in the operating temperature region of the semiconductor material.
- This mixture can be, for example, in the form of a solution or a gel.
- solution In the embodiment in which the organic semiconductor material is “solution”, the following solutes and solvents can be used.
- organic material that exhibits semiconductor properties.
- OPC organic semiconductor
- examples of such organic semiconductors include the following (for details of the organic semiconductor, reference is made to: Paul M. Borsenberger & David S. Weiss “Organic Photoreceptors for Xerography”, Marcel Dekker Inc., New York, Basel, Hong Kong, ISBN 0-8247-0173-9, 1998).
- the solvent for providing the organic semiconductor material of the present invention is not particularly limited.
- a “solvent”, for example, an aprotic solvent is preferably used.
- aprotic refers to a substance having no hydrogen atom in its chemical structural formula that reacts with metal Na to generate hydrogen gas. More practically, it refers to a substance that does not give stoichiometric hydrogen generation to metal Na in its “dry state” at the lower limit temperature of the operating temperature region of the semiconductor material (in the present invention, for example, ethanol Is not aprotic).
- the organic semiconductor material of the present invention exhibits “semiconductor” properties by observing conduction (electronic conduction) by at least one of holes or electrons by evaluation by the Time-of-flight method. .
- the operating temperature range is not particularly limited. From the viewpoint of use in a daily environment, this “operating temperature range” is preferably about ⁇ 60 ° C. to + 300 ° C., more preferably about ⁇ 200 ° C. to + 200 ° C. (particularly about ⁇ 20 ° C. to + 120 ° C.). .
- a liquid that does not show isotropic phase that is, orientation does not show polarizing properties under crossed Nicols when observed with a polarizing microscope, and therefore does not transmit light and becomes black.
- the sample is sandwiched between a slide glass and a cover glass, or injected into a liquid crystal cell, and heated as necessary, so that the liquid state of the sample is observed with a polarizing microscope, and light transmission is possible under crossed Nicols. What is necessary is just to confirm by being interrupted
- the “mobility” of the organic semiconductor material of the present invention is preferably 10 ⁇ 7 cm 2 / Vs or more, more preferably 10 ⁇ 6 cm 2 / Vs or more, particularly 10 ⁇ 5 cm 2 / Vs or more (in particular 10 ⁇ 4 cm 2 / Vs or more).
- “having fluidity” in the present invention means satisfying any of the following.
- a material under test eg, a substance that appears to have shape-retentivity temporarily
- the organic semiconductor material of the present invention can be distinguished from a mere solid by having substantially no shape retention in the operating temperature range.
- the impurities in question are only trapped electrically with respect to the ionic impurities and the substance. Needless to say, it is a substance that forms a level.
- the impurity when the impurity is a substance that does not electrically form a trap level with respect to the substance, it only acts as a diluent and does not significantly impair the basic characteristics of the organic semiconductor. That is, when the substance is used as an organic semiconductor, the chemical purity is not a problem, but the electrical purity due to the mixing of “electrically active impurities” that impair the function as the organic semiconductor is a problem.
- the concentration of electrically active impurities needs to be suppressed to 100 ppm or less. This is because when such an impurity concentration is high, electron conduction disappears and ion conduction due to ionization of impurities is induced.
- the degree of purification is surely better as the chemical purity is higher, but as mentioned above, especially when considering the use as a semiconductor, the chemical purity itself is not a problem and it is electrically active.
- the concentration of impurities becomes a problem. For this reason, it is necessary to make a judgment according to an evaluation method for electrically active impurities as described later.
- ionic conduction is conduction that occurs when ionized molecules and atoms (ions) move through a medium. Therefore, the mobility is governed by the ionic radius and the viscosity of the medium. The larger the ionic radius, the smaller the mobility, and the higher the viscosity, the smaller the mobility. This relationship is known as the Walden rule.
- the mobility of ionic conduction in a general organic liquid takes a value of 10 ⁇ 5 cm 2 / Vs or less.
- the electric field dependence is generally observed in the conduction by the electronic conduction of the liquid phase (isotropic phase), whereas the electric field dependence of the mobility is generally not seen in the ionic conduction.
- the activation energy of conduction by ionic conduction is generally considered to be due to temperature dependence of viscosity, and is different from the activation energy by electron conduction. Using this to compare the temperature dependence of viscosity with the temperature dependence of mobility is also a reference for judgment. However, these differences in characteristics only provide a guide and are not a strict confirmation method.
- a reliable and simple method to determine whether the conduction mechanism is electron conduction or ion conduction is to add a substance (diluent) that does not become an electronic trap and check the change in mobility before and after dilution. It is.
