Patent Application
20190256356
The present invention the field of preparation of a high performance flexible transparent conductive film, and particularly relates to a single-walled carbon nanotube flexible transparent conductive thin film with carbon welded structure and its preparation method thereof.
The transparent conductive film is an important component of electronic devices such as touch screens, flat panel displays, photovoltaic cells, and organic light emitting diodes. At present, indium tin oxide (ITO) is the most mature transparent conductive film for commercial applications. However, the scarcity of rare metal indium makes the cost of ITO increase gradually. On the other hand, with the rise of flexible electronics, the brittleness of ITO cannot meet the future application. Due to its good optoelectronic properties, structural stability, flexibility and other characteristics, the two-dimensional network transparent conductive film interwoven with single-walled carbon nanotubes with its high transparent conductivity and excellent flexibility is expected to replace the scarce and brittle indium tin oxide as a new generation of transparent conductive film and is widely used.
At present, there are mainly two methods for preparing a single-walled carbon nanotube flexible transparent conductive film. One is a wet method (solution method), in which a single-walled carbon nanotube is first dispersed in a solution, and then a single-walled carbon nanotube is deposited on a flexible substrate by filtration, spraying, suspension coating or printing. The limitation of this method is that the physical and chemical processes of dispersing single-walled carbon nanotubes can destroy the intrinsic structure of the carbon nanotubes, introduce pollutants such as surfactants, and thereby reduce the performance of the obtained transparent conductive film. The other method is a dry method in which a collecting device is installed at the end of the reaction system for growing single-walled carbon nanotubes, and the grown single-walled carbon nanotubes are directly collected on the porous substrate; and the carbon nanotubes are transferred to a flexible substrate by an imprint process to form a transparent conductive film. (Document 1: Kaskela A, Nasibulin A G, Timmermans M Y, et al. Aerosol-synthesized SWCNT networks with tunable conductivity and transparency by a dry transfer technique[J]. Nano letters, 2010, 10(11): 4349-4355.) This method has the advantages of maintaining the intrinsic structure of the carbon nanotubes and does not introduce pollution, and is low in consumption and simple, which is easy to large-scale production. Therefore, a series of development, such as reducing tube bundle size, reducing contact resistance, patterning, etc., have been made in the dry preparation of carbon nanotube transparent conductive films (Document 2: Mustonen K, Laiho P, Kaskela A, et al. Uncovering the ultimate performance of single-walled carbon nanotube films as transparent conductors[J]. Applied Physics Letters, 2015, 107(14): 143113. Document 3: Fukaya N, Kim D Y, Kishimoto S, et al. One-step sub-10 μm patterning of carbon-nanotube thin films for transparent conductor applications[J]. ACS nano, 2014, 8(4): 3285-3293).
It has been reported that the photoelectric properties of single-walled carbon nanotube transparent conductive films obtained by dry transfer (sheet resistance greater than 200Ω/□ (ohm/sq) @ 90% transmittance) are not comparable to those of ITO (less than 50Ω/□ @ 90% transmittance), and are much lower than those predicted based on single-walled single-walled carbon nanotubes. This is mainly because the commonly produced single-walled carbon nanotubes are aggregated into bundles of ten to several tens of nanometers in diameter due to the strong van der Waals force between the tubes, and the single-walled carbon nanotubes in the tube bundle do not contribute to the conductivity of the film but absorb a large amount of light, thus reducing the photoelectric properties of the film. (Document 4: Radosavljević M, Lefebvre J, Johnson A T. High-field electrical transport and breakdown in bundles of single-wall carbon nanotubes[J]. Physical Review B, 2001, 64(24): 241307.) Kauppinen et al. reduced the yield of carbon nanotubes by reducing the amount of catalyst supplied, and obtained single-walled carbon nanotubes with a single root ratio of more than 50%. The best photoelectric performance of the prepared transparent conductive film is 310 Ω/□ @ 90% transmittance. (Document 2: Mustonen K, Laiho P, Kaskela A, et al. Uncovering the ultimate performance of single-walled carbon nanotube films as transparent conductors[J]. Applied Physics Letters, 2015, 107(14): 143113.) On the other hand, due to the nanometer size of single-walled carbon nanotubes, the contact resistance between the tubes is considered to be a major contributor to the sheet resistance. Researchers usually use nitric acid doping to reduce the contact resistance between carbon nanotubes. (Document 5: Jackson R, Domercq B, Jain R, et al. Stability of doped transparent carbon nanotube electrodes[J]. Advanced Functional Materials, 2008, 18(17): 2548-2554.) However, this chemical doping effect is not stable, resulting in a gradual rise in sheet resistance.
