CN112635672A - Method for regulating and controlling microstructure of organic small-molecule semiconductor film and application of method in transistor - Google Patents
Method for regulating and controlling microstructure of organic small-molecule semiconductor film and application of method in transistor Download PDFInfo
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- CN112635672A CN112635672A CN201910914421.8A CN201910914421A CN112635672A CN 112635672 A CN112635672 A CN 112635672A CN 201910914421 A CN201910914421 A CN 201910914421A CN 112635672 A CN112635672 A CN 112635672A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 27
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 14
- 230000001276 controlling effect Effects 0.000 title claims abstract description 13
- 229920006254 polymer film Polymers 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 20
- YWIGIVGUASXDPK-UHFFFAOYSA-N 2,7-dioctyl-[1]benzothiolo[3,2-b][1]benzothiole Chemical compound C12=CC=C(CCCCCCCC)C=C2SC2=C1SC1=CC(CCCCCCCC)=CC=C21 YWIGIVGUASXDPK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000390 Poly(styrene-block-methyl methacrylate) Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 21
- 239000010409 thin film Substances 0.000 abstract description 16
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- 239000004926 polymethyl methacrylate Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 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
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- 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
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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
- H10K85/10—Organic polymers or oligomers
Abstract
The invention provides a method for regulating and controlling a microstructure of an organic small-molecule semiconductor film and application of the method in a transistor, belonging to the field of photoelectric components. Comprises a substrate, a dielectric layer, a soluble polymer film modifying layer, and an organic small molecule 2, 7-Dioctyl [1]]benzothieno[3，2‑b][1]A system of mixing benzothiophene (C8-BTBT) and inert polymer, and a metal electrode pair. The invention adjusts and controls the microstructure of the organic semiconductor film through the modification of the dissolvable polymer film, thereby preparing the organic thin film transistor with high mobility. When the mixed semiconductor layer is spin-coated by a solution method, the soluble polymer film modification layer can be dissolved into the solution, so that the molecular crystallization and the film roughness of the small molecular semiconductor are influenced, and the large-grain semiconductor with large crystal grain and high film roughness can be prepared under the optimized conditionA semiconductor film having a smooth surface. We use SiO as a material2The mobility of the transistor with the bottom gate structure prepared for the medium exceeds 7cm2/Vs。
Description
Technical Field
The invention relates to the technical field of photoelectric components, in particular to a method for regulating and controlling a micro-structure of an organic small-molecule semiconductor film and application of the method in a transistor.
Background
The performance of the thin film transistor is directly determined by the development status of the display technology. Therefore, the development of innovative thin film transistors is required for the technological development of the current society. Organic small molecule semiconductors are of great interest to researchers because of their high mobility. 2, 7-Dioctyl 1 benzothiazeno 3, 2-b 1 benzothiazophene (C8-BTBT) is a P-type semiconductor with high mobility, which is a widely researched organic small molecule semiconductor material at present, but has some problems, such as too low viscosity of precursor solution to spin-coat on a substrate
In recent years, researchers mix organic small molecule semiconductors with polymers, utilize the excellent solution processability of the polymers to assist the formation of small molecules on a substrate, and prepare high-performance organic thin film transistors by vertical phase separation. The microstructure of the hybrid film, including molecular crystallization and film roughness, has a large effect on its performance. We provide a method for regulating and controlling the microstructure of an organic small molecule semiconductor film. The microstructure of the semiconductor micromolecule is regulated and controlled by modifying the dissolvable polymer film, so that the high-performance organic thin film transistor is prepared.
Disclosure of Invention
In view of the above, the present invention provides a method for controlling the microstructure of an organic small molecule semiconductor thin film and an application thereof in a transistor.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for regulating and controlling a microstructure of an organic small molecule semiconductor film and application of the microstructure in a transistor. The organic polymer composite material comprises a substrate, a dielectric layer, a soluble polymer film modification layer, an organic micromolecule 2, 7-Dioctyl [1] benzothiopheno [3, 2-b ] [1] benzothiophene (C8-BTBT) and inert polymer mixed system and a metal electrode pair which are sequentially arranged.
Preferably, the substrate comprises glass, flexible PET substrate or the like
Preferably, the dielectric layer includes an organic or inorganic insulating layer or the like
Preferably, the dissolvable polymer film modifying layer is polymer PS, PMMA and the like which are easily dissolved in organic solvent
The invention also provides a method for regulating and controlling the microstructure of the organic small molecule semiconductor film and application of the method in a transistor, which comprises the following steps:
providing a substrate, a dielectric layer, a soluble polymer film modification layer, a mixed system of organic micromolecules 2, 7-Dioctyl [1] benzothiopheno [3, 2-b ] [1] benzothiophene (C8-BTBT) and inert polymer, and a metal electrode pair. (ii) a
(1) Covering a metal electrode on the flexible substrate to form a gate electrode;
(2) preparing a dielectric layer on the substrate plated with the electrode;
(3) preparing a dissolvable polymer film modifying layer on the dielectric layer;
(4) preparing a C8-BTBT/polymer mixed semiconductor layer on the soluble polymer film Ti layer;
(5) preparing a source-drain electrode pair at a fixed position on the semiconductor layer;
preferably, the soluble polymer thin film modification layer in the step (3) should be easily soluble in the solvent in the mixed semiconductor solution.
The invention provides a method for regulating and controlling a microstructure of an organic small molecule semiconductor film and application of the method in a transistor, belonging to the field of photoelectric components. Comprises a substrate, a dielectric layer and a soluble polymer which are arranged in sequence; film modifying layer, organic small molecule 2, 7-Dioctyl [1]]benzothieno[3，2-b][1]A system of mixing benzothiophene (C8-BTBT) and inert polymer, and a metal electrode pair. The invention adjusts and controls the microstructure of the organic semiconductor film through the modification of the dissolvable polymer film, thereby preparing the organic thin film transistor with high mobility. When the mixed semiconductor layer is spin-coated by a solution method, the soluble polymer film modification layer can be dissolved into the solution, so that the molecular crystallization of the small molecular semiconductor and the film roughness can be influenced, and the preparation can be carried out under the optimized conditionA semiconductor thin film having large crystal grains and a smooth surface is obtained. We use SiO as a material2The mobility of the transistor with the bottom gate structure prepared for the medium exceeds 7cm2/Vs。
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a schematic view of a device structure in embodiment 1 of the present invention;
FIG. 2 is a transfer characteristic curve and an output characteristic curve of an organic thin film transistor modified by a soluble polymer film in example 2 of the present invention;
Detailed Description
The invention provides a method for regulating and controlling a microstructure of an organic small-molecule semiconductor film and application of the method in a transistor, belonging to the field of photoelectric components. The organic polymer composite material comprises a substrate, a dielectric layer, a soluble polymer film modification layer, an organic micromolecule 2, 7-Dioctyl [1] benzothiopheno [3, 2-b ] [1] benzothiophene (C8-BTBT) and inert polymer mixed system and a metal electrode pair which are sequentially arranged.
The method for regulating and controlling the microstructure of the organic small molecule semiconductor thin film and the application of the method in the transistor are characterized in that the substrate comprises a flexible plastic base such as PET (polyethylene terephthalate), and preferably has a planar structure.
In the invention, the dielectric layer is an organic or inorganic dielectric layer, and the coverage area is wide.
In the invention, the soluble polymer film modification layer is a polymer which is easily soluble in an organic solvent.
In the invention, the organic micromolecule C8-BTBT polymer mixed system is characterized in that the polymer accounts for 5-10% of a small proportion.
The invention adjusts and controls the microstructure of the organic semiconductor film through the modification of the dissolvable polymer film, thereby preparing the organic thin film transistor with high mobility. When the mixed semiconductor layer is spin-coated by a solution method, the soluble polymer film modification layer can be dissolved into the solution, so that the molecular crystallization and the film roughness of the small molecular semiconductor are influenced, and the mixed semiconductor layer can be prepared under the optimized conditionsThe semiconductor film with large crystal grains and smooth surface is prepared. We use SiO as a material2The mobility of the transistor with the bottom gate structure prepared for the medium exceeds 7cm2/Vs。
The invention also provides a preparation method of the thin film transistor mixed by the organic micromolecules and the polymer, which comprises the following steps:
1) providing a substrate, a dielectric layer, a soluble polymer film modification layer, organic small molecule 2, 7-Dioctyl [1] benzothiopheno [3, 2-b ] [1] benzothiophene (C8-BTBT, inert polymer mixed system and a metal electrode pair.
2) Covering a metal electrode on the flexible substrate to form a gate electrode;
3) preparing a dielectric layer on the substrate plated with the electrode;
4) preparing a dissolvable polymer film modifying layer on the dielectric layer;
5) preparing a C8-BTBT/polymer mixed semiconductor layer on the soluble polymer film Ti layer;
6) preparing a source-drain electrode pair at a fixed position on the semiconductor layer;
the invention provides a precursor solution for gathering. The precursor solution in the invention comprises a PS precursor solution and a PMMA precursor solution. And preparing a modified film on the dielectric layer by the precursor solution through a spin coating method.
The invention provides a mixed precursor solution of C8-BTBT and polymer, and in the invention, the C8BTBT/PMMA precursor solution preferably comprises C8BTBT, PMMA and chlorobenzene. In the invention, the molar ratio of the C8BTBT to the PMMA to the chlorobenzene is 5 mol: 1ml, and the components are simply mixed and dissolved. The C8BTBT, PMMA and chlorobenzene of the present invention can be prepared by using commercially available products well known to those skilled in the art, wherein the purity of the C8BTBT is preferably 99%, and the purity of the PMMA (M) is preferably 99%w996kDa) and chlorobenzene were purchased from Sigma-Aldrich.
In the present invention, the spin coating of the hybrid semiconductor is preferably performed on a spin coater. The rotating speed of the spin coater is preferably 4000-7000 r/min, and more preferably 5500 r/min; the rotation time is preferably 20 to 40s, and more preferably 30 s.
The invention covers the metal source and drain electrodes at fixed positions on the surface of the mixed semiconductor. 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 invention, the mode of covering the metal electrode pair is preferably evaporation plating, more preferably vacuum evaporation plating, and in the invention, the temperature of the vacuum evaporation plating is preferably 1000-1200 ℃, 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 3-4 x 10-4Pa. In the present invention, the target material for vapor deposition is preferably gold.
The method for regulating the microstructure of the organic small molecule semiconductor thin film and the application thereof in the transistor provided by the invention are described in detail below with reference to the examples, but the method and the application thereof are not to be construed as limiting the scope of the invention.
Example 1
25mg of C8BTBT and 5mg of PMMA were put in a sample bottle containing 5mL of chlorobenzene, and stirred to obtain a C8BTBT/PMMA mixed precursor solution. 600mg of PS was filled in a sample bottle containing 5ml of deionized water, and the PS precursor solution was obtained all by stirring. 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.
Preparation of clean Si/SiO2Substrate
The obtained PS precursor solution is spin-coated on a substrate, and 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 70 ℃, and the heating time is preferably 15 minutes.
And spin-coating the obtained C8BTBT/PMMA mixed precursor solution on the modification layer in a nitrogen glove box through a spin coater to obtain the mixed semiconductor layer. The rotation speed of the spin coater is preferably 6000rpm, the rotation time is preferably 30s, the mixed semiconductor layer is heated in a nitrogen glove box, the heating temperature is preferably 70 ℃, and the heating time is preferably 15 minutes.
And adhering the obtained mixed semiconductor layer to a mask plate with a specific shape, and evaporating a layer of source and drain electrodes in vacuum. And removing the mask to obtain the prepared transistor.
The performance of the organic thin film transistor modified by the soluble polymer film in the embodiment is shown in fig. 1, and the mobility of the organic thin film transistor can be obtained from fig. 1 and exceeds 7cm2Vs, on-off ratio over 106。
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.
Claims (4)
1. A method for regulating and controlling a micro-structure of an organic micromolecule semiconductor film and an application of the micro-structure in a transistor comprise a substrate, a gate electrode, a dielectric layer, a soluble polymer film modification layer, a mixed system of organic micromolecules 2, 7-Dioctyl [1] benzothieno [3, 2-b ] [1] benzothiophene (C8-BTBT) and an appropriate polymer and a metal electrode pair which are sequentially arranged.
2. The dissolvable polymer film modifying layer according to claim 1, being a polymer that is readily soluble in organic solvents, such as PS PMMA.
3. The system of claim 1, wherein the mixture of small organic molecules and semiconductors is spin-coated onto the dissolvable polymer film at a high speed, preferably at a speed of 4000r/min to 7000 r/min.
4. The method for regulating and controlling the microstructure of the organic small molecule semiconductor film and the application thereof in the transistor according to any one of claims 1 to 3, comprising the following steps:
(1) covering a metal electrode on the flexible substrate to form a gate electrode;
(2) preparing a dielectric layer on the substrate plated with the electrode;
(3) preparing a dissolvable polymer film modifying layer on the dielectric layer;
(4) preparing a C8-BTBT/polymer mixed semiconductor layer on the soluble polymer film Ti layer;
(5) and preparing a source-drain electrode pair at a fixed position on the semiconductor layer.
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| CN201910914421.8A CN112635672A (en) | 2019-09-24 | 2019-09-24 | Method for regulating and controlling microstructure of organic small-molecule semiconductor film and application of method in transistor |
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| CN201910914421.8A CN112635672A (en) | 2019-09-24 | 2019-09-24 | Method for regulating and controlling microstructure of organic small-molecule semiconductor film and application of method in transistor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115440886A (en) * | 2022-11-08 | 2022-12-06 | 中国人民解放军国防科技大学 | Micromolecule-polymer composite organic semiconductor film and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| CN107195781A (en) * | 2017-05-24 | 2017-09-22 | 华南师范大学 | A kind of high mobility transistor for small molecule of being adulterated based on PMMA and preparation method thereof |
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- 2019-09-24 CN CN201910914421.8A patent/CN112635672A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195781A (en) * | 2017-05-24 | 2017-09-22 | 华南师范大学 | A kind of high mobility transistor for small molecule of being adulterated based on PMMA and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHUAN LIU等: "Critical Impact of Gate Dielectric Interfaces on the Contact Resistance of High-Performance Organic Field-Effect Transistors", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| KENJI KOTSUKI等: "The importance of spinning speed in fabrication of spin-coated organic thin film transistors: Film morphology and field effect mobility", 《APPLIED PHYSICAL LETTERS》 * |
| YAO NI等: "The strong continuous induction effect based on isotype heterojunction transistors with different polymer modifications", 《ORGANIC ELECTRONICS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115440886A (en) * | 2022-11-08 | 2022-12-06 | 中国人民解放军国防科技大学 | Micromolecule-polymer composite organic semiconductor film and preparation method thereof |
| CN115440886B (en) * | 2022-11-08 | 2023-01-24 | 中国人民解放军国防科技大学 | Micromolecule-polymer composite organic semiconductor film and preparation method thereof |
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Application publication date: 20210409 |