CN115724421A - Oriented carbon nanotube array structure and preparation method and application thereof - Google Patents
Oriented carbon nanotube array structure and preparation method and application thereof Download PDFInfo
- Publication number
- CN115724421A CN115724421A CN202110964715.9A CN202110964715A CN115724421A CN 115724421 A CN115724421 A CN 115724421A CN 202110964715 A CN202110964715 A CN 202110964715A CN 115724421 A CN115724421 A CN 115724421A
- Authority
- CN
- China
- Prior art keywords
- substrate
- carbon nanotube
- template
- microstructure
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 160
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 160
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 172
- 238000000034 method Methods 0.000 claims abstract description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001338 self-assembly Methods 0.000 claims abstract description 37
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- 230000005669 field effect Effects 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- -1 polydimethylsiloxane Polymers 0.000 claims description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 28
- 239000004065 semiconductor Substances 0.000 claims description 26
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000000806 elastomer Substances 0.000 claims description 19
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 12
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 11
- 238000007639 printing Methods 0.000 claims description 11
- 239000002109 single walled nanotube Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000013007 heat curing Methods 0.000 claims description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 6
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- YHYBNVZCQIDLSQ-UHFFFAOYSA-N 1-fluorododecane Chemical compound CCCCCCCCCCCCF YHYBNVZCQIDLSQ-UHFFFAOYSA-N 0.000 claims description 5
- OZINGDHETXYRTF-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCOOP(O)(O)=O Chemical compound CCCCCCCCCCCCCCCCCCOOP(O)(O)=O OZINGDHETXYRTF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000002612 dispersion medium Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- 238000005411 Van der Waals force Methods 0.000 claims description 3
- HQNCOGCRGVVZTA-UHFFFAOYSA-N dodecoxy dihydrogen phosphate Chemical compound CCCCCCCCCCCCOOP(O)(O)=O HQNCOGCRGVVZTA-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000001029 thermal curing Methods 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 239000004636 vulcanized rubber Substances 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 30
- 239000000126 substance Substances 0.000 description 19
- 238000001723 curing Methods 0.000 description 13
- 239000002238 carbon nanotube film Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- PVQXITGZQAYAAL-UHFFFAOYSA-N 1-fluorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCF PVQXITGZQAYAAL-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 229920003225 polyurethane elastomer Polymers 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000001259 photo etching Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- ZCNHNWPHEXSBQS-UHFFFAOYSA-N dodecoxy(fluoro)phosphinic acid Chemical compound CCCCCCCCCCCCOP(O)(F)=O ZCNHNWPHEXSBQS-UHFFFAOYSA-N 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
Abstract
The invention discloses an oriented carbon nanotube array structure and a preparation method and application thereof. The preparation method comprises the following steps: assembling self-assembly molecules on the surface of a substrate to form a first microstructure so as to obtain a patterned substrate, wherein the bonding force of the first microstructure and the carbon nano tube is greater than that of the substrate and the carbon nano tube; and dipping the patterned substrate in the carbon nanotube ink, then pulling and taking out, and then carrying out annealing treatment, thereby forming an oriented carbon nanotube array structure corresponding to the first microstructure on the substrate. The method effectively combines the template method and the lifting technology, fully exerts the specific advantages of the two technologies, does not need to introduce a second phase solution, has low requirements on experimental conditions and equipment, has short period, can control the density and distribution of the prepared oriented carbon nanotube array structure, can be applied to a field effect transistor, and is beneficial to improving the carrier transmission capability and the device stability.
Description
Technical Field
The invention belongs to the technical field of carbon nano-material preparation, and particularly relates to an oriented carbon nano-tube array structure, and a preparation method and application thereof.
Background
Carbon nanotubes have excellent electrical, mechanical, and optical properties, and thus have received much attention in the field of nanomaterials. However, in the carbon nanotube film with random distribution, many carbon nanotubes are cross-entangled to form numerous tube junctions, which will affect the charge transport in the carbon nanotubes. Therefore, when the excellent properties of the carbon nanotubes are utilized, the structural and spatial regularity of the carbon nanotubes must be ensured, which requires that the carbon nanotubes are arranged in a stretching and orienting manner as much as possible.
At present, there are two main methods for preparing aligned carbon nanotubes, direct method and indirect method. The direct method comprises a chemical vapor deposition method, a lattice orientation growth method, an electromagnetic field assisted method and the like. The method orients the carbon nanotubes in a manner at the beginning of their synthesis. However, the method has high requirements on equipment, harsh experimental conditions and complex experimental process. For example, chemical vapor deposition requires growth at high temperatures, which limits the use of flexible substrates that are not resistant to high temperatures. The method of applying electromagnetic field needs to add special electrodes, and the obtained carbon nano tube has poor orientation degree, low density, complex preparation process and harsh preparation conditions. The indirect method mainly comprises a solution shearing method, a suction filtration method and the like. The research group of professor Baozhinun obtains the oriented carbon nanotube array by using a solution shearing method, and the method has the defects that the used substrate needs photoetching patterning, but the photoetching process is complex and the conditions are harsh. Patent CN 101338452A discloses a method for preparing a high-density carbon nanotube film, which comprises obtaining a carbon nanotube film on a substrate, and pressing carbon nanotubes along a direction parallel to the substrate to obtain a high-density carbon nanotube film array. However, the degree of orientation of the carbon nanotubes obtained by the method is not controllable. In addition, it is reported that a two-phase pulling method is used to obtain an oriented carbon nanotube film, for example, patent CN 110589804A discloses that a second phase solution incompatible with the carbon nanotube solution is dropped in the carbon nanotube solution to combine with a pulling technique to prepare an oriented carbon nanotube film array. In addition, patent CN1872673A discloses a cross pulling method for preparing a cross array of carbon nanotubes, which is simple and easy to implement, but has high requirements on the pulling speed and the pulling direction, and most of the prepared carbon nanotubes are cross-arranged, and the orientation effect is not good, so that the problem of a large number of tube junctions between carbon tubes cannot be reduced. Therefore, the development of a preparation method of the oriented carbon nanotube, which has the advantages of simple process, low cost, rapidness, high efficiency and wide application range, plays an important role in accelerating the industrial application of the oriented carbon nanotube.