An object of the present invention is to provide a single-walled carbon nanotube flexible transparent conductive film with carbon welded structure and its preparation method thereof so as to solve the key problems of single-walled carbon nanotubes aggregated to absorb large amounts of light and reduce contact resistance between tubes and to obtain a single-walled carbon nanotube flexible transparent conductive film with comparable performance to flexible ITO and high stability.
The present invention is implemented by the following technical solutions:
A single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure, that a highly crystalline graphene sp2 carbon island is constructed to cover a connecting junction between single-walled carbon nanotubes, wherein the graphene sp2 carbon island is welded at the intersection between individual single-walled carbon nanotubes, forming a single-walled carbon nanotube film having a sp2 carbon island welded structure; in a single-walled carbon nanotube network, a ratio of single carbon nanotubes is 80 to 88% and the connecting portion of the single carbon nanotubes is tightly connected through carbon welded structure.
In the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure, the crystalline IG/ID of graphene carbon islands and single-walled carbon nanotubes in the carbon-welded structure is 150˜180, the sp2 C—C bond ratio is 97 to 99%, and the antioxidant temperature exceeds 750-800° C.
In the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure, the single-walled carbon nanotubes have a length of 10˜200 μm and a diameter of 1.4˜2.4 nm.
A preparation method of the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure, which uses volatile metal organic compound ferrocene as a catalyst precursor, sulfur-containing organic compound thiophene as a growth promoter, hydrocarbon ethylene and toluene as carbon source, hydrogen as a carrier gas to grow carbon nanotubes under 1100° C. in a reaction furnace, and the high-quality single-walled carbon nanotube flexible transparent conductive thin film is collected in situ at the end of a furnace tube of the reaction furnace.
In particular, the preparation method of the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure comprises the steps of:
(1) Under the protection of argon gas, a temperature of the reactor furnace is first increased to 1100±50° C., then a carrier gas hydrogen and a main carbon source ethylene are introduced;
(2) Being carried by the carrier gas, supplying a solution consisting of auxiliary carbon source toluene, catalyst precursor ferrocene and growth promoter thiophene by an injection pump which then volatilizes and enters into a 1100±50° C. high temperature zone; ferrocene and thiophene being cleaved to form catalyst particles, ethylene and toluene being cracked to carbon atoms under catalysis of the catalyst and nucleating on the catalyst particles and growing the single-walled carbon nanotubes;
(3) the single-walled carbon nanotubes flowing along a gas flow to the end of the furnace tube, and finally being filtered by a porous filter positioned at the end of the furnace tube to form a macroscopic two-dimensional carbon nanotube thin film.
According to the preparation method of the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure, in the process of growing single-walled carbon nanotubes by floating catalyst chemical vapor deposition, through reducing a concentration of the catalyst and the carbon source and a staying time in a constant temperature zone, a portion of carbon source being decomposed by the catalyst form sp2 carbon islands, which is welded at an intersection between individual single-walled carbon nanotubes such that a single-walled carbon nanotube film having a sp2 carbon island welded structure is finally formed; before and after the preparation method, the flow rate of argon gas is 180˜220 ml/min; during the preparation method, the flow rate of hydrogen is 4500˜8000 ml/min, the flow rate of ethylene is 2˜20 ml/min, and the supply rate of the solution is 0.1˜0.24 ml/hr, the solution formulation is toluene: ferrocene: thiophene=10 g: (0.05˜0.6) g: (0.025˜0.9) g.
According to the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure, imprinting method is used to transfer the carbon nanotube thin film to a flexible substrate to construct the flexible transparent conductive thin film.
According to the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure, the flexible substrate is polyethylene terephthalate, polyethylene naphthalate or polycarbonate.
According to the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure, the single-walled carbon nanotube flexible transparent conductive thin film has excellent uniformity with a transmittance error of ±0.4% and a sheet resistance error of ±4.3%.