- the viscosity after dilution decreases and the intermolecular distance increases at the same time due to dilution.
- the conductivity before dilution is ionic conduction
- the mobility after dilution increases due to the decrease in viscosity.
- the conduction mechanism can be easily determined by selecting the diluent while paying attention to the viscosity, or by systematically measuring the change in mobility by changing the concentration of the diluent.
- the target substance has a low viscosity and a low-viscosity diluent is limited, and there is no significant difference in viscosity after dilution, use a highly viscous substance as the diluent.
- the conduction mechanism can also be confirmed.
- the mobility of both electron conduction and ionic conduction decreases simultaneously due to dilution.
- it is effective to add a polymer substance that can greatly increase the viscosity by adding a small amount, for example, 10 mol% or less, and the viscosity is large compared to the difference in average intermolecular distance when a diluent is added. Since it changes, it becomes easy to determine the difference in the conduction mechanism.
- the conductivity of the target substance in the liquid phase is evaluated by the Time-of-flight method to determine whether it is electron conductive or ionic conductive, and whether it can be used as an organic semiconductor. Can be determined.
- the mobility of a substance can be determined by measuring the Hall effect, measuring the transient photocurrent by the time-of-flight method, analyzing the characteristics of elements such as transistors.
- most of the organic semiconductor materials according to the present invention exhibit extremely small conductivity exhibited by an insulator, have a very low carrier concentration, and contact with an electrode is often not ohmic. For this reason, in order to measure the mobility of a material bulk, the measurement of the transient photocurrent by the time-of-flight method is the most effective means.
- the mobility of electron conduction in pure substances is larger than the mobility of ion conduction accompanying mass transfer.
- the signal appearing with purification can be judged to be due to electron conduction, and the signal seen in the slow time region can be judged to be ionic conduction due to impurities.
- the mobility of ionic conduction may increase, and it may be difficult to distinguish it from electronic conduction. Is high, and when only a single conduction signal is observed in the transient photocurrent waveform by the time-of-flight method from the beginning, the absolute value of the mobility, its temperature / electric field dependence, and the mobility change due to the diluent Therefore, it is necessary to judge the conduction mechanism comprehensively.
- the method of evaluating the change in mobility due to the addition of diluent is effective, and the movement before and after dilution when a substance with a higher viscosity than that of the target substance is added and when a small substance is added. It is particularly useful to examine the behavior of the degree.
- the conduction mechanism of the target substance it is possible to determine the conduction mechanism by the method described so far by proceeding purification and measuring the transient photocurrent waveform by Time-of-flight method.
- the impurity to be a trap is selected with reference to the HOMO and LUMO levels of the target substance, and the transient photocurrent of the sample to which the impurity is added is measured by the Time-of-flight method, By observing ion conduction due to the added impurity, the conduction mechanism before adding the impurity can be determined.
- the substance to be added as an impurity is selected so that the ionic radius is not extremely different from the target substance, and the concentration thereof does not become a diluent, for example, 0.01 to 1 mol. It is necessary to select a small amount of about%, and a small change in viscosity after addition. If measurement is performed under such conditions, although there is a difference in ion radius, the value of ion conduction in the target substance can be known, which is useful for determining the conduction mechanism.
- the conduction mechanism before the addition of the impurity is electron conduction or ionic conduction.
- the liquid phase (isotropic phase) of an organic substance that has been confirmed to have reduced impurities by purification and confirmed electronic conduction can be used as an organic semiconductor.
- it can be diluted with the above-mentioned diluent.
- the addition of a small amount can greatly increase the viscosity without causing a significant decrease in mobility, so it is extremely effective depending on the application, and also effective in suppressing ionic conduction. .
- the present invention it is fundamental that impurities that cause ionic conduction of organic substances are reduced and conduction suppresses ionic conduction to realize original electronic conduction.
- the purification of the substance is important in order to reduce impurities that cause ionic conduction, but the conduction mechanism of the purified substance is not ionic conduction but electronic conduction. It is essential to confirm that.
- the transient photocurrent measurement by the Time-of-flight method and the change in the transit time of the charge by the addition of a diluent capable of increasing or increasing the viscosity compared to the viscosity of the pure substance can be done by comparing with ion conductivity characteristics observed when a substance that electrically forms trap levels is doped with a very small amount of the substance, or by combining these.
- Measurement example 1 The present invention will be described while showing points to note in the measurement of transient photocurrent by the Time-of-flight method for distinguishing between electron conduction and ion conduction, the structure of the sample used for the measurement, and the waveform of the actually observed transient photocurrent. To do.