Disclosure of Invention
The main objective of the present invention is to provide an aligned carbon nanotube array structure, and a preparation method and an application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an oriented carbon nanotube array structure, which comprises the following steps:
assembling self-assembly molecules on the surface of a substrate to form a first microstructure so as to obtain a patterned substrate, wherein the bonding force of the first microstructure and the carbon nano tube is greater than that of the substrate and the carbon nano tube;
and dipping the patterned substrate in carbon nanotube ink, then pulling and taking out, and then carrying out annealing treatment, thereby forming an oriented carbon nanotube array structure corresponding to the first microstructure on the substrate.
The embodiment of the invention also provides an oriented carbon nanotube array structure prepared by the method.
The embodiment of the invention also provides a preparation method of the semiconductor device, which comprises the following steps: the method comprises the steps of preparing an oriented carbon nanotube array structure by any one of the methods by adopting semiconductor single-walled carbon nanotube ink, and manufacturing a semiconductor device by utilizing the oriented carbon nanotube array structure.
The embodiment of the invention also provides a semiconductor device which is characterized by comprising the oriented carbon nanotube array structure, wherein the carbon nanotube adopts a semiconductor single-walled carbon nanotube.
The embodiment of the invention also provides a preparation method of the carbon nano tube pattern structure, which comprises the following steps:
assembling self-assembly molecules on the surface of a substrate to form a set pattern so as to obtain a patterned substrate, wherein the bonding force between the set pattern and the carbon nano tube is greater than the bonding force between the substrate and the carbon nano tube;
and dipping the patterned substrate in carbon nanotube ink, then pulling and taking out, and then carrying out annealing treatment, thereby forming a carbon nanotube pattern structure corresponding to the set pattern on the substrate.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method provided by the invention has simple process and easy operation;
(2) The method effectively combines the template method and the lifting technology, fully exerts the specific advantages of the two technologies, does not need to introduce a second-phase solution, has low requirements on experimental conditions and equipment, and has controllable density and high experimental efficiency of the prepared oriented carbon nanotube film;
(3) The preparation temperature of the oriented carbon nanotube is lower, the preparation temperature in the whole process is not higher than 120 ℃, the oriented carbon nanotube film can be obtained on the surfaces of multiple substrates, the substrate selection range is expanded, a second phase solution is not required to be introduced in the preparation process, the operation is simple, and the dependence on the pulling speed and the pulling direction is avoided; self-assembling molecules can be selected widely; the experimental equipment is simple, the cost is low, and the method is economic and environment-friendly;
(4) The density and distribution of the directional carbon nano tube array structure prepared by the invention are controllable, and the directional carbon nano tube array structure can be applied to a field effect transistor, and is beneficial to improving the transmission capability of carriers and improving the stability of devices.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some embodiments recorded in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a method for fabricating an aligned carbon nanotube array structure according to an exemplary embodiment of the present invention;
FIG. 2 is a schematic illustration of the preparation of a carbon nanotube ink in accordance with an exemplary embodiment of the present invention;
FIGS. 3 a-3 b are UV-visible near-IR spectra of carbon nanotube inks and photo-graphs of the carbon nanotube inks used in accordance with an exemplary embodiment of the present invention;
FIGS. 4 a-4 b are SEM images of aligned carbon nanotube array structures prepared in example 1 of the present invention;
FIGS. 5 a-5 b are SEM images of aligned carbon nanotube array structures prepared in example 6 of the present invention;
FIG. 6 is an SEM image of an aligned carbon nanotube array structure prepared in example 10 of the present invention;
FIG. 7 is a schematic view of the structure of a device produced in example 1 of the present invention;
FIG. 8 is a drawing of a silver electrode prepared in example 1 of the present invention;
fig. 9 is an electrical diagram of a device prepared in example 1 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making an invasive task, are within the scope of the present invention.
One aspect of the embodiments of the present invention provides a method for preparing an aligned carbon nanotube array structure, including:
assembling self-assembly molecules on the surface of a substrate to form a first microstructure so as to obtain a patterned substrate, wherein the bonding force of the first microstructure and the carbon nano tube is greater than that of the substrate and the carbon nano tube;
and dipping the patterned substrate in carbon nanotube ink, then pulling and taking out, and then carrying out annealing treatment, thereby forming an oriented carbon nanotube array structure corresponding to the first microstructure on the substrate.
In some more specific embodiments, the preparation method specifically comprises:
attaching one side surface of the template with a second microstructure to the surface of the substrate and applying pressure to ensure that the side surface of the template with the second microstructure is in conformal contact with the surface of the substrate, wherein the second microstructure corresponds to the first microstructure;
and applying a self-assembly molecule solution around the template, depositing self-assembly molecules at the groove formed between the template and the substrate under the action of capillary force, and then carrying out drying and first thermal curing treatment, thereby forming the first microstructure.
Further, the pressure applied to the template is 1 to 10g.
Further, the template is formed of an elastomer.
Furthermore, the template is an elastomer template with a micro-nano stripe structure, and the width of the micro-nano stripe structure in the elastomer template with the micro-nano stripe structure is any one of 160nm, 320nm and 640nm.
Further, the size of the elastic phantom may include any one of 1cm × 1cm, 1.5cm × 1.5cm, and 2cm × 2cm, and is not limited thereto.
Further, the micro-nano stripe structure of the elastomer template is obtained by copying a commercial optical disc structure.
The elastomer template is obtained by directly copying the CD structure, and has simple process and no need of photoetching technology
Furthermore, the material of the elastomer includes any one or a combination of two or more of thermoplastic polyurethane, thermoplastic vulcanized rubber, and polydimethylsiloxane, but is not limited thereto.
