CN118028809A - Method for preparing carbon nano tube photoluminescent material based on rare earth metal composite film - Google Patents

Method for preparing carbon nano tube photoluminescent material based on rare earth metal composite film Download PDF

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CN118028809A
CN118028809A CN202410120664.5A CN202410120664A CN118028809A CN 118028809 A CN118028809 A CN 118028809A CN 202410120664 A CN202410120664 A CN 202410120664A CN 118028809 A CN118028809 A CN 118028809A
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rare earth
film
earth metal
sputtering
preparing
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CN118028809B (en
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李成明
黄毅丹
任飞桐
魏俊俊
陈良贤
刘金龙
张建军
欧阳晓平
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University of Science and Technology Beijing USTB
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Abstract

A method for preparing a carbon nano tube photoluminescent material based on a rare earth metal composite film belongs to the field of luminescent materials. The method comprises the steps of taking double-sided polished silicon or silicon oxide as a substrate material, firstly preparing transition metal Fe or N i on the substrate by a radio frequency magnetron sputtering method to form a catalyst film, and then sputtering a layer of rare earth metal film Eu on the obtained transition metal catalyst film by radio frequency magnetron sputtering, wherein the thickness of the rare earth Eu film is 10-20nm. Then preparing the multi-wall carbon nano tube by a plasma enhanced chemical vapor deposition technology. The invention utilizes magnetron sputtering to deposit the rare earth metal and transition metal composite film, grows the carbon nano tube photoluminescent material with low cost, high purity and stable quality performance, combines the carbon nano tube with photothermal conversion performance with the rare earth material, and obviously improves the luminescent performance of the composite nano material.