- the Time-of-flight method used for the evaluation in the present invention is that an electric field is applied to a measurement sample, a charge that is unevenly distributed in the vicinity of the electrode is generated, and a displacement current when the charge reaches the counter electrode is measured by an oscilloscope or the like.
- a method of measuring as a function of time Assuming that the electric charge moves toward the counter electrode at a constant speed, if the electric field across the sample is uniform and the conditions that the charge travel distance can be regarded as the thickness of the sample can be set, the electric charge from the current waveform to the counter electrode By estimating the time required to reach, that is, the transit time of the charge, the mobility in the sample can be determined from the thickness of the sample, the electric field strength, and the transit time of the charge.
- FIG. 1 shows an example of the structure of a sample that can be used for the above measurement and a measurement system.
- the thickness of the liquid crystal cell used for measurement has a great influence on the determination of mobility, and therefore it is necessary to obtain it accurately by using both measurement of capacitance and measurement of interference pattern by measurement of optical characteristics. It is also effective to perform measurement using the same cell. In addition, when applying a high electric field, attention must be paid to cell deformation.
- a sample liquid is injected into a cell in which two glass or quartz substrates with electrodes are fixed to a certain thickness via a spacer.
- care must be taken because impurities may be dissolved from a member used for manufacturing the spacer or cell and mixed into the sample.
- the thickness of the sample is generally about 10 times that of the cell.
- the electrode of the sample cell is irradiated with light, a translucent metal electrode prepared by vapor deposition or sputtering so that one side becomes translucent or a transparent electrode such as ITO is used as the electrode. In this case, care must be taken so that the blocking contact can suppress charge injection from the electrode to the sample.
- the measurement conditions corresponding to the measurement time region are selected by paying attention to the electric capacity of the measurement cell, the resistance value of the measurement sample, the connected resistance value, and the time constant of the measurement system.
- a voltage is applied to this sample, and pulse light irradiation is performed using a nitrogen pulse laser, a harmonic of a YAG laser, or the like to generate electric charges.
- the amount of charge generated by light irradiation must be 10% or less of the amount of charge determined by the geometric capacity of the sample and the applied voltage, and the influence of space charge must be suppressed.
- the light irradiation time must be short enough to be ignored compared to the charge travel time.
- pulsed light pulse width is several tens of ns or less
- a nitrogen laser or a YAG laser can be used as the light source.
- FIG. 1 shows an apparatus configuration for Time-of-flight measurement.
- FIG. 2 shows a schematic diagram of a typical transient photocurrent waveform to be measured.
- a typical photocurrent waveform measured by the Time-of-flight method generally, a measurement waveform of an organic liquid shows a shoulder indicating a running time when plotted on a normal scale as shown on the left side.
- organic semiconductor materials are different from inorganic semiconductor materials such as Si, and their definition is not strict. “Organic materials that can be used as electronic elements for functions generated by the flow of current through the substance” are organic It is called a semiconductor.
- organic semiconductor materials have a very low concentration of thermally generated carriers (holes and electrons) and are therefore classified as insulators in terms of conductivity.
- carriers can be transported, carriers can be introduced into organic semiconductors by using carriers generated by light irradiation or carrier injection from electrodes.
- a function that appears with recombination can be used to manufacture various electronic elements such as an optical sensor, an EL element, a transistor, and a solar cell. This basically does not depend on the form of a substance such as a solid or a liquid as long as electronic conduction occurs in the material.
- the characteristics of the liquid substance as an organic semiconductor can be ensured. Therefore, in accordance with the example described above, various electronic devices using the liquid organic semiconductor can be manufactured. is there.
- Example 1 The mobility is 10 ⁇ 3 cm 2 / Vs or higher and there is no need to suspect ion conduction
- Purified TPD N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-diphenyl] -4,4'-diamine)
- TPD N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-diphenyl] -4,4'-diamine
- the transient photocurrent was measured by the Time-of-flight method, and the mobility was determined from the charge travel time.
- the obtained mobility value is 4 ⁇ 10 ⁇ 3 cm 2 / Vs and 4 ⁇ 10 ⁇ 3 cm 2 / Vs at the measurement temperature of 150 ° C., respectively. Therefore, it can be judged that it is not ionic conduction but electronic conduction by holes and electrons.
- the mobility of positive charge and negative charge is 4 ⁇ 10 ⁇ 3 cm 2 / Vs and 9 ⁇ 10 ⁇ 5 cm 2 / Vs at 100 ° C., respectively. It can be determined that the electron conduction is caused by holes.