Further, the first microstructure comprises orientation-arranged micro-scale stripes and/or nano-scale stripes; the width of the nano-scale stripes is 160 nm-640 nm.
Furthermore, the first microstructure is convexly arranged on the surface of the substrate.
Further, the second microstructure includes micro-scale grooves and/or nano-scale grooves formed on the surface of the template.
Further, a capillary structure is formed at the bonding interface of the template and the substrate.
Further, the self-assembling molecules are capable of binding to the carbon nanotubes by at least physical action, including van der Waals forces.
Further, the substrate includes a rigid substrate and/or a flexible substrate, and is not limited thereto.
Furthermore, the material of the substrate includes any one or a combination of two or more of hafnium oxide, silicon wafer, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and glass, but is not limited thereto.
Further, the material of the rigid substrate includes any one or a combination of two or more of hafnium oxide, silicon wafer, and glass, but is not limited thereto.
Furthermore, the material of the flexible substrate includes polyethylene terephthalate and/or polyethylene naphthalate, but is not limited thereto.
Further, the preparation method specifically comprises the following steps: and after applying the self-assembly molecular solution around the template, naturally drying the self-assembly molecular solution, putting the template and the substrate together into a sealed cavity for vacuumizing treatment, then carrying out the first heat curing treatment, cooling to room temperature, and removing the template, thereby forming a first microstructure on the substrate.
Further, the concentration of the self-assembly molecule solution is 0.013-0.5 wt%.
Further, the concentration of the self-assembly molecule solution is selected from any one of 0.013wt%, 0.025wt%, 0.05wt%, 0.075wt%, 0.1wt%, 0.15wt%, 0.25wt%, and 0.5wt%.
Further, the solvent in the self-assembly molecule solution includes any one or a combination of two or more of toluene, xylene, and a carboxylic ester solvent, and is not limited thereto.
Further, a solution of self-assembling molecules is applied around the template, at least by printing and/or drop coating.
Further, the natural drying time is 10-20 min.
Further, the time of the vacuum pumping treatment is 10-15 min, and the vacuum degree is 4-15 Pa.
Further, the temperature of the first heat curing treatment is 90-120 ℃, and the time is 5-15 min.
In some more specific embodiments, the preparation method specifically comprises: and dipping the patterned substrate in the carbon nano tube ink, pulling and taking out, and then sequentially carrying out second heat curing, cleaning and annealing treatment to form the oriented carbon nano tube array structure.
Further, the preparation method specifically comprises the following steps: and dipping the patterned substrate in the carbon nanotube ink, and vertically pulling out the substrate.
Further, the pulling-out speed is 10 to 500 μm/s.
Further, the temperature of the second heat curing treatment is 90-120 ℃, and the time is 3-5 min.
Further, the cleaning solvent used in the cleaning process includes toluene and/or xylene, and is not limited thereto.
Furthermore, the temperature of the annealing treatment is 90-120 ℃, and the time is 10-20 min.
In some more specific embodiments, the self-assembly molecule includes a phosphate self-assembly molecule, and the substituent group of the phosphate self-assembly molecule includes any one or a combination of two or more of a fluoro group, a hydroxyl group, and an amino group, but is not limited thereto.
Further, the self-assembly molecule of phosphoric acid includes any one or a combination of two or more of dodecyl fluoro phosphoric acid, octadecyl hydroxy phosphoric acid, dodecyl hydroxy phosphoric acid, and octadecyl amino phosphoric acid, and is not limited thereto.
In some more specific embodiments, the carbon nanotube ink includes carbon nanotubes, a dispersant, and a dispersion medium.
Further, the carbon nanotube includes a single-walled carbon nanotube and/or a multi-walled carbon nanotube, and is not limited thereto.
Further, the dispersant includes a polymer including any one or a combination of two or more of poly [ nitrogen- (9-heptadecyl) carbazole ], poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (1, 4-benzo 2, 1-3-thiadiazole) ], poly [ N, N '-di (2-octyldodecyl) -isoindigo-co- (9, 9-dioctylfluorenyl-2, 7-diyl) ], poly [ N, N' -di (2-octyldodecyl) -isoindigo-co-N- [1- (octylnonyl) -carbazolyl-2, 7-diyl ], and is not limited thereto.
Further, the dispersion medium includes any one or a combination of two or more of toluene, xylene, and a carboxylic ester solvent, and is not limited thereto.
The schematic diagram of the preparation of the carbon nanotube ink of the present invention is shown in fig. 2.
Further, the absorption peak intensity of the carbon nanotube ink in the ultraviolet, visible and near infrared ranges from 0.2 to 1, as shown in fig. 3a to 3 b.
In some more specific embodiments, the carbon nanotube ink is a semiconductor single-walled carbon nanotube ink.
In some more specific embodiments, the method of preparing aligned carbon nanotubes may comprise:
(1) Dissolving carbon nanotubes, and selectively dispersing the semiconductor single-walled carbon nanotube ink;
(2) Preparing phosphoric acid self-assembly molecular solutions with different concentrations and different molecular weights; wherein, the solvent of the prepared phosphoric acid self-assembly molecular solution can be one or more of ethanol, propanol, deionized water and the like;
(3) Applying a grooved elastomer template (e.g., thermoplastic polyurethane, polydimethylsiloxane, etc.), cutting elastomer templates of different sizes, and applying a pressure over the template to bring it into conformal contact with the substrate (maintain contact); wherein the substrate can be hafnium oxide, silicon wafer, PET, PEN, glass, etc.;
(4) Depositing (such as printing, dripping and coating) prepared phosphoric acid self-assembly molecular solutions with different concentrations and types around the template, vacuumizing for about 20 minutes after the solutions are naturally volatilized, taking out a sample, placing the sample on a hot table, heating and curing, cooling at room temperature, and then removing the template to obtain a substrate with a micro-nano structure;
(5) And (3) placing the substrate with the micro-nano structure obtained in the step (4) into the carbon nano tube ink prepared in the step (1) to lift the substrate at a certain speed, and finally cleaning the substrate with a solvent and curing to obtain the oriented carbon nano tube array structure.
