CN102856211A - Manufacture method for active layer of carbon nano tube field effect transistor - Google Patents
Manufacture method for active layer of carbon nano tube field effect transistor Download PDFInfo
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- CN102856211A CN102856211A CN2012103656352A CN201210365635A CN102856211A CN 102856211 A CN102856211 A CN 102856211A CN 2012103656352 A CN2012103656352 A CN 2012103656352A CN 201210365635 A CN201210365635 A CN 201210365635A CN 102856211 A CN102856211 A CN 102856211A
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Abstract
The invention relates to the technology of semi-conductors and provides a manufacture method for an active layer of a carbon nano tube field effect transistor. The manufacture method includes the following steps: dispersing carbon nano tubes in organic solvents, adding high-molecular polymer, stirring at room temperature to enable the high-molecular polymer to fully dissolve in the organic solvents so as to form a mixed system of the carbon nano tubes and the high-molecular polymer, and ejecting the mixed system onto a receiving board at the voltage of 10-100 KV by adopting an electronic spinning device; and enabling the organic solvents to volatilize so as to form the active layer. The method for manufacturing the carbon nano tube field effect transistor has the advantages of being low in cost, small in requirements for the environment and easy in manufacture technology, the obtained organic electronic devices have strong water oxidizing resisting performance, the method for manufacturing the active layer is well simplified, and performance of the active layer is improved simultaneously.
Description
Technical field
The present invention relates to the preparation method of semiconductor FET device, relate in particular to a kind of carbon nanotube field-effect transistor and preparation method thereof.
Background technology
The carbon nano-tube of two-dimensional network shape (CNT) enjoys numerous people's concern owing to it has good transmission characteristic and is expected in recent years playing a significant role aspect electronic device such as field effect transistor (TFT) and the chemical sensitisation.In order to make better it playing a role aspect the electronic device, so the good two-dimentional cross-linked network structure carbon nano-tube film of preparation quality has very important significance.
At present, mainly contain two kinds of dry method and wet methods for the preparation of the method for the carbon nano-tube film of two-dimensional network shape, dry method mainly refers to the CVD method, and this method needs higher reaction temperature and operation more complicated usually.Solwution method mainly comprises spin coating, LB film and mode of printing.But the solwution method for the preparation of network-like carbon nano-tube film all exists a problem at present, and carbon nano-tube is easily assembled in the process that becomes network structure film, thereby causes the film of different-shape size large stretch of Cluster Phenomenon to occur.In addition, exist molecules align in spin coating and the LB film forming procedure unordered, easily sneak into the shortcoming of impurity, and the printing film forming exist the physicochemical properties such as viscosity to ink, surface tension require very harsh, the high defective of cost of printing equipment itself simultaneously.Therefore, develop a kind of low cost, the preparation method that can improve better the carbon nano-tube film quality simultaneously obtains high performance transistor and seems particularly urgent.
Summary of the invention
For addressing the above problem, the invention provides the preparation method of the active layer of this carbon nanotube field-effect transistor, described active layer is by adopting electrical spinning method that the composition that carbon nano-tube, high molecular polymer and organic solvent form is ejected on the dash receiver, infrared heating volatilization organic solvent obtains active layer.
Wherein, described carbon nano-tube and high molecular polymer mass ratio are 1:1 ~ 10:1.
The mass concentration of described high molecular polymer in described organic solvent is 1 ~ 20wt%.Can guarantee the crystallinity of active layer, and prevent carbon nano-tube in the gathering of film forming procedure, but make simultaneously mixed solution have the condition that certain viscosity reaches electrospinning.
Further, the compound method of described composition be with described carbon nanotube dispersed in described organic solvent, then add high molecular polymer and be stirred to fully dissolving.
Further, described high molecular polymer belongs to soluble high molecular polymers, comprises PVP, polyvinyl alcohol, polyethylene, poly-(butadiene-styrene), polyamide, polyacrylonitrile, polyacrylic acid, polystyrene, polymethyl methacrylate at least a
Further, described organic solvent is the organic solvent that can dissolve above-mentioned high molecular polymer, for example is chloroform, ethanol, and acetone, a kind of in carrene or the toluene.
Dash receiver further, described electrical spinning method is under 10～100KV voltage described composition to be ejected on the dash receiver.
Described Electrospun equipment is provided with the spray fiber tube, and the tube head internal diameter of described spray fiber tube is 0.5～5mm; Described spray fiber tube is 5～30cm to the distance of described dash receiver.
Further, described carbon nanotube field-effect transistor also comprises substrate, and the material of described substrate is at least a in glass, pottery, silicon, the plastics.
Further, described carbon nanotube field-effect transistor also comprises source electrode and drain electrode, and the material of described source electrode, drain electrode is at least a in gold, silver, copper, the PEDOT:PSS polymer.