- Example 2 6- (4′-octylphenyl) -2-dodecyloxynaphthalene (8-PNP-O12) was injected into a glass cell provided with an ITO electrode (4 mm square) in an isotropic phase (liquid phase: sample thickness 15 ⁇ m), and nitrogen at 337 nm Laser pulse light (pulse width: 600 ps, 3 ⁇ J / pulse) was irradiated, and the transient photocurrent observed when +150 V and ⁇ 150 V were applied to the electrode on the light irradiation side was measured with a digital oscilloscope. In the waveform (black) shown in FIG.
- FIG. 5 shows changes in the transient photocurrent waveform when the n-octadecane concentration was changed from 16 mol% to 42 mol% (green: 42 mol%, red; 30 mol%, blue: 16 mol%).
- FIG. 4 shows a plot of the mobility obtained from the two travel times in that case by the concentration of n-octadecane. In the change due to dilution of the two mobilities of 8-PNP-O12 in FIG.
- black represents the mobility obtained from the fast charge travel time
- red Represents the mobility obtained from the travel time of the slow charge.
- the electron conduction shown in black decreases with dilution, and the mobility due to ionic conduction shown in red increases with dilution.
- Example 3 Similarly to Example 2, 2-phenylnaphthalene was injected into a glass cell in which an ITO electrode (4 mm square) was placed in an isotropic phase (liquid phase: sample thickness: 16.31 ⁇ m), and a nitrogen laser pulse of 337 nm at 105 ° C.
- Light pulse width: 600 ps, 3 ⁇ J / pulse
- the transient photocurrent waveform is shown in FIG. In the positive charge waveform, there is a shoulder indicating a fast one charge travel, and in the negative charge travel, there are two shoulders corresponding to two different travel times.
- Example 2 As in Example 2, a hole from dilution experiments, each as electron mobility, 8.9 ⁇ 10 -4 cm 2 /Vs,8.8 ⁇ 10 -4 cm 2 / Vs, a mobility of negative ions 2.1 ⁇ 10 ⁇ 5 cm 2 / Vs.
- Example 4 As in Example 2, ⁇ , ⁇ ′-dioctylterthiophene was injected into a glass cell in which an isotropic phase (liquid phase: sample thickness: 16.45 ⁇ m) and an ITO electrode (4 mm square) was placed, and at 100 ° C. Nitrogen laser pulse light (pulse width: 600 ps, 3 ⁇ J / pulse) is irradiated, and the transient photocurrent observed when +15 to 50 V and -15 V to 50 V are applied to the electrode on the light irradiation side is measured with a digital oscilloscope. As a result, the transient photocurrent waveform shown in FIG. 6 was obtained. Two shoulders corresponding to two different travel times were found in the transient photocurrent waveforms of positive charge and negative charge, respectively.
- Nitrogen laser pulse light pulse width: 600 ps, 3 ⁇ J / pulse
- Example 2 As in Example 2, from the dilution experiment, the mobility of holes and electrons was 9.3 ⁇ 10 ⁇ 5 cm 2 / Vs, respectively, and the mobility of positive and negative ions was 2.0 ⁇ 10 ⁇ 5 respectively. It was determined to be cm 2 / Vs, 2.9 ⁇ 10 ⁇ 5 cm 2 / Vs.
- Example 5 As in Example 2, ⁇ , ⁇ ′-dihexylcycloterthiophene was injected into a glass cell in which an ITO electrode (4 mm square) was placed in the isotropic phase (liquid phase: sample thickness: 13.86 ⁇ m), as in Example 2. Digital oscilloscope shows transient photocurrent observed when nitrogen laser pulse light (pulse width: 600 ps) is irradiated at 200 ° C. and +15 to 50 V and ⁇ 15 V to 50 V are applied to the light irradiation side electrode. As a result of measurement, a transient photocurrent waveform shown in FIG. 7 was obtained. The positive charge waveform showed two shoulders corresponding to two different travel times, and the negative charge showed one shoulder.
- nitrogen laser pulse light pulse width: 600 ps
- Example 6 Similarly to Example 2, ⁇ , ⁇ ′-didodecyloxy-2-methylphenyl (12O-TPMe-O12) was placed in a glass cell in which an ITO electrode (4 mm square) was placed in an isotropic phase (liquid phase: sample thickness: 10 ⁇ m). Injected, irradiated with 337 nm nitrogen laser pulse light (pulse width: 600 ps) at 170 ° C., and transient photocurrents observed when +40 to 100 V and ⁇ 40 V to 100 V were applied to the electrode on the light irradiation side. When measurement was performed with a digital oscilloscope, the transient photocurrent waveform shown in FIG. 8 was obtained. Each positive charge waveform had a shoulder corresponding to one running time.
