CN110707215B - Preparation process of organic field effect transistor with carbonyl sulfide and ammonia gas as doping agents - Google Patents
Preparation process of organic field effect transistor with carbonyl sulfide and ammonia gas as doping agents Download PDFInfo
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000005669 field effect Effects 0.000 title claims abstract description 15
- 239000002019 doping agent Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000004065 semiconductor Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 28
- 239000010408 film Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- AZUXXYCNTKYZJB-UHFFFAOYSA-N chloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[SiH2]Cl AZUXXYCNTKYZJB-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000007738 vacuum evaporation 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]
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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
- H10K71/30—Doping active layers, e.g. electron transporting layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention discloses a preparation process of an organic field effect transistor with carbonyl sulfide and ammonia gas as dopants, which comprises the following steps: (1) providing a substrate; (2) preparing a modification layer on the insulating layer of the substrate; (3) Preparing a P-type organic semiconductor material layer on the modification layer of the substrate; (4) Doping the P-type organic semiconductor material layer of the substrate with carbonyl sulfide and ammonia gas in a volume ratio of 3-5 as N-type dopants to form an N-type semiconductor material layer; (5) And preparing a source electrode and a drain electrode on the N-type semiconductor material layer of the substrate. The COS is used for converting the P-type organic field effect transistor material into the N-type material, the range of the P-type material is greatly widened, the N-type material type of the organic semiconductor is greatly enriched, the surface appearance of the thin film is changed by introducing NH3 gas into the COS atmosphere, the contact between the source electrode and the drain electrode and the P3HT thin film is greatly changed, and therefore the threshold voltage of the device is reduced.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation process of an organic field effect transistor with carbonyl sulfide and ammonia gas as dopants.
Background
Organic field effect transistors have been rapidly developed in recent years as the most basic constituent unit of flexible electronics. Different from the conventional silicon-based semiconductor technology in which a doping technology is used to realize P-type and N-type regions, the organic semiconductor material utilizes the structural design of molecules to obtain P-type and N-type materials. However, although the structural design of molecules brings about countless different kinds of semiconductor materials, the materials are mainly P-type organic semiconductors due to the energy levels inherent to organic semiconductors. Meanwhile, in the current stage, the material design means for the N-type molecules mainly adds electron-withdrawing groups to reduce the HOMO and LUMO of the organic semiconductor material, so that the conversion from the P-type organic semiconductor material to the N-type organic semiconductor material is realized. However, the LUMO of the material is too low, and thus, the N-type organic semiconductor material is easily oxidized in air. Therefore, there is a strong lack of an N-type organic semiconductor material which is stable in air in the field of organic semiconductors. Meanwhile, a large amount of organic solvents and other chemical substances are applied to the structural design and synthesis of molecules, so that the cost for treating the three wastes is very high. For practical applications of organic semiconductors, there is an urgent need for N-type materials that match the P-type energy level. Therefore, it is urgent to expand the kinds and the number of N-type organic semiconductors.
Disclosure of Invention
The invention aims to provide a preparation process of an organic field effect transistor by taking carbonyl sulfide and ammonia gas as doping agents, wherein a P-type organic field effect transistor material is converted into an N-type material through COS, the range of the P-type material is greatly widened, the N-type material variety of an organic semiconductor is greatly enriched, and the change of the surface appearance of a film is realized by introducing NH3 gas in COS atmosphere. Therefore, the contact between the source and drain electrodes and the P3HT film is greatly changed, and the threshold voltage of the device is reduced.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation process of an organic field effect transistor with carbonyl sulfide and ammonia gas as dopants comprises the following steps:
(1) Providing a substrate, wherein the substrate is provided with an insulating layer;
(2) Preparing a modification layer on the insulating layer of the substrate provided in the step (1);
(3) Preparing a P-type organic semiconductor material layer on the modification layer of the substrate obtained in the step (2);
(4) Doping the P-type organic semiconductor material layer of the substrate obtained in the step (3) with N-type dopants by using carbonyl sulfide and ammonia gas in a volume ratio of 3-5;
(5) And (4) preparing a source electrode and a drain electrode on the N-type semiconductor material layer of the substrate obtained in the step (4).
Further, in the step (4), the silicon wafer is placed in a mixed atmosphere of carbonyl sulfide and ammonia gas for annealing for 1 hour, and the N-type semiconductor material layer is prepared.
Further, in the step (1), the substrate is a silicon wafer, a glass plate, a PI plate or a PMMA plate, and the insulating layer is a silicon dioxide material layer, an aluminum oxide material layer or a tantalum pentoxide material layer.
Further, the substrate is a silicon wafer with a silicon dioxide film, the silicon wafer is 100 crystal face P type heavy doping, and the thickness of the silicon wafer is 300mm.
Further, in the step (2), the modification layer is an octadecyl trichlorosilane material layer or an octyl trichlorosilane material layer.
Further, in the step (2), the substrate is soaked in a 1mol/L toluene solution of octadecylchlorosilane for 24 hours to prepare the octadecyltrichlorosilane material layer.
Further, in the step (3), the molecular structure of the P-type organic semiconductor material layer is selected from any one of the following 12 molecular structures:
further, in the step (3), a chlorobenzene solution of P3HT is prepared at a concentration of 10mol/L, and then the chlorobenzene solution of P3HT is spin-coated on the insulating surface of the substrate at a spin-coating speed of 5000r/min to a spin-coating thickness of 100nm, so as to prepare the P3HT material layer.
Further, the source electrode and the drain electrode are gold electrodes, silver electrodes, copper electrodes or aluminum electrodes.
Further, a gold electrode having a thickness of 50nm was vacuum-deposited as a source electrode and a drain electrode, and the thickness of the gold electrode was 50nm.
As mentioned above, COS has the electron-rich property of sulfur and oxygen in its molecular formula, and is an organic molecule, so that it is very suitable for use as N-type dopant of organic semiconductor thin film, the substrate is used as gate electrode, the insulating layer is arranged between the semiconductor layer and the gate electrode, and the modifying layer is used for improving SiO 2 Surface topography and reduction due to SiO 2 The carrier trap formed by the exposed hydrogen bonds on the surface ensures the performance of the deviceAnd more preferably.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the invention discloses a preparation process of an organic field effect transistor by taking carbonyl sulfide and ammonia as doping agents, which utilizes the electron-rich characteristic of COS to dope a P-type organic semiconductor material to form an N-type semiconductor material, so that the P-type organic field effect transistor material is converted into the N-type material, the range of the P-type material is greatly expanded, the N-type material variety of the organic semiconductor is greatly enriched, the problem that the traditional N-type material design method is very easy to oxidize by air is avoided, and NH is utilized to simultaneously 3 The shape of the film is changed, the contact between the source electrode and the drain electrode and the P3HT film is improved, and therefore the threshold voltage of the device is reduced.
Drawings
FIG. 1 is a schematic diagram of an organic field effect transistor according to the present disclosure;
FIG. 2 is a flow chart of a disclosed manufacturing process;
in FIG. 3, a is COS + NH disclosed by the present invention 3 AFM height map of the annealed silicon wafer;
FIG. 3 b shows COS + NH disclosed in the present invention 3 Phase diagram of the annealed silicon wafer;
FIG. 3 c is an AFM height map of a pure COS annealed silicon wafer as disclosed herein;
in FIG. 3 d is the AFM phase diagram of the pure COS annealed silicon wafer as disclosed in the present invention.
Wherein, 1, a substrate; 2. an insulating layer; 3. a finishing layer; 4. a layer of organic semiconductor material; 5. a source electrode; 6. a drain electrode;
SiO 2 silicon dioxide; ODTS, octadecylchlorosilane; tol, toluene; p3HT, poly-3-hexylthiophene; COS, carbonyl sulfide; NH 3 And ammonia gas.
Detailed Description
The invention is further described with reference to the accompanying drawings and examples:
example one
Referring to fig. 1, the organic field effect transistor includes a substrate 1, an insulating layer 2, a modification layer 3, an organic semiconductor material layer 4, a source electrode 5, and a drain electrode 6.
Referring to fig. 2, the process steps of the organic field effect transistor are as follows:
(1) taking a silicon dioxide silicon wafer with the thickness of 300nm as a starting point, the crystal phase: 100 crystal plane, P-type heavy doping;
(2) soaking the silicon wafer in 1mol/L toluene solution of octadecylchlorosilane for 24 hours;
(3) then P3HT is coated on the surface layer of the silicon wafer in a spin mode,
dissolving P3HT in chlorobenzene; concentration: 10mol/L;
spin coating speed: 5000r/min
Final film thickness: 100nm;
(4) then placing the silicon wafer in COS and NH3 for annealing for 1h; v (COS): v (NH 3) = 4;
the purpose of the COS anneal is to diffuse COS molecules into the P3HT material. The electron density of the P3HT film is improved by utilizing the characteristic of rich electrons of COS, so that the P3HT is converted into an N-type semiconductor material, and NH is introduced into the COS system 3 And then, the electron density in the semiconductor layer is further increased, the film appearance of the material is improved, and the threshold voltage of the device is reduced while the mobility of the device is improved.
(5) Finally, gold electrodes with the thickness of 50nm are subjected to vacuum evaporation to form source and drain electrodes.
Final properties table of the product:
the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation process of an organic field effect transistor with carbonyl sulfide and ammonia gas as dopants is characterized by comprising the following steps:
(1) Providing a substrate, wherein the substrate is provided with an insulating layer;
(2) Preparing a modification layer on the insulating layer of the substrate provided in the step (1);
(3) Preparing a P3HT material layer on the modification layer of the substrate obtained in the step (2);
(4) Doping the P3HT material layer of the substrate obtained in the step (3) with N-type dopants by using carbonyl sulfide and ammonia gas in a volume ratio of 3-5;
(5) And (5) preparing a source electrode and a drain electrode on the N-type semiconductor material layer of the substrate obtained in the step (4).
2. The process according to claim 1, wherein in the step (4), the silicon wafer is annealed in a mixed atmosphere of carbonyl sulfide and ammonia gas for 1 hour to obtain the N-type semiconductor material layer.
3. The process according to claim 1, wherein in the step (1), the substrate is a silicon wafer, a glass plate, a PI plate or a PMMA plate, and the insulating layer is a silicon dioxide material layer, an aluminum oxide material layer or a tantalum pentoxide material layer.
4. The preparation process according to claim 3, wherein the substrate is a silicon wafer with a silicon dioxide film, the silicon wafer is heavily P-type doped with 100 crystal planes, and the thickness of the silicon wafer is 300mm.
5. The process of claim 1, wherein in step (2), the modifying layer is a layer of octadecyltrichlorosilane or octyltrichlorosilane.
6. The process according to claim 5, wherein in the step (2), the substrate is immersed in a toluene solution of 1mol/L of octadecyltrichlorosilane for 24 hours to obtain the layer of octadecyltrichlorosilane.
7. The process according to claim 1, wherein in step (3), the molecular structure of the layer of P3HT material is selected from any one of the following 12 molecular structures:
8. the process according to claim 7, wherein in step (3), the P3HT material layer is prepared by first preparing a 10mol/L P3HT chlorobenzene solution, and then spin-coating the P3HT chlorobenzene solution on the insulating surface of the substrate at a spin speed of 5000r/min to a spin thickness of 100 nm.
9. The process according to claim 1, wherein the source electrode and the drain electrode are gold, silver, copper or aluminum electrodes.
10. The production process according to claim 9, wherein a 50nm thick gold electrode is vacuum-evaporated as the source electrode and the drain electrode, and the thickness of the gold electrode is 50nm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105340097A (en) * | 2013-04-23 | 2016-02-17 | 诺瓦尔德股份有限公司 | A method for producing an organic field effect transistor and an organic field effect transistor |
| WO2016047587A1 (en) * | 2014-09-25 | 2016-03-31 | 富士フイルム株式会社 | Organic field effect transistor, method for producing organic semiconductor crystal, and organic semiconductor element |
| CN106165105A (en) * | 2014-03-26 | 2016-11-23 | 富士胶片株式会社 | Non-luminescent organic semiconductor device coating fluid, organic transistor, compound, non-luminescent organic semiconductor device organic semiconducting materials, the effective material of organic crystal, the manufacture method of organic transistor and the manufacture method of organic semiconductor film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005122293A2 (en) * | 2004-06-08 | 2005-12-22 | Princeton University | Formation of ordered thin films of organics on metal oxide surfaces |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105340097A (en) * | 2013-04-23 | 2016-02-17 | 诺瓦尔德股份有限公司 | A method for producing an organic field effect transistor and an organic field effect transistor |
| CN106165105A (en) * | 2014-03-26 | 2016-11-23 | 富士胶片株式会社 | Non-luminescent organic semiconductor device coating fluid, organic transistor, compound, non-luminescent organic semiconductor device organic semiconducting materials, the effective material of organic crystal, the manufacture method of organic transistor and the manufacture method of organic semiconductor film |
| WO2016047587A1 (en) * | 2014-09-25 | 2016-03-31 | 富士フイルム株式会社 | Organic field effect transistor, method for producing organic semiconductor crystal, and organic semiconductor element |
Non-Patent Citations (1)
| Title |
|---|
| Recent progress in the development of n-type organic semiconductors for organic field effect transistors;Jesse T. E. Quinn,ET AL;《J. Mater. Chem. C》;20171231;全文 * |
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