CN115440886B - Micromolecule-polymer composite organic semiconductor film and preparation method thereof - Google Patents
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Abstract
The invention discloses a micromolecule-polymer composite organic semiconductor film and a preparation method thereof, which is characterized in that benzo [ B ] benzo [4,5] thieno [2,3-D ] thiophene (BTBT) based micromolecules and polymer materials are mixed and then dissolved in an organic solvent, and then micromolecule-polymer composite organic semiconductor solution is obtained under the stirring condition; and then, the organic semiconductor solution is spread on a substrate by low-speed spin coating through an eccentric spin coating method, and then the micromolecule-polymer composite organic semiconductor film is prepared by high-speed spin coating. The related structural morphology and the electrical property of the organic semiconductor film can be effectively regulated and controlled through matching of the solution concentration, the proportion of the small molecules and the polymer material and spin coating parameters, and the organic semiconductor film material with excellent carrier transport performance is obtained.
Description
Technical Field
The invention belongs to the technical field of semiconductor materials, and particularly relates to a micromolecule-polymer composite organic semiconductor film and a preparation method thereof.
Background
The organic semiconductor film has the characteristics of solution processing, large-area preparation, good flexibility, low cost and the like, so that the organic semiconductor film has great application potential in the aspects of organic field effect transistors, organic light emitting diodes, organic photovoltaic devices, organic thermoelectric devices and the like. The mobility of the organic semiconductor film as an important index for judging the related performance of the organic semiconductor film is strongly influenced by factors such as crystallinity, molecular accumulation mode, charge trap, film morphology and the like.
At present, there are related researches, such as chinese invention patent application, with the publication numbers: the preparation method of the CN110943166A single-layer organic semiconductor film comprises the following steps: dissolving a small molecule organic compound with alkyl branched chains and a long chain homologue of the small molecule organic compound to prepare a mixed solution; spin-coating the mixed solution on a first substrate, and covering the first substrate coated with the mixed solution on a second substrate; the single-layer organic semiconductor film can be grown in a large area by introducing corresponding long chain homologues into organic molecules and utilizing the geometrical mismatch between the molecular layers with different lengths and the confinement effect between the substrates, and in the preparation method of the single-layer organic semiconductor film, the patterned growth of the single-layer organic semiconductor film can be realized by constructing hydrophilic and hydrophobic regions on the second substrate.
For another example, the Chinese invention patent has the publication numbers: CN113571638B is a method for enhancing the aggregation state stability of an organic semiconductor film, an organic semiconductor film is constructed, then a small amount of nano particles are introduced to the surface or the inner part of the constructed organic semiconductor film, the nano particles are uniform and discontinuous, the electrical performance of the organic semiconductor film is not influenced, the grain boundary, dislocation, stacking fault, surface and the like of the organic semiconductor film are pinned by the nano particles, the potential barrier of the organic semiconductor film for structural change of the aggregation state is increased, the aggregation state stability of the organic semiconductor film is enhanced, and the highest working temperature and the storage life of an organic field effect transistor are greatly increased. Under the condition of normal-temperature storage, the appearance of the organic semiconductor with stable introduced nano particles hardly changes, and the stability of the electrical properties of the organic transistor device prepared by the organic semiconductor film in a high-temperature working environment and an actual atmospheric environment is ensured.
However, the nucleation and crystallization of small organic molecules and the growth behavior are complicated, and weak van der waals forces between molecules exist in three dimensional directions of space during the growth process, so the crystallinity, grain size and crystal orientation of the organic thin film are very sensitive to the preparation conditions, such as solvent evaporation rate and liquid surface tension.
However, the existing preparation method has some defects, such as poor controllability and low repeatability of a blade coating method, and the prepared organic film single crystal is mixed with single crystals with other shapes; the vacuum evaporation preparation method needs long time and has high requirements on instruments and equipment; the thin film material prepared by the central spin coating method under the action of radial force in all directions is generally a polycrystalline material with rich crystal boundaries, and the preparation of crystals with ordered molecular arrangement is difficult.
Therefore, how to realize the controllable growth preparation of the organic semiconductor film is an important challenge for realizing the functional application of the organic semiconductor film. Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
The invention aims to solve the technical problem of realizing the controllable growth preparation of an organic semiconductor film and provides a micromolecule-polymer composite organic semiconductor film and a preparation method thereof.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation method of a micromolecule-polymer composite organic semiconductor film comprises the steps of respectively dissolving benzo [ B ] benzo [4,5] thieno [2,3-D ] thiophene (BTBT) micromolecules and polymer materials into an organic solvent, mixing the materials according to a certain proportion to obtain a mixed solution, eccentrically spin-coating the mixed solution on a substrate, firstly spin-coating the mixed solution at a low speed, and then spin-coating the mixed solution at a high speed to obtain the micromolecule-polymer composite organic semiconductor film.