- Example 7 As in Example 2, Toluene was injected at room temperature into a quartz cell (liquid phase: sample thickness: 23.51 ⁇ m) provided with an ITO electrode (4 mm square), and at 23 ° C., pulsed light from a 260 nm YAG laser was injected. Irradiation was performed, and the transient photocurrent observed when +200 V and ⁇ 200 V were applied to the electrode on the light irradiation side was measured with a digital oscilloscope, and the transient photocurrent waveform shown in FIG. 9 was obtained. The shoulder corresponding to one travel time was seen in the waveform of positive and negative charges, respectively. When a dilution experiment with n-hexane was performed in the same manner as in Example 2, a slight decrease in mobility was observed as shown in FIG.
- Example 8 Since the change in Example 7 is not clear, a styrene monomer that has been sufficiently purified is thermally polymerized without a catalyst, the resulting polystyrene is added to toluene, and the transient photocurrent is measured in the same manner. The mobility was determined as shown in
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Abstract
Description
本発明の他の目的は、液体で電子デバイスを実現できる、新しい有機半導体材料を提供することにある。
本発明の有機半導体材料は、上記知見に基づいて完成されたものである。
本発明者らの知見によれば、本発明の有機半導体材料が電子および/又はホール伝導性を有するメカニズムは、以下のように推定されている。
物質の選択では、デバイス機能、デバイスの駆動条件、電極材料の選択、デバイスの使用環境等の点から、材料中の電荷の輸送にかかわる準位のエネルギーレベルを選択することが必要となる。このため、本発明の半導体として用いる物質には、少なくとも一つの芳香族共役π−電子系を構造に有する有機物質を用いる必要がある。
本発明において使用可能な「少なくとも一つの芳香族共役π−電子系を構造に有する有機物質」は、特に制限されない。光学的特性の点からは、例えば、260nm以上の波長領域に光吸収ピーク(εMax)を有する物質が好適に使用可能である。
本発明において、有機半導体材料は単一物質(例えば、化合物)であってもよく、また「混合物」の形態であっても良い。該混合物の形態は特に制限されないが、半導体材料の作動温度領域の下限温度で、均一で相分離をしないものであることが好ましい。この混合物は、例えば、溶液やゲルの形態であることができる。
有機半導体材料が「溶液」である態様においては、下記の溶質および溶媒が使用可能である。
半導体の性質を示す有機材料である限り、特に制限されない。例えば、電子写真分野において、従来より有機半導体(いわゆる「OPC」)感光体材料として使用されて来た種々の材料が使用可能である。このような有機半導体の例としては、以下のものを挙げることができる(該有機半導体の詳細に関しては、必要に応じて、文献:Paul M.Borsenberger & David S.Weiss″Organic Photorecepters for Xerography″,Marcel Dekker Inc.,New York,Basel,Hongkong,ISBN 0−8247−0173−9,1998を参照することができる)。
上記溶質との組合せにおいて、本発明の有機半導体材料を与える溶媒は、特に制限されない。このような「溶媒」としては、例えば、アプロティックな溶媒を用いることが好ましい。本発明において、アプロティックとは、その化学構造式中に、金属Naと反応して水素ガスを発生させるような水素原子を有しない物質を言う。より実際的には、半導体材料の作動温度領域の下限温度で、その「乾燥状態」において金属Naに対して化学量論的な水素発生を与えない物質を言う(本発明においては、例えば、エタノールはアプロティックではない)。
本発明の有機半導体材料が「半導体」の性質を示すことは、Time−of−flight法による評価によって、少なくとも正孔または電子のいずれか一方による伝導(電子性伝導)を観測することによって確認できる。
本発明において、作動温度領域は特に制限されない。日常的な環境下における使用の点からは、この「作動温度領域」は−60℃~+300℃程度が好ましく、更には−200℃~+200℃程度(特に−20℃~+120℃程度)が好ましい。
本発明の有機半導体材料が「等方相」であることは、以下の方法によって確認することができる。