The schematic flow chart of the method for preparing the aligned carbon nanotube array structure of the present invention can be shown in fig. 1.
The preparation method can obtain different lyophilic and lyophobic stripe structures on the surfaces of multiple substrates by utilizing the self-assembly behavior of phosphoric acid self-assembly molecules with different fluorine groups, hydroxyl groups or amino groups on the surfaces of the substrates and combining the capillary force action of the grooves of the elastomer template, wherein the fluorine groups, the hydroxyl groups or the amino groups of the phosphoric acid self-assembly molecules are exposed to the outside and combined with the carbon nanotubes through van der Waals force to obtain the density-controllable oriented carbon nanotubes (can be oriented carbon nanotube films).
The method effectively combines the template method and the lifting technology, fully exerts the specific advantages of the two technologies, does not need to introduce a second-phase solution, has low requirements on experimental conditions and equipment, and has controllable density and high experimental efficiency of the prepared oriented carbon nanotube film; the total experiment duration is not more than 2 hours, so that the experiment efficiency is improved to a great extent;
another aspect of the embodiments of the present invention also provides an aligned carbon nanotube array structure prepared by the foregoing method.
Another aspect of the embodiments of the present invention also provides a method for manufacturing a semiconductor device, including: the method comprises the steps of preparing an oriented carbon nanotube array structure by any one of the methods by using semiconductor single-walled carbon nanotube ink, and manufacturing a semiconductor device by using the oriented carbon nanotube array structure.
Further, the semiconductor device includes a field effect transistor.
In another aspect of the embodiments of the present invention, a semiconductor device is further provided, which includes the foregoing aligned carbon nanotube array structure, wherein the carbon nanotubes are semiconductor single-walled carbon nanotubes.
Further, the semiconductor device includes a field effect transistor.
Another aspect of an embodiment of the present invention also provides a method for preparing a carbon nanotube pattern structure, including:
assembling self-assembly molecules on the surface of a substrate to form a set pattern so as to obtain a patterned substrate, wherein the bonding force between the set pattern and the carbon nano tube is greater than the bonding force between the substrate and the carbon nano tube;
and dipping the patterned substrate in carbon nanotube ink, then pulling and taking out, and then carrying out annealing treatment, thereby forming a carbon nanotube pattern structure corresponding to the set pattern on the substrate.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and the detailed embodiments and specific operation procedures are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were commercially available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Referring to fig. 1, the method for preparing the aligned carbon nanotube array structure in this embodiment includes the following steps: using 0.5wt% of octadecyl fluorine-based phosphoric acid molecules as a substance for fixing the carbon nano tube, selecting a single-side polished silicon sheet with an oxide layer as a substrate, wherein the thickness of the oxide layer is 500 nanometers, and cutting a 2cm multiplied by 2Gm polydimethylsiloxane elastomer as a template; attaching a polydimethylsiloxane template to a silicon wafer substrate, and applying 10g of pressure above the template to ensure that the substrate is in conformal contact with the template; uniformly depositing octadecyl fluorine-based phosphoric acid molecular solution around the template, vacuumizing for 15min in a vacuum drying oven, taking out a sample, heating at 120 ℃ for 5min on a heating table, cooling at room temperature, and removing the polydimethylsiloxane template; placing the patterned substrate in a semiconducting carbon nanotube ink with an absorption peak of 0.8, and lifting the substrate upwards at a speed of 200 mu m/s; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 20min; the substance grown on the silicon wafer substrate is the oriented carbon nanotube array structure, as shown in fig. 4 a-4 b.
The carbon nanotube ink used in this example was selectively isolated from commercial carbon nanotubes encapsulated with poly [ nitrogen- (9-heptadecyl) carbazole ] (PCZ), and the schematic diagram is shown in fig. 2.
The prepared aligned carbon nanotube is used as a semiconductor conductive material, and a silver source and drain electrode is printed by an ink-jet printing method, wherein the structure of the device is shown in figure 7; the gate electrode is a silicon substrate, the dielectric layer is 500-nanometer silicon dioxide, the oriented carbon nanotube is used as a semiconductor channel material, and the ink-jet printed silver electrode is used as a source drain electrode (as shown in figure 8), so that the preparation of the device can be simply completed; fig. 9 is a graph of the electrical performance of the fabricated transistor.
In the embodiment, hydroxyl in phosphoric acid in octadecyl fluo-based phosphoric acid molecules can form hydrogen bond interaction with SI-O bond on the substrate; the elastomer template is a micro-nano stripe structure directly copying a commercial optical disk, and after the template is attached to a substrate and contacts with the substrate in a shape-preserving manner, octadecyl fluorine-based phosphoric acid molecular solution is filled into a gap between the template and the substrate under the action of capillary force and vacuum force of a groove of the elastomer template; after solidification, the template is removed, and a stripe structure is left on the substrate, wherein the structure corresponds to the stripe structure of the template. The fluorine atoms in the fluorine-based phosphoric acid molecules are exposed above the substrate, and when the carbon nanotube ink is pulled up, hydrogen bonds are formed with the fluorine atoms due to the exposed hydroxyl groups outside the carbon nanotubes. Under the action of the force, the carbon tube can be tightly attached to the position of the substrate with the fluorine-based phosphoric acid molecules; because the size of the copied template is in the micro-nano level, the oriented carbon nanotube film with controllable density can be obtained by combining the size limitation and the meniscus shearing action of dipping and pulling. In the prior art, a photoetching technology is mostly adopted for obtaining the micro-nano structure, and the technology has complex process and high cost; the method for obtaining the oriented carbon nano tube by dip-coating adopts a two-phase solution coating method, and the two-phase solution coating method has more variable parameters and is difficult to control. The method provided by the embodiment of the invention is simple to operate, low in cost, fast and efficient.