Description

Method for preparing carbon nano tube photoluminescent material based on rare earth metal composite film
Technical Field
The invention belongs to the field of luminescent materials, relates to a preparation method of a carbon nano tube photoluminescent material, and in particular relates to a method for preparing a carbon nano tube photoluminescent material based on a rare earth metal composite film.
Background
The carbon nano tube has a one-dimensional tubular structure and unique mechanical, electrical and optical properties. Has wide application in the fields of wave absorbing materials, electronic devices, field emission and the like. In recent years, photoluminescence of functionalized carbon nanotubes has received increasing attention, by preparing ordered arrays of carbon nanotubes and by modifying their electronic properties by doping. Various carbon nanotube-based composites are prepared by wrapping or filling a number of inorganic materials, including metals (e.g., W, au, pt, sb and Fe) and oxides (e.g., tiO2, znO, siOx, snO 2、EuO2, and RuO 2). However, only carbon nanotubes were observed to exhibit weak infrared emissions. Accordingly, many efforts have been made to obtain a high quality carbon nanotube fluorescent material having excellent light emitting efficiency, purity, sufficient brightness and long-term stability. The rare earth element can be doped on the surface of the carbon nano tube as a fluorophore to cause fluorescence, and the luminescent performance of the composite nano material is obviously improved by utilizing the radiation light of the transition of the rare earth ion energy level.
Studies have shown that Eu 3+ ions have a complex energy level structure, and that the energy level transition between 5D0-7F2 radiates red light, and that the wavelength range of the radiation spectrum covers the red to blue spectral region of visible light. Eu has a special valence electron structure compared to other rare earth elements: 4f 76s2, according to the flood specification: the outer layer electron number is most stable when reaching the full shell or half thereof, so Eu atoms easily lose 2 valence electrons to become Eu 2+ ions. The presence of the Eu 2+ ion state allows the spectral wavelength of the Eu radiation to cover a larger spectral range.
Chen Yongsheng (CN 1712349 a) discloses an arc synthesis method of single-walled carbon nanotubes, wherein graphite material is used as a cathode, a mixture of carbon-containing material and catalyst (oxide of transition metal and rare earth element) is used as an anode, and the catalyst is uniformly dispersed in the consumed anode. The cathode and anode arc discharge under inert atmosphere to produce single-walled carbon nanotubes. The above arc process for preparing carbon nanotubes has the following drawbacks: the catalyst is complex to prepare, the solid carbon source is volatilized under the high-temperature condition, the carbon nano tube is synthesized after condensation, and the purity and the yield of the product are low.
The CVD method has controllability, catalyst deposition is not limited by a substrate, and the carbon nano tube can be prepared in a low-temperature environment. Patent CN1558441a discloses a method for preparing carbon nanotubes on a glass substrate, which uses glass as a substrate, first deposits a layer of ii I main group metal or rare earth metal fluoride film on the glass substrate by electron beam evaporation, then deposits iron, diamond, nickel, palladium or alloy film composed of these materials as catalyst, and then grows carbon nanotubes thereon by conventional growth technique. However, the use of rare earth metal films as carbon nanotube catalysts or dopants by rf magnetron sputtering has not been explored.
In conclusion, the magnetron sputtering is utilized to deposit a rare earth metal and transition metal composite film, and the carbon nano tube photoluminescent material is grown. The carbon nano tube with the light-heat conversion performance is combined with the rare earth material, so that the luminous performance of the composite nano material is improved.
Disclosure of Invention
The invention aims to provide a method for improving the luminous performance of a multiwall carbon nanotube. The invention adopts a simple method to prepare the rare earth metal and transition metal catalyst composite film, uniformly and efficiently reduces the rare earth metal and transition metal catalyst composite film to catalyst nano particles at a lower temperature, and then the multi-wall carbon nano tube is produced by chemical vapor deposition, so that the multi-wall carbon nano tube with low cost, high purity and stable quality performance can be produced. The technical scheme adopted for solving the technical problems is as follows: a method for preparing a carbon nano tube photoluminescent material based on a rare earth metal composite film comprises the following steps:
a. double-sided polished silicon or silicon oxide as substrate material, and deionized acetone, alcohol, and deionized water are used for the substrate
Carrying out ultrasonic cleaning and drying treatment on water;
b. c, forming a transition metal catalyst film on the substrate treated in the step a through radio frequency magnetron sputtering of transition metal Fe or Ni;
c. c, sputtering a layer of rare earth metal film Eu on the catalyst film obtained in the step b through radio frequency magnetron sputtering;
d. C, preparing the multi-wall carbon nano tube on the rare earth metal and transition metal composite film obtained in the step c through a plasma enhanced chemical vapor deposition technology.
Further, when the rare earth film is prepared by radio frequency magnetron sputtering, pre-sputtering is performed for about 30 minutes before formal film plating in order to remove possible pollution on the surface of the target.
Further, in the step b, the working air pressure of the radio frequency magnetron sputtering is 10Pa, the annealing temperature is 200 ℃, and the sputtering power is 60W; fe with 99.999% purity or Ni with 99.999% purity of the sputtering target material; the sputtering gas is high-purity Ar with the purity of 99.999 percent, and the background vacuum is 2 multiplied by 10 -4 Pa; the thickness of the catalyst film is 10nm when the catalyst film is Fe film; the thickness of the catalyst thin film was 20nm when it was a Ni thin film.