A preparation method of a small molecule-polymer composite organic semiconductor film comprises the following steps:
1) Will benzo [ B ]]Benzo [4,5]Thieno [2,3-D]Dissolving thiophene (BTBT) -based micromolecule and polymer material in an organic solvent according to the mass ratio of (9-6) to (1-4), wherein the mass-volume ratio of the total solute to the solvent is 1-5mg ml -1 Then evenly mixing to obtain mixed liquid;
the benzo [ B ] benzo [4,5] thieno [2,3-D ] thiophene (BTBT) based small molecule has a structure shown in a formula (a):
wherein R1 and R2 are each independently H, hydroxyl, carboxyl, substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl, heterocycloalkylene, ketoalkyl, alkoxy, alkenyl, ketoalkenyl, alkynyl, aryl, arylene, heteroaryl, heteroarylene, ketoaryl, ketoheteroaryl, haloalkyl, haloketoalkyl, haloalkenyl, haloketoalkenyl, haloalkynyl, haloaryl, haloheteroaryl, one or more non-adjacent CH' s 2 Independently substituted by-O-, OH-, -S-, -NH-, -CO-, -COO-, -COOH-, -OCO-) -OCO-O-, -SO 2 -, -S-CO-, -CO-S-, -CH = CH-, -C ≡ C-substituted, or substituted with aryl or heteroaryl;
the polymer material is one or more of Polystyrene (PS), polymethyl methacrylate (PMMA) and poly (4-styrene sulfonic acid) (PSS), and the polymer material is mixed in any proportion;
the organic solvent is one or more of toluene, chlorobenzene and chloroform, and the organic solvent is mixed in any proportion;
2) Eccentrically spin-coating the mixed solution obtained in the above step on a substrate, comprising the following steps:
(1) providing a bottom substrate, and fixing the bottom substrate on a spin coater;
(2) providing a substrate of a semiconductor film, carrying out ultrasonic cleaning on the substrate by using one or more of deionized water, acetone, isopropanol and ethanol in any proportion during mixing, then blowing nitrogen, drying, treating the dried substrate by using ultraviolet ozone, and fixing the substrate on a bottom layer substrate and on one side of a spin coating center;
(3) eccentric spraying: firstly, spreading the mixture by low-speed spin coating, and then carrying out high-speed spin coating to obtain the micromolecule-polymer composite organic semiconductor film.
In the invention:
the bottom substrate in the step (1) is selected from one of rigid substrates such as a glass sheet, a silicon wafer and the like;
the substrate of the semiconductor film in the step (2) is one of a rigid substrate such as a glass sheet and a silicon wafer or a flexible substrate such as polyethylene terephthalate and polyimide;
and (3) firstly performing low-speed spin coating and spreading, and then performing high-speed spin coating, specifically, performing the first stage at an acceleration of 20-200rpm/s until the rotation speed reaches 200-1100rpm and then lasts for 10-40s, and performing the second stage at an acceleration of 20-200rpm/s until the rotation speed reaches 1100-4000rpm and then lasts for 10-40s on the basis of the rotation speed of the first stage.
The invention also relates to a micromolecule-polymer composite organic semiconductor film which is obtained by adopting the preparation method of the micromolecule-polymer composite organic semiconductor film, the thickness of the film is 3-30nm, and the mobility of an organic field effect transistor prepared by using the film is 0.55-4.55cm 2 V -1 s -1 。
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional center spin coating method, the preparation method of the micromolecule-polymer composite organic semiconductor film utilizes the eccentric spin coating method to prepare the organic semiconductor film, the centrifugal force along the radial direction can enable crystals to grow directionally, and the organic semiconductor film with uniform surface appearance can be obtained through two different spin coating speed stages.
2. According to the preparation method of the micromolecule-polymer composite organic semiconductor film, disclosed by the invention, the film forming property can be improved by adding the polymer material into the organic semiconductor solution, a complete and uniform film is formed, and the flatness of the film is reduced, so that the defects are reduced.