Example 2
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: using 0.25wt% of octadecyl fluorine-based phosphoric acid molecules as a substance for fixing the carbon nano tube, selecting a single-side polished silicon wafer with an oxide layer of which the thickness is 500 nanometers as a substrate, and cutting a polyurethane elastomer with the thickness of 1.5cm multiplied by 1.5cm as a template; attaching a polyurethane elastomer template to a silicon wafer substrate, and applying 6g of pressure above the template to ensure that the substrate is in conformal contact with the template; uniformly depositing octadecyl fluophosphate molecular solution to the periphery of a template (such as printing, dripping and coating) and naturally volatilizing for 20min; transferring to a vacuum drying oven, vacuumizing for 15min, taking out a sample, heating at 120 ℃ for 5min on a heating table, cooling at room temperature, and then removing the elastomer template; placing the patterned substrate in a semiconducting carbon nanotube ink with an absorption peak of 0.6, and pulling the substrate upwards at a speed of 100 micrometers/s; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 15min; the substance growing on the silicon chip substrate is the directional carbon nanotube array structure.
Example 3
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: using 0.1wt% of octadecyl fluorine-based phosphoric acid molecules as a substance for fixing the carbon nano tube, selecting a single-side polished silicon wafer with an oxide as a substrate, wherein the thickness of the oxide layer is 500 nanometers, and cutting a polyurethane elastomer with the thickness of 1cm multiplied by 1cm as a template; the method comprises the following steps of (1) attaching a polyurethane elastomer template to a silicon wafer substrate, and applying 4g of pressure above the template to enable the substrate to be in conformal contact with the template; uniformly depositing the octadecyl fluoro-phosphate molecular solution to the periphery of a template (such as printing, dripping and coating) and naturally volatilizing for 15min; transferring to a vacuum drying oven, vacuumizing for 10min, taking out the sample, heating at 120 ℃ for 5min on a heating table, cooling at room temperature, and then removing the polyurethane elastomer template; placing the patterned substrate in a semiconducting carbon nanotube ink with an absorption peak of 0.4, and lifting the substrate upwards at a speed of 60 mu m/s; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 10min; the substance growing on the silicon chip substrate is the oriented carbon nanotube array structure.
Example 4
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: taking 0.05wt% of octadecyl fluoro-based phosphoric acid molecules as a substance for fixing the carbon nano tube, selecting a single-side polished silicon wafer with an oxide as a substrate, wherein the thickness of the oxide layer is 500 nanometers, and cutting 1cm multiplied by 1cm of polydimethylsiloxane as a template; attaching a template to a silicon wafer substrate, and applying 2g of pressure above the template to ensure that the substrate is in conformal contact with the template; uniformly depositing (such as printing, dripping and coating) octadecyl fluoro phosphoric acid molecular solution to the periphery of the template; transferring the sample to a vacuum drying oven, vacuumizing for 10min, taking out the sample, heating the sample on a heating table at 120 ℃ for 5min, cooling at room temperature, and then removing the template; placing the patterned substrate in a semiconductor carbon nanotube ink with an absorption peak of 0.3, and pulling the substrate upwards at a speed of 30 μm/s, wherein the ultraviolet visible near-infrared absorption spectrum of the carbon nanotube ink is shown in figure three; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 10min; the substance growing on the silicon chip substrate is the oriented carbon nanotube array structure.
Example 5
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: 0.025wt% of dodecyl fluorine-based phosphoric acid molecules are used as a substance for fixing the carbon nano tube, a selected substrate is a single-side polished silicon wafer with an oxide, the thickness of the oxide layer is 500 nanometers, and 1cm multiplied by 1cm of polydimethylsiloxane is cut as a template; attaching the template to a silicon wafer substrate, and applying 4g of pressure above the template to ensure that the substrate is in conformal contact with the template; uniformly depositing the dodecyl fluorine-based phosphoric acid molecular solution to the periphery of the template (such as printing, dripping and the like); transferring the sample to a vacuum drying oven, vacuumizing for 10min, taking out the sample, heating the sample on a heating table at 110 ℃ for 5min, cooling at room temperature, and then removing the template; placing the patterned substrate in a semiconducting carbon nanotube ink with an absorption peak of 0.6, and pulling the substrate upwards at a speed of 40 μm/s; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 10min; the substance growing on the silicon chip substrate is the oriented carbon nanotube array structure.
Example 6
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: a single-side polished silicon wafer with an oxide is selected as a substrate, and the thickness of the oxide layer is 500 nanometers. Taking 0.03wt% of octadecyl hydroxy phosphoric acid molecules as a substance for fixing the carbon nano tube, and cutting a thermoplastic polyurethane elastomer with the thickness of 1cm multiplied by 1cm as a template; the polyurethane template is attached to a silicon wafer substrate, and 4g of pressure is applied to the upper part of the template to ensure that the substrate is in conformal contact with the template; uniformly depositing the octadecyl hydroxyl phosphate molecular solution to the periphery of the template (such as printing, dripping and coating) and naturally volatilizing for 20min; transferring to a vacuum drying oven, vacuumizing for 10min, taking out the sample, heating at 120 ℃ for 5min on a heating table, cooling at room temperature, and then removing the template; placing the patterned substrate in a semiconducting carbon nanotube ink with an absorption peak of 0.6 and pulling the substrate upwards at a speed of 40 μm/s; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 10min; the substance grown on the silicon wafer substrate is the oriented carbon nanotube array structure, as shown in fig. 5-5 b.