The design idea of the present invention is:
The invention utilizes the difference in decomposition temperature between the gas phase carbon source and the liquid phase carbon source to realize the decomposition of the carbon source in the medium-high temperature to high temperature range in the reaction system, thereby inhibiting the agglomeration and growing of the catalyst particles or poisoning by excessive adsorption of carbon.
Through using very low carbon source and catalyst concentration to reduce the number of nucleation of carbon nanotubes, thus reducing the chance of contact between carbon nanotubes and tube bundles formation; through the use of high carrier gas flow rate to reduce the staying time of the catalyst and the carbon source in the growing zone, so that some carbon atoms cannot participate in the growth of the carbon nanotubes in time to form a highly crystalline graphene carbon islands. Under the combined action of thermal motion and van der Waals force, some of the graphene carbon islands are adsorbed on the surface of the carbon nanotubes, thereby suppressing the formation of tube bundles. Due to the filtration of the porous membrane, the carbon nanotubes are deposited and overlap each other on the surface of the membrane. As the reaction progresses, the graphene carbon islands in the gas stream are deposited at the connecting junction between individual tubes, then a graphene island welded structure is formed eventually. In the high-performance flexible single-walled carbon nanotube film welded by graphene islands, the first function of the graphene island welding structure is to reduce the contact resistance between the carbon nanotubes, and the second function is to solve the problem of large absorption of light caused through suppressing tube aggregation and bundling.
The advantages and benefits of the present invention are:
1. The invention designs and prepares a carbon-welded single-walled carbon nanotube flexible transparent conductive thin film for the first time, which effectively solves the problem of large contact resistance between tubes and large amount of light absorbed by tube bundles in conventional single-walled carbon nanotube films.
2. The single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure of the present invention has a sheet resistance of only 41Ω/□ at 90% transmittance (550 nm visible light); at the same transmittance, the sheet resistance is 5.5 times lower than that of the lowest reported value of the conventional the undoped original carbon nanotube transparent conductive film, and is at the same level as the optimal performance of the flexible substrate ITO transparent conductive film.
3. The preparation method of the single-walled carbon nanotube flexible transparent conductive thin film with carbon-welded structure of the present invention has the characteristics of simple process and easy to large-scale production, thus solving the key scientific and technical problems of poor stability and complicated process of carbon nanotube transparent conductive film; that it is expected to play an important role in the fields of touch screen, liquid crystal display and organic light display.
4. In the process of growing single-walled carbon nanotubes by floating catalyst chemical vapor deposition of the present invention, through reducing a concentration of the catalyst and the carbon source and a staying time in a constant temperature zone, a portion of carbon source being decomposed by the catalyst form sp2 carbon islands, which is then welded at an intersection between individual single-walled carbon nanotubes and a single-walled carbon nanotube film having a sp2 carbon island welded structure is finally formed.
5. The invention designs and prepares a single carbon nanotube bonded by a carbon welding structure, thus reducing the contact resistance between the carbon nanotubes, inhibiting the formation of the tube bundle and absorption of a large amount of light, and obtaining a high-performance flexible transparent conductive film. Therefore, the present invention is of great significance for the application of carbon nanotube film in the field of high performance optoelectronic devices.
Referring to
In the process of a specific embodiment of the present invention, the present invention adopts injection floating catalyst CVD method to control the preparation of the carbon-welded single-walled carbon nanotube flexible transparent conductive film. The volatile metal organic compound ferrocene is used as a catalyst precursor, the sulfur-containing organic compound thiophene is a growth promoter, the hydrocarbon ethylene and toluene are carbon sources, the hydrogen is a carrier gas. The carbon nanotubes are grown at 1100° C. and the high-quality single-walled carbon nanotube flexible transparent conductive film is collected in situ at the end of the furnace tube. The particular steps are as follows:
(1) Under the protection of argon gas, the temperature of the reactor furnace is first increased to 1100° C., then the carrier gas hydrogen and the main carbon source ethylene are introduced;
(2) Being carried by the carrier gas, the solution supplied by the injection pump (including auxiliary carbon source toluene, catalyst precursor ferrocene and growth promoter thiophene) volatilizes rapidly and enters into the high temperature zone (1100° C.); ferrocene and thiophene are cleaved to form catalyst particles, under the catalysis of the catalyst, ethylene and toluene crack out carbon atoms, and nucleating and growing single-walled carbon nanotubes on the catalyst particles;
(3) Carbon nanotubes flow along the gas flow to the end of the furnace tube, and is finally filtered by the porous filter positioned at the end of the furnace tube to form a macroscopic two-dimensional carbon nanotube film, thus realizing in-situ gas phase collection of carbon nanotube film on porous substrate; if the collection time is different, the resulting film thickness is different.
