CN109628994A - A kind of preparation method of orthogonal black phosphorus crystal and black phosphorus quantum dot using orthogonal black phosphorus crystal preparation - Google Patents
A kind of preparation method of orthogonal black phosphorus crystal and black phosphorus quantum dot using orthogonal black phosphorus crystal preparation Download PDFInfo
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- CN109628994A CN109628994A CN201910029192.1A CN201910029192A CN109628994A CN 109628994 A CN109628994 A CN 109628994A CN 201910029192 A CN201910029192 A CN 201910029192A CN 109628994 A CN109628994 A CN 109628994A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
Abstract
The present invention relates to a kind of preparation method of orthogonal black phosphorus crystal and utilize the black phosphorus quantum dot of the orthogonal black phosphorus crystal preparation.The preparation of the rhombic system black phosphorus crystal are as follows: by red phosphorus, simple substance Sn and simple substance I2It is sealed in quartz ampoule, is put in single temperature zone tube furnace together, black phosphorus monocrystalline is prepared by the temperature programming and cooling of optimization；The preparation of black phosphorus quantum dot are as follows: the black phosphorus monocrystalline of above-mentioned preparation is clayed into power and is scattered in nmp solution, stirs, obtains solution A, it disperses NaOH in nmp solution, it is uniformly mixing to obtain solution B, solution A is added in solution B, then 4~32h of pyroreaction prepares black phosphorus quantum dot.Cost is relatively low by the present invention, low for equipment requirements, easily realization and higher operational safety, and black phosphorus monocrystalline performance obtained is good, and purity is high provides the black phosphorus source of high quality for the preparation of subsequent black phosphorus quantum dot.And the preparation of black phosphorus quantum dot can scale, it is high-efficient, by control the time control quantum dot size the advantages of.
Description
Technical field
The invention belongs to technical field of nanometer material preparation more particularly to a kind of preparation methods and benefit of orthogonal black phosphorus crystal
The black phosphorus quantum dot prepared with the orthogonal black phosphorus crystal.
Background technique
The research of black phosphorus at present also in primary developing stage, find for the first time black phosphorus presence be in 1914,
Bridgman heats white phosphorus at 1.2Gpa and has obtained black phosphorus to 200 DEG C, then in nineteen fifty-five, German chemist Krebs, H. with
Mercury makees catalyst and heats 360 DEG C under normal pressure as crystal seed using a small amount of black phosphorus, converts black phosphorus for white phosphorus；1981, Tokyo was big
Subject scholar Maruyama, Y. synthesize acicular black phosphorus using the bismuth with elementary dissolution white phosphorus recrystallization of melting.However white phosphorus
Severe toxicity and ignition quality do not allow these methods to circulate.2007, Nilges, Tom were by red phosphorus, Au, Sn and SnI4For original
Material under vacuum conditions, is heated to 600 DEG C and obtains black phosphorus, but the introducing of noble metal improves production cost and the purity of black phosphorus has
It is reduced；Chinese invention patent CN104630879A, CN106498492A and CN106087050A disclose it is a kind of using red phosphorus,
The preparation method of AuSn, tin tetraiodide, tin diiodide, the black phosphorus monocrystalline that indium metal is raw material, it is at high cost and be harmful to the human body, very
Difficult scale carries out industrial production.Chinese invention patent CN105133009A disclose it is a kind of using red phosphorus, tin, iodine be raw material prepare
Black phosphorus monocrystalline, it is comparatively cleaner, but what is applied is that double temperature-area tubular furnaces need that complicated heating schedule is arranged, to setting
Standby requirement is very high, and without reference to specific impurity-removing method.In addition, all oxygen-free environments in the above patent are all in hand
It is operated in the environment of casing, process is too cumbersome, and the requirement of oxygen-free environment is too harsh.
Zero dimension black phosphorus quantum dot is a kind of emerging functional nanomaterials.Zero dimension black phosphorus quantum dot is to make for the first time for 2015
The novel black phosphorus nanostructure of standby one kind, it is in bio-imaging, fluorescence sense, nonlinear optical absorption, treatment of cancer, intelligence
There is potential application prospect in the fields such as electronics, photoelectricity, flexible device.Since 2015, many researchs are devoted to
The various synthetic methods of black phosphorus quantum dot are explored, these methods contain ultrasonic removing, solvent heat treatment, stirring crusher machine, ball
Gall a variety of synthetic methods such as broken and pulse laser irradiation.There are document report ultrasound stripping method (X, Prof.Haiming at present
Xie, 2015,127 (12): 3724-3728.) and solvent-thermal method prepare black phosphorus quantum dot (XU Y, Wang Z, Guo Z, et
al.Solvothermal Synthesis and Ultrafast Photonics of Black Phosphorus Quantum
Dotos [J] .advaced Optical Materials, 2016.), but both of which time consumption and energy consumption, and it is cumbersome, it produces
Rate is not high.
