CN111834531B - Organic semiconductor material, preparation method and application - Google Patents
Organic semiconductor material, preparation method and application Download PDFInfo
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- CN111834531B CN111834531B CN201910299056.4A CN201910299056A CN111834531B CN 111834531 B CN111834531 B CN 111834531B CN 201910299056 A CN201910299056 A CN 201910299056A CN 111834531 B CN111834531 B CN 111834531B
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- pyridazine compound
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 238000012546 transfer Methods 0.000 claims abstract description 35
- 238000004528 spin coating Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 3
- -1 aromatic pyridazine compound Chemical class 0.000 claims description 143
- 238000003756 stirring Methods 0.000 claims description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 230000005693 optoelectronics Effects 0.000 claims 1
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- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 61
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 60
- 239000000243 solution Substances 0.000 description 51
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- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 27
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- LZJCVNLYDXCIBG-UHFFFAOYSA-N 2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine Chemical compound S1C(SCCS2)=C2SC1=C(S1)SC2=C1SCCS2 LZJCVNLYDXCIBG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- XQTLDIFVVHJORV-UHFFFAOYSA-N tecnazene Chemical compound [O-][N+](=O)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl XQTLDIFVVHJORV-UHFFFAOYSA-N 0.000 description 4
- 125000006617 triphenylamine group Chemical group 0.000 description 4
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- 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 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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- GPKUICFDWYEPTK-UHFFFAOYSA-N methoxycyclohexatriene Chemical group COC1=CC=C=C[CH]1 GPKUICFDWYEPTK-UHFFFAOYSA-N 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
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- 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
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- 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
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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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
- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Electromagnetism (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Thin Film Transistor (AREA)
Abstract
The invention discloses an organic semiconductor material which is a charge transfer type compound and is represented as a general formula Dp:B:AqP and q are not less than 0 and not 0 at the same time; when P is 0, the P-type organic semiconductor material is characterized by performance; when q is 0, it is characterized by exhibiting N-type organic semiconductor material properties. The invention also discloses a preparation method and application of the organic semiconductor material. The organic semiconductor has conductive performance and can be used for photoelectric devices, and the organic semiconductor material has longer charge separation state life and higher carrier mobility and can be used as an organic field effect transistor material; can also be used as a transmission material for solar cells; the organic semiconductor film prepared by the spin coating method is flat and smooth, and has wide application prospect in the field of flexible devices.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to an organic semiconductor material, a preparation method and application thereof.
Background
In the 21 st century, the life of human beings changes with the earth, and the human beings comprehensively enter the electronic information society. The demand for electronic products is increasing, the demand for semiconductors, which are the basic constituent units of modern information systems, is increasing, the development of semiconductors is pushed to a great extent, more and more scientists are engaged in the research on the performance of semiconductors, and the development of semiconductor materials is increasing. The organic light-emitting diode is widely applied to the fields of organic field effect transistors, organic light-emitting diodes, organic solar cells and the like.
At present, the research on semiconductor materials mainly focuses on organic semiconductor materials and inorganic semiconductor materials, and compared with inorganic semiconductor materials, organic semiconductor materials have the advantages of being capable of being designed functionally, easy to regulate and control energy levels, cheap and available, capable of being designed flexibly and the like, and are receiving more and more attention. Especially with the application and industrialization of organic light emitting display screens, large-area organic semiconductors are more concerned and the rapid development of the organic light emitting display screens is promoted. With the continuous efforts of scientists, more and more organic semiconductor materials are designed and prepared, and most of the organic small molecular compounds with large pi conjugated system, such as pi electron condensed ring compounds with high delocalization, thiophene polymers, triphenylammonia polymers, perylene imide compounds, graphene and high molecular compounds or small molecule doped high molecular polymers, etc. are widely researched. With continuous exploration of scientists, P-type semiconductor materials make great progress, the mobility of the existing P-type semiconductor materials is high, and various performances are greatly broken through, but the materials with high mobility of the P-type semiconductor are mostly crystal materials, although the crystal has high carrier mobility, the structural characteristics and physical characteristics of the crystal make the preparation of the crystal into a large-area flexible material difficult, and the carrier mobility of an amorphous semiconductor material is relatively low, so that the application of the P-type semiconductor material is limited to a great extent. Therefore, although the carrier mobility of the crystalline semiconductor material is greatly improved in recent years, the application of a large area is difficult, and although the amorphous semiconductor material can realize coating and printing of a large area, the amorphous semiconductor material has a problem of low carrier mobility.
On the other hand, the N-type organic semiconductor material is far behind the P-type semiconductor material due to the limitation of the material itself and the influence of external conditions. The existing main problems of the existing N-type semiconductor material are that the designed N-type organic semiconductor material is less, the obtained carrier mobility is lower, the N-type organic semiconductor material is unstable, and the N-type organic semiconductor material is easy to lose efficacy when meeting oxygen and water. More importantly, most of the existing N-type organic semiconductor materials with relatively high mobility are crystalline materials, and the problem of difficult large-area application exists, so that the design and preparation of P-type and N-type organic semiconductor materials with high carrier mobility are crucial to realizing large-area coating.
Although scientists have developed new organic semiconductor molecules to have great adjustability for the energy level of organic semiconductor materials, the energy level of organic semiconductors has a limited range of adjustability, and the carrier mobility of a single organic semiconductor material is still low. In order to improve and balance the injection and transmission of carriers of the organic semiconductor, it is necessary to design a more efficient carrier injection and transmission material, but it is difficult to meet the actual requirements simply by developing a novel organic material, and in order to improve the carrier transmission performance of the organic material, the carrier transmission material can be doped to form a charge transfer complex. The charge transfer between two saturated valence molecules to generate a stoichiometric molecule consisting of non-bonded forces is called a charge-transfer Complex (CTC), the charge-supplying part of the charge-transfer Complex is called an electron donor (D), the charge-accepting part is called a charge acceptor (a), the charge-transfer Complex is also called an electron donor-acceptor Complex, which is a Complex formed by two molecules rich in electrons and poor in electrons, the electron acceptor and the electron donor interact with each other to completely or partially transfer charges to form a Complex, and with the development of the charge-transfer Complex theory, its research and application have been expanded into many scientific fields, such as organic synthesis in organic chemistry, organic reaction mechanism and analytical separation of organic compounds, a functional polymer compound. Organic conductors and superconductors in material science, organic magnetic bodies, nonlinear optical materials, photosensitive films, and the like. The reaction mechanism in biochemistry, pharmacology and pharmaceutics, etc. are widely used. The mechanism of the charge transfer complex is: mulliken first proposed a charge transfer theory based on quantum mechanics in 1952, which suggests that the charge transfer complex can be regarded as a resonance hybrid of two different structures, which can be represented by the following formula:
D+A→D,A→D+-A-
the formula D, A shows that the interaction between the D molecule and the A molecule is weak and no charge transfer effect occurs, the intermolecular effect is mainly Van der Waals force, and D+-A-This means that electrons are transferred from the D molecule to the A molecule, and the intermolecular action is a charge transfer action. The method improves the conductivity of the semiconductor material to a certain extent, but the charge transfer type semiconductor material reported at present is less.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an organic semiconductor material which has longer charge separation state life and higher carrier mobility.