(4) At the end of the preparation method, the reaction furnace and the temperature controller start to cool down, the injection pump stops working, the supply of hydrogen and ethylene is stopped, and then argon gas is introduced to discharge the gas in the reaction tube.
Wherein before and after the preparation method, the flow rate of argon gas is 200 ml/min; during the preparation method, the flow rate of hydrogen is 4500-8000 ml/min, the flow rate of ethylene is 2-20 ml/min, and the supply rate of the solution is 0.1-0.24 ml/hr. the solution formulation is toluene: ferrocene: thiophene=10 g: (0.05˜0.6) g: (0.025˜0.9) g.
According to the high-performance single-walled carbon nanotube flexible transparent conductive film obtained by the present invention, a highly crystalline graphene carbon island is designed and covered at the connecting junction of the singled-walled carbon nanotube, this carbon island structure solves the problem of large-scale absorption of light by single-walled carbon nanotubes and the large contact resistance between carbon nanotubes due to van der Waals force, and finally a high performance flexible transparent single-walled carbon nanotube conductive film is obtained. The proportion of single carbon nanotubes in a single-walled carbon nanotube network can achieve as high as 85%. This avoids the problem that the tube bundle (the tube bundle size is usually tens of nanometers) absorbs a large amount of light in the conventional single-walled carbon nanotube network and the carbon nanotube inside the tube bundle does not contribute to the conductivity. The carbon-welded structure tightly connects the junction between the carbon tubes, hence greatly reducing the joint resistance between the carbon tubes. The carbon islands and the single-walled carbon nanotubes in carbon welded structures are highly crystalline (IG/ID is 175, sp2 C—C bond ratio is 98.8%, and antioxidant temperature exceeds 700° C.), the length of the carbon nanotubes is long (10 to 200 μm) and the diameter the carbon nanotubes is great (1.4˜2.4 nm). By mounting a porous substrate at the end of the furnace tube for in-situ collection of carbon nanotube film, not only the complicated subsequent solution treatment of dispersion film forming and the introduction of impurities are eliminated, but also the integrity of the intrinsic structure of the carbon nanotubes is ensured.
The present invention can utilize a simple imprint method to transfer the carbon nanotube film to the flexible substrate (For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), etc.) and constructing a flexible transparent conductive film. The film has a sheet resistance of only 41Ω/□ at 90% transmittance (550 nm visible light). At the same transmittance, the sheet resistance of the undoped original carbon nanotube transparent conductive film is 5.5 times lower than the lowest reported value of the conventional pure carbon nanotube transparent conductive film, reaching the level of commercial ITO flexible film. The resulting single-walled carbon nanotube film has excellent uniformity (light transmittance error is ±0.4%, sheet resistance error is ±4.3%), air stability, high temperature and high humidity stability. Also, good performance stability is maintained after repeated bending and single large angle bending test.
Among the products obtained by the method of the present invention, evaluation of the high performance characterization technique for the single-walled carbon nanotube transparent conductive film includes: Photoelectric performance test, air stability test, accelerated aging test, repeated bending test and single bending test.
The present invention is further described in detail below with the exemplary embodiment and accompanying figures.
According to this embodiment, under the protection of argon gas at a flow rate of 200 ml/min, the temperature of the reactor is first increased to 1100° C., then hydrogen gas, carbon source, catalyst precursor ferrocene and growth promoter thiophene are introduced at a flow rate of 8060 ml/min. Wherein the volume concentration of ethylene in the gas phase carbon source is 1.4×10−3 in the reaction system, the volume concentration of toluene in the reaction system is 6.1×10−3, and the volume concentration of the catalyst precursor ferrocene in the reaction system is 1.5×10−6, and the volume concentration of the growth promoter thiophene in the reaction system is of 5×10−7. The carbon nanotubes being produced flow along the gas flow to the end of the furnace tube, and a macroscopic two-dimensional carbon nanotube film is finally formed on the porous filter positioned at the end of the furnace tube to form. Through controlling the collection time, the films with different light transmittances are obtained.