Summary of the invention
For above-mentioned defect existing in the prior art, the purpose of the present invention is to provide a kind of low costs, hypotoxicity, letter
It is single, quickly, safe and convenient, the preparation method with repeatability and the good orthogonal black phosphorus crystal of operability and orthogonal using this
The black phosphorus quantum dot of black phosphorus crystal preparation.Range of the size for the black phosphorus quantum dot that the present invention prepares in 2.5nm~16nm
It is interior.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of preparation method of orthogonal black phosphorus crystal, comprising the following steps:
A. quartz ampoule is taken, firing 3 at the place 5~10cm of the quartzy nozzle of distance with acetylene torch rifle is in angular distribution and to quartz
The distribution of the point of pipe inner recess, depression points should be maintained on the same horizontal plane.
B. it is cooled down in the natural environment to quartz ampoule, argon gas is full of into quartz ampoule；Then by red phosphorus, simple substance Sn, simple substance I2
It is fitted into quartz ampoule, and is put into quartzy column sealing into quartz ampoule, quartz ampoule is vacuumized, when vacuum degree reaches 1pa, use second
Alkynes flame gun is fired against the position where quartz column, until being fully sealed, the red phosphorus, simple substance SnWith simple substance I2Matter
Amount is than being 1:2:0.52；Depression points play the role of support to quartz column and help, fix in step a, and the position of depression points determines quartz
The position of column, and then determine the volume of quartz ampoule confined space after sealing, and preparing the entire reaction process of black phosphorus monocrystalline
Confined space in pressure change.
C. the quartz ampoule being sealed is put in single temperature zone tube furnace, the one end for having drug is placed on to the center of tube furnace
Between, the heating schedule of tube furnace is set: 400 DEG C of 700 DEG C -10h-of room temperature -10h -, 700 DEG C -10h -, 400 DEG C -5h--
Room temperature；Start single temperature zone tube furnace；Cooled down by the way of air cooling-down after completion of the reaction；
D. when single temperature zone tubular type furnace temperature is down to room temperature, quartz ampoule is taken out, black phosphorus list can be obtained in the fire end of quartz ampoule
It is brilliant.
Further, the above method further include removal of impurities purification step, specifically: take out black phosphorus product of single crystal and be dissolved in water and
In the mixed solution of hydrochloric acid, after standing for 24 hours, removing supernatant must be precipitated, and then be precipitated using milli-Q water, until pH=7 and
Ultrapure clarification of water after washed, then washed with dehydrated alcohol, finally it is dried in vacuo under the conditions of 50 DEG C in a vacuum drying oven.
Further, the volume ratio of the water and hydrochloric acid is 1:5.
Further, the mixed solution of 120ml water and hydrochloric acid is added in every 450g black phosphorus monocrystalline.
The present invention also provides the black phosphorus quantum dots using black phosphorus single crystal preparation obtained above.
Further, the black phosphorus quantum dot specifically uses following steps to prepare:
A. it by the black phosphorus monocrystalline grind into powder of above-mentioned preparation, and is scattered in N-Methyl pyrrolidone (NMP), magnetic agitation is straight
To being completely dissolved, solution A is obtained；The black phosphorus monocrystal of 1mg is added in the N-Methyl pyrrolidone of every 1ml；
B. it disperses NaOH in N-Methyl pyrrolidone, magnetic agitation obtains solution B up to being completely dissolved；The N- first of every 7ml
The NaOH of 2mmol is added in base pyrrolidones；
C. solution A is added into solution B, is transferred in reaction kettle, is then placed in high temperature furnace after stirring, adds under the conditions of 160 DEG C
Hot 4h~32h is centrifuged gained reaction solution after system is cooled to room temperature, and retains supernatant, obtains being dissolved in N- methylpyrrole
Black phosphorus quantum dot in alkanone；The solution A of 4ml is added in every 35ml solution B.Black phosphorus quantum dot with the extension of reaction time
Size gradually becomes smaller and shape is more and more uniform.
Compared with prior art, the present invention has following positive beneficial effect:
1, it is required to glove box anaerobic equipment in the prior art and prepares black phosphorus crystal, the present invention is in no glove box, without Muffle
Under the instrument that furnace, three-temperature-zone or double temperature-area tubular furnace high standards are matched, black phosphorus monocrystalline is prepared under the conditions ofs argon gas etc. using quartz ampoule.
At low cost, quick, safe and convenient, operability are good.
2, the present invention is with red phosphorus, simple substance Sn, simple substance I2It is big (visually as it can be seen that size is in 1cm that particle has been prepared for raw material
Left and right), the high black phosphorus monocrystalline of crystallinity.Then by further carrying out removal of impurities purification to black phosphorus monocrystalline, the black of high-purity is obtained
Phosphorus monocrystalline controls the size and shape of black phosphorus quantum dot subsequently through the reaction time of control autoclave；It is removed using this
The black phosphorus monocrystalline of miscellaneous method of purification purifying, purity is high carry out element point by a part to the black phosphorus single-crystal surface after purification
Analysis, discovery are made of individual P element, then without other elements, show that the BP of preparation is with high purity, high-quality.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of black phosphorus monocrystalline prepared by embodiment 1.