Example 7
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: hafnium oxide is selected as a substrate, 0.013wt% of dodecyl fluorine-based phosphoric acid molecules are adopted as a substance for fixing the carbon nano tube, and 1cm multiplied by 1cm of polydimethylsiloxane is cut as a template; attaching a template to a silicon wafer substrate, and applying 1g of pressure above the template to ensure that the substrate is in conformal contact with the template; uniformly depositing the dodecyl fluorine-based phosphoric acid molecular solution to the periphery of a template (such as printing, dripping and the like) and naturally volatilizing for 10min; transferring to a vacuum drying oven, vacuumizing for 10min, taking out the sample, heating at 90 ℃ for 15min on a hot table, cooling at room temperature, and then removing the template; placing the patterned substrate in a semiconductor carbon nanotube ink with an absorption peak of 1, and pulling the substrate upwards at a speed of 10 mu m/s; taking down the substrate, heating and curing the carbon nano tube at 90 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 90 ℃ for 20min; the substance growing on the silicon chip substrate is the oriented carbon nanotube array structure.
Example 8
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: cutting a flexible base PEN (PEN) of 2cm multiplied by 2cm as a substrate, and performing oxygen plasma treatment on the surface of the substrate, wherein the parameters are 100W and 2min; using 0.5wt% octadecyl fluorine-based phosphoric acid molecules as a substance for fixing the carbon nano tube, and cutting 1cm multiplied by 1cm of polydimethylsiloxane as a template; attaching the template and the PEN substrate, and applying 4g of pressure above the template to ensure that the substrate is in conformal contact with the template; uniformly depositing octadecyl fluorine-based phosphoric acid molecular solution to the periphery of a template (such as printing, dripping and the like) and naturally volatilizing for 20min; transferring to a vacuum drying oven, vacuumizing for 15min, taking out a sample, heating at 120 ℃ for 5min on a heating table, cooling at room temperature, and then removing the template; placing the patterned substrate in a semiconducting carbon nanotube ink with an absorption peak of 0.8, and pulling the substrate upwards at a speed of 500 micrometers/s; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 10min; the substance growing on the silicon chip substrate is the oriented carbon nanotube array structure.
Example 9
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: cutting a flexible base PEN (PEN) of 2cm multiplied by 2cm as a substrate, and performing oxygen plasma treatment on the surface of the substrate, wherein the parameter is 100W and 3min; taking 0.03wt% of octadecyl hydroxy phosphoric acid molecules as a substance for fixing the carbon nano tube, and cutting a polyurethane elastomer with the thickness of 1cm multiplied by 1cm as a template; attaching the template and the PEN substrate, and applying 3g of pressure above the template to ensure that the substrate is in conformal contact with the template; uniformly depositing the octadecyl hydroxyl phosphate molecular solution to the periphery of the template (such as printing, dripping and coating) and naturally volatilizing for 15min; transferring to a vacuum drying oven, vacuumizing for 10min, taking out the sample, heating at 120 ℃ for 5min on a heating table, cooling at room temperature, and then removing the template; placing the patterned substrate in a semiconducting carbon nanotube ink with an absorption peak of 0.6, and pulling the substrate upwards at a speed of 40 μm/s; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 15min; the substance growing on the silicon chip substrate is the directional carbon nanotube array structure.
Example 10
The preparation method of the oriented carbon nanotube array structure in the embodiment comprises the following steps: cutting a 3cm × 3cm silicon wafer as a substrate, and performing oxygen plasma treatment on the surface of the substrate with the parameter of 100W, and 3min; cutting 2cm × 2cm polydimethylsiloxane elastomer as a template; directly attaching a polydimethylsiloxane elastomer template to a silicon wafer substrate, and applying 3g of pressure above the template to ensure that the substrate is in conformal contact with the template; vacuumizing for 15min in a vacuum drying oven, taking out a sample, heating for 5min at 120 ℃ on a heating table, cooling at room temperature, and then removing the template; placing the patterned substrate in a semiconducting carbon nanotube ink with an absorption peak of 0.6 and pulling the substrate upwards at a speed of 40 μm/s; taking down the substrate, heating and curing the carbon nano tube at 120 ℃, washing the carbon nano tube with toluene for several times, and finally annealing the carbon nano tube at 120 ℃ for 10min; the substance grown on the silicon wafer substrate is the aligned carbon nanotube array structure, as shown in fig. 6.
The patterned substrate is obtained by adhering to the substrate with a thickness of several nanometers by contacting the raised portions of the elastomeric template with the substrate; under the action of certain pressure, the raised part of the elastomer substrate is closely contacted with the substrate, when the template is taken off, a layer of polydimethylsiloxane substrate is adhered on the substrate, the polydimethylsiloxane cannot be adhered with the carbon nano tubes, the substrate can be adhered with the carbon nano tubes so as to form different lyophilic and lyophobic structures, and the carbon nano tubes are directionally arranged in the lifting process.
In summary, compared with the prior art, the method for preparing aligned carbon nanotubes provided by the present invention does not limit the material and shape of the substrate, and can be any rigid and flexible substrate supporting the thin film. Besides the silicon substrate, hafnium oxide, glass, quartz, PEN, PET, paper, etc. can be selected. The self-assembly molecular solution for fixing the carbon nano tube is not limited to one, and can be octadecyl fluoro-based phosphoric acid, dodecyl fluoro-based phosphoric acid, octadecyl hydroxy-phosphoric acid, dodecyl hydroxy-phosphoric acid and the like, or self-assembly molecules are not needed, the difference lies in that the mechanism for fixing the carbon tube and the morphological density of the prepared carbon tube are different, the template is not limited to one, and materials such as polydimethylsiloxane, polyurethane, polymethyl methacrylate, thermoplastic vulcanized rubber and the like can be used. The preparation condition is mild, the requirements on curing temperature, pulling speed and pulling direction are low, the selection of the substrate, the template and the self-assembly molecular material is wide, the operation is simple, the micro-nano stripe structure template can be obtained without photoetching technology, the cost is low, the introduction of a second phase solution is not needed, the density of the prepared oriented carbon nanotube film is controllable, the density of the carbon nanotube can be adjusted and controlled by improving the concentration of the adjusting and controlling ink, and the experiment can be completed within 2h, so that the method is expected to be used for industrial high-efficiency preparation application of large-area oriented carbon nanotubes.