A sample of the single-walled carbon nanotube film prepared as described above (labeled as 1#) is used for characterization tests of TEM, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, sheet resistance, transmittance, and also for high temperature heat treatment, air stability, accelerated aging, repeated bending and single large angle bending tests.
Scanning electron microscopy (
Transfer the collected carbon-welded single-walled carbon nanotube film to the flexible PET substrate by imprinting, the measured film sheet resistance of 90% transmittance (550 nm visible light) is only 41Ω/□. Also, the film has excellent uniformity: the uniformity of a film of 8×8 cm2 is tested (
Test conditions: 250 h @60° C. & 90% relative humidity
According to this embodiment, under the protection of argon gas at a flow rate of 200 ml/min, the temperature of the reactor is first increased to 1100° C., then hydrogen gas, carbon source, catalyst precursor ferrocene and growth promoter thiophene are introduced at a flow rate of 6530 ml/min. Wherein the volume concentration of ethylene in the gas phase carbon source is 2.4×10−3 in the reaction system, the volume concentration of toluene in the reaction system is 4.4×10−3, and the volume concentration of the catalyst precursor ferrocene in the reaction system is 1.1×10−6, and the volume concentration of the growth promoter thiophene in the reaction system is of 3.7×10−7. The carbon nanotubes being produced flow along the gas flow to the end of the furnace tube, and is finally deposited on the porous filter positioned at the end of the furnace tube to form a macroscopic two-dimensional carbon nanotube film. Through controlling the collection time, the films with different light transmittances are obtained.
A sample of the single-walled carbon nanotube film prepared as described above is used for characterization tests of Transmission electron microscopy, sheet resistance and transmittance. Transmission electron microscopy (TEM) characterization showed that the carbon nanotubes in the film are covered with graphene islands, forming a single-walled carbon nanotube network structure welded by graphene islands. Transfer the collected carbon-welded single-walled carbon nanotube film to the flexible PET substrate by imprinting, the measured film sheet resistance of 90% transmittance (550 nm visible light) is only 50 Ω/□.
Under the protection of argon gas at a flow rate of 200 ml/min, the temperature of the reactor is first increased to 1100° C., then hydrogen gas, carbon source, catalyst precursor ferrocene and growth promoter thiophene are introduced at a flow rate of 4560 ml/min. Wherein the volume concentration of ethylene in the gas phase carbon source is 2.4×10−3 in the reaction system, the volume concentration of toluene in the reaction system is 1.1×10−3, and the volume concentration of the catalyst precursor ferrocene in the reaction system is 2.7×10−6, and the volume concentration of the growth promoter thiophene in the reaction system is of 8.9×10−7. The carbon nanotubes being produced flow along the gas flow to the end of the furnace tube, and a macroscopic two-dimensional carbon nanotube film is formed in the porous filter positioned at the end of the furnace tube to. Through controlling the collection time, the films with different light transmittances are obtained.
A sample of the single-walled carbon nanotube film prepared as described above (labeled as 2#) is used for characterization tests of transmission electron microscopy, sheet resistance, and transmittance. The TEM image is shown in
The results of the embodiments and the comparative example show that the present invention successfully design and prepare a graphene island welding high performance single-wall carbon nanotube network film in which the single-walled carbon nanotubes have high quality, high single tube rate, long length and large diameter, which makes the prepared transparent conductive film reach the best reported level of ITO film on the flexible substrate for the first time, that is 5.5 times of the best performance of the reported conventional carbon nanotube film without any treatment. Also, the transparent conductive film also has good chemical stability and flexibility. The present invention realizes the preparation of high-performance single-walled carbon nanotube transparent conductive film, and solves the key scientific and technical problems of poor photoelectric performance and complicated process of the conventional carbon nanotube transparent conductive film.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201610459221.4 | Jun 2016 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2017/087254 | 6/6/2017 | WO | 00 |