Further, in the step c, the working air pressure of the radio frequency magnetron sputtering is 10Pa; the annealing temperature is 200 ℃; the sputtering power is 100-150W; eu metal with the purity of the sputtering target material being 99.95%; the sputtering gas is high-purity Ar with the purity of 99.999%; the background vacuum was 2X 10 -4 Pa. The rare earth film is Eu film with the thickness of 10-20nm.
Further, in the step d, the working pressure of the chemical vapor deposition is 150Pa, the growth temperature is 450-650 ℃, the plasma radio frequency power is 300W, the reaction gas is 99% high-purity acetylene, and the carrier gas is 99.99% high-purity hydrogen and 99.99% high-purity argon; the length of the carbon nanotube is 20 μm.
Further, in the case of preparing multi-walled carbon nanotubes by chemical vapor deposition, in order to convert the catalyst thin film into catalyst nanoparticles, an annealing treatment is performed at a growth temperature for about 15 minutes before the preparation.
Compared with the prior art, the invention has the beneficial effects that
The invention prepares rare earth metal and transition metal composite film by using radio frequency magnetron sputtering technology, prepares carbon nano tube by using plasma enhanced chemical vapor deposition technology, and after spectral analysis, the emission spectrum of all samples is composed of characteristic emission spectrum line of Eu 3+, which corresponds to Eu 3+ ions from 5D0 excitation energy level to 7FJ (J=)
1,2,3 And 4) energy level transition, the luminescent performance of the nano material is obviously enhanced. The method has simple technological requirements, low manufacturing cost and high quality of the produced carbon nano tube.
Drawings
FIG. 1 is a schematic diagram of a rare earth metal composite film grown carbon nanotube.
FIG. 2 shows PL spectra of samples (A samples) of multi-walled carbon nanotubes prepared at different growth temperatures in example 1.
FIG. 3 shows PL spectra of samples (B samples) of multi-walled carbon nanotubes prepared with rare earth films of different thicknesses in example 2.
Fig. 4 is a raman characterization graph of the carbon nanotubes in example 3 and comparative example 1 in a method for preparing a carbon nanotube photoluminescent material based on a rare earth metal composite film according to the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the attached drawings and the detailed description. The following examples are illustrative only and are not to be construed as limiting the scope of the invention.
Example 1:
A, carrying out ultrasonic cleaning and drying treatment on a substrate by using a silicon wafer; then sputtering an iron film on the treated silicon substrate as a catalyst, wherein the thickness of the iron film is 10 nanometers; then sputtering a layer of europium film on the obtained film, wherein the sputtering power is 100W, and the thickness is 10 nanometers; and growing the carbon nano tube by plasma enhanced chemical vapor deposition, wherein the growth temperature is increased from 450 ℃ to 650 ℃, the radio frequency power of the plasma is 300W, and the working pressure is kept constant at 150 Pa.
FIG. 2 shows PL spectra of Eu-doped carbon nanotube samples (A samples) prepared at different growth temperatures. It can be seen from the graph that the PL spectra of the three samples each have a strong peak at 610nm, which corresponds to the red light in the visible region, which originates from the 5D0-7F2 energy level transition of the Eu 3+ 4f shell. As the growth temperature was increased from 450 ℃ to 650 ℃, the spectral peak centered at 610nm was significantly enhanced, indicating that increasing the annealing temperature did not significantly change the peak position, but significantly increased the peak intensity at 610 nm.
Example 2:
B, performing ultrasonic cleaning and drying treatment on the substrate by using a silicon wafer; then sputtering a nickel film on the treated silicon substrate as a catalyst, wherein the thickness of the nickel film is 20 nanometers; then sputtering a europium film on the obtained film, wherein the sputtering power is increased from 100W to 150W, and the thickness is 10-20 nanometers; and growing the carbon nano tube by plasma enhanced chemical vapor deposition, wherein the growth temperature is 650 ℃, the radio frequency power of the plasma is 300W, and the working air pressure is kept constant at 150 Pa.
FIG. 3 is the PL spectra of samples of multi-walled carbon nanotubes (B samples) prepared with rare earth films of different thicknesses. As can be seen from the graph, the rare earth films with different thicknesses can not change the position of an emission peak, only a red spectrum peak with the center at 610nm is radiated, all spectrum peaks are enhanced along with the increase of the thickness of the rare earth film from 10nm to 20nm, and the spectrum peak is highest when the thickness of the europium film is 20 nm.
Example 3:
C, carrying out ultrasonic cleaning and drying treatment on the sample and the substrate by using a silicon oxide wafer; then sputtering an iron film on the treated silicon oxide substrate as a catalyst, wherein the thickness of the iron film is 10 nanometers; then sputtering a layer of europium film on the obtained film, wherein the sputtering power is 150W, and the thickness is 20 nanometers; and growing the carbon nano tube by plasma enhanced chemical vapor deposition, wherein the growth temperature is 650 ℃, the radio frequency power of the plasma is 300W, and the working air pressure is kept constant at 150 Pa.
Comparative example 1:
Ultrasonic cleaning and drying are carried out on the substrate by using a silicon oxide wafer; then sputtering an iron film on the treated silicon oxide wafer substrate as a catalyst, wherein the thickness of the iron film is 10 nanometers; the carbon nano tube is grown by plasma enhanced chemical vapor deposition, the growth temperature is 650 ℃, the radio frequency power of the plasma is 300W, and the working air pressure is kept to be 150 Pa.
FIG. 4 is a graph showing the Raman characterization of carbon nanotubes (excitation wavelength 532 nm) in example 3 and comparative example 1, showing that the ratio of D-band to G-band is lower and defect concentration is reduced, compared with carbon nanotubes grown without sputtering europium film, in the rare earth metal-transition metal catalyst composite film grown by the same chemical vapor deposition process, indicating that the latter is composed of higher quality multi-walled carbon nanotubes.