In addition, the inventors of the present invention have also made experiments with reference to the above examples and by using other raw materials, process operations, and process conditions described in the present specification, and have obtained preferable results.
It should be understood that the technical solutions of the present invention are not limited to the above specific embodiments, and all technical modifications made according to the technical solutions of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the scope of the claims.
Claims (10)
1. A method for preparing an oriented carbon nanotube array structure is characterized by comprising the following steps:
assembling self-assembly molecules on the surface of a substrate to form a first microstructure so as to obtain a patterned substrate, wherein the bonding force of the first microstructure and the carbon nano tube is greater than that of the substrate and the carbon nano tube;
and dipping the patterned substrate in the carbon nanotube ink, then pulling and taking out, and then carrying out annealing treatment, thereby forming an oriented carbon nanotube array structure corresponding to the first microstructure on the substrate.
2. The method according to claim 1, comprising:
attaching one side surface of the template with a second microstructure to the surface of the substrate and applying pressure to ensure that the side surface of the template with the second microstructure is in conformal contact with the surface of the substrate, wherein the second microstructure corresponds to the first microstructure;
and applying a self-assembly molecule solution around the template, depositing self-assembly molecules at the grooves formed between the template and the substrate under the action of capillary force, and then carrying out drying and first thermal curing treatment to form the first microstructure.
3. The method of claim 2, wherein: the template is formed of an elastomer; preferably, the material of the elastomer comprises any one or the combination of more than two of thermoplastic polyurethane, thermoplastic vulcanized rubber and polydimethylsiloxane;
and/or the first microstructure comprises orientation arranged micro-scale stripes and/or nano-scale stripes; preferably, the width of the nano-scale stripes is 160nm to 640nm;
and/or the first microstructure is convexly arranged on the surface of the substrate;
and/or the second microstructure comprises micron-scale grooves and/or nanometer-scale grooves formed on the surface of the template;
and/or a capillary structure is formed at the combination interface of the template and the substrate;
and/or, the self-assembling molecules are capable of binding to the carbon nanotubes by at least physical effects, including van der waals forces;
and/or the substrate comprises a rigid substrate and/or a flexible substrate; preferably, the substrate is made of hafnium oxide, silicon wafer, polyethylene terephthalate, polyethylene naphthalate or glass.
4. The preparation method according to claim 2, characterized by specifically comprising: after self-assembly molecular solution is applied around the template, the self-assembly molecular solution is naturally dried, then the template and the substrate are placed into a sealed cavity together for vacuum pumping treatment, then the first thermal curing treatment is carried out, then the template is cooled to room temperature, and then the template is removed, so that a first microstructure is formed on the substrate;
preferably, the concentration of the self-assembly molecule solution is 0.013-0.5 wt%; preferably, the solvent in the self-assembly molecular solution comprises any one or a combination of more than two of toluene, xylene and carboxylic ester solvents;
preferably, a self-assembling molecular solution is applied around the template at least by printing and/or dispensing;
preferably, the natural drying time is 10-20 min;
preferably, the time of the vacuum pumping treatment is 10-15 min, and the vacuum degree is 4-15 Pa;
preferably, the temperature of the first heat curing treatment is 90-120 ℃, and the time is 5-15 min.
5. The preparation method according to claim 1, characterized by specifically comprising: dipping the patterned substrate in carbon nanotube ink, pulling and taking out, and then sequentially carrying out second heat curing, cleaning and annealing treatment to form the oriented carbon nanotube array structure;
preferably, the preparation method specifically comprises the following steps: dipping the patterned substrate in carbon nanotube ink, and vertically pulling and taking out the substrate; preferably, the pulling and taking-out speed is 10 to 500 mu m/s;
preferably, the temperature of the second heat curing treatment is 90-120 ℃, and the time is 3-5 min; preferably, the cleaning solvent used in the cleaning treatment includes toluene and/or xylene; preferably, the temperature of the annealing treatment is 90-120 ℃, and the time is 10-20 min.
6. The method of claim 1, wherein: the self-assembly molecule comprises a phosphoric acid self-assembly molecule, and a substituent group contained in the phosphoric acid self-assembly molecule comprises any one or the combination of more than two of fluorine group, hydroxyl group and amino group; preferably, the phosphoric acid self-assembly molecule comprises any one or a combination of more than two of dodecyl fluorine-based phosphoric acid, octadecyl hydroxy phosphoric acid, dodecyl hydroxy phosphoric acid and octadecyl amino phosphoric acid;
and/or the carbon nanotube ink comprises carbon nanotubes, a dispersant and a dispersion medium; preferably, the carbon nanotubes comprise single-walled carbon nanotubes and/or multi-walled carbon nanotubes; preferably, the dispersant comprises a polymer comprising any one or a combination of two or more of poly [ nitrogen- (9-heptadecyl) carbazole ], poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (1, 4-benzo 2, 1-3-thiadiazole) ], poly [ N, N '-di (2-octyldodecyl) -isoindigo-co- (9, 9-dioctylfluorenyl-2, 7-diyl) ], poly [ N, N' -di (2-octyldodecyl) -isoindigo-co-N- [1- (octylnonyl) -carbazolyl-2, 7-diyl ]; preferably, the dispersion medium comprises any one or a combination of more than two of toluene, xylene and carboxylic ester solvents;
and/or the carbon nanotube ink is a semiconductor single-walled carbon nanotube ink.
7. An aligned carbon nanotube array structure prepared by the method of any one of claims 1-6.
8. A method for manufacturing a semiconductor device, characterized by comprising: preparing an oriented carbon nanotube array structure by the method of any one of claims 1-6 using semiconductor single-walled carbon nanotube ink, and then using the oriented carbon nanotube array structure to fabricate a semiconductor device; preferably, the semiconductor device includes a field effect transistor.