Further, the manufacture method of described source electrode, drain electrode is one of aerosol print process, ink jet printing method, magnetron sputtering, photoetching or vacuum evaporation sedimentation.
Beneficial effect: the manufacture method that the invention provides a kind of its active layer of carbon nanotube field-effect transistor.Utilized the carbon nano-tube of two-dimensional network shape as active layer, thereby made transistor have good transmission characteristic.Realize the making of low-cost, large-scale nanoscale, high performance field effect transistors by Electrospinning.Simultaneously, the environment that this preparation method requires is very loose, need under the anhydrous and oxygen-free environment such as glove box, not implement, simplified technique, and the organic electronic device that makes has very strong water resistant oxygen ability, simplify well the manufacture method of active layer, improved simultaneously the performance of active layer, obtained high performance carbon nanotube field-effect transistor.
Description of drawings
Fig. 1 is the structural representation of the carbon nanotube field-effect transistor of the embodiment of the invention 1 bottom gate-top contact type.
Fig. 2 is the making flow chart of the embodiment of the invention 1 active layer.
Fig. 3 is the pattern schematic diagram of the embodiment of the invention 1 active layer.
Fig. 4 is the structural representation of the carbon nanotube field-effect transistor of the embodiment of the invention 2 tops grid-top contact type.
Fig. 5 is the structural representation of the carbon nanotube field-effect transistor of the embodiment of the invention 3 tops grid-end contact-type.
Fig. 6 is the structural representation of the carbon nanotube field-effect transistor of the embodiment of the invention 4 bottom gates-end contact-type.
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the invention is described in detail.
The present embodiment is take the carbon nanotube field-effect transistor of bottom gate-top contact type as example.As shown in Figure 1, this carbon nanotube field-effect transistor is followed successively by substrate 1, grid 2, insulating barrier 3, active layer 5, source electrode 4a and drain electrode 4b from bottom to up.Wherein, the preparation method of active layer 5 is as follows:
Adopt in the present embodiment carbon nano-tube (hereinafter to be referred as: be that organic solvent, high molecular polymer are polyacrylonitrile for raw material, chloroform CNT).In conjunction with the step S101 to S103 among Fig. 2, the making flow process of the present embodiment active layer: at first, CNT is dispersed in the chloroform through strong stirring 2h, then be the ratio adding polyacrylonitrile of 1:1 according to the mass ratio with CNT, lower to magnetic agitation instrument stirring 0.5h at 20 ℃, in the middle of being dissolved in described chloroform fully to polyacrylonitrile, form CNT and polyacrylonitrile based.Wherein, the mass concentration of polyacrylonitrile in chloroform is 1wt%.
Then, the mixed system that forms in the above-mentioned steps is placed in the spray fiber tube of Electrospun equipment, wherein, the tube head internal diameter of spray fiber tube is 0.5mm; Surface that simultaneously will active layer 5 be deposited is as dash receiver ground connection, and the spray fiber tube is 5cm to the distance of dash receiver.Under 10KV voltage, by the spray fiber tube of Electrospun, described mixed system is ejected on dash receiver (the being insulating barrier 3) surface.
Under 20 ° of C-150 ° of C, heat with infrared lamp, treat the organic solvent volatilization, form the composite nano-fiber membrane with cross-linked structure, as shown in Figure 3, namely can be used as active layer 5 and be produced on the CNT field-effect transistor.
Below, will make detailed description to the whole preparation process of CNT field-effect transistor of this bottom gate-top contact.
The present embodiment is take glass as substrate 1, on substrate 1, make successively grid 2, insulating barrier 3, then adopt the active layer 5 preparation sides of above-mentioned introduction to form active layer 5 at insulating barrier 3, adopt at last the aerosol print process to make source electrode 4a and drain electrode 4b in active layer 5 relative both sides, wherein, the making material of source electrode 4a and drain electrode 4b is gold.Can form the CNT field-effect transistor of bottom gate-top contact type behind the infrared drying.
The present embodiment is made the CNT field-effect transistor of top grid-top contact type, as shown in Figure 4.The CNT field effect transistor structure of the present embodiment is: be followed successively by from bottom to up substrate 1, active layer 5, source electrode 4a and drain electrode 4b, insulating barrier 3, grid 2.