Claims (6)

1. The method for preparing the carbon nano tube photoluminescent material based on the rare earth metal composite film is characterized by comprising the following steps of:
a. double-sided polished silicon or silicon oxide is used as a substrate material, and acetone, alcohol and deionized water are used for ultrasonic cleaning and drying treatment of the substrate;
b. c, forming a transition metal catalyst film on the substrate treated in the step a through radio frequency magnetron sputtering of transition metal Fe or Ni;
c. c, sputtering a layer of rare earth metal film Eu on the catalyst film obtained in the step b through radio frequency magnetron sputtering;
d. C, preparing the multi-wall carbon nano tube on the rare earth metal and transition metal composite film obtained in the step c through a plasma enhanced chemical vapor deposition technology.
2. The method for preparing a carbon nanotube photoluminescent material based on a rare earth metal composite film according to claim 1, wherein when the rare earth metal composite film is prepared by radio frequency magnetron sputtering, pre-sputtering is performed for 30 minutes before formal coating in order to remove possible pollution on the surface of a target.
3. The method for preparing a carbon nanotube photoluminescent material based on a rare earth metal composite film according to claim 1, wherein in the step b, the working air pressure of the radio frequency magnetron sputtering is 10Pa, the annealing temperature is 200 ℃, and the sputtering power is 60W; fe with 99.999% purity or Ni with 99.999% purity of the sputtering target material; the sputtering gas is high-purity Ar with the purity of 99.999 percent, and the background vacuum is 2 multiplied by 10 -4 Pa; the thickness of the catalyst film is 10nm when the catalyst film is Fe film; the thickness of the catalyst thin film was 20nm when it was a Ni thin film.
4. The method for preparing a carbon nanotube photoluminescent material based on a rare earth metal composite film according to claim 1, wherein in the step c, the working air pressure of the radio frequency magnetron sputtering is 10Pa; the annealing temperature is 200 ℃; the sputtering power is 100-150W; eu metal with the purity of the sputtering target material being 99.95%; the sputtering gas is high-purity Ar with the purity of 99.999%; the background vacuum is 2X 10 -4 Pa; the rare earth film is Eu film with the thickness of 10-20nm.
5. The method for preparing a carbon nanotube photoluminescent material based on a rare earth metal composite film according to claim 1, wherein in the step d, the working pressure of the chemical vapor deposition is 150Pa, the growth temperature is 450-650 ℃, the plasma radio frequency power is 300W, the reaction gas is 99% high-purity acetylene, and the carrier gas is 99.99% high-purity hydrogen and 99.99% high-purity argon; the length of the carbon nanotube is 20 μm.
6. The method for preparing a carbon nanotube photoluminescent material based on a rare earth metal composite film according to claim 1, wherein in preparing the multiwall carbon nanotubes by a chemical vapor deposition technique, an annealing treatment is performed for 15min at a growth temperature before the preparation in order to convert the catalyst film into the catalyst nanoparticles.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1558441A (en) * 2004-01-16 2004-12-29 清华大学 Method for preparing carbon nanotube on glass substrates
CN101722000A (en) * 2008-10-29 2010-06-09 苏州纳米技术与纳米仿生研究所 Preparation method of high-efficiency composite catalyst film for overlength carbon nano tube growth
CN106531287A (en) * 2016-11-09 2017-03-22 华中科技大学 Ultra-high-purity carbon nanotube conductive paste and preparation method thereof
CN112981364A (en) * 2021-02-05 2021-06-18 北京科技大学 Quick thermal response ultra-black material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1558441A (en) * 2004-01-16 2004-12-29 清华大学 Method for preparing carbon nanotube on glass substrates
CN101722000A (en) * 2008-10-29 2010-06-09 苏州纳米技术与纳米仿生研究所 Preparation method of high-efficiency composite catalyst film for overlength carbon nano tube growth
CN106531287A (en) * 2016-11-09 2017-03-22 华中科技大学 Ultra-high-purity carbon nanotube conductive paste and preparation method thereof
CN112981364A (en) * 2021-02-05 2021-06-18 北京科技大学 Quick thermal response ultra-black material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙灵鑫等: "碳纳米管纤维及其表面金属化研究进展", 《高科技纤维与应用》, no. 2, 30 April 2022 (2022-04-30), pages 49 - 55 *

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