Another object of the present invention is to provide a method for preparing the above organic semiconductor material.
Another object of the present invention is to provide a use of the above organic semiconductor material.
The invention is realized by the following technical scheme:
an organic semiconductor material which is a charge transfer type compound and is represented by a general formula (I),
Dp:B:Aq(Ⅰ)，
p and q are not less than 0 at the same time;
when P is 0, the P-type organic semiconductor material is characterized by performance;
when q is 0, the compound is characterized by exhibiting the properties of an N-type organic semiconductor material;
wherein D is
B is represented by a general formula (II),
wherein R is1Comprises the following steps:
or R1Comprises the following steps:
wherein R is1"is C1～8The alkyl group of (a) is,
or R1Comprises the following steps:
or R1Comprises the following steps:
a is
Wherein R is2、R3、R4、R5Is F or H;
in the above technical scheme, R1' is hydrogen, methyl or methoxy; r1"is a methyl group.
A preparation method of the organic semiconductor material comprises the following steps:
step 1, mixing and stirring an aromatic pyridazine compound and an organic solvent for 60-120 min at a stirring temperature of 0-60 ℃ to obtain an aromatic pyridazine compound solution, wherein the concentration of the aromatic pyridazine compound in the aromatic pyridazine compound solution is 5 x 10-4～1.5×10-3mol/L；
or step 2, adding one of acceptor molecules or donor molecules into the aromatic pyridazine compound solution, and stirring for 180-360 min at the stirring temperature of 0-80 ℃; adding the other one of acceptor molecules or donor molecules into the aromatic pyridazine compound solution, and stirring for 180-360 min at the temperature of 0-80 ℃; the molar ratio of the acceptor molecule to the aromatic pyridazine compound is 1-3: 1, and the molar ratio of the donor molecule to the aromatic pyridazine compound is 2-4: 1;
the molecular formula of the aromatic pyridazine compound is shown as a general formula (II),
wherein R is1Comprises the following steps:
or R1Comprises the following steps:
wherein R is1"is C1～8The alkyl group of (a) is,
or R1Comprises the following steps:
or R1Comprises the following steps:
the donor molecule is
The receptor molecule is
Wherein R is2、R3、R4、R5Is F or H;
in the above technical scheme, R1' is hydrogen, methyl or methoxy;
in the above technical scheme, R1"is a methyl group.
In the above technical scheme, the organic solvent is dichloromethane, chlorobenzene or acetonitrile.
The application of the organic semiconductor material in manufacturing photoelectric materials.
The organic semiconductor material is applied to solar cells.
A flexible film prepared from the semiconductor material is prepared by adopting a spin-coating method.
The invention has the advantages and beneficial effects that:
the invention relates to preparation and application of an organic semiconductor, wherein the organic semiconductor has conductive performance and can be used for photoelectric devices, and the organic semiconductor material has longer charge separation state life and higher carrier mobility and can be used as an organic field effect transistor material; can also be used as a transmission material for solar cells; the organic semiconductor film prepared by the spin coating method is flat and smooth, and has wide application prospect in the field of flexible devices.
Drawings
FIG. 1 shows examples 1 of the present invention (MTPA)2Ab and P type semiconductor composite material [ (MTPA)2Ab]Surface topography testing of films prepared by TCNQ:
a：(MTPA)2ab film Optical Microscope (OM) image; b: [ (MTPA)2Ab]TCNQ thin film Optical Microscope (OM) images; c: (MTPA)2Ab is thinAn in-film mechanical microscope (AFM) image; d: [ (MTPA)2Ab]Original force microscopy (AFM) images of TCNQ thin films.
FIG. 2 shows examples 1 of the present invention (MTPA)2Ab. P-type semiconductor composite material [ (MTPA)2Ab]TCNQ and TCNQ infrared spectra:
a：TCNQ；b:(MTPA)2Ab；c：[(MTPA)2Ab]:TCNQ
FIG. 3 shows a P-type semiconductor composite [ (MTPA) in example 1 of the present invention2Ab]TCNQ transient absorption Spectroscopy:
nanosecond transient absorption spectrum full spectrum, b: kinetic decay curve.
FIG. 4 shows a diagram of the present invention in example 2 (MTPA)2Ab and P type semiconductor composite material [ (MTPA)2Ab]:F4Uv-vis absorption spectrum of TCNQ, solvent dichloromethane:
a:(MTPA)2Ab，b：[(MTPA)2Ab]:F4TCNQ。
FIG. 5 shows a P-type semiconductor composite [ (MTPAF) according to example 2 of the present invention2Ab]:F4TCNQ transient absorption spectroscopy dynamic decay curves.
FIG. 6 shows P-type semiconductor composite [ (M-O-TPA) in example 4 of the present invention2Ab]:F4TCNQ, in the uv-vis absorption spectrum, solvent dichloromethane.
FIG. 7 shows a P-type semiconductor composite [ (YD) in example 5 of the present invention2Ab]:F4TCNQ, in the uv-vis absorption spectrum, solvent dichloromethane.