9. A semiconductor device comprising the aligned carbon nanotube array structure of claim 7, wherein the carbon nanotubes are semiconductor single-walled carbon nanotubes; preferably, the semiconductor device includes a field effect transistor.
10. A method for preparing a carbon nano tube pattern structure is characterized by comprising the following steps:
assembling self-assembly molecules on the surface of a substrate to form a set pattern so as to obtain a patterned substrate, wherein the bonding force between the set pattern and the carbon nano tube is greater than the bonding force between the substrate and the carbon nano tube;
and dipping the patterned substrate in carbon nanotube ink, then pulling and taking out, and then carrying out annealing treatment, thereby forming a carbon nanotube pattern structure corresponding to the set pattern on the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110964715.9A CN115724421A (en) | 2021-08-23 | 2021-08-23 | Oriented carbon nanotube array structure and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110964715.9A CN115724421A (en) | 2021-08-23 | 2021-08-23 | Oriented carbon nanotube array structure and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115724421A true CN115724421A (en) | 2023-03-03 |
Family
ID=85289534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110964715.9A Pending CN115724421A (en) | 2021-08-23 | 2021-08-23 | Oriented carbon nanotube array structure and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115724421A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040163758A1 (en) * | 2000-04-21 | 2004-08-26 | International Business Machines Corporation | Patterning solution deposited thin films with self-assembled monolayers |
| CN1730382A (en) * | 2005-09-02 | 2006-02-08 | 清华大学 | Carbon tube nanometer tube figuring technique |
| US20070166557A1 (en) * | 2004-05-28 | 2007-07-19 | Matthias Keil | Modified metal mold for use in imprinting processes |
| CN101012109A (en) * | 2007-02-01 | 2007-08-08 | 上海交通大学 | Method of manufacturing phosphate group silicane-carbon nano tube composite film on glass substrate surface |
| CN102557014A (en) * | 2010-12-30 | 2012-07-11 | 国家纳米科学中心 | Method for forming patterns of graphene oxide and patterns of graphene |
| CN107151311A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Bioxindol class conjugated polymer, semiconductor CNT inks, its preparation method and application |
| CN110902670A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented film, preparation method and application thereof |
-
2021
- 2021-08-23 CN CN202110964715.9A patent/CN115724421A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040163758A1 (en) * | 2000-04-21 | 2004-08-26 | International Business Machines Corporation | Patterning solution deposited thin films with self-assembled monolayers |
| US20070166557A1 (en) * | 2004-05-28 | 2007-07-19 | Matthias Keil | Modified metal mold for use in imprinting processes |
| CN1730382A (en) * | 2005-09-02 | 2006-02-08 | 清华大学 | Carbon tube nanometer tube figuring technique |
| CN101012109A (en) * | 2007-02-01 | 2007-08-08 | 上海交通大学 | Method of manufacturing phosphate group silicane-carbon nano tube composite film on glass substrate surface |
| CN102557014A (en) * | 2010-12-30 | 2012-07-11 | 国家纳米科学中心 | Method for forming patterns of graphene oxide and patterns of graphene |
| CN107151311A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Bioxindol class conjugated polymer, semiconductor CNT inks, its preparation method and application |
| CN110902670A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented film, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| PENG YITIAN ET: "Patterned deposition of multi-walled carbon nanotubes on self-assembled monolayers", 《CHINESE SCIENCE BULLETIN》, vol. 51, no. 2, pages 147 - 150, XP019317780 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101119913B1 (en) | Electronic device comprising graphene thin film and method of fabricating the same | |
| US8847313B2 (en) | Transparent electronics based on transfer printed carbon nanotubes on rigid and flexible substrates | |
| KR101410929B1 (en) | Method of transferring carbon nanotube | |
| KR101220421B1 (en) | Method of forming graphene pattern utilizing imprint | |
| WO2007026778A1 (en) | Transistor, organic semiconductor device, and method for manufacture of the transistor or device | |
| CN107068745A (en) | A kind of field-effect transistor and preparation method thereof | |
| JP5092269B2 (en) | Organic semiconductor thin film and organic semiconductor device manufacturing method | |
| US20110117695A1 (en) | Fabrication method of organic thin-film transistors | |
| WO2007105405A1 (en) | Method and device for mounting anisotropically-shaped member, method of manufacturing electronic device, electronic device, and display | |
| EP1656695A1 (en) | Method for sealing thin film transistors | |
| CN106784186B (en) | L B quantum dot film, light-emitting diode and preparation method | |
| Li et al. | Alignment and patterning of organic single crystals for field-effect transistors | |
| Moonen et al. | Flexible thin-film transistors using multistep UV nanoimprint lithography | |
| CN108735820B (en) | Carbon nanotube thin film transistor with photoresist as gate insulating layer and manufacturing and application thereof | |
| CN115724421A (en) | Oriented carbon nanotube array structure and preparation method and application thereof | |
| CN108374200A (en) | A kind of preparation method of nanometer of linear organic single-crystal domain | |
| US20220177313A1 (en) | Graphene nanoribbon composite structure and method for making the same | |
| US11658232B2 (en) | Field effect transistor based on graphene nanoribbon and method for making the same | |
| CN103177969A (en) | Preparation method of metallic oxide thin film transistor | |
| US20120049173A1 (en) | Organic Field Effect Transistor with Block Copolymer Layer | |
| CN114604820A (en) | Thick film material nano pattern etching method | |
| CN109378267B (en) | Molybdenum sulfide film and preparation method thereof | |
| KR102072888B1 (en) | Method for doping of graphene films by using graphene oxides | |
| US11948793B2 (en) | Field effect transistor based on graphene nanoribbon and method for making the same | |
| KR101042333B1 (en) | Method of manufacturing structure for light source and method of manufacturing light source using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |