CN112652717A - Method for improving carrier mobility of organic thin film transistor device through solvent vapor heat treatment - Google Patents
Method for improving carrier mobility of organic thin film transistor device through solvent vapor heat treatment Download PDFInfo
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- CN112652717A CN112652717A CN202011441237.5A CN202011441237A CN112652717A CN 112652717 A CN112652717 A CN 112652717A CN 202011441237 A CN202011441237 A CN 202011441237A CN 112652717 A CN112652717 A CN 112652717A
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- 239000002904 solvent Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000010438 heat treatment Methods 0.000 title claims abstract description 18
- 239000010409 thin film Substances 0.000 title claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 230000003746 surface roughness Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 7
- 230000003993 interaction Effects 0.000 description 6
- 238000000654 solvent vapour annealing Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000011368 organic material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RJBIEUUXYQTZNX-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1.ClC1=CC=C(Cl)C(Cl)=C1 RJBIEUUXYQTZNX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007725 thermal activation 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 potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- 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]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/464—Lateral top-gate IGFETs comprising only a single gate
-
- 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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
- H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
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- Manufacturing & Machinery (AREA)
- Thin Film Transistor (AREA)
Abstract
The invention discloses a method for improving carrier mobility of an organic thin film transistor device through heat treatment of solvent vapor. According to the invention, the active layer of the organic thin film transistor device is placed in a solvent steam environment for thermal annealing treatment, so that the surface roughness of the active layer is obviously increased, the mobility of the current carrier of the device is improved, and a new post-treatment process is provided for improving the mobility of the current carrier of the OTFT device.
Description
Technical Field
The invention belongs to the field of organic thin film transistor devices, and particularly relates to a method for improving carrier mobility of an organic thin film transistor device through solvent vapor heat treatment.
Background
The carrier mobility of an organic thin film transistor is closely related to the morphology of an organic semiconductor thin film. The morphology of organic semiconductor materials generally includes amorphous, polycrystalline, single crystal and nanowire crystals. Pi-pi stacking of molecules within an organic semiconductor delocalizes carriers within polymers or small molecules. For long range ordered materials (such as single crystal or polycrystalline), the distance of intermolecular delocalization is relatively long, and for low crystallinity or amorphous materials the delocalization length is relatively short, since the latter is highly localized at the grain boundaries and requires a jump from one molecule to another by thermal activation. This requires a high degree of crystallization of the organic material to achieve high carrier mobility. There are two main processes for obtaining a highly crystalline organic semiconductor film, one is crystallization during film deposition, and the other is crystallization after film deposition. The latter is also called post annealing treatment, and the main method is by thermal annealing treatment, vacuum annealing treatment, gas annealing treatment, and Solvent Vapor Annealing (SVA).
The main function of the solvent vapor annealing treatment is to promote the rearrangement of organic material molecules, the crystallization or phase separation of the film, change the surface appearance of the organic film, further influence the transmission characteristics of current carriers in the organic film and improve the performance of the device. The solvent vapor annealing process is a complex process, the result of which depends on the interaction between solvent molecules, organic molecules and the substrate. On the one hand, when the interaction between the solvent molecules and the organic molecules is strong, the molecular chains of the organic molecules are relaxed and undergo rearrangement. On the other hand, if the interaction of the solvent molecules with the organic molecules is weak, the rearrangement of the organic molecules by the solvent vapor annealing treatment is weak. De Luca et al reported the heat treatment of organic polymer films with different solvent vapors and investigated the effect of solvent molecule polarity and solubility on the molecular arrangement of polymer films.
In an organic conjugated polymer system, Sirringhaus firstly reports the influence of solvent drying time on the crystallinity of a conjugated polymer, and a high-boiling 1,2,5-Trichlorobenzene (TCB) solvent is added into a poly (3-hexylthiophene) (P3HT) solution to obtain an OTFT device with the carrier mobility of 0.12 cm2V-1s-1This is because the solution of P3HT added with 1,2,4-trichlorobenzene (1,2,4-trichlorobenzene) with high boiling point has better crystallinity after spin coating. However, different temperatures of different solvents have different crystallization effects and different effects on the carrier mobility of the OTFT device. How to further improve the crystallinity and the carrier mobility of the thin film of the OTFT device hasTo be studied.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a method for improving the carrier mobility of an organic thin film transistor device through solvent vapor heat treatment.
Based on the solubility of the organic semiconductor material in the solvent, the invention discovers that different solvent steam annealing treatments have different influences on the carrier mobility of the OTFT device, wherein the solvent is methanol, xylene or chlorobenzene.
The purpose of the invention is realized by the following technical scheme:
a method for improving carrier mobility of an organic thin film transistor device by solvent vapor heat treatment comprises the following steps:
preparing a source drain electrode on a substrate, preparing an active layer by a spin coating method, placing the active layer in a solvent steam environment, carrying out thermal annealing treatment at 80-200 ℃ for 0.5-3 hours, and sequentially preparing an insulating layer and a grid electrode on the treated active layer.
The organic thin film transistor device comprises a substrate, a source drain electrode, an active layer, an insulating layer and a grid electrode from bottom to top in sequence.
Preferably, the active layer material is poly [4- (4, 4-dihexadecyl) organic semiconductor material
-4Hcyclopenta [1,2-b:5, 4-b' ] dithiophen-2-yl) -alt- [1,2,5] thiadiazolo- [3,4-c ] pyridine ] (PCDTPT) with a thickness of 40-150 nm.
Preferably, the solvent is at least one of methanol, xylene, and chlorobenzene.
Preferably, the substrate is a glass substrate; the source and drain electrodes are made of gold, and the thickness of the source and drain electrodes is 30-100 nm.
Preferably, the insulating layer is made of PMMA (polymethyl methacrylate) and has a thickness of 400-600 nm.
Preferably, the gate material is aluminum, and the thickness of the gate material is 60-200 nm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the top-gate bottom-contact device structure provided by the invention starts from the strength of the interaction between organic semiconductor material molecules and solvent molecules, the influence of solvent vapor annealing treatment on the carrier mobility of an OTFT device is researched, solvents are methanol, xylene and chlorobenzene respectively, the surface roughness of the OTFT device is gradually increased along with the enhancement of the interaction force between the solvent molecules and PCDTPT molecules after vapor heat treatment, and the situation that the PCDTPT molecular chains are relaxed and rearranged during the heat treatment of the solvent vapor, so that the surface is rougher is shown. When annealing treatment is carried out for 1 hour at 140 ℃ in chlorobenzene vapor, the carrier mobility of the OTFT device is the highest, mainly because the interaction between the solvent molecules and the PCDTPT molecules of the organic material is the strongest, the molecular chains of the molecules of the organic material are relaxed, self-assembly is carried out, the arrangement is more ordered, and the mobility is improved. The invention provides a novel post-treatment process for improving the carrier mobility of an OTFT device.
Drawings
FIG. 1 is a schematic view of the vapor heat treatment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
The organic thin film transistor device comprises a substrate, a source drain electrode, an active layer, an insulating layer and a grid electrode from bottom to top in sequence.
The experiment designs a top-gate bottom-contact device structure, firstly a layer of gold source and drain electrodes with the thickness of 40nm is evaporated on a cleaned glass substrate in vacuum through a mask, then an active layer material PCDTPT (solvent is chlorobenzene, the concentration is 5mg/ml) is coated in a spinning mode, the thickness is 60nm, then thermal annealing treatment is carried out in different environments, then an insulating layer material PMMA is coated in a spinning mode, the thickness is 450nm, and finally a layer of 100nm aluminum gate is evaporated through a mask process;
the thermal annealing treatment conditions in different environments are respectively as follows:
device 1: neither heat treatment nor solvent vapor treatment of the device, i.e. no treatment of the active layer;
device 2: heat treatment is carried out for 1 hour at 140 ℃ in nitrogen;
device 3: heat treatment in methanol vapor at 140 deg.c for 1 hr;
device 4: carrying out heat treatment in xylene vapor at 140 ℃ for 1 hour;
device 5: heat treatment is carried out in chlorobenzene vapor at 140 ℃ for 1 hour.
