CN113921714A - Micromolecule and polymer blended bipolar organic thin film transistor and preparation method thereof - Google Patents
Micromolecule and polymer blended bipolar organic thin film transistor and preparation method thereof Download PDFInfo
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- CN113921714A CN113921714A CN202111059073.4A CN202111059073A CN113921714A CN 113921714 A CN113921714 A CN 113921714A CN 202111059073 A CN202111059073 A CN 202111059073A CN 113921714 A CN113921714 A CN 113921714A
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Abstract
本发明提供了一种小分子与聚合物共混的双极性有机薄膜晶体管及其制备方法，属于光电元器件领域。包括依次设置的衬底、金属电极对、PMMA介电层、有机小分子半导体C8‑BTBT与聚合物半导体N2200混合体系以及高速中心旋涂法、栅电极。本发明通过控制混合体系的比例用高速中心旋涂法使共混体系发生相分离，使得该体系既能够传输电子也能够传输空穴。我们所制备的双极性有机薄膜晶体管具有良好的性能，其空穴迁移率达0.148，电子迁移率达0.32，开关比为103。The invention provides a bipolar organic thin film transistor in which small molecules and polymers are blended and a preparation method thereof, belonging to the field of optoelectronic components. It includes a substrate, a metal electrode pair, a PMMA dielectric layer, a mixed system of organic small molecule semiconductor C8-BTBT and polymer semiconductor N2200, a high-speed center spin coating method, and a gate electrode, which are arranged in sequence. By controlling the proportion of the mixed system, the present invention uses a high-speed center spin coating method to separate the phase of the mixed system, so that the system can transport both electrons and holes. Our prepared bipolar organic thin film transistor has good performance, and its hole mobility reaches 0.148 , the electron mobility reaches 0.32 , the switching ratio is 10 3 .
Description
The technical field is as follows:
the invention relates to the technical field of photoelectric components, in particular to a micromolecule and polymer blended bipolar organic thin film transistor and a preparation method thereof.
Background art:
organic thin film transistors are basic elements for constructing signal processing circuits and systems, have great prospects in the aspects of intelligent surfaces of displays, sensors and other electronic functions, and the performance of the organic thin film transistors directly determines the development condition of display technology, so that continuous development and innovation of the organic thin film transistors are requirements for modern technological development.
Compared with a unipolar transistor, the bipolar transistor can transmit electrons and holes, and the prepared organic circuit has the advantages of low operating voltage, low energy consumption, low cost and the like, and has a great application prospect. The most widely studied P-type small molecule semiconductor is 2,7-Dioctyl [1]]benzothieno[3,2-b][1]benzothiazophene (C8-BTBT), which has high crystallinity and high charge carrier mobility. But small molecules have anisotropy in charge transport, and
-
the interaction between bonds easily makes the film dehumidify on the substrate, so that the film-forming appearance of the small molecule semiconductor is uneven, and further, the solution processing is difficult and the device performance is poor. The polymer semiconductor has good solution processability, and in recent years, scientific researchers propose a method for blending small molecules and the polymer semiconductor, so that the film forming property of a blended film and the performance of a device can be effectively improved.
Here we propose to use a high electron-transporting N-type polymer semiconductor poly [ [ N, N-bis (2-octyldodecyl) -nap-
3, blending 1,4,5,8-bis (carboximide) -2,6-diyl ] -alt-5, 50- (2,20-bithiophene) ] (N2200) and C8-BTBT, and preparing the bipolar organic thin film transistor with C8-BTBT at the upper layer and N2200 at the lower layer by high-speed central spin coating and vertical phase separation.
The invention content is as follows:
in view of the above, the present invention is directed to an organic thin film transistor capable of realizing bipolar and a process for fabricating the same.
In order to achieve the above object, the present invention provides the following technical solutions:
a bipolar thin film transistor with organic micromolecule P-type semiconductor and N-type polymer semiconductor blended comprises a substrate, a metal electrode pair, an organic micromolecule semiconductor and polymer semiconductor mixed system, a dielectric layer, a high-speed center spin coating method and a gate electrode which are sequentially arranged.
Preferably the substrate is glass.
Preferably, the metal electrode pair has a pitch of 50 nm.
The invention also provides a preparation method of the thin film transistor mixed by the organic micromolecule semiconductor and the polymer semiconductor, which comprises the following steps:
providing a substrate, a metal electrode pair, a mixed precursor solution of C8-BTBT and N2200, a PMMA dielectric layer and a gate electrode.
(1) And covering a metal electrode pair on the substrate to form a source electrode and a drain electrode.
(2) And spin-coating a mixed precursor solution of C8-BTBT and N2200 on the substrate plated with the electrode at a high speed center to form a semiconductor layer.
(3) PMMA is spin-coated on the semiconductor layer as a dielectric layer.
(4) And covering a metal electrode at a fixed position on the surface of the dielectric layer to form a gate, thus obtaining the bipolar organic thin film transistor with the vertical phase separation organic small molecule semiconductor C8-BTBT at the upper layer and the polymer semiconductor N2200 at the lower layer.
Preferably, the step (2) of spin coating in a nitrogen glove box is performed, and the obtaining of the C8-BTBT and N2200 mixed semiconductor layer further comprises: the C8-BTBT and N2200 mixed semiconductor layer was heated in a nitrogen glove box at 120 ℃ for 2h, while the center spin speed was required to be 3000 rpm.
Preferably, the step (3) of spin coating in a nitrogen glove box is performed, and obtaining the PMMA dielectric layer further comprises: the PMMA dielectric layer was heated in a nitrogen glove box at a temperature of 70 ℃ for 2h, requiring a central spin speed of 3000 rpm.
The invention provides a micromolecule and polymer blended bipolar organic thin film transistor and a preparation method thereof, belonging to the field of photoelectric components. The device comprises a substrate, a metal electrode pair, an organic small molecule semiconductor C8-BTBT and polymer semiconductor N2200 blending system, a dielectric layer, a high-speed center spin coating method and a gate electrode which are sequentially arranged. The invention is provided withThe blending system is phase separated by controlling the proportion of the blending system and using a high-speed center spin coating method, and the blending system has excellent performance. In the blending system, the problem that small molecules are not easy to form films is solved, so that the small molecules have better crystallinity. The prepared bipolar transistor has good performance, and the hole mobility of the bipolar transistor reaches 0.148
The electron mobility reaches 0.32
On/off ratio of 10
。
Description of the drawings:
the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a structural diagram of an organic thin film transistor in which an organic small molecule semiconductor C8-BTBT and a polymer semiconductor N2200 are blended in example 1 of the present invention.
FIG. 2 is a graph showing the transfer characteristics of the organic thin film transistor test in which the small organic molecule semiconductor C8-BTBT is blended with the polymer semiconductor N2200 in example 1 of the present invention.
The specific implementation mode is as follows:
the invention provides a bipolar thin film transistor with blended organic micromolecule P-type semiconductor and N-type polymer semiconductor, which comprises a substrate, a metal electrode pair, an organic micromolecule semiconductor and polymer semiconductor mixed system, a dielectric layer, a high-speed center spin coating method and a gate electrode which are sequentially arranged.
In the invention, the bipolar thin film transistor formed by blending the organic small molecule P-type semiconductor and the N-type polymer semiconductor is characterized in that the small molecule proportion of the blending system is smaller, and is preferably 1-10%.
The high-speed center spin coating is characterized in that the spin coating speed is preferably 2000r/min to 4000r/min for a mixed semiconductor layer of organic micromolecules C8-BTBT and polymer N2200.
According to the invention, the organic micromolecule P-type semiconductor C8-BTBT and the N-type polymer semiconductor N2200 are blended, and after high-speed central spin coating, the bipolar thin film transistor with uniform performance is prepared through vertical phase separation. The mixed system and the process can solve the problem that small molecules are difficult to form films, and can transmit electrons and holes. The prepared bipolar transistor has good performance, and the hole mobility of the bipolar transistor reaches 0.148
The electron mobility reaches 0.32
On/off ratio of 10
。
The invention also provides a preparation method of the thin film transistor mixed by the organic micromolecule semiconductor and the polymer semiconductor, which comprises the following steps:
(1) and providing a glass substrate, a mixed precursor solution of C8-BTBT and N2200 and a dielectric layer.
(2) And covering the metal electrode pair on the glass substrate to form a source electrode and a drain electrode.
(3) And spin-coating a mixed precursor solution of C8-BTBT and N2200 on the substrate plated with the electrode at a high speed center to form a semiconductor layer.