3. The micromolecule-polymer composite organic semiconductor film obtained by the invention has good surface appearance, compact and complete growth and no crack, and related electrical properties and crystallization appearance of the organic semiconductor film can be effectively regulated and controlled through matching of the solution concentration, the proportion of micromolecules and polymer materials and the rotating speed, so that the organic semiconductor film material with excellent carrier transport performance is obtained.
Drawings
FIG. 1 is a schematic view of an eccentric spin-coating process in the preparation method of a small molecule-polymer composite organic semiconductor thin film according to the present invention;
FIG. 2 is a molecular structure diagram of C8-BTBT used in example 1 of the present invention;
FIG. 3 is a molecular structure diagram of polystyrene used in example 1 of the present invention;
FIG. 4 is an optical photograph of the organic semiconductor thin film prepared in comparative example 1 of the present invention;
FIG. 5 is a graph showing a transfer curve of an organic semiconductor thin film obtained in comparative example 1 of the present invention for producing an organic field effect transistor;
FIG. 6 is a graph showing a transfer curve of an organic semiconductor thin film obtained in example 1 of the present invention for producing an organic field effect transistor;
FIG. 7 is a comparison of XRD patterns of organic semiconductor thin films prepared by the eccentric spin coating method of example 1 of the present invention and the central spin coating method of comparative example 2;
FIG. 8 is a transfer graph of the organic semiconductor thin film obtained in comparative example 2 of the present invention for producing an organic field effect transistor.
Detailed Description
The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
Example 1:
a preparation method of a small molecule-polymer composite organic semiconductor film comprises the following steps:
1) Solution preparation: respectively weighing 2mg of C8-BTBT powder and 0.8mg of Polystyrene (PS) block on an analytical balance, placing the C8-BTBT powder and the PS block into a reagent bottle, adding 1.4ml of toluene solvent into the bottle to dissolve the C8-BTBT powder and the PS block, then adding a magnetic stirrer into the bottle, placing the reagent bottle on a magnetic stirrer, stirring for 24 hours, fully promoting the dissolution of the C8-BTBT and the PS, and preparing for subsequent spin coating;
2) Substrate cleaning: cutting with a silicon knife to obtain SiO with a size of 1cm × 1cm 2 The method comprises the following steps of taking a Si piece as a substrate, placing the cut substrate in a cleaning frame, subsequently ultrasonically cleaning the substrate for 2 minutes by sequentially using ultrapure water, acetone and isopropanol to remove solid impurities, soluble pollutants and residual organic solvents on the surface of the substrate, blow-drying the isopropanol on the surface of the substrate by using a nitrogen flow spray gun, then cleaning the substrate in an ultraviolet-ozone cleaning machine for 15 minutes to further remove residual organic matters and soluble ions on the surface and improve the wettability of the surface of the substrate, fully cleaning the substrate by the above cleaning process to prevent the residual impurities on the substrate from influencing the growth of a subsequent film, and finally transferring the clean substrate into an ultra-clean glove box for later use;
3) Solution spin coating:
firstly, adsorbing a glass sheet on a spin coater sucker to form a bottom substrate, and fixing the glass sheet by using an adhesive tape to ensure that the glass sheet is kept stable in the eccentric spin coating process;
then, the cleaned SiO film is bonded with double-sided adhesive tape 2 Fixing the/Si substrate on a bottom substrate glass sheet 2cm away from the spin coating center, sucking 20uL of C8-BTBT/PS solution by using a liquid transfer gun, and dripping the solution on the surface of the substrate, and then performing eccentric spin coating on the substrate at a set rotating speed (the first stage lasts for 20s after the rotating speed is increased to 800rpm by 50rpm/s, and the second stage finishes after the rotating speed is increased to 3000rpm by 100rpm/s on the basis of the rotating speed of the first stage and lasts for 20 s), thereby finally obtaining the C8-BTBT/PS film.