FIG. 8 shows examples 6 of the present invention (MTPA)2Ab and N-type organic semiconductor composite material (TTF)2:[(MTPA)2Ab]Surface topography testing of the prepared films:
a：(MTPA)2ab film Optical Microscope (OM) image; b (TTF)2:[(MTPA)2Ab]A thin film Optical Microscope (OM) view; c: (MTPA)2Ab thin film field emission Scanning Electron Microscopy (SEM); d: (TTF)2:[(MTPA)2Ab]Thin film field emission Scanning Electron Microscopy (SEM); e: (MTPA)2Ab thin film original force microscopy (AFM) images; f: (TTF)2:[(MTPA)2Ab]Thin film original force microscopy (AFM) images.
FIG. 9 shows an N-type semiconductor composite (MTPA) in example 6 of the present invention2Ab、(TTF)2:[(MTPA)2Ab]And TTF infrared spectrum:
a：(MTPA)2Ab；b:TTF；c：(TTF)2:[(MTPA)2Ab]
FIG. 10 shows an N-type semiconductor composite (TTF) in example 6 of the present invention2:[(MTPA)2Ab]Transient absorption spectrum:
nanosecond transient absorption spectrum full spectrum, b: kinetic decay curve.
FIG. 11 shows an N-type semiconductor composite material (TTF) in example 6 of the present invention2:[(MTPA)2Ab]Mobility spectrometry:
a hole mobility curve, b: electron mobility curve.
FIG. 12 shows an N-type semiconductor composite material (TTF) in example 10 of the present invention2:[(MTPA)2Ab]:F4TCNQ, in the uv-vis absorption spectrum, solvent dichloromethane.
FIG. 13 shows an N-type semiconductor composite material (TTF) in example 11 of the present invention2:[(YD)2Ab]:F4TCNQ, in the uv-vis absorption spectrum, solvent dichloromethane.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Purchasing drugs and drug sources
The instruments and models involved were tested in the following examples:
example one
P-type organic semiconductor material 4,4 '-di (4-N, N' -di (P-tolyl) aminostyryl) benzo [ c]Cinnoline 7,7,8, 8-tetracyanoterephthalquinodimethane, i.e., [ (MTPA)2Ab]The preparation method of TCNQ comprises the following steps:
mixing aromatic pyridazine compound (MTPA)2Ab
(0.013mmol) and 10ml of methylene chloride were placed in a single-neck flask, and the mixture was stirred for 60 minutes at room temperature to obtain an aromatic pyridazine compound solution in which the concentration of the aromatic pyridazine compound was 1.3X 10-3mol/L；
Adding TCNQ into the aromatic pyridazine compound solution
Stirring the solution at 0.013mmol, wherein the molar ratio of the TCNQ to the aromatic pyridazine compound is 1:1, stirring for 180min, and the stirring temperature is room temperature, and after the reaction is finished, spin-coating the reaction solution by using a spin coater to prepare a film; the parameters selected during spin coating are 3000r/min, 30s and 1.3 × 10-3mol/L。
FIGS. 1a and 1b are compounds (MTPA)2Ab (see FIG. 1a) and Complex [ (MTPA)2Ab]Optical microscope pictures of TCNQ (as in FIG. 1b) films, from which we can see (MTPA)2The Ab compound film is less uniform and less dense than the Ab compound film [ (MTPA)2Ab]The film of the TCNQ composite is relatively flat, uniform and compact. Indicating that the formation of the complex helped to form a dense film. To more clearly analyze the effect of TCNQ addition on the compactness and flatness of the film, we performed atomic force microscopy tests on it, FIGS. 1c and 1d are pyridazine compounds(MTPA)2Ab (as in FIG. 1c) and B: AqCompound ([ (MTPA)2Ab]TCNQ) (as shown in figure 1d) of the film atomic force microscope picture, from the atomic force microscope test results (figure 1c and 1d) can see that the composite film has better smoothness, the test results show that the composite is easier to form a film, can be spin-coated on a large area to prepare a film, and is beneficial to the preparation of a flexible device.
To Prove (MTPA)2Formation of a Complex between the Ab molecule and TCNQ, Pair (MTPA)2Ab and [ (MTPA)2Ab]The TCNQ was subjected to infrared spectroscopy and the results are shown in FIG. 2. (shown as b in FIG. 2) (MTPA)2The C-N framework vibration peak of Ab is shown at 1600cm-1、1500cm-1At least one of (1) and (b); the characteristic peak of TCNQ is located at 1417cm-1(as shown in a in fig. 2), which is consistent with the infrared characteristic peak reported in the literature; characteristic absorption peak (2181 cm) of CN functional group in TCNQ (a in FIG. 2)-1) Compared with [ (MTPA)2Ab]Characteristic absorption peak (2219 cm) of (CN functional group) in TCNQ (c in FIG. 2)-1) A significant shift occurred, which indicates CN bond sum (MTPA) in TCNQ2The azo group in Ab has obvious function to arrange orderly, thereby leading to obvious peak shift, indicating that a complex is formed, and further proving that the azo group of the pyridazine compound can form a complex with TCNQ. The infrared test proves that the aromatic pyridazine compound has the effect on TCNQ, and the test proves the formation of a charge transfer type complex.
Transient absorption test:
upon excitation at 450nm, [ (MTPA)2Ab]The transient absorption spectrum of TCNQ in toluene is shown in FIG. 3a, the negative absorption peak at about 450-500nm shown in FIG. 3a is attributed to the ground state bleaching peak of the composite, the positive absorption peaks at about 420nm and at about 500-700nm are attributed to the absorption peaks of azo negative ion and triphenylamine positive ion, respectively, and the negative absorption peak at 460nm is attributed to [ (MTPA)2Ab]TCNQ ground state bleaching Peak, Pair [ (MTPA)2Ab]TCNQ was exponentially fitted to the absorption decay curve as shown in FIG. 3b, and the lifetime of the charge separated state was 10 μ s. Formation of a long-lived charge-separated state is beneficial to carrier mobilityThereby obtaining higher carrier mobility. The compound has longer charge separation state life, so the compound can be used as a charge separation type dye to be applied to a dye-sensitized solar cell, the charge separation type dye is used as a photosensitizer to be beneficial to photoinduced electron transfer, the charge recombination is reduced, and the photoelectric conversion efficiency of the solar cell can be effectively improved.
And (3) researching the conductivity of the film, and testing the conductivity of the P-type semiconductor compound by testing the square resistance.
P-type semiconductor compound [ (MTPA)2Ab]The testing method for the TCNQ conductivity is as follows:
firstly, the conductive glass is cleaned, firstly, the glass is cleaned by using a glass cleaning solution, and then, the cleaning solution is cleaned by using clear water. Then ultrasonically cleaning the mixture for 30min by using ethanol, and drying the mixture by using nitrogen. And (4) carrying out hydrophilic surface treatment on the dried glass.
A square groove with length and width of 4nm is prepared by etching conductive glass, and P-type semiconductor compound [ (MTPA) is dripped or spin-coated on the conductive glass2Ab]The square resistance was tested after TCNQ samples. And (5) conducting performance test by using a universal meter.
The test result shows that the conductivity of the pyridazine compound is greatly changed after the TCNQ is added, the independent pyridazine compound has no conductivity, and the [ (MTPA) is prepared after the TCNQ is added2Ab]The TCNQ film has greatly raised conducting performance and resistance2Ab infinitely decreases to 12000M Ω/sq [ (MTPA)2Ab]TCNQ). This result indicates that the conductive properties of the complex formed by adding TCNQ to the pyridazine compound can be improved to a large extent, and the fundamental reason is that the conductive properties are greatly improved because the intermolecular carrier transport properties are improved after the complex is formed. Meanwhile, we prepared a film by a dispensing method and a breath coating method and tested the conductivity of the film, and the dispensing method prepared a film [ (MTPA)2Ab]TCNQ has a resistance of 8000M omega/sq, and a thin film [ (MTPA) is prepared by a breath coating method2Ab:]The resistance of TCNQ is 500M omega/sq, and the test results show that the method for preparing the thin film by different methods has influence on the conductive performance of the compoundThe effect is larger, the thin film prepared by the breath coating method is more compact, so the resistance is smaller, the conductivity is better, and the result shows that the preparation of the charge transfer type compound is beneficial to the improvement of the conductivity of the compound.
Example two
P-type organic semiconductor material 4,4 '-di (4-N, N' -di (P-tolyl) aminostyryl) benzo [ c] Cinnoline 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoterephthalquinodimethane, i.e., [ (MTPA)2Ab]:F4The preparation method of TCNQ comprises the following steps:
mixing aromatic pyridazine compound (MTPA)2Ab
(0.005mmol) and 10ml of dichloromethane were put into a single-neck flask, and stirred for 120min at 60 ℃ to obtain an aromatic pyridazine compound solution having an aromatic pyridazine compound concentration of 5X 10-4mol/L；
Adding F into the aromatic pyridazine compound solution4TCNQ
0.005mmol and stirring, said F4The molar ratio of TCNQ to the aromatic pyridazine compound is 1:1, the stirring time is 360min, the stirring temperature is 80 ℃, and after the reaction is finished, the reaction solution is spin-coated by a spin coating instrument to prepare a film; the parameters are 3000r/min, the spin coating time is 30s, and the solubility is 5 multiplied by 10 during spin coating-4mol/L。
F4When the molar ratio of TCNQ to the aromatic pyridazine compound was 1:1, the ultraviolet test was performed. From the results of the UV absorption spectrum (see FIG. 4a) (MTPA)2The ultraviolet visible absorption spectrum of Ab in solution is mainly 300-500nm, (MTPA)2Ab absorption peak at 300-375nm is attributed to pi-pi electron transition of aromatic ring and azo group in molecule, and (MTPA)2The maximum absorption peak of Ab at about 450nm is attributed to charge transfer absorption of triphenylamine group to azo group in moleculeAnd (5) peak collection. From FIG. 4b we see that F4The addition of TCNQ resulted in the formation of new peaks at 760nm and 870nm for the complex, which peaks were F4TCNQ receives an absorption peak of electrons, Explanation (MTPA)2Ab and F4TCNQ forms a charge transfer complex, (MTPA)2Ab may be directed to F4TCNQ transfers electrons.
Transient absorption test:
to [ (MTPA)2Ab]:F4TCNQ was fitted exponentially to the absorption decay curve as shown in FIG. 5, and the lifetime of the charge separated state was 15.5. mu.s. The charge transfer type compound has longer charge separation state life, is beneficial to the separation of electrons and holes, and has longer charge separation state life, so that the compound can be used as a charge separation type dye to be applied to a dye-sensitized solar cell, the charge separation type dye is used as a photosensitizer, is beneficial to photoinduction electron transfer, reduces charge recombination, and can effectively improve the photoelectric conversion efficiency of the solar cell.
Study on conductivity of thin film
Conducting performance test is carried out on the prepared film, and the test result shows that F4B-A formed by addition of TCNQqThe result that the P-type conductive compound can improve the conductivity of the pyridazine compound, so that the conductivity of the pyridazine compound is improved, the square resistance is reduced from infinity to 10000M omega/sq, and the resistance is further reduced compared with TCNQ (12000M omega/sq), shows that F4The TCNQ has stronger electron accepting capability, so the electron transfer type conductive composite has better conductive performance.
EXAMPLE III
P-type organic semiconductor compound 4,4 '-di (4-N, N' -di (P-tolyl) aminostyryl) benzo [ c]Cinnoline 1,2,4, 5-benzenetetracarboxylic acid nitrile, [ (MTPA)2Ab]The preparation method of the TCNB comprises the following steps:
mixing aromatic pyridazine compound (MTPA)2Ab
(0.005mmol) and 10ml of dichloromethane were put into a single-neck flask and mixed, followed by stirringThe time is 120min, the stirring temperature is 0 ℃, and an aromatic pyridazine compound solution is obtained, wherein the concentration of the aromatic pyridazine compound in the aromatic pyridazine compound solution is 5 multiplied by 10-4mol/L；
Adding TCNB into the aromatic pyridazine compound solution
Stirring the solution by 0.01mmol, wherein the molar ratio of the TCNB to the aromatic pyridazine compound is 2:1, stirring the solution for 180min at room temperature, and after the reaction is finished, spin-coating the reaction solution by a spin coater to prepare a film; the parameters are 3000r/min, the spin coating time is 30s, and the solubility is 1 multiplied by 10 during the spin coating-3mol/L。
And (3) testing the conductivity:
conducting performance test is carried out on the prepared film, and the test result shows that B: A formed by adding TCNBqThe P-type conductive compound can improve the conductivity of the pyridazine compound, so that the conductivity of the pyridazine compound is improved, the square resistance is reduced to 15800M omega/sq from infinity, and compared with the infinite resistance of the pyridazine compound, the addition of the TCNB is favorable for improving the conductivity of the pyridazine compound.