本発明の有機半導体材料が「電子および/又はホール伝導」を示すことは、例えば、後述する「希釈法」による、移動度の測定によって確認することができる。
本発明の有機半導体材料の「移動度」は、10−7cm2/Vs以上であることが好ましく、更には10−6cm2/Vs以上、特に10−5cm2/Vs以上(とりわけ10−4cm2/Vs以上)であることが好ましい。
本発明の有機半導体材料が「流動性」を有することは、以下の方法によって確認することができる。本発明において、この「流動性」は、完全な流動性でなくても良い(例えば、コールタールのように、ドロドロした材料でも使用可能である)。
(a)保形性(shape−retaining property)を有しないこと;または
(b)被試験材料(例えば、一時的に保形性を有するように見える物質)を、底辺が1×1cm(w×d)、高さ(h)が10cmの直方体状に成形して、常温・常圧の状態で1週間放置する。この場合に、高さが9cm以下(すなわち、当初の高さとの相対比で0.9以下)になっていた場合に、「流動性あり」(すなわち、実質的に保形性を有しない)と判定する。この流動性は、作動温度領域の下限温度で測定する。
このように、本発明の有機半導体材料は、その作動温度領域において、実質的に保形性を有しないことによって、単なる固体と区別することができる。
物質の高純度化では、イオン性不純物の低減はもとより、当該物質に対して、電気的にトラップ準位を形成する不純物分子の低減を図ることが不可欠である。すなわち、一般には母体となる物質のHOMO準位とLUMO準位の間に、電子の輸送を目的とする場合はLUMO準位、正孔の輸送を目的とする場合はHOMO準位を有する物質(不純物分子)の低減を図ることが不可欠である。一般に、不純物分子の濃度は100ppm濃度以下にする必要があり、通常の機器分析を用いても構造決定はもとより、検出することすら困難な場合が多い。
次に、本発明に関わるもう一つの重要な柱となる有機液体中の電気的に活性な不純物の評価方法について述べる。
一方、有機物の非結晶性物質における電子伝導は電荷が分子から分子へ渡り歩くホッピング伝導であるため、ホッピングのサイトとなる分子間距離とサイト間のエネルギー準位の違いが移動度を支配し、一般に純物質の場合、移動度は10−4cm2/Vs以上の値となる場合が多い。この値は、大きなダイポールをもつ物質の構造や微量の浅いトラップ準位を形成する不純物が含まれる場合は、10−5cm2/Vs以下の値となる場合もある。したがって、移動度の絶対値が10−4cm2/Vs以下である場合はその値から伝導機構を判定することは一般に困難である。また、物質中に含まれる不純物の濃度によっては、電子伝導とイオン伝導の共存が見られる場合もある。いずれにしても、この伝導機構の違いはTime−of−flight法による過渡光電流測定と以下に述べる判定法によって確認することが不可欠となる。
有機物の液体の電子伝導とイオン伝導を区別するのに有効な方法の一つは、移動度の値とその電場、温度依存性から判断することである。移動度の測定温度が200℃以下の場合、10−3cm2/Vs以上の移動度は電子伝導である可能性が極めて高い。移動度が10−4cm2/Vsのオーダーの場合は電子伝導の可能性は高いと考えられるが、確認が必要となる。
伝導機構が電子伝導であるか、イオン伝導であるかを判定する確実で簡便な方法は、電子的にトラップとならない物質(希釈剤)を添加し、希釈前後の移動度の変化を確認することである。
一般に、対象とする物質の精製を進めていくと、トラップとなる不純物の濃度は逐次、減少して行く。Time−of−flight法により観測される過渡光電流波形は、不純物の濃度が高い場合、イオン伝導に基づくシグナルのみが観測され、精製が進むと電子伝導を示すシグナルが見え始め、イオン伝導によるシグナルとが同時に観測されるようになる。過渡光電流波形に電子伝導とイオン伝導の二つの伝導に基づくシグナルが観測される場合、電子伝導とイオン伝導の伝導に対する寄与は、過渡光電流の電子伝導と過渡光電流の波形分離を行い、それぞれの電流の時間による積分値から電荷量を求めることによって評価することができる(このような測定方法の詳細に関しては、必要に応じて、文献:Chemical Physics Letters 397(2004)319−323;Japanese Journal of Applied Physics Vol.44,No.6A,(2005),pp.3764−3768;J.Phys.Chem.B 2005,109,22120−22125;Physical Review B 72,193203(2005);Journal of Applied Physics,102,(2007)093718を参照することができる)。更に精製を進めると、最終的にはイオン伝導に基づくシグナルは消え、電子伝導を示すシグナルのみが観測されるようになる。
本発明において使用可能な「移動度測定方法」を、以下に示す。
一般に純物質の電子伝導の移動度は、物質移動を伴うイオン伝導の移動度より大きいため、精製に伴い、過渡光電流波形にこのような振る舞いが観測される場合は、走行時間の早い領域に精製に伴って現れるシグナルは電子伝導によるものと判断でき、遅い時間領域に見られるシグナルは不純物によるイオン伝導と判断することができる。
電子伝導とイオン伝導を区別するためのTime−of−flight法による過渡光電流の測定における注意点、測定に用いる試料の構造、実際に観測される過渡光電流の波形を示しながら本発明を説明する。
有機半導体材料とは、一般に、Siなどの無機半導体材料と異なり、その定義は厳密ではなく、「その物質中を電流が流れることによって生じる機能を電子素子として利用することができる有機材料」を有機半導体と呼んでいる。
