WO2010061595A1 - 有機半導体素子 - Google Patents
有機半導体素子 Download PDFInfo
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- WO2010061595A1 WO2010061595A1 PCT/JP2009/006360 JP2009006360W WO2010061595A1 WO 2010061595 A1 WO2010061595 A1 WO 2010061595A1 JP 2009006360 W JP2009006360 W JP 2009006360W WO 2010061595 A1 WO2010061595 A1 WO 2010061595A1
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- organic
- organic semiconductor
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- semiconductor element
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- H—ELECTRICITY
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- 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
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/14—Carrier transporting layers
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- 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]
- H10K50/17—Carrier injection layers
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- 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
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- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/917—Electroluminescent
Definitions
- the present invention relates to an organic semiconductor element containing a neutral radical compound having a ⁇ electron system.
- Organic semiconductor elements include types such as organic solar cells, organic electroluminescence elements (organic EL elements), and organic field effect transistors.
- organic EL elements organic electroluminescence elements
- organic field effect transistors Conventionally, various compounds such as phthalocyanine, pentacene, and oligothiophene have been developed as organic compounds that become p-type semiconductors that transport holes in organic semiconductor elements.
- n-type semiconductors responsible for electron transport are limited to fullerene, perylenetetracarboxylic acid diimide, perfluoropentacene, etc., and their development research is delayed compared to p-type. This is thought to be due to the instability of the organic molecular anion body (to be exact, the radical anion species) generated by the closed-shell organic molecule accepting one electron.
- Patent Document 1 Although not in the field of organic semiconductor elements, regarding secondary batteries, those using an organic compound having a phenalenyl skeleton or a derivative thereof as an active material contained in a positive electrode are known (see Patent Document 1).
- an example of an organic compound having a phenalenyl skeleton is a trioxotriangulene (TOT) derivative (see the formula (a-3) in [Chemical Formula 4] cited in Patent Document 1). ).
- TOT trioxotriangulene
- Patent Document 1 does not suggest that the organic compound is used as a semiconductor layer of an organic semiconductor element to function as an organic semiconductor element.
- JP 2007-227186 A (molecular crystalline secondary battery)
- An object of this invention is to provide an organic-semiconductor element provided with the semiconductor layer which has a light absorption performance in an infrared region by having a narrow band gap, and high carrier mobility.
- the organic semiconductor element of the present invention is an organic semiconductor element provided with at least one semiconductor layer, wherein the semiconductor layer is a trioxotriangulene (TOT) derivative, which is a neutral radical compound represented by the following [Chemical Formula 2]. It is contained as a material.
- TOT trioxotriangulene
- neutral radical compound refers to an electrically neutral organic compound having unpaired electrons.
- semiconductor material refers to a material that is contained in a semiconductor layer and provides semiconductor characteristics to the semiconductor layer.
- the semiconductor layer may have a crystal arrangement in which the neutral radical compound of [Chemical Formula 2] overlaps in a columnar shape.
- the TOT derivative is a neutral radical compound having a condensed polycyclic molecular structure having a huge ⁇ -electron system, and electron spins are widely delocalized throughout the molecular skeleton.
- spin localization refers to a structure in which electron spins are localized in a part of the molecular skeleton
- spin delocalization refers to a structure in which electron spins are widely distributed throughout the molecular skeleton.
- FIGS. 1 (a) to 1 (c) the structures of tert-butyl compounds in which R in [Chemical Formula 1] is a t-butyl group are shown in FIGS. 1 (a) to 1 (c).
- FIG. 1A is a structural diagram showing a spin-localized molecular structure of a trioxotriangulene (TOT) derivative having three tert-butyl groups.
- FIG. 1B is a structural diagram showing a “spin delocalized” molecular structure reflecting an actual electronic structure.
- FIG. 1C is a schematic diagram showing the spin density distribution obtained from the quantum chemical calculation. A dark sphere large sphere indicates a positive spin density distribution, and a light sphere small sphere indicates a negative spin density distribution. .
- the crystal of the TOT derivative is obtained as a black hexagonal prism crystal.
- FIGS. 2 (a) to 2 (d) crystal structures obtained by X-ray crystal analysis of the tert-butyl compound are shown in FIGS. 2 (a) to 2 (d).
- FIG. 2A is a diagram showing the dimer structure ( ⁇ -dimer) of the TOT derivative, and also shows the state of the electron distribution of SOMO (Singly Occupied Molecular Orbital).
- FIG. 2 (b) is a diagram showing that ⁇ -dimers are stacked in a columnar shape (columnar shape) in a one-dimensional direction (the direction of the arrow in FIG.
- FIG. 2 (c) is a schematic view showing the crystal structure of a TOT derivative in which a large number of ⁇ -dimers are stacked (the tert-butyl group is omitted) as an electron cloud spread.