Example four
P-type organic semiconductor compound 4,4 '-bis (4-N, N' -bis (P-methoxyphenyl) aminostyryl) benzo [ c] Cinnoline 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoterephthalquinodimethane, i.e., [ (M-O-TPA)2Ab]:F4A preparation method of TCNQ.
Mixing aromatic pyridazine compound (M-O-TPA)2Ab
(0.013mmol) and 10ml of dichloromethane were put into a single-neck flask, and stirred at 30 ℃ for 60min to obtain an aromatic pyridazine compound solution in which the concentration of the aromatic pyridazine compound was 1.3X 10-3mol/L；
To the aromatic pyridazineAdding F into the oxazine compound solution4TCNQ
0.013mmol and stirring, said F4The molar ratio of TCNQ to the aromatic pyridazine compound is 1:1, the stirring time is 180min, the stirring temperature is 30 ℃, and after the reaction is finished, the reaction solution is spin-coated by a spin coating instrument to prepare a film; the parameters are 3000r/min, the spin coating time is 30s, and the solubility is 1.3 multiplied by 10 during spin coating-3mol/L。
F4When the molar ratio of TCNQ to the aromatic pyridazine compound was 1:1, the ultraviolet test was performed. From the ultraviolet absorption spectrum (FIG. 6), it is seen that the absorption peak at 300-375nm is attributed to pi-pi electron transition of aromatic ring and azo group in the molecule, and the maximum absorption peak at about 450nm is attributed to charge transfer absorption peak of triphenylamine group to azo group in the molecule. Peaks at 760nm and 870nm were F4TCNQ receives an absorption peak of electrons, indicating (M-O-TPA)2Ab and F4TCNQ forms a charge transfer type complex, (M-O-TPA)2Ab may be directed to F4TCNQ transfers electrons.
Prepared [ (M-O-TPA)2Ab]:F4The TCNQ film is subjected to conductivity test, and the test result shows that F4Addition of TCNQ to form B: AqThe P-type conductive compound can improve the conductivity of the pyridazine compound, so that the conductivity of the pyridazine compound is improved, the square resistance is reduced from infinity to 8400M omega/sq, which is slightly higher than [ (MTPA)2Ab]:F4The result shows that the methoxyl compound has stronger electron donating capacity, so that the electron transfer type conductive composite has better conductive performance.
EXAMPLE five
P-type organic semiconductor compound 2, 9-di-2, 4-P-tolyl (1,2,3,3a,4,8 b-hexahydrocyclopenta [ b)]Indolylaminophenyl) benzo [ c] Cinnoline 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoterephthalquinodimethane, i.e., [ (YD)2Ab]:F4A preparation method of TCNQ.
Mixing aromatic pyridazine compound (YD)2Ab
(0.013mmol) and 10ml of methylene chloride were placed in a single-neck flask, and the mixture was stirred for 60 minutes at room temperature to obtain an aromatic pyridazine compound solution in which the concentration of the aromatic pyridazine compound was 1.3X 10-3mol/L；
Adding F into the aromatic pyridazine compound solution4TCNQ
0.013mmol and stirring, said F4The molar ratio of TCNQ to the aromatic pyridazine compound is 1:1, the stirring time is 180min, the stirring temperature is room temperature, and after the reaction is finished, the reaction solution is spin-coated by a spin coating instrument to prepare a film; the parameters are 3000r/min, the spin coating time is 30s, and the solubility is 1.3 multiplied by 10 during spin coating-3mol/L。
F4When the molar ratio of TCNQ to the aromatic pyridazine compound was 1:1, the ultraviolet test was performed. From the ultraviolet absorption spectrum (FIG. 7), it is seen that the absorption peak at 300-375nm is attributed to pi-pi electron transition of aromatic ring and azo group in the molecule, and the maximum absorption peak at about 450nm is attributed to charge transfer absorption peak of triphenylamine group to azo group in the molecule. Peaks at 760nm and 870nm were F4TCNQ obtains the absorption peak of the electron, Explanation (YD)2Ab and F4TCNQ forms a charge transfer type complex, (YD)2Ab may be directed to F4TCNQ transfers electrons.
Will prepare [ (YD)2Ab]:F4The TCNQ film is subjected to conductivity test, and the test result shows that F4Addition of TCNQ to form B: AqThe result shows that the electron donating capability of the indoline compound is stronger than that of the triphenylammonia compound, so that the electron transfer type conductive composite is formedThe conductive property of the material is better.
N-type semiconductor Performance Studies
EXAMPLE six
N-type organic semiconductor compound (tetrathiafulvalene)24,4 '-bis (4-N, N' -bis (p-tolyl) aminostyryl) benzo [ c]Cinnoline, i.e. (TTF)2:[(MTPA)2Ab]The preparation method comprises the following steps:
mixing aromatic pyridazine compound (MTPA)2Ab
(0.005mmol) and 10ml of dichloromethane were placed in a single-neck flask, and the mixture was stirred for 60 minutes at room temperature to obtain an aromatic pyridazine compound solution in which the concentration of the aromatic pyridazine compound was 5X 10-4mol/L；
Adding TTF into the aromatic pyridazine compound solution
Stirring the mixture by 0.01mmol, wherein the molar ratio of the TTF to the aromatic pyridazine compound is 2:1, stirring for 180min, and the stirring temperature is room temperature, and after the reaction is finished, spin-coating the reaction solution by a spin coater to prepare a film; the parameters selected during spin coating are 3000r/min, 30s and 1 × 10-3mol/L。
FIG. 8 is a photograph showing the surface morphology of spin-on films, and FIG. 8a and FIG. 8b are each an aromatic pyridazine compound (MTPA)2Ab and (TTF)2:[(MTPA)2Optical Microscope (OM) pictures of Ab complex, (FIG. 8c) and (FIG. 8d) are respectively aromatic pyridazine compound (MTPA)2Ab and (TTF)2:[(MTPA)2Scanning Electron Microscope (SEM) pictures of Ab complex, (FIG. 8e) and (FIG. 8f) are respectively aromatic pyridazine compound (MTPA)2Ab and (TTF)2:[(MTPA)2Atomic Force Microscope (AFM) pictures of the Ab complex, from which we can see (MTPA)2The film of the Ab compound is not very uniform,the compactness is poor, and the film of the Dp-B type compound is relatively flat, very uniform and good in compactness. Indicating that the formation of the complex helped to form a dense film.