(移動度が10−3cm2/Vs以上でイオン伝導を疑う必要のないもの)
液晶セルに精製したTPD(N,N′−diphenyl−N,N′−bis(3−methylphenyl)−[1,1′−diphenyl]−4,4′−diamine)を等方相温度で注入し、上記、Time−of−flight法で過渡光電流を測定し、電荷の走行時間から移動度を決定した。得られた移動度の値は、測定温度150℃において、正電荷、負電荷の値は、それぞれ、4×10−3cm2/Vs、4×10−3cm2/Vsであり、その値の大きさから、イオン伝導ではなく、正孔、電子による電子性の伝導と判断できる。
ITO電極(4mm角)を設置したガラスセルに6−(4’−octylphenyl)−2−dodecyloxynaphtalene(8−PNP−O12)を等方相(液体相:試料厚 15μm)において注入し、337nmの窒素レーザーパルス光(パルス幅:600ps、3μJ/パルス)の照射を行い、光照射側の電極に+150V、−150Vを印加し際に観測される過渡光電流をデジタルオシロスコープにより測定を行った。図5(左:正電荷の過渡光電流波形、右:負電荷による過渡光電流波形)に示す波形(黒色)には異なる時間領域に走行時間に対応する二つの肩が見られた。この伝導を明らかにするためn−octadecaneを用いた希釈実験を行った。n−octadecaneの濃度を16モル%から42モル%まで変えたときの過渡光電流波形の変化の様子を図5(緑:42モル%、赤;30モル%、青:16モル%)に示す。
実施例2と同様に、2−Phenylnaphthaleneを等方相(液体相:試料厚:16.31μm)においてITO電極(4mm角)を設置したガラスセルに注入し、105℃において、337nmの窒素レーザーパルス光(パルス幅:600ps、3μJ/パルス)の照射を行い、光照射側の電極に+10~100V、−10V~100Vを印加した際に観測される過渡光電流をデジタルオシロスコープにより測定を行ったおける過渡光電流波形を図5に示す。正電荷の波形には早いひとつ電荷の走行を示す肩が見られ、負の電荷の走行には二つの異なる走行時間に対応した「二つの肩」が見られる。
実施例2と同様に、ω,ω’−dioctylterthiopheneを等方相(液体相:試料厚:16.45μm)にITO電極(4mm角)を設置したガラスセルに注入し、100℃において、337nmの窒素レーザーパルス光(パルス幅:600ps、3μJ/パルス)の照射を行い、光照射側の電極に+15~50V、−15V~50Vを印加した際に観測される過渡光電流をデジタルオシロスコープにより測定を行ったところ、図6に示す過渡光電流波形が得られた。正電荷、および、負電荷の過渡光電流波形には、それぞれ二つの異なる走行時間に対応した二つの肩が見られた。
実施例2と同様に、ω,ω’−dihexylcyquaterthiopheneを実施例2と同様に、等方相(液体相:試料厚:13.86μm)においてITO電極(4mm角)を設置したガラスセルに注入し、200℃において、337nmの窒素レーザーパルス光(パルス幅:600ps)の照射を行い、光照射側の電極に+15~50V、−15V~50Vを印加した際に観測される過渡光電流をデジタルオシロスコープにより測定を行ったところ、図7に示す過渡光電流波形が得られた。正電荷の波形には二つの異なる走行時間に対応した二つの肩が見られ、負電荷の走行には一つの肩が見られた。
実施例2と同様に、ω,ω’−didodecyloxy−2−methylterphenyl(12O−TPMe−O12)を等方相(液体相:試料厚:10μm)においてITO電極(4mm角)を設置したガラスセルに注入し、170℃において、337nmの窒素レーザーパルス光(パルス幅:600ps)の照射を行い、光照射側の電極に+40~100V、−40V~100Vを印加した際に観測される過渡光電流をデジタルオシロスコープにより測定を行ったところ、図8に示す過渡光電流波形が得られた。正電荷の波形にはそれぞれひとつの走行時間に対応した肩が見られた。
実施例2と同様に、Tolueneを室温においてITO電極(4mm角)を設置した石英セル(液体相:試料厚:23.51μm)に注入し、23℃において、260nmのYAGレーザからのパルス光の照射を行い、光照射側の電極に+200V、−200Vを印加した際に観測される過渡光電流をデジタルオシロスコープにより測定を行ったところ、図9に示す過渡光電流波形が得られた。正、および、負電荷の波形にはそれぞれひとつの走行時間に対応した肩が見られた。実施例2と同様に、n−Hexaneによる希釈実験を行ったところ、わずかではあるが、図9に示すように、移動度の低下が見られた。
上記実施例7における変化は明確ではないため、精製を充分に行ったスチレンモノマーを無触媒で熱重合し、得られたポリスチレンをトルエンに加え、同様に、過渡光電流の測定を行い、図10に示すように移動度を決定した。
2 電極
3 スペーサ
4 試料
5 電源(極性は正、負)
6 外部抵抗
7 デジタルオシロスコープ
Claims (6)
- 少なくとも一つの芳香族共役π−電子系を有する有機物質を含む有機半導体材料であって;且つ、
作動温度領域において、等方相を示し、電子および/又はホール伝導を示し、且つ、流動性を有することを特徴とする有機半導体材料。 - 前記等方相が、偏光顕微鏡によるクロスニコル下での薄層試料の観察によって確認される請求項1に記載の有機半導体材料。
- 10−7cm2/Vs以上の電子および/又はホールの移動度を有する請求項1または2に記載の有機半導体材料。
- 作動温度領域において、実質的に保形性(shape−retaining property)を有しない請求項1~3のいずれかに記載の有機半導体材料。
- 前記有機半導体材料が、混合物の形態を有する請求項1~4のいずれかに記載の有機半導体材料。
- 前記有機半導体材料が、溶液の形態を有する請求項5に記載の有機半導体材料。
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JP2011531997A JP5681109B2 (ja) | 2009-09-16 | 2010-09-15 | 液体有機半導体材料 |
US13/496,451 US20120175604A1 (en) | 2009-09-16 | 2010-09-15 | Liquid organic semiconductor material |
KR1020157025354A KR20150110826A (ko) | 2009-09-16 | 2010-09-15 | 액체 유기 반도체 재료 |
US16/155,444 US20190044082A1 (en) | 2009-09-16 | 2018-10-09 | Liquid organic semiconductor material |
US17/135,694 US20210119165A1 (en) | 2009-09-16 | 2020-12-28 | Liquid organic semiconductor material |
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US16/155,444 Division US20190044082A1 (en) | 2009-09-16 | 2018-10-09 | Liquid organic semiconductor material |
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JP2015502549A (ja) * | 2011-12-23 | 2015-01-22 | サノフィ−アベンティス・ドイチュラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | 薬剤の包装のためのセンサ装置 |
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TW201426777A (zh) * | 2012-12-22 | 2014-07-01 | Univ Nat Pingtung Sci & Tech | 以磁力控制大型超級電容池充放電之方法及該超級電容池 |
CN107076657B (zh) * | 2015-01-29 | 2020-03-31 | 株式会社Lg化学 | 用于测量聚合物膜的金属离子渗透率的方法和装置 |
CN107076701B (zh) * | 2015-01-29 | 2019-05-14 | 株式会社Lg化学 | 用于测量聚合物膜的金属离子渗透率的方法和用于测量聚合物膜的金属离子渗透率的装置 |
WO2019167186A1 (ja) | 2018-02-28 | 2019-09-06 | 株式会社東陽テクニカ | 測定容器、測定システム及び測定方法 |
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JP2005285445A (ja) * | 2004-03-29 | 2005-10-13 | Dainippon Printing Co Ltd | 液晶性有機半導体材料およびそれを用いた有機半導体構造物 |
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JP4997688B2 (ja) * | 2003-08-19 | 2012-08-08 | セイコーエプソン株式会社 | 電極、薄膜トランジスタ、電子回路、表示装置および電子機器 |
JP2005294587A (ja) * | 2004-03-31 | 2005-10-20 | Dainippon Printing Co Ltd | 電荷輸送層の形成方法並びに有機半導体構造物及びその製造方法 |
JP4774679B2 (ja) * | 2004-03-31 | 2011-09-14 | 大日本印刷株式会社 | 有機半導体装置 |
US7569415B2 (en) * | 2005-09-30 | 2009-08-04 | Alcatel-Lucent Usa Inc. | Liquid phase fabrication of active devices including organic semiconductors |
US20070075308A1 (en) * | 2005-09-30 | 2007-04-05 | Florian Dotz | Active semiconductor devices |
EP1837929A1 (en) * | 2006-03-23 | 2007-09-26 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Liquid Charge Transporting Material |
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JP5913644B2 (ja) | 2016-04-27 |
JPWO2011034206A1 (ja) | 2013-02-14 |
KR20120081093A (ko) | 2012-07-18 |
JP5681109B2 (ja) | 2015-03-04 |
US20210119165A1 (en) | 2021-04-22 |
KR20150110826A (ko) | 2015-10-02 |
US20190044082A1 (en) | 2019-02-07 |
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