Wherein, in the making step of the present embodiment active layer 5, high molecular polymer adopts polyvinyl alcohol, with the mass ratio of CNT be 1:4, being dissolved into the mass concentration that forms behind the ethanol behind the mixed system is 10wt%.Be the spray fiber tube of 5mm again by the tube head internal diameter, making alive 100KV is ejected into described mixed system on the dash receiver (being substrate 1) at distance spray fiber tube tube head 30cm place.But all the other step reference examples 1 of active layer 5 preparation methods are described.Further, the substrate 1 of the present embodiment is pottery, and the making material of source electrode 4a and drain electrode 4b be silver-colored, and the method by ink jet printing is produced on described active layer 5 tops.Then successively source electrode 4a, drain electrode 4b and between active layer 5 make insulating barriers 3, grid 2, can form the CNT field-effect transistor of top grid-top contact type behind the infrared drying.
The present embodiment is made the CNT field-effect transistor of top grid-end contact-type, as shown in Figure 5.The CNT field effect transistor structure of the present embodiment is: be followed successively by from bottom to up substrate 1, source electrode 4a and drain electrode 4b, active layer 5, insulating barrier 3, grid 2.
Wherein, in the making step of the present embodiment active layer 5, high molecular polymer adopts polystyrene, with the mass ratio of CNT be 1:10, being dissolved into the mass concentration that forms behind the toluene behind the mixed system is 15wt%.Be the spray fiber tube of 1mm again by the tube head internal diameter, making alive 20KV, with described mixed system be ejected into distance spray fiber tube tube head 10cm place dash receiver (be source electrode 4a, drain 4b and between substrate 1) on the surface.But all the other step reference examples 1 of active layer 5 preparation methods are described.Further, the substrate 1 of the present embodiment is silicon, and the making material of source electrode 4a and drain electrode 4b is copper, is produced on described substrate 1 top by the magnetic control spray technology.Then successively source class, drain electrode 4b and between substrate 1 make active layer 5, insulating barrier 3, grid 2, can form the CNT field-effect transistor of top grid-end contact-type behind the infrared drying.
Embodiment 4
The present embodiment is made the CNT field-effect transistor of bottom gate-top contact type, as shown in Figure 6.The CNT field effect transistor structure of the present embodiment is: be followed successively by from bottom to up substrate 1, grid 2, insulating barrier 3, active layer 5, source electrode 4a and drain electrode 4b.
Wherein, in the making step of the present embodiment active layer 5, high molecular polymer adopts polymethyl methacrylate, with the mass ratio of CNT be 1:8, being dissolved into the mass concentration that forms behind the acetone behind the mixed system is 20wt%.Be the spray fiber tube of 2.5mm again by the tube head internal diameter, making alive 50KV is ejected into described mixed system on the dash receiver (being substrate 1) at distance spray fiber tube tube head 15cm place.But all the other step reference examples 1 of active layer 5 preparation methods are described.Further, the present embodiment substrate 1 is plastics, makes successively grid 2, insulating barrier 3, source electrode 4a and drain electrode 4b and active layer 5 on plastic 1.Wherein the making material of source electrode 4a and drain electrode 4b is the PEDOT:PSS polymer, is produced on described active layer 5 tops by photoetching process, at last by forming the CNT field-effect transistor of bottom gate-end contact-type behind the infrared drying.
Wherein, high molecular polymer is the high polymer of a kind of solubility, except the high molecular polymerization beyond the region of objective existence that the present embodiment relates to, can also be PVP, polyethylene, poly-(butadiene-styrene), polyamide,, polymer that polyacrylic acid etc. is commonly used, those skilled in the art should know: can dissolve well above-mentioned high molecular polymer, can also adopt embodiment to mention organic solvent in addition, for example carrene CNT and high molecular polymer mixing.
In other embodiments, carbon nano-tube and high molecular polymer mass ratio are controlled in 1:1 ~ 10:1 scope, and the mass concentration of high molecular polymer in described organic solvent is controlled at 1 ~ 20wt%, described electrical spinning method operating voltage is controlled at 10～100KV, and the tube head internal diameter of its spray fiber tube is 0.5～5mm; The spray fiber tube is 5～30cm to the distance of described dash receiver.The active layer of making in the above-mentioned parameter scope all can arrive preferable quality and performance.
In addition, the material of carbon nanotube field-effect transistor substrate is at least a in glass, pottery, silicon, the plastics; The material of source electrode, drain electrode is at least a in gold, silver, copper, the PEDOT:PSS polymer; And the manufacture method of source electrode, drain electrode is one of aerosol print process, ink jet printing method, magnetron sputtering, photoetching or vacuum evaporation sedimentation.
The invention provides a kind of structure of CNT effect transistor, with and the manufacture method of active layer.Realize the making of low-cost, large-scale nanoscale, efficient field-effect transistor by Electrospinning.Simultaneously, the environment that this preparation method requires is very loose, need under the anhydrous and oxygen-free environment such as glove box, not implement, simplified technique, and the organic electronic device that makes has very strong water resistant oxygen ability, simplify well the manufacture method of active layer, improved simultaneously the performance of active layer, obtained high performance CNT field-effect transistor.