To Prove (MTPA)2Formation of a Complex between the Ab molecule and TTF, Pair (MTPA)2Ab and (TTF)2:[(MTPA)2Ab was subjected to infrared spectroscopy and the results are shown in FIG. 9. (as shown in FIG. 9) (as a in FIG. 9) (MTPA)2The C-N framework vibration peak of Ab is shown at 1600cm-1、1500cm-1Here, and (TTF)2:[(MTPA)2Ab at 3062cm-1，2360cm-1And 2163cm-1(see c in FIG. 9) all generated new absorption peaks with significant shift, which indicates TTF and (MTPA)2The azo group in Ab has obvious function to arrange orderly, thereby leading to obvious peak shift, indicating that a complex is formed, and further proving that the azo group of the pyridazine compound can form a complex with TTF. The infrared test proves that the compound has the effect on TTF.
Study on conductivity of thin film
The conductivity of the organic semiconductor compound was tested by testing the sheet resistance.
The conductivity of the organic semiconductor compound is tested by the following method:
firstly, the conductive glass is cleaned, firstly, the glass is cleaned by using a glass cleaning solution, and then, the cleaning solution is cleaned by using clear water. Then ultrasonically cleaning the mixture for 30min by using ethanol, and drying the mixture by using nitrogen. The dried glass is subjected to a hydrophilic surface treatment.
A square groove with the length and width of 4nm is prepared by etching conductive glass, and is coated on the conductive glass by dropping or spin coating (TTF)2:[(MTPA)2Ab]The samples were then tested for sheet resistance.
The test results are shown in Table 1, and it can be seen from Table 1 that the electric resistance of the pyridazine compound could not be measured in the existing span range, indicating that the electric resistance of the pyridazine compound is very large. After the pyridazine compound is added with TTF, the conductivity is greatly changed, and the resistance is changed from ((MTPA)2Ab infinityReduced to 12180M Ω/sq ((TTF)2:(MTPA)2Ab). The result shows that the conductive performance of the compound can be improved to a great extent by adding TTF into the pyridazine compound to form the compound, and the fundamental reason is that after the compound is formed, the mobility of carriers among molecules is improved, so the conductive performance is greatly improved.
TABLE 1(MTPA)2Ab and Complex (TTF)2:(MTPA)2Conductivity of Ab in different solvents
Transient absorption:
upon excitation at 450nm, (TTF)2:[(MTPA)2Ab]The transient absorption spectrum in toluene is shown in FIG. 10a, wherein the negative absorption peak at about 450-500nm is attributed to the ground state bleaching peak of the coordination complex, the positive absorption peaks at about 420nm and at about 500-700nm are attributed to the absorption peaks of azo negative ion and triphenylamine positive ion, respectively, and the negative absorption peak at 460nm is attributed to (TTF)2:[(MTPA)2Ab]Without significant reduction of the transient absorption signal when oxygen is introduced into the system, these positive absorption peaks being attributed to the charge separated state of the azo compound, pair (TTF)2:[(MTPA)2Ab]An absorption decay curve was fitted exponentially to FIG. 10b, and the lifetime of the charge separated state was 35.1. mu.s. The formation of a long-life charge separation state is beneficial to improving the carrier mobility, so that higher carrier mobility is obtained. The compound has longer charge separation state life, so the compound can be used as a charge separation type dye to be applied to a dye-sensitized solar cell, the charge separation type dye is used as a photosensitizer to be beneficial to photoinduced electron transfer, the charge recombination is reduced, and the photoelectric conversion efficiency of the solar cell can be effectively improved.
Mobility data:
it was tested for electron and hole mobility using SCLC method (as shown in FIG. 11), and pyridazine compound (TTF) was obtained by the test2:[(MTPA)2Ab]Respectively, hole mobility (as shown in FIG. 11 a) and electron mobility (as shown in FIG. 11 b)h＝8.6×10-6cm2·V-1s-1、μe＝3.9×10-3cm2·V-1s-1. The electron mobility of the compound exceeds that of many polymers, so that the compound can be used as an electron transport material for various electronic devices.
EXAMPLE seven
N-type organic semiconductor compound (bis (ethylene dithiol) tetrathiafulvalene)2:4,4 '-bis (4-N, N' -bis (p-tolyl) aminostyryl) benzo [ c]Cinnoline, i.e. (BEDT-TTF)2:[(MTPA)2Ab]The preparation method comprises the following steps:
mixing aromatic pyridazine compound (MTPA)2Ab
(0.005mmol) and 10ml of dichloromethane were put into a single-neck flask, and stirred for 120min at 60 ℃ to obtain an aromatic pyridazine compound solution having an aromatic pyridazine compound concentration of 5X 10-4mol/L；
Adding 0.015mmol of BEDT-TTF into the aromatic pyridazine compound solution, stirring, wherein the molar ratio of the BEDT-TTF to the aromatic pyridazine compound is 1:1, the stirring time is 360min, the stirring temperature is 80 ℃, and after the reaction is finished, spin-coating the reaction solution by using a spin coater to prepare a film; the parameters are 3000r/min, the spin coating time is 30s, and the solubility is 1.5 multiplied by 10 during spin coating-3mol/L。
Study on conductivity of thin film
Conducting performance tests are carried out on the prepared film, and test results show that the N-type organic conducting compound formed by adding the BEDT-TTF can improve the conducting performance of the aromatic pyridazine compound, so that the conducting performance of the aromatic pyridazine compound is improved, the square resistance is reduced from infinity to 13000M omega/sq, and compared with the infinity of the resistance of the aromatic pyridazine compound, the formation of the compound is favorable for increasing the conducting performance.