Example 1 the surface roughness of the active layer of the device obtained by different treatment methods is shown in table 1 below and the carrier mobility of the device is shown in table 2 below.
TABLE 1 surface roughness of active layer
TABLE 2 Carrier mobility of devices
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A method for improving the carrier mobility of an organic thin film transistor device by solvent vapor heat treatment is characterized by comprising the following steps:
preparing a source drain electrode on a substrate, preparing an active layer by a spin coating method, placing the active layer in a solvent steam environment, carrying out thermal annealing treatment at 80-200 ℃ for 0.5-3 hours, and sequentially preparing an insulating layer and a grid electrode on the treated active layer.
2. The method of claim 1, wherein the active layer is made of PCDTPT, an organic semiconductor material.
3. The method of claim 1, wherein the solvent is at least one of methanol, xylene, and chlorobenzene.
4. The method of claim 1, wherein the active layer has a thickness of 40-150 nm.
5. The method for improving the carrier mobility of the organic thin film transistor device through the solvent vapor thermal treatment according to claim 1, wherein the organic thin film transistor device comprises a substrate, a source/drain electrode, an active layer, an insulating layer and a gate electrode from bottom to top in sequence.
6. The method for improving the carrier mobility of the organic thin film transistor device through the solvent vapor heat treatment according to claim 1, wherein the insulating layer is made of PMMA and has a thickness of 400-600 nm.
7. The method for improving the carrier mobility of the organic thin film transistor device through the solvent vapor heat treatment according to claim 1, wherein the source electrode and the drain electrode are made of gold, and the thickness of the source electrode and the drain electrode is 30-100 nnm.
8. The method of claim 1, wherein the gate material is aluminum with a thickness of 60-200 nm.
9. The method of claim 1, wherein the substrate is a glass substrate.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150214486A1 (en) * | 2012-09-07 | 2015-07-30 | Hsin-Rong Tseng | Field-effect transistors based on macroscopically oriented polymers |
| CN105552228A (en) * | 2016-02-05 | 2016-05-04 | 福州大学 | Organic thin film transistor and method for improving mobility of organic thin film transistor |
| US20170054096A1 (en) * | 2012-09-07 | 2017-02-23 | The Regents Of The University Of California | High mobility polymer organic field-effect transistors by blade-coating semiconductor:insulator blend solutions |
| US20170069859A1 (en) * | 2011-06-17 | 2017-03-09 | The Regents Of The University Of California | Doping-induced carrier density modulation in polymer field-effect transistors |
| CN108288672A (en) * | 2018-01-16 | 2018-07-17 | 华东师范大学 | A kind of preparation method of Organic Thin Film Transistors |
| CN110265548A (en) * | 2019-06-04 | 2019-09-20 | 华东师范大学 | A kind of indium doping N type organic thin-film transistor and preparation method thereof |
-
2020
- 2020-12-11 CN CN202011441237.5A patent/CN112652717A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170069859A1 (en) * | 2011-06-17 | 2017-03-09 | The Regents Of The University Of California | Doping-induced carrier density modulation in polymer field-effect transistors |
| US20150214486A1 (en) * | 2012-09-07 | 2015-07-30 | Hsin-Rong Tseng | Field-effect transistors based on macroscopically oriented polymers |
| US20170054096A1 (en) * | 2012-09-07 | 2017-02-23 | The Regents Of The University Of California | High mobility polymer organic field-effect transistors by blade-coating semiconductor:insulator blend solutions |
| CN105552228A (en) * | 2016-02-05 | 2016-05-04 | 福州大学 | Organic thin film transistor and method for improving mobility of organic thin film transistor |
| CN108288672A (en) * | 2018-01-16 | 2018-07-17 | 华东师范大学 | A kind of preparation method of Organic Thin Film Transistors |
| CN110265548A (en) * | 2019-06-04 | 2019-09-20 | 华东师范大学 | A kind of indium doping N type organic thin-film transistor and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张鹏: ""液相法制备高性能的有机场效应晶体管"", 《中国优秀博硕士学位论文全文数据库(硕士) 信息科技辑》 * |
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