Claims (11)
1. the preparation method of a carbon nanotube field-effect transistor active layer is characterized in that, described active layer is to be ejected on the dash receiver by the composition that adopts electrical spinning method that carbon nano-tube, high molecular polymer and organic solvent are formed to form.
2. the preparation method of described active layer according to claim 1 is characterized in that, described carbon nano-tube and high molecular polymer mass ratio are 1:1 ~ 10:1.
3. the preparation method of described active layer according to claim 2 is characterized in that, the mass concentration of described high molecular polymer in described organic solvent is 1 ~ 20wt%.
4. according to claim 1 and 2 or the preparation method of 3 described active layers, it is characterized in that, the compound method of described composition be with described carbon nanotube dispersed in described organic solvent, then add high molecular polymer and be stirred to fully dissolving.
5. the preparation method of described active layer according to claim 4, it is characterized in that, described high molecular polymer comprises PVP, polyvinyl alcohol, polyethylene, poly-(butadiene-styrene), polyamide, at least a in polyacrylonitrile, polyacrylic acid, polystyrene, the polymethyl methacrylate.
6. the preparation method of described active layer according to claim 5 is characterized in that, described organic solvent is chloroform, ethanol, acetone, a kind of in carrene or the toluene.
7. according to claim 1 and 2 or the preparation method of 3 described active layers, it is characterized in that described electrical spinning method is under 10～100KV voltage described composition to be ejected on the dash receiver.
8. the preparation method of described active layer according to claim 7 is characterized in that, the working equipment of described electrical spinning method comprises the spray fiber tube, and the tube head internal diameter of described spray fiber tube is 0.5～5mm; Described spray fiber tube is 5～30cm to the distance of described dash receiver.
9. the preparation method of described active layer according to claim 1 is characterized in that, described carbon nanotube field-effect transistor also comprises substrate, and the material of described substrate is at least a in glass, pottery, silicon, the plastics.
10. the preparation method of described active layer according to claim 9 is characterized in that, described carbon nanotube field-effect transistor also comprises source electrode and drain electrode, and the material of described source electrode, drain electrode is at least a in gold, silver, copper, the PEDOT:PSS polymer.
11. the preparation method of described active layer is characterized in that according to claim 10, the manufacture method of described source electrode, drain electrode is one of aerosol print process, ink jet printing method, magnetron sputtering, photoetching or vacuum evaporation sedimentation.
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| CN104576744A (en) * | 2013-10-24 | 2015-04-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube thin-film transistor, AMOLED (active matrix organic light emitting diode) pixel flexible driving circuit and manufacturing method thereof |
| WO2017004840A1 (en) * | 2015-07-07 | 2017-01-12 | 深圳市华星光电技术有限公司 | Thin film transistor and manufacturing method thereof, and array substrate |
| WO2018068170A1 (en) * | 2016-10-10 | 2018-04-19 | Boe Technology Group Co., Ltd. | Thin film transistor, display panel and display apparatus having the same, and fabricating method thereof |
| CN109326714A (en) * | 2018-08-29 | 2019-02-12 | 北京大学 | Preparation method, preparation facilities and the electronic device of carbon nanotube field-effect pipe |
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| WO2006091823A2 (en) * | 2005-02-25 | 2006-08-31 | The Regents Of The University Of California | Electronic devices with carbon nanotube components |
| WO2012047040A2 (en) * | 2010-10-07 | 2012-04-12 | 포항공과대학교 산학협력단 | Electric field auxiliary robotic nozzle printer and method for manufacturing organic wire pattern aligned using same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104576744A (en) * | 2013-10-24 | 2015-04-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube thin-film transistor, AMOLED (active matrix organic light emitting diode) pixel flexible driving circuit and manufacturing method thereof |
| WO2017004840A1 (en) * | 2015-07-07 | 2017-01-12 | 深圳市华星光电技术有限公司 | Thin film transistor and manufacturing method thereof, and array substrate |
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| WO2018068170A1 (en) * | 2016-10-10 | 2018-04-19 | Boe Technology Group Co., Ltd. | Thin film transistor, display panel and display apparatus having the same, and fabricating method thereof |
| US10431758B2 (en) | 2016-10-10 | 2019-10-01 | Boe Technology Group Co., Ltd. | Thin film transistor, display panel and display apparatus having the same, and fabricating method thereof |
| CN109326714A (en) * | 2018-08-29 | 2019-02-12 | 北京大学 | Preparation method, preparation facilities and the electronic device of carbon nanotube field-effect pipe |
| CN109326714B (en) * | 2018-08-29 | 2020-06-26 | 北京大学 | Preparation method and preparation device of carbon nanotube field effect transistor and electronic device |
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