Example eight
N-type organic semiconductor compound (tetrathiafulvalene)24,4 '-bis (4-N, N' -bis (p-methoxyphenyl) aminostyryl) benzo [ c]Cinnoline, i.e. (TTF)2:[(M-O-TPA)2Ab]The preparation method comprises the following steps:
mixing aromatic pyridazine compound (M-O-TPA)2Ab
(0.005mmol) and 10ml of dichloromethane were placed in a single-neck flask, and the mixture was stirred for 60 minutes at room temperature to obtain an aromatic pyridazine compound solution in which the concentration of the aromatic pyridazine compound was 5X 10-4mol/L；
Adding TTF into the aromatic pyridazine compound solution
0.015mmol of the TTF and the aromatic pyridazine compound are stirred, the molar ratio of the TTF to the aromatic pyridazine compound is 3:1, the stirring time is 360min, the stirring temperature is 80 ℃, and after the reaction is finished, the reaction solution is spin-coated by a spin coater to prepare a film; the parameters are 3000r/min, the spin coating time is 30s, and the solubility is 1.5 multiplied by 10 during spin coating-3mol/L。
To be prepared (TTF)2:[(M-O-TPA)2Ab]Conducting performance tests are carried out on the film, and the test result shows that the N-type conducting compound formed by adding TTF can improve the conducting performance of the pyridazine compound, so that the conducting performance of the pyridazine compound is improved, and the square resistance is infinitely reduced to 8200M omega/sq and is lower than (TTF)2:[(MTPA)2Ab]This result indicates that the electron donating ability of the methyltriphenylamino compound is stronger than that of the triphenylamino compound, and thus the electron transfer type conductivity is obtainedThe conductivity of the composite is better.
Example nine
N-type organic semiconductor compound (tetrathiafulvalene)22, 9-di-2, 4-p-tolyl group (1,2,3,3a,4,8 b-hexahydrocyclopenta [ b ]]Indolylaminophenyl) benzo [ c]Cinnoline, i.e. (TTF)2:[(YD)2Ab]The preparation method comprises the following steps:
mixing aromatic pyridazine compound (YD)2Ab
(0.005mmol) and 10ml of dichloromethane were placed in a single-neck flask, and the mixture was stirred for 60 minutes at room temperature to obtain an aromatic pyridazine compound solution in which the concentration of the aromatic pyridazine compound was 5X 10-4mol/L；
Adding TTF 0.01 to the aromatic pyridazine compound solution
mmol and stirring, wherein the molar ratio of the TTF to the aromatic pyridazine compound is 2:1, the stirring time is 360min, the stirring temperature is room temperature, and after the reaction is finished, the reaction liquid is spin-coated by a spin coating instrument to prepare a film; the parameters are 3000r/min, the spin coating time is 30s, and the solubility is 1 multiplied by 10 during the spin coating-3mol/L。
Will prepare (TTF)2:[(YD)2Ab]The film is subjected to conductivity test, and test results show that the N-type conductive compound formed by adding TTF can improve the conductivity of the pyridazine compound, so that the conductivity of the pyridazine compound is improved, the square resistance is reduced from infinity to 7600M omega/sq, which is lower than (TTF)2:[(MTPA)2Ab]The result shows that the electron donating capability of the indoline compound is stronger than that of the triphenylamine compound, so that the electron transfer type conductive compound has better conductivity.
Example ten
Bipolar semiconductor compound (tetrathiafulvalene)2[4,4 '-bis (4-N, N' -bis (p-) ]Tolyl) aminostyryl) benzo [ c]Cinnoline](2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoterephthalquinodimethane), i.e. (TTF)2:[(MTPA)2Ab]:F4The preparation method of TCNQ comprises the following steps:
mixing aromatic pyridazine compound (MTPA)2Ab
(0.005mmol) and 10ml of dichloromethane were placed in a single-neck flask, and the mixture was stirred for 60 minutes at room temperature to obtain an aromatic pyridazine compound solution in which the concentration of the aromatic pyridazine compound was 5X 10-4mol/L；
Adding F into the aromatic pyridazine compound solution4TCNQ
0.005mmol and stirring, said F4The molar ratio of TCNQ to the aromatic pyridazine compound is 1:1, the stirring time is 360min, the stirring temperature is 80 ℃, and the reaction is finished to obtain a compound [ (MTPA)2Ab]:F4TCNQ. Adding TTF into the aromatic pyridazine compound solution
0.01mmol and stirring, the TTF and the complex [ (MTPA)2Ab]:F4The molar ratio of TCNQ is 2:1, the stirring time is 360min, the stirring temperature is room temperature, and the organic semiconductor compound (TTF) is obtained after the reaction is finished2:[(MTPA)2Ab]:F4TCNQ. Spin-coating the reaction solution by a spin coater to prepare a film; the parameters selected during spin coating are 3000r/min, 30s and 1 × 10-3mol/L。
Pair complex (TTF)2：[(MTPA)2Ab]:F4TCNQ was subjected to uv testing. As shown in FIG. 12 from the ultraviolet absorption spectrum, the absorption peak at 300-375nm was ascribed to the π - π electron transition of the aromatic ring and azo group in the molecule, and (MTPA)2Ab around 450nmThe maximum absorption peak is attributed to the charge transfer absorption peak of the triphenylamine group to the azo group in the molecule. The maximum absorption peak at about 450nm is attributed to the charge transfer absorption peak from the indoline group to the azo group in the molecule. Peaks at 760nm and 870nm were F4TCNQ receives an absorption peak of electrons, Explanation (MTPA)2Ab and F4TCNQ forms a charge transfer complex, (MTPA)2Ab may be directed to F4TCNQ transfers electrons.
Study on conductivity of thin film
General compound (TTF)2:[(MTPA)2Ab]:F4The TCNQ compound is tested for conductivity and the test effect is poor, and the possible reason is guessed to be TTF and F4The TCNQ is added together to weaken the carrier mobility of the compound, so that the conductive performance of the compound is poor.