(4) PMMA is spin-coated on the semiconductor layer as a dielectric layer.
(5) And covering a metal electrode at a fixed position on the surface of the dielectric layer to form a gate, thus obtaining the bipolar organic thin film transistor with the vertical phase separation organic small molecule semiconductor C8-BTBT at the upper layer and the polymer semiconductor N2200 at the lower layer.
The invention covers the metal source electrode and the metal drain electrode pair at fixed positions on the surface of the substrate. The operation of the covered metal electrode pair is not particularly limited in the present invention, and the preparation of the electrode is well known to those skilled in the artThe technical scheme is very good. In the present invention, the method of covering the metal electrode pair is preferably vapor deposition, and more preferably vacuum vapor deposition. In the invention, the temperature of the vacuum evaporation is preferably 1000-1200 ℃, and more preferably 1050-1150 ℃; the time of vacuum evaporation is preferably 20-30 min, and more preferably 24-26 min; the vacuum degree of the vacuum evaporation is preferably 4-5 multiplied by 10-4Pa. In the present invention, the target material for vapor deposition is preferably gold.
The invention provides a mixed precursor solution of C8-BTBT and N2200. In the present invention, the C8-BTBT/N2200 precursor solution preferably includes C8-BTBT, N2200 and chlorobenzene. In the invention, the ratio of the mole number of C8-BTBT and N2200 to the volume of chlorobenzene is 10 mol: 1 mol: 1ml, simply mixed and dissolved. The C8-BTBT, N2200 and chlorobenzene of the invention can be prepared by using commercial products which are well known to those skilled in the art. In the present invention, the purity of C8-BTBT is preferably 99%, and N2200 (M)
>50KDa)，PMMA( M
= 996 kDa) and chlorobenzene were purchased from Sigma-Aldrich.
In the present invention, a C8-BTBT/N2200 semiconductor layer was prepared by spin coating on a substrate with an evaporated electrode.
In the present invention, the spin coating is preferably performed on a spin coater. In the invention, the rotation speed of the spin coater is preferably 2000-4000 r/min, more preferably 3000r/min, and the rotation time is preferably 30 s.
In the present invention, the spin coating is preferably performed in a nitrogen glove box, and the semiconductor layer is obtained and then heated at 120 ℃ for 2 hours.
After a semiconductor layer is manufactured, the PMMA dielectric layer is prepared on the surface of the semiconductor layer by a spin coating method.
In the present invention, the spin coating is preferably performed on a spin coater. In the invention, the rotation speed of the spin coater is preferably 2000-4000 r/min, more preferably 3000r/min, and the rotation time is preferably 60 s.
In the present invention, the spin coating is preferably performed in a nitrogen glove box, and is heated at 70 ℃ for 2 hours after the dielectric layer is obtained.
The invention covers a metal gate electrode at a fixed position on the surface of the dielectric layer. The operation of the covered metal electrode pair is not particularly limited in the present invention, and the technical scheme for preparing the electrode, which is well known to those skilled in the art, can be adopted. In the present invention, the method of covering the metal electrode pair is preferably vapor deposition, and more preferably vacuum vapor deposition. In the invention, the temperature of the vacuum evaporation is preferably 1000-1200 ℃, and more preferably 1050-1150 ℃; the time of vacuum evaporation is preferably 20-30 min, and more preferably 24-26 min; the vacuum degree of the vacuum evaporation is preferably 4-5 multiplied by 10-4Pa. In the present invention, the target material for vapor deposition is preferably aluminum.
In the present invention, the bipolar organic thin film transistor is preferably used under inert conditions without water and oxygen. In the present invention, the connection mode of the bipolar organic thin film transistor is not particularly limited, and a connection mode with a power supply, which is well known to those skilled in the art, may be adopted.
The present invention provides a bipolar organic thin film transistor with small molecules blended with polymer and a method for making the same, which are described in detail below with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1:
5mg of N2200 and 0.5mg of C8-BTBT were put into a sample bottle containing 1mL of chlorobenzene, and stirred to obtain a precursor solution of N2200/C8-BTBT. 35mg of PMMA was put in a 1mL butanone sample bottle and stirred to obtain a PMMA precursor solution. In the invention, the sample bottle needs to be cleaned by acetone, isopropanol and deionized water before use, and the invention adopts acetone, isopropanol and deionized water for 1 time respectively in sequence.
A clean glass substrate is attached to a mask plate with a specific shape, and a layer of gold electrode with the thickness of 30nm is evaporated in vacuum to be used as a source electrode and a drain electrode.
And spin-coating the obtained C8-BTBT/N2200 mixed precursor solution on a glass substrate covered with the source electrode and the drain electrode in a nitrogen glove box through a spin coater to obtain a blended semiconductor layer. The rotation speed of the spin coater is preferably 3000rpm, and the rotation time is preferably 30 s. And heating the mixed semiconductor layer in a nitrogen glove box, wherein the heating temperature is preferably 120 ℃, and the heating time is preferably 2 hours.
And spin-coating the obtained PMMA precursor solution on a substrate covered with a semiconductor layer in a nitrogen glove box through a spin coater. The rotation speed of the spin coater is preferably 3000r/min, and the rotation time is preferably 60 s. And heating the PMMA dielectric layer in a nitrogen glove box, wherein the heating temperature is preferably 70 ℃, and the heating time is preferably 2 hours.
The obtained dielectric layer is attached to a mask plate with a specific shape, and a layer of aluminum electrode with the thickness of 3nm is evaporated in vacuum. And removing the mask plate to obtain the bipolar organic thin film transistor.
The structure of the bipolar organic thin film transistor in this embodiment is shown in fig. 1.
The transfer curve of the thin film transistor blended by the organic small molecule and the polymer in the embodiment is shown in fig. 2, and from fig. 2, the hole mobility of the thin film transistor blended by the organic small molecule P-type semiconductor and the N-type polymer semiconductor can be obtained to reach 0.148
The electron mobility reaches 0.32
On/off ratio of 10
。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119730551A (en) * | 2025-02-28 | 2025-03-28 | 天津大学 | Polymer organic photoelectric transistor and preparation method and application thereof |
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| US20100032662A1 (en) * | 2007-04-04 | 2010-02-11 | Cambridge Display Technology Ltd. | Organic Thin Film Transistors |
| JP2012033904A (en) * | 2010-06-30 | 2012-02-16 | National Institute For Materials Science | Method for forming organic semiconductor thin film, semiconductor element, and organic field effect transistor |
| US20120037891A1 (en) * | 2008-12-18 | 2012-02-16 | Postech Academy-Industry Foundation | Method of manufacturing multilayered thin film through phase separation of blend of organic semiconductor/insulating polymer and organic thin film transistor using the same |
| CN104919596A (en) * | 2012-11-30 | 2015-09-16 | 佛罗里达大学研究基金会有限公司 | Bipolar Vertical Field Effect Transistor |
| CN105679940A (en) * | 2016-04-19 | 2016-06-15 | 中国科学院化学研究所 | Bipolar polymer field effect transistor and preparation method and application thereof |
| CN112635673A (en) * | 2019-09-24 | 2021-04-09 | 湖北大学 | High-mobility flexible low-voltage organic thin film transistor and preparation method thereof |
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2021
- 2021-09-14 CN CN202111059073.4A patent/CN113921714A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100032662A1 (en) * | 2007-04-04 | 2010-02-11 | Cambridge Display Technology Ltd. | Organic Thin Film Transistors |
| US20120037891A1 (en) * | 2008-12-18 | 2012-02-16 | Postech Academy-Industry Foundation | Method of manufacturing multilayered thin film through phase separation of blend of organic semiconductor/insulating polymer and organic thin film transistor using the same |
| JP2012033904A (en) * | 2010-06-30 | 2012-02-16 | National Institute For Materials Science | Method for forming organic semiconductor thin film, semiconductor element, and organic field effect transistor |
| CN104919596A (en) * | 2012-11-30 | 2015-09-16 | 佛罗里达大学研究基金会有限公司 | Bipolar Vertical Field Effect Transistor |
| CN105679940A (en) * | 2016-04-19 | 2016-06-15 | 中国科学院化学研究所 | Bipolar polymer field effect transistor and preparation method and application thereof |
| CN112635673A (en) * | 2019-09-24 | 2021-04-09 | 湖北大学 | High-mobility flexible low-voltage organic thin film transistor and preparation method thereof |
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| CN119730551A (en) * | 2025-02-28 | 2025-03-28 | 天津大学 | Polymer organic photoelectric transistor and preparation method and application thereof |
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Application publication date: 20220111 |