Example 2:
a preparation method of a small molecule-polymer composite organic semiconductor film comprises the following steps:
1) Solution preparation: respectively weighing 9mg of BOP-BTBT-OMe (wherein BOP is methoxyphenyl and OMe is methoxyl) powder and 4.0mg of PMMA and PSS on an analytical balance, placing the powder and the PSS into a reagent bottle, adding 6ml of chlorobenzene solvent into the bottle to dissolve the powder and the PMMA and the PSS, then adding a magnetic stirrer into the bottle, placing the reagent bottle on the magnetic stirrer to stir for 24 hours, fully promoting the BOP-BTBT-OMe/PMMA/PSS to dissolve, and preparing for subsequent spin coating;
2) Substrate cleaning: cutting a glass sheet with the size of 1cm multiplied by 1cm by a silicon knife to be used as a substrate, placing the cut substrate in a cleaning frame, subsequently ultrasonically cleaning the substrate for 2 minutes by using ultrapure water, acetone and isopropanol in sequence to remove solid impurities, soluble pollutants and residual organic solvents on the surface of the substrate, then blow-drying the isopropanol on the surface of the substrate by using a nitrogen flow spray gun, then placing the substrate in an ultraviolet-ozone cleaning machine for cleaning for 15 minutes to further remove residual organic matters and soluble ions on the surface and improve the wettability of the surface of the substrate, wherein the substrate can be fully cleaned by the above cleaning process to prevent the residual impurities on the substrate from influencing the growth of a subsequent film, and finally transferring the clean substrate into an ultra-clean glove box for later use;
3) Solution spin coating:
firstly, adsorbing another glass sheet on a spin coater sucker to form a bottom substrate, and fixing the bottom substrate by using an adhesive tape to ensure that the glass sheet is kept stable in the eccentric spin coating process;
then, fixing the cleaned glass sheet substrate on the position 2cm away from the spin coating center on the bottom substrate glass sheet by using a double-sided adhesive tape, sucking 20uL of BOP-BTBT-OMe/PMMA/PSS solution by using a liquid transfer gun, dripping the solution on the surface of the substrate, and then carrying out eccentric spin coating on the substrate at a set rotating speed (the first stage is continued for 40s after the acceleration of 20rpm/s is increased to the rotating speed of 200rpm, and the second stage is completed after the acceleration of 20rpm/s is increased to the rotating speed of 1100rpm and is continued for 10s on the basis of the rotating speed of the first stage), thereby finally obtaining the BOP-BTBT-OMe/PMMA/PSS film.
Example 3:
a preparation method of a small molecule-polymer composite organic semiconductor film comprises the following steps:
1) Solution preparation: 6mg of Ph are weighed out on an analytical balance F CO-BTBT-CF 3 (wherein Ph F CO is perfluorophenylcarbonyl, CF 3 Is perfluoromethyl) powder and 1.0mg of Polystyrene (PS) and polymethyl methacrylate (PMMA) and poly (4-styrenesulfonic acid) (PSS) in any ratio, the mixture is placed in a reagent bottle, 3.5ml of chloroform solvent is added to the bottle to dissolve the two, then a magnetic stirrer is added to the bottle, and the reagent bottle is placed on the magnetic stirrer to be stirred for 24 hours, so that Ph is sufficiently promoted F CO-BTBT-CF 3 dissolving/PS/PMMA/PSS for subsequent spin coating;
2) Substrate cleaning: cutting a polyethylene terephthalate sheet with the size of 1cm multiplied by 1cm by a silicon knife to be used as a substrate, placing the cut substrate in a cleaning frame, subsequently and sequentially ultrasonically cleaning the substrate by using ultrapure water, acetone and isopropanol for 2 minutes to remove solid impurities, soluble pollutants and residual organic solvents on the surface of the substrate, then blowing the isopropanol on the surface of the substrate by using a nitrogen flow spray gun, then putting the substrate into an ultraviolet-ozone cleaning machine for cleaning for 15 minutes to further remove residual organic matters and soluble ions on the surface and improve the wettability of the surface of the substrate, wherein the substrate can be fully cleaned by the cleaning process to prevent the residual impurities on the substrate from influencing the growth of a subsequent film, and finally transferring the clean substrate into an ultra-clean glove box for later use;
3) Solution spin coating:
firstly, adsorbing a glass sheet on a spin coater sucker to form a bottom substrate, and fixing the glass sheet by using an adhesive tape to ensure that the glass sheet is kept stable in the eccentric spin coating process;
then, the polyethylene terephthalate substrate was fixed to the bottom substrate glass plate 2cm away from the spin-coating center using a double-sided tape, and 20uL of Ph was sucked by a pipette F CO-BTBT-CF 3 The solution of/PS/PMMA/PSS is dripped on the surface of the substrate, then the substrate is rotated at a set speed (the first stage lasts for 10s after the speed is accelerated to 1100rpm at 200rpm/s, and the second stage is accelerated to rotate at 200rpm/s based on the speed of the first stageAfter the speed is 4000rpm for 40 seconds), eccentric spin coating is carried out, and finally Ph is obtained F CO-BTBT-CF 3 a/PS/PMMA/PSS film.
Comparative example 1:
the difference from example 1 is that the film is prepared without adding the PS material, and the rest is the same as example 1.
Comparative example 2:
the difference from example 1 is that the spin-coating stage was performed by spin-coating using a center spin-coating method, i.e., the substrate was placed at the center of the spin-coating, and the spin-coating was performed at an acceleration of 100rqm/s to a spin speed of 3000rqm for 20 seconds.
Experimental example:
the organic semiconductor thin films prepared in example 1 and comparative examples 1 and 2 were used to prepare organic field effect transistors, and carrier mobility measurements were performed.
First, siO having an organic semiconductor thin film obtained in example 1 or comparative example 1 was used 2 the/Si sheet is fixed on a mask plate with the channel size of 1000um multiplied by 150um, then the mask plate is placed in a vacuum evaporation instrument chamber for fixing, and Ag with the thickness of 40nm is evaporated on the film in a thermal evaporation mode to be used as a source electrode and a drain electrode. In the process of thermal evaporation, the evaporation rate is controlled at 0.1 As by controlling the working current of the evaporation instrument -1 (ii) a So far, OFET devices based on C8-BTBT/PS films have been prepared (OFET structure is BGTC structure, wherein metal is used as a source electrode and a drain electrode, and heavily doped Si is used as a grid electrode).
Discussion:
1. analysis of the product obtained by example 1 and the product obtained by comparative example 1:
the organic semiconductor thin film prepared in comparative example 1 does not contain a PS material, and has a great influence on the film-forming property of the thin film and the performance of the thin film when used for preparing a field effect transistor subsequently.
The polymer material can effectively improve the continuity of the organic semiconductor film, and avoids the performance reduction of the field effect transistor prepared by the reduction of the continuity of the film, however, as shown in figure 4, an organic semiconductor film optical microscope without PS has low coverage rate and poor continuity, and the field effect transistor prepared by the polymer material has transfer characteristic curveThe line is shown in fig. 5, and the maximum gate voltage is applied, the current of the device is only 10 lower at the maximum -5 A is about right, and the mobility of the device is lower and is only 0.28cm 2 V -1 s -1 . The transfer characteristics of the transistor fabricated with the film of comparative example 1, as shown in FIG. 6, reach 10 for the device current at the maximum applied gate voltage -4 A is about right, and the mobility of the device can reach 4.10cm 2 V -1 s -1 And the performance of the transistor is obviously improved.
2. Analysis of the product obtained by example 1 and the product obtained by comparative example 2:
the organic semiconductor thin film prepared in comparative example 2 adopts the center spin coating method, and since the thin film material prepared by the organic semiconductor easily subjected to radial force in each direction in the spin coating process is generally a polycrystalline material with rich grain boundaries and is difficult to prepare crystals with ordered molecular arrangement, as shown in fig. 7, compared with the XRD pattern of the sample of example 1, the thin film prepared by the center spin coating method has a wide XRD crystal peak and low intensity, whereas the thin film prepared by the eccentric spin coating method has a sharp crystal peak and high intensity, which fully indicates that the method can obtain a thin film with more excellent crystallinity. The organic field effect transistor prepared in comparative example 2 has a maximum device current of only 10 lower at the maximum applied gate voltage as shown in fig. 8 -6 A is about right, and the transfer rate of the device is only 0.02cm 2 V -1 s -1 。
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (5)
1. A preparation method of a small molecule-polymer composite organic semiconductor film is characterized by comprising the following steps: the method comprises the following steps:
1) Benzo [ B ] will]Benzo [4,5]Thieno [2,3-D]Dissolving the thienyl micromolecule and the polymer material into an organic solvent according to the mass ratio of (9-6) to (1-4), wherein the mass volume ratio of the total solute to the solvent is 1-5mg ml -1 Then evenly mixing to obtain mixed liquid;
the benzo [ B ] benzo [4,5] thieno [2,3-D ] thienyl small molecule has the structure shown in the formula (a):
wherein R1 and R2 are each independently H, hydroxyl, carboxyl, substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl, heterocycloalkylene, ketoalkyl, alkoxy, alkenyl, ketoalkenyl, alkynyl, aryl, arylene, heteroaryl, heteroarylene, ketoaryl, ketoheteroaryl, haloalkyl, haloketoalkyl, haloalkenyl, haloketoalkenyl, haloalkynyl, haloaryl, haloheteroaryl, one or more non-adjacent CH' s 2 Independently substituted by-O-, OH-, -S-, -NH-, -CO-, -COO-, -COOH-, -OCO-) -OCO-O-, -SO 2 -, -S-CO-, -CO-S-, -CH = CH-, -C ≡ C-substituted, or substituted with aryl or heteroaryl;
the polymer material is one or more of polystyrene, polymethyl methacrylate and poly (4-styrene sulfonic acid), and the polymer material is mixed in any proportion;
the organic solvent is one or more of toluene, chlorobenzene and chloroform, and the organic solvent is mixed in any proportion;
2) Eccentrically spin-coating the mixed solution obtained in the above step on a substrate, comprising the following steps:
(1) providing a bottom substrate, and fixing the bottom substrate on a spin coater;
(2) providing a substrate of a semiconductor film, carrying out ultrasonic cleaning on the substrate by using one or more of deionized water, acetone, isopropanol and ethanol in any proportion during mixing, then blowing nitrogen, drying, treating the dried substrate by using ultraviolet ozone, and fixing the substrate on a bottom layer substrate and on one side of a spin coating center;
(3) eccentric spraying: firstly, spreading by low-speed spin coating, and then carrying out high-speed spin coating to obtain the micromolecule-polymer composite organic semiconductor film.
2. The method for preparing a small molecule-polymer composite organic semiconductor thin film according to claim 1, wherein: the bottom substrate in the step (1) is selected from one of a glass sheet and a silicon chip rigid substrate.
3. The method for preparing a small molecule-polymer composite organic semiconductor thin film according to claim 1, wherein: the substrate of the semiconductor film in the step (2) is one selected from a glass sheet, a silicon wafer rigid substrate or a polyethylene terephthalate and polyimide flexible substrate.
4. The method for preparing a small molecule-polymer composite organic semiconductor thin film according to claim 1, wherein: and (3) firstly performing low-speed spin coating and spreading, and then performing high-speed spin coating, specifically, performing the first stage at an acceleration of 20-200rpm/s until the rotation speed reaches 200-1100rpm and then lasts for 10-40s, and performing the second stage at an acceleration of 20-200rpm/s until the rotation speed reaches 1100-4000rpm and then lasts for 10-40s on the basis of the rotation speed of the first stage.
5. A small molecule-polymer composite organic semiconductor thin film characterized by: the small molecule-polymer composite organic semiconductor film is prepared by the method of any one of claims 1 to 4, the thickness of the film is 3 to 30nm, and the mobility of an organic field effect transistor prepared by the film is 0.55 to 4.55cm 2 V -1 s -1 。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108447990A (en) * | 2018-02-23 | 2018-08-24 | 南京大学 | The method for promoting organic field effect tube device performance based on monomolecular semiconductive thin film |
| CN111961038A (en) * | 2020-07-20 | 2020-11-20 | 陕西莱特光电材料股份有限公司 | Compound, organic electroluminescent device and electronic device |
| CN112635672A (en) * | 2019-09-24 | 2021-04-09 | 湖北大学 | Method for regulating and controlling microstructure of organic small-molecule semiconductor film and application of method in transistor |
| CN112968127A (en) * | 2021-02-22 | 2021-06-15 | 湖南大学 | Method for preparing porous organic semiconductor film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10756284B2 (en) * | 2009-12-16 | 2020-08-25 | Heliatek Gmbh | Photoactive component having organic layers |
| CN102651455B (en) * | 2012-02-28 | 2015-11-25 | 京东方科技集团股份有限公司 | OLED, AMOLED device and manufacture method thereof |
| CN106633002B (en) * | 2016-12-09 | 2020-06-19 | 华南理工大学 | Triarylamine end group content-adjustable polymer with main chain containing S, S-dioxo-dibenzothiophene as well as preparation method and application thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108447990A (en) * | 2018-02-23 | 2018-08-24 | 南京大学 | The method for promoting organic field effect tube device performance based on monomolecular semiconductive thin film |
| CN112635672A (en) * | 2019-09-24 | 2021-04-09 | 湖北大学 | Method for regulating and controlling microstructure of organic small-molecule semiconductor film and application of method in transistor |
| CN111961038A (en) * | 2020-07-20 | 2020-11-20 | 陕西莱特光电材料股份有限公司 | Compound, organic electroluminescent device and electronic device |
| CN112968127A (en) * | 2021-02-22 | 2021-06-15 | 湖南大学 | Method for preparing porous organic semiconductor film |
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