EXAMPLE eleven
Bipolar semiconductor compound (tetrathiafulvalene)22, 9-di-2, 4-p-tolyl group (1,2,3,3a,4,8 b-hexahydrocyclopenta [ b ]]Indolylaminophenyl) benzo [ c]Cinnoline (2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoterephthalquinodimethane), i.e. (TTF)2:[(YD)2Ab]:F4The preparation method of TCNQ comprises the following steps:
mixing aromatic pyridazine compound (YD)2Ab
(0.007mmol) and 10ml of dichloromethane were placed in a single-neck flask and stirred for 60min at room temperature to obtain an aromatic pyridazine compound solution having an aromatic pyridazine compound concentration of 7X 10-4mol/L；
Adding F into the aromatic pyridazine compound solution4TCNQ
0.007mmol and stirring, F4The molar ratio of TCNQ to the aromatic pyridazine compound is 1:1, the stirring time is 180min, and the stirring is carried outStirring at room temperature, and finishing the reaction to obtain a compound [ (YD)2Ab]:F4TCNQ. Adding TTF into the aromatic pyridazine compound solution
0.014mmol and stirring, the TTF and the complex [ (YD)2Ab]:F4The molar ratio of TCNQ is 2:1, the stirring time is 180min, the stirring temperature is room temperature, and the reaction is finished. Spin-coating the reaction solution by a spin coater to prepare a film; the parameters selected during spin coating are 3000r/min, 30s and 1.4 × 10-3mol/L。
Pair complex (TTF)2:[(YD)2Ab]:F4TCNQ was subjected to uv testing. Results from ultraviolet absorption Spectroscopy 13 (TTF)2:[(YD)2Ab]:F4The absorption peak of the ultraviolet visible absorption spectrum of TCNQ in the solution at 300-375nm is attributed to pi-pi electron transition of aromatic ring and azo group in the molecule, and the maximum absorption peak at about 450nm is attributed to the charge transfer absorption peak of indoline group to azo group in the molecule. Peaks at 760nm and 870nm were F4TCNQ obtains the absorption peak of the electron, Explanation (YD)2Ab and F4TCNQ forms a charge transfer type complex, (YD)2Ab may be directed to F4TCNQ transfers electrons.
Study on conductivity of thin film
General compound (TTF)2:[(YD)2Ab]:F4The TCNQ compound is tested for conductivity and the test effect is poor, and the possible reason is guessed to be TTF and F4The TCNQ is added together to weaken the carrier mobility of the compound, so that the conductive performance of the compound is poor.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. An organic semiconductor material, characterized in that the organic semiconductor material is a charge transfer type complex represented by general formula (I),
Dp:B:Aq(Ⅰ)，
p and q are not less than 0 at the same time;
when P is 0, the P-type organic semiconductor material is characterized by performance;
when q is 0, the compound is characterized by exhibiting the properties of an N-type organic semiconductor material;
wherein D is
B is represented by a general formula (II),
wherein R is1Comprises the following steps:
or R1Comprises the following steps:
wherein R is1"is C1～8Alkyl groups of (a);
a is
Wherein R is2、R3、R4、R5Is F or H.
2. An organic semiconductor material according to claim 1, wherein R is1' is hydrogen, methyl alkyl or methoxyA group; r1"is a methyl group.
3. A method for preparing an organic semiconductor material according to claim 1, comprising the steps of:
step 1, mixing and stirring an aromatic pyridazine compound and an organic solvent for 60-120 min at a stirring temperature of 0-60 ℃ to obtain an aromatic pyridazine compound solution, wherein the concentration of the aromatic pyridazine compound in the aromatic pyridazine compound solution is 5 x 10-4～1.5×10-3mol/L；
Step 2, adding an acceptor molecule or a donor molecule into the aromatic pyridazine compound solution and stirring, wherein the molar ratio of the acceptor molecule to the aromatic pyridazine compound is 1-3: 1, the molar ratio of the donor molecule to the aromatic pyridazine compound is 2-4: 1, the stirring time is 180-360 min, and the stirring temperature is 0-80 ℃;
the molecular formula of the aromatic pyridazine compound is shown as a general formula (II),
wherein R is1Comprises the following steps:
or R1Comprises the following steps:
wherein R is1"is C1～8Alkyl groups of (a);
the donor molecule is
The receptor molecule is
Wherein R is2、R3、R4、R5Is F or H.
4. A method for preparing an organic semiconductor material according to claim 1, comprising the steps of:
step 1, mixing and stirring an aromatic pyridazine compound and an organic solvent for 60-120 min at a stirring temperature of 0-60 ℃ to obtain an aromatic pyridazine compound solution, wherein the concentration of the aromatic pyridazine compound in the aromatic pyridazine compound solution is 5 x 10-4～1.5×10-3mol/L；
Step 2, adding one of acceptor molecules or donor molecules into the aromatic pyridazine compound solution, and stirring for 180-360 min at the stirring temperature of 0-80 ℃; adding the other one of acceptor molecules or donor molecules into the aromatic pyridazine compound solution, and stirring for 180-360 min at the temperature of 0-80 ℃; the molar ratio of the acceptor molecule to the aromatic pyridazine compound is 1-3: 1, and the molar ratio of the donor molecule to the aromatic pyridazine compound is 2-4: 1;
the molecular formula of the aromatic pyridazine compound is shown as a general formula (II),
wherein R is1Comprises the following steps:
Or R1Comprises the following steps:
wherein R is1"is C1～8Alkyl groups of (a);
the donor molecule is
The receptor molecule is
Wherein R is2、R3、R4、R5Is F or H.
5. The method for producing an organic semiconductor material according to claim 3 or 4, wherein R is1' is hydrogen, methyl or methoxy.
6. The method for producing an organic semiconductor material according to claim 3 or 4, wherein R is1"is a methyl group.
7. The method for producing an organic semiconductor material according to claim 3 or 4, wherein the organic solvent is dichloromethane, chlorobenzene, or acetonitrile.
8. Use of the organic semiconductor material according to claim 1 for the production of an optoelectronic material.
9. Use of the organic semiconducting material of claim 1 in a solar cell.
10. A flexible film made of the semiconductor material according to claim 1, wherein the flexible film is formed by spin coating.
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| CN104769734A (en) * | 2012-11-08 | 2015-07-08 | 国家科学研究中心 | Novel method for manufacturing organic electronic devices |
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| CN104769734A (en) * | 2012-11-08 | 2015-07-08 | 国家科学研究中心 | Novel method for manufacturing organic electronic devices |
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