- FIG. 2D shows the appearance of a single crystal.
- the TOT derivative crystal forms ⁇ -dimers so that positions where the SOMO coefficient is large (position where the positive electron spin density distribution is large) overlap each other.
- the dimer has a short non-bonding distance (2.89-3.36 A), as shown in FIG.
- another ⁇ -dimer is laminated on the top and bottom of this ⁇ -dimer at a distance of 3.34-3.64A, and has a one-dimensional column structure (column structure) (FIGS. 2B and 2C). )reference).
- the decomposition temperature of the TOT derivative is 300 degrees Celsius or higher even in the air, high stability comparable to that of closed shell molecules is obtained, and the durability and life as an organic semiconductor element are excellent.
- an organic semiconductor element since it has a large carrier mobility of 0.01 to 20 cm 2 / Vs, an excellent n-type semiconductor material is provided by using a TOT derivative by utilizing the magnitude of this carrier mobility. can do.
- a neutral radical compound composed of a TOT derivative is used as the organic semiconductor material. Therefore, an organic thin film solar cell or a hybrid solar cell that photoelectrically converts light in the infrared region, A stable organic semiconductor element that can be applied to a high organic EL element, an organic transistor having a high operating frequency, and the like can be suitably obtained.
- FIG. 1A is a structural diagram showing a spin-localized molecular structure of a trioxotriangulene (TOT) derivative having three tert-butyl groups.
- FIG. 1B is a structural diagram showing a “spin delocalized” molecular structure reflecting an actual electronic structure.
- FIG. 1 (c) is a schematic diagram showing the spin density distribution obtained from the quantum chemical calculation.
- FIG. 2 (a) is a diagram showing a dimer structure ( ⁇ -dimer) obtained by laminating two TOT derivatives obtained by X-ray crystallography
- FIG. 2 (b) is a diagram showing the ⁇ -dimer of the TOT derivative.
- FIG. 2 (c) is a diagram showing the crystal structure of a TOT derivative in which a large number of ⁇ -dimers are stacked as an electron cloud spread (the tert-butyl group is omitted).
- FIG. 2D shows the appearance of a single crystal.
- 1 is a schematic diagram of an organic thin-film solar cell 1 in which a TOT derivative is incorporated in a semiconductor layer 14.
- FIG. 3 is a schematic diagram of a tandem hybrid solar battery in which a TOT derivative is incorporated in a semiconductor layer of an organic thin film cell 21.
- FIG. 3 is a schematic diagram of an organic EL element in which a TOT derivative is incorporated in an electron transport layer 36 and an electron injection layer 37.
- FIG. 4 is a schematic diagram of an organic transistor (bottom contact type) in which a TOT derivative is incorporated in a semiconductor layer 46.
- FIG. 4 is a schematic diagram of an organic transistor (top contact type) in which a TOT derivative is incorporated in a semiconductor layer 46.
- FIG. It is a figure which shows the electronic absorption spectrum of the measured TOT derivative
- a schematic diagram and a measurement circuit diagram of a photocurrent measuring cell in which a TOT derivative is incorporated in an organic thin film layer 49 are shown.
- 4 is a graph showing the results of measuring the photoconductivity of TOT derivative-P3HT.
- Organic thin film solar cell By using a TOT derivative that has a narrow SOMO-LUMO energy gap and absorbs a wide range of long-wavelength light reaching the infrared region as an n-type semiconductor layer for organic thin-film solar cells, light in the infrared region is used as power. An organic thin film solar cell to be converted can be produced.
- the TOT derivative can arbitrarily control the level of frontier orbitals by molecular design such as changing the structure of the substituent.
- the characteristics required for the pn junction layer of the solar cell such as the work function of the electrode (Fermi level), the level of the valence band (HOMO, SOMO) and the conduction band (LUMO) of the semiconductor are precisely tuned. It becomes possible.
- FIG. 3 is a schematic cross-sectional view of an organic thin film solar cell using a TOT derivative as an n-type semiconductor layer.
- the organic thin film solar cell 1 is formed by laminating a transparent electrode layer 12 such as tin dioxide (SnO 2 ), a p-type semiconductor layer 13, an n-type semiconductor layer 14, and a reflective electrode layer 15 in this order on a transparent glass substrate 11. ing.
- a buffer layer may be provided between the transparent electrode layer 12 and the p-type semiconductor layer 13, and a buffer layer may be provided between the n-type semiconductor layer 14 and the reflective electrode layer 15.
- the n-type semiconductor and the p-type semiconductor do not necessarily have a stacked structure, and may have a bulk heterojunction structure.
- an i (intrinsic semiconductor) layer may be inserted between the p-type semiconductor layer 13 and the n-type semiconductor layer 14.
- a mixed layer of a p-type semiconductor and an n-type semiconductor may be used.
- an organic thin film solar cell having only the i layer using the mixed layer without the p-type semiconductor layer 13 and the n-type semiconductor layer 14 can be realized.
- the TOT derivative acts as an n-type semiconductor, it needs to be combined with a p-type semiconductor in order to obtain a heterojunction solar cell.
- pentacene, tetrathiafulvalene, thienothiophene, polythiophene, polyphenylene vinylene, and the like can be exemplified as the optimum p-type semiconductor.
- An example of the manufacturing method will be briefly described.
- the transparent electrode layer 12 is deposited on the transparent glass substrate 11 by sputtering or the like.
- a p-type semiconductor layer 13 is then formed by vacuum deposition or coating, and an n-type semiconductor layer 14 is formed on the p-type semiconductor layer 13 by vacuum deposition or coating.
- the optimum conditions are set while adjusting parameters such as the temperature of the deposition source and the substrate, the temperature rise profile, the deposition time, and the distance between the deposition source and the substrate.
- the optimum conditions are set by adjusting parameters such as the solvent type, concentration, temperature, and drying conditions of the solution to be coated.
- the organic thin-film solar cell 1 manufactured with the above-described configuration can generate a short-circuit current of 7 mA / cm 2 or more by irradiation with infrared light having a wavelength of 0.8 ⁇ m or more (AM1.5; 1 kW / m 2 light source). It is expected to be. Furthermore, a hybrid (tandem) with a silicon solar cell is also possible.
- FIG. 4 is a diagram schematically showing a cross section of the hybrid solar cell.
- the hybrid solar cell 2 includes a transparent electrode layer 17 such as tin dioxide (SnO 2 ) on a transparent glass substrate 16 and a top cell (“cell” is 1). 18), a bottom cell 19 formed of polycrystalline silicon is laminated, and an organic thin film cell 21 using the TOT derivative of the present invention is formed on the bottom cell 19 via a transparent electrode layer 20, The reflective electrode layer 22 is laminated on the top.
- the structure of the organic thin film cell 21 is a laminate of the p-type semiconductor layer 13 and the n-type semiconductor layer 14 as shown in FIG. As described above, it is not necessarily a stacked body, and may have a bulk heterojunction structure, and may include a buffer layer and an i layer.
- Silicon-based solar cells use sunlight in the ultraviolet / visible region shorter than 800 nm, and contribute little to photoelectric conversion in the near infrared to infrared region. Therefore, as shown in FIG. 4, by combining the organic thin film cell 21 using the TOT derivative on the back side of the silicon cells 18 and 19, the light in the infrared region passing through the silicon cell can be changed to a current. It becomes possible. Thereby, the conversion efficiency of the conventional silicon solar cell can be further improved.
- the organic EL element 3 includes a transparent electrode layer 32, a hole injection layer 33, a hole transport layer 34, a light emitting layer 35, an electron transport layer 36, and an electron injection layer on a transparent glass substrate 31. 37 and a reflective electrode layer 38 are laminated. In addition to the illustrated structure, a layer for blocking electrons and holes is inserted as necessary. Some structures do not include an electron injection layer or a hole injection layer.
- the TOT derivative of the present invention can be applied to the electron transport layer 36 and the electron injection layer 37 as n-type semiconductor layers. Factors that govern important characteristics such as luminous efficiency and lifetime in organic EL devices are largely dependent on the combination of materials, so the band gap of the frontier orbit of the TOT derivative, LUMO energy level, interface contact state, etc. The desired performance can be obtained by fine tuning according to the light emitting material to be used.
- the transparent electrode layer 32 is deposited on the transparent glass substrate 31 by sputtering or the like. Then, a hole injection layer 33, a hole transport layer 34, and a light emitting layer 35 are formed by a vacuum deposition method or a coating method, and then an electron transport layer 36 and an electron injection layer 37 containing a TOT derivative are vacuum deposited or coated. Form by the method. Finally, a reflective electrode layer 38 is formed on the electron injection layer 37 by sputtering or the like. In some cases, one or more of the hole injection layer 33, the hole transport layer 34, the electron transport layer 36, and the electron injection layer 37 can be omitted. As the coating method, for example, a spin coating method, an ink jet method, a spray coating method, a gravure printing method, or the like can be adopted.
- the optimum conditions are set while adjusting parameters such as the temperature of the deposition source and the substrate, the temperature rise profile, the deposition time, and the distance between the deposition source and the substrate.
- the optimum conditions are set by adjusting parameters such as the solvent type, concentration, temperature, and drying conditions of the solution to be coated.
- the TOT derivative can arbitrarily control the energy level of the frontier orbitals by changing the functional group introduced as a substituent. Therefore, compared with conventionally known n-type organic semiconductor materials such as fullerene-based and copper phthalocyanine-based materials, it is possible to easily draw out the potential inherent to the light-emitting material. Furthermore, as a feature not found in conventional organic semiconductor elements, TOT derivatives can store electrons up to the tetraanion, which acts as a buffer against local current concentration in organic EL elements. In other words, it can contribute to extending the life of the element.
- the TOT derivative of the present invention can also be used as the host material of the light emitting layer.
- ⁇ Organic field effect transistor> 6 and 7 show typical element structures of organic field effect transistors. 6 shows a bottom contact structure in which the organic semiconductor thin film is formed after the source / drain electrodes are formed, and FIG. 7 shows a top contact structure in which the source / drain electrode is formed after the organic semiconductor thin film is formed. In any structure, the current flows along the channel layer formed in the lateral direction of the organic semiconductor thin film, and this current is controlled by the voltage applied to the gate electrode.
- the bottom-contact organic field effect transistor 4A has a source electrode 44 and a drain electrode 45 formed on a gate insulating film 43, and a semiconductor layer 46 using the TOT derivative of the present invention formed thereon.
- a film is formed.
- a metal layer to be the gate electrode 42 is formed on the substrate 41, and a gate insulating film 43 such as silicon dioxide or polyimide is formed thereon.
- a source electrode 44 and a drain electrode 45 are patterned thereon, a semiconductor layer 46 using the TOT derivative of the present invention is formed by a vapor deposition process or a coating process, and finally the whole is protected by a sealing film 47.
- a semiconductor layer 46 using the TOT derivative of the present invention is formed on a gate insulating film 43, and a source electrode 44 and a drain electrode 45 are formed thereon. Is formed.
- an organic thin film using the TOT derivative of the present invention is formed on the gate insulating film 43 by a vapor deposition process or a coating process, and a source electrode 44 and a drain electrode 45 are provided thereon. .
- top gate structure in which a source / drain electrode is formed on a substrate, an organic semiconductor film is provided thereon, a gate insulating film is formed, and a gate electrode is formed thereon.
- the TOT skeleton is a rigid planar ⁇ -electron molecule composed of only carbon and oxygen atoms.
- a TOT derivative is generated by introducing an electron donating or electron accepting functional group into the TOT skeleton.
- the reaction mixture was poured into ice water and 100 mL of 2M hydrochloric acid and 100 mL of dichloromethane were added while stirring well. After separating the organic layer, the aqueous layer was extracted with dichloromethane 50 mL ⁇ 2, and the organic layers were combined. This organic layer was dried over anhydrous sodium sulfate and filtered, and dichloromethane was distilled off to obtain 15.6 g of 1-bromo-2-chloromethyl-4-isopropylbenzene as a pale yellow transparent oil.
- This yellow powder was placed in a 200 mL eggplant flask, 55 mL of dimethyl sulfoxide (DMSO) was added and suspended, 8.7 g (104 mmol) of sodium bicarbonate was added, and the mixture was stirred at 100 ° C. for 8 hours. After cooling to room temperature, 100 mL of 2M hydrochloric acid, 150 mL of dichloromethane, and 100 mL of a saturated aqueous sodium chloride solution were added. The organic layer was separated, the aqueous layer was extracted with dichloromethane 20 mL ⁇ 3, and the organic layers were combined. The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off. The resulting product was washed with ethyl acetate and hexane to obtain 913 mg of triformyl as a white powder.
- DMSO dimethyl sulfoxide
- This blue solid was put into a 100 mL eggplant-shaped flask and suspended in 40 mL of 2M hydrochloric acid. After stirring at 60 ° C. for 1 hour, the mixture was allowed to cool and insolubles were collected by filtration and washed with 2M hydrochloric acid to obtain 269 mg of a hydroxyl compound as a purple solid. This was placed in a 30 mL eggplant-shaped flask, suspended in 4 mL of a 10 wt% tetrabutylammonium hydroxide aqueous solution, and stirred at 60 ° C. for 1 hour. Insoluble matter was collected by filtration, washed with distilled water at 60 ° C., and dried at 70 ° C.
- a tert-butyl fine powder and a KBr fine powder mixed together into a plate shape under pressure are used.
- a wide range of low energy absorption reaching the long wavelength side and the infrared region was observed with the maximum at 1134 nm (1.1 eV).
- the absorbed energy does not correspond to the energy gap between SOMO and LUMO, but is attributed to a transition between levels of a larger level difference.
- the wavelength corresponding to the level difference of 0.2 eV greatly protrudes to the right from the graph of FIG. 8, and is outside the measurement range.
- a wide range of low energy absorption has been observed that will reach wavelengths corresponding to a gap of 0.2 eV.
- FIG. 9 shows an outline of the photoconductivity measurement cell and the measurement circuit thus obtained.
- the cell was irradiated with light from a halogen lamp (50 W) from a distance of 10 cm, and the photoconductivity (current-voltage characteristics) of the cell was measured.
- FIG. 10 shows the photoconductivity in a dark place.
- the photoconductivity was also measured for a cell made of only P3HT without using an n-type semiconductor and a cell using C 60 which is a general n-type semiconductor instead of a tert-butyl body.
- P3HT Figure 11 the measurement results for only shown in FIG. 12 the measurement result of the cell using a C 60.
- the slope of the photopic current is large. However, its origin is different.
- the photopic current is based on the internal photoelectric effect.
- the difference in the slope of the photopic current case for dark currents of C 60 is small, in the case of C 60, it has been shown to be the contribution of the internal photoelectric effect small.
- the tert-butyl body internal photoelectric effect than C 60 is confirmed to be remarkable.
- An organic field effect transistor having a bottom contact structure as shown in FIG. 6 was produced as follows. A conductive silicon wafer substrate with a thermal oxide film functioning as a gate electrode and gate insulating film was used, and a source electrode and a drain electrode were formed thereon by gold vapor deposition. A tert-butyl derivative single crystal of TOT was placed thereon. The mobility was measured in air without using a sealing film.
- TOT derivatives can arbitrarily control the level of frontier orbitals by molecular design such as changing the structure of substituents.
- Table 1 shows the LUMO and SOMO energy levels of the derivatives with different substituents R on the TOT skeleton and their energy differences (according to the ROB3LYP / 6-31G // UB3LYP / 6-31G method). Calculation result).
- the SOMO energy level is relatively high as expected, and the electron accepting functional group (iC 3 F 7 , C 6 In the case of F 5 , CN, COOH, NO 2 ), the SOMO energy level was relatively low.
- the SOMO-LUMO energy difference is smaller in all cases than in the case of tert-butyl group or isopropyl group. In this way, it is possible to change the SOMO energy level from the highest level to the lowest level in the range of about 1.7 eV by simply selecting the substituent, and the SOMO-LUMO energy difference is changed from the highest gap to the lowest gap. It is useful in terms of molecular design to be able to vary within a range of about 0.3 eV to about 0.3 eV.
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Abstract
Description
しかし電子の輸送を担うn型半導体は、フラーレン、ペリレンテトラカルボン酸ジイミドやパーフルオロペンタセンなどに限定されており、その開発研究はp型に比べて遅れている。これは閉殻有機分子が一電子を受容することによって生成する有機分子アニオン体(正確にはラジカルアニオン種)の不安定性が本質的な理由であろうと考えられる。
また、これまでに知られている代表的な有機半導体は、HOMO(Highest Occupied Molecular Orbital;最高被占軌道)-LUMO(Lowest Unoccupied Molecular Orbital;最低空軌道)間のエネルギー差が1.0 ~ 1.7 eVもある。このため、赤外領域に相当する低エネルギーの光を吸収することができない。低エネルギーの光を吸収する有機半導体素子が実現できれば、バンドギャップの大きな半導体素子とタンデム構造にして、太陽光の吸収効率を上げることができる。
本発明は、狭いバンドギャップを持つことにより赤外領域に光吸収性能を有し、かつキャリア移動度の高い半導体層を備える有機半導体素子を提供することを目的とする。
前記半導体層において、[化2]の前記中性ラジカル化合物が柱状に重なった結晶配置をとっている場合がある。
TOT誘導体は、中性の開殻有機分子としては25πもの巨大なπ電子系を有する平面性の高い縮合多環型の「スピン非局在型」中性ラジカル化合物である。よって、分子間の強い相互作用、高い自己集積能が期待できる。
TOT誘導体は、縮退したLUMOを有する。従来知られている代表的な有機半導体素子のHOMO-LUMOエネルギー差が1.0~1.7 eVもあるのとは異なり、計算によれば、三つのtert-ブチル基を有するTOT誘導体のSOMO-LUMOエネルギー差(エネルギーギャップ)はわずか0.2 eV程度しかない(ROBLYP/6-31G(d, p)//UBLYP/6-31G(d, p) 法による計算結果)。軌道間の電子反発等の問題がこのエネルギー差に大きく関与しているが、フロンティア軌道エネルギー間のギャップがこのように極端に小さい有機分子は今まで知られていない。このような小さなエネルギー差を利用して、赤外領域まで達する幅広い長波長光エネルギーの吸収が可能になり、太陽電池などの光電変換素子において光電流の向上に直結する赤外光の活用が可能となる。
また、有機半導体素子としては、0.01~20 cm2/Vsという大きなキャリア移動度を有するので、このキャリア移動度の大きさを活用することで、TOT誘導体により優れたn型半導体材料を提供することができる。
本発明における上述の、又はさらに他の利点、特徴及び効果は、添付図面を参照して次に述べる実施形態の説明により明らかにされる。
<有機薄膜太陽電池>
狭いSOMO - LUMOエネルギーギャップを有し、赤外領域まで達する幅広い長波長の光を吸収するTOT誘導体を、有機薄膜太陽電池のn型半導体層として利用することにより、赤外領域の光を電力に変換する有機薄膜太陽電池を製作することができる。
なお[実施例]において後述するように、TOT誘導体は置換基の構造を変えるなどの分子設計によりフロンティア軌道のレベルを任意にコントロールすることが可能となる。これによって、太陽電池のpn接合層として要求される特性、例えば電極の仕事関数(フェルミ準位)、半導体の価電子帯(HOMO, SOMO)及び伝導帯(LUMO)のレベルなどを精密にチューニングすることが可能となる。
製造方法の一例を簡単に説明すると、透明ガラス基板11に、スパッタリング法などにより透明電極層12を蒸着する。その上からp型半導体層13を真空蒸着法あるいは塗布法により形成し、p型半導体層13の上にn型半導体層14を真空蒸着法あるいは塗布法により形成する。この薄膜形成プロセスにおいて分子同士のスタックが最適となるような条件を設定する必要がある。具体的には、真空蒸着法の場合には蒸着源及び基板の温度・昇温プロファイル・蒸着時間、蒸着源と基板の距離などのパラメーターを調整しながら、最適条件を設定する。また塗布法の場合にはスピンコート、インクジェット、グラビア印刷など塗布プロセスの選択に加え、塗布する溶液の溶媒種、濃度、温度、乾燥条件などのパラメーターを調整して最適条件を設定する。最後にn型半導体層14上に反射電極層15をスパッタリング法などにより形成する。
さらにシリコン系太陽電池とのハイブリッド化(タンデム化)も可能である。図4は、ハイブリッド型太陽電池の断面を模式的に示す図である。
有機EL素子3は、図5に示すように、透明ガラス基板31の上に、透明電極層32、正孔注入層33、正孔輸送層34、発光層35、電子輸送層36、電子注入層37、反射電極層38を積層した構造である。図示した構造に加えて、必要に応じて電子や正孔をブロックする層が挿入される。また電子注入層や正孔注入層を含まない構造もある。
<有機電界効果トランジスタ>
図6及び図7に、有機電界効果トランジスタの代表的な素子構造を示す。図6は、ソース・ドレイン電極を作製した後に有機半導体薄膜を形成するボトムコンタクト構造、図7は、有機半導体薄膜を形成した後にソース・ドレイン電極を作製するトップコンタクト構造を示す。いずれの構造でも、電流は、有機半導体薄膜の横方向に形成されるチャネル層に沿って流れ、この電流がゲート電極に印加される電圧によって制御される。
本発明のTOT誘導体を有機薄膜に使用することにより、動作周波数の高い電界効果トランジスタを実現することが出来る。
このような有機電界効果トランジスタは、例えばディスプレイ駆動用のTFTとして利用される。
以上で、本発明の実施の形態を説明したが、本発明の実施は、前記の形態に限定されるものではなく、本発明の範囲内で種々の変更を施すことが可能である。
TOT骨格は、炭素原子と酸素原子のみからなる剛直な平面型π電子系分子である。このTOT骨格に電子供与性や電子受容性官能基を導入することによりTOT誘導体を生成する。
TOT誘導体のR=t-ブチル基の構造を有する化合物は、特開2007-227186号公報(特許文献1)に記載された方法により合成した。
アルゴン雰囲気下、300mLのシュレンク管に1-ブロモ-4-イソプロピルベンゼン12.5g(64mmol)を入れ、四塩化炭素40mLとクロロメチルメチルエーテル28.9mL(384mmol)を加えた。これを-30℃に冷却し、塩化アルミニウム17.1g(128mmol)を加えた後0℃まで昇温して20分間撹拌後、室温まで昇温して5分間撹拌した。反応液を氷水に注ぎ入れてよく撹拌しながら、2M塩酸100mLとジクロロメタン100mLを加えた。有機層を分離後、水層をジクロロメタン50mL×2で抽出し、有機層を合一した。この有機層を無水硫酸ナトリウム上で乾燥後ろ過し、ジクロロメタンを留去することにより1-ブロモ-2-クロロメチル-4-イソプロピルベンゼン15.6gを淡黄色透明オイルとして得た。
TOT誘導体の一例として、tert-ブチル体の微粉末とKBrの微粉末とを混合して圧力をかけて板状にしたもの(「KBrペレット」という)を用いて、前記tert-ブチル体の赤外領域の電子スペクトルを測定すると、図8に示すように、1134 nm (1.1 eV) を極大とし、その長波長側、赤外領域まで達する幅広い低エネルギーの吸収が観測された。なお、この1.1 eVの?吸収エネルギーはSOMO-LUMO間のエネルギーギャップに相当するものではなく、もっと大きなレベル差の準位間の遷移に帰属される。0.2eVの準位差に対応する波長は、図8のグラフから右へ大きくはみだしており、測定範囲外である。しかし、0.2eVのギャップに対応する波長にまで達するであろう幅広い低エネルギーの吸収が観測されたことは間違いない。
<光導電性の測定>
太陽電池や有機EL素子としての特性確認のため、TOT誘導体のうちtert-ブチル体を用いて光導電性(Photoconductivity)の測定を実施した。光導電性測定用セルは以下のように製作した。
同様に比較のため、n型半導体を用いずにP3HTのみで作製したセル、およびtert-ブチル体の代わりに一般的なn型半導体であるC60を用いたセルについても光導電性を測定した。P3HTのみの場合の測定結果を図11に、C60を用いたセルの測定結果を図12に示す。
図6に示すようなボトムコンタクト構造の有機電界効果トランジスタを以下のとおり作製した。ゲート電極兼ゲート絶縁膜として機能する熱酸化膜付き導電性シリコンウェハー基板を用い、この上にソース電極とドレイン電極を金蒸着により形成した。その上にTOTのtert-ブチル誘導体単結晶を設置した。封止膜は使用せず、空気中で移動度を測定した。
ID=Ci(VG-Vth)VDμ(L/W) [2]
(ただし、Ciはゲート絶縁膜のキャパシタンス、Vthはしきい電圧、Lは伝導チャネルの長さ、Wは伝導チャネルの幅)
この計算により、移動度μとして、0.12cm2/Vsという大きな値が得られた。さらにTOT誘導体が大気中で安定に動作するn型有機半導体であることが確認できた。したがって、高い周波数まで使用できる実用的な有機電界効果トランジスタが得られることが確認できた。
TOT誘導体は置換基の構造を変えるなどの分子設計によりフロンティア軌道のレベルを任意にコントロールすることが可能である。表1に、TOT骨格上の置換基Rを変化させた誘導体のLUMOのエネルギー準位及びSOMOのエネルギー準位とそれらのエネルギー差を示す(ROB3LYP/6-31G//UB3LYP/6-31G 法による計算結果)。
このように置換基を選択するだけでSOMOのエネルギーレベルを最も高いレベルから最も低いレベルまで約1.7 eVの範囲で変化させることが可能であり、SOMO-LUMOエネルギー差を最も高いギャップから最も低いギャップまで約0.3 eVの範囲で変化させることが可能であるということは、分子設計上有用である。
置換基選択のもう一つ重要な観点は、スピン間相互作用(SOMO-SOMO相互作用)以外の他の分子間相互作用の導入と結晶構造の多次元化である。TOT誘導体は、図2に示したように、縦方向の一次元性高い結晶構造を有している。そのため、巨大なπ電子系とその骨格上に広く非局在化した電子スピンによるπ-π型の強いSOMO-SOMO相互作用(2500 K, 5.0 kcal/mol)の他に強い非結合性相互作用が存在していないためと考えられる。このような電子スピン系に分子間相互作用が可能なNH2基やCOOH基等を導入した場合は、横方向にも構造を持った、次元性の高い結晶構造の形成が予想できる。従って、横方向での電子的なコミュニケーションも期待でき、薄膜の構造や半導体としての性質を変化・調整できる可能性がある。
2 ハイブリッド型太陽電池
3 有機EL素子
12,17,32 透明電極層
13 p型半導体層
14 n型半導体層
15,22,38 反射電極層
11,16,31 透明ガラス基板
18 トップセル
19 ボトムセル
20 透明電極層
21 有機薄膜セル
33 正孔注入層
34 正孔輸送層
35 発光層
36 電子輸送層
37 電子注入層
4A,4B 有機トランジスタ
41 基板
42 ゲート電極
43 ゲート絶縁膜
44 ソース電極
45 ドレイン電極
46 半導体層
47 封止膜
48 ITO透明電極付きガラス基板
49 有機薄膜層
50 金電極
Claims (12)
- 前記半導体層において、[化1]の前記中性ラジカル化合物が柱状に重なった結晶配置をとっている、請求項1に記載の有機半導体素子。
- [化1]の前記中性ラジカル化合物は、前記1価の基Rが、プロトン、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、t-ブチル基、シクロヘキシル基、2,2,2-トリフルオロエチル基、ペンタフルオロエチル基、ヘプタフルオロイソプロピル基、フェニル基、4-メトキシフェニル基、ペンタフルオロフェニル基、ナフチル基、ベンジル基、メトキシ基、エトキシ基、n-ブトキシ基、t-ブトキシ基、フェニルオキシ基、アミノ基、ジメチルアミノ基、ジエチルアミノ基、イソプロピルアミノ基、カルボキシル基、メトキシカルボニル基、エトキシカルボニル基、イソプロポキシカルボニル基、t-ブトキシカルボニル基、トリフルオロメトキシカルボニル基、シアノ基、ニトリル基、ハロゲンからなる群より選ばれる1価の有機基である、請求項1又は請求項2に記載の有機半導体素子。
- [化1]の前記中性ラジカル化合物の半占軌道と最低空軌道のエネルギーギャップが0.1~1.0eVである、請求項1~請求項3のいずれか1項に記載の有機半導体素子。
- 前記有機半導体素子が有機薄膜太陽電池である請求項1~請求項4のいずれか1項に記載の有機半導体素子。
- 前記半導体層は、p型有機半導体材料とp-n型接合を形成するn型半導体層である、請求項5に記載の有機半導体素子。
- 前記有機薄膜太陽電池がシリコン系太陽電池と組み合わされたハイブリッド型太陽電池である、請求項5又は請求項6に記載の有機半導体素子。
- 前記有機半導体素子が有機電界効果トランジスタである請求項1~請求項4のいずれか1項に記載の有機半導体素子。
- 前記有機半導体素子が有機EL素子である請求項1~請求項4のいずれか1項に記載の有機半導体素子。
- 前記半導体層は、発光層に電子を供給する電子注入層又は電子輸送層である、請求項9に記載の有機半導体素子。
- 前記半導体層は、0.01~20cm2/Vsのキャリア移動度を有する、請求項1~請求項10のいずれか1項に記載の有機半導体素子。
- 前記半導体層は、[化1]の前記中性ラジカル化合物を塗布プロセスで製膜して得られるものである、請求項1~請求項11のいずれか1項に記載の有機半導体素子。
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JP2014049559A (ja) * | 2012-08-30 | 2014-03-17 | Konica Minolta Inc | タンデム型の光電変換素子およびこれを用いた太陽電池 |
CN105261706A (zh) * | 2015-09-01 | 2016-01-20 | 华南理工大学 | 一种平面异质结敏化的有机荧光发光二极管及其制备方法 |
JP2017022287A (ja) * | 2015-07-13 | 2017-01-26 | 株式会社カネカ | 有機ラジカル化合物の薄膜 |
WO2018030237A1 (ja) * | 2016-08-09 | 2018-02-15 | 株式会社カネカ | Tot化合物およびそれを利用した非水電解液二次電池 |
JP2019019106A (ja) * | 2017-07-20 | 2019-02-07 | 学校法人 名古屋電気学園 | トリオキソトリアンギュレン系中性ラジカル化合物の錯体 |
JP2021508415A (ja) * | 2017-12-18 | 2021-03-04 | キング アブドラ ユニバーシティ オブ サイエンス アンド テクノロジー | 非フラーレン及び/又はホールスカベンジャーに基づく活性層並びにオプトエレクトロニクスデバイス |
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JP2010184918A (ja) * | 2009-02-13 | 2010-08-26 | Chemiprokasei Kaisha Ltd | 有機ラジカル化合物、それを用いた有機デバイス |
US20130019936A1 (en) * | 2011-07-21 | 2013-01-24 | Kuang-Chien Hsieh | Organic solar cell with patterned electrodes |
JP2014049559A (ja) * | 2012-08-30 | 2014-03-17 | Konica Minolta Inc | タンデム型の光電変換素子およびこれを用いた太陽電池 |
JP2017022287A (ja) * | 2015-07-13 | 2017-01-26 | 株式会社カネカ | 有機ラジカル化合物の薄膜 |
CN105261706A (zh) * | 2015-09-01 | 2016-01-20 | 华南理工大学 | 一种平面异质结敏化的有机荧光发光二极管及其制备方法 |
WO2018030237A1 (ja) * | 2016-08-09 | 2018-02-15 | 株式会社カネカ | Tot化合物およびそれを利用した非水電解液二次電池 |
JP2019019106A (ja) * | 2017-07-20 | 2019-02-07 | 学校法人 名古屋電気学園 | トリオキソトリアンギュレン系中性ラジカル化合物の錯体 |
JP2021508415A (ja) * | 2017-12-18 | 2021-03-04 | キング アブドラ ユニバーシティ オブ サイエンス アンド テクノロジー | 非フラーレン及び/又はホールスカベンジャーに基づく活性層並びにオプトエレクトロニクスデバイス |
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