Fig. 2 is the Raman figure of black phosphorus monocrystalline prepared by embodiment 1.
Fig. 3 is the overall picture scanning electron microscope (SEM) photograph of black phosphorus monocrystalline prepared by embodiment 1.
Fig. 4 is the cross-sectional scans electron microscope of black phosphorus monocrystalline prepared by embodiment 1.
Fig. 5 is the eds figure of black phosphorus monocrystalline prepared by embodiment 1.
Fig. 6 is the UV-visible absorption spectrum of black phosphorus monocrystalline prepared by embodiment 1, and illustration is black phosphorus monocrystalline solution.
Fig. 7 is the transmission electron microscope picture for the black phosphorus quantum dot that 2 mesohigh reaction kettle of embodiment reacts 4h preparation.
Fig. 8 is the transmission electron microscope picture for the black phosphorus quantum dot that 2 mesohigh reaction kettle of embodiment reacts 20h preparation.
Fig. 9 is the uv-visible absorption spectra for the black phosphorus quantum dot that 2 mesohigh reaction kettle of embodiment reacts 20h preparation
Figure, illustration are black phosphorus quantum dot solution.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless specifically indicated, the present invention uses reagent, method and apparatus is routinely try for the art
Agent, method and apparatus.
Embodiment 1
A kind of preparation method of orthogonal black phosphorus crystal, comprising the following steps:
A. it takes outside one through 1.8cm, internal diameter 1.5cm, the quartz ampoule of long 25cm, with acetylene torch rifle the 5 of the quartzy nozzle of distance
It is in angular distribution and the point to quartz ampoule inner recess that 3 are fired at~10cm.
B. it is cooled down 10 minutes in the natural environment to quartz ampoule, then is full of argon gas into quartz ampoule；Then 500mg is red
Phosphorus, 1000mg simple substance Sn, 260mg simple substance I2It is fitted into quartz ampoule, and is put into the quartzy column sealing of 2cm long into quartz ampoule, by stone
English pipe is fixed on vacuum sealing tube instrument, is vacuumized 30 minutes or so.When vacuum degree reaches 1pa, with acetylene torch rifle against 2cm
Position where long quartz column is fired, until being fully sealed.
C. the quartz ampoule being sealed is put in single temperature zone tube furnace, the one end for having drug is placed on to the center of tube furnace
Between, the heating schedule of tube furnace is set: 400 DEG C of 700 DEG C -10h-of room temperature -10h -, 700 DEG C -10h -, 400 DEG C -5h--
Room temperature, program after setting completed, start single temperature zone tube furnace；Temperature-fall period is by the way of air cooling-down.
D. when single temperature zone tubular type furnace temperature is down to room temperature, quartz ampoule is taken out, black phosphorus list can be obtained in the fire end of quartz ampoule
Brilliant 450g.
E. the black phosphorus monocrystalline obtained need to be purified further, therefore break quartz ampoule, take out product and be dissolved in 120ml water and
In the mixed solution of hydrochloric acid, after standing for 24 hours, removing upper solution must be precipitated, then milli-Q water filtering is added into precipitating,
The impurity for removing to deacidify and be dissolved in water, until pH=7 and it is washed after ultrapure clarification of water, then with dehydrated alcohol wash three times,
Vacuum drying obtains the black phosphorus monocrystalline 360g that silver-colored black has metallic luster under the conditions of 50 DEG C in vacuum oven.The water and salt
The volume ratio of acid is 1:5.
Fig. 1 show the X-ray diffractogram of black phosphorus monocrystalline, can only see from X-ray diffraction (XRD) figure (020),
(040) and the characteristic diffraction peak in (060) face without other miscellaneous peaks or other allotrope peaks of phosphorus shows these crystal categories
In rhombic system black phosphorus monocrystalline, due to the peak intensity of characteristic diffraction peak, show that the black phosphorus of preparation has very high crystallinity.
Fig. 2 show the Raman figure of black phosphorus monocrystalline, in 361cm-1、436cm-1And 463cm-1There is apparent peak in place,
The reason is thatWithCaused by the vibration of phonon modes.At theseWithIn mode, P atom shakes in layer plane
It swings, andIn phonon modes, P atomic vibration is appeared.Raman characterization result again shows that black phosphorus monocrystalline obtained is orthorhombic
System.
Fig. 3 and Fig. 4 show the scanning electron microscope (SEM) photograph of black phosphorus monocrystalline.Fig. 3 illustrates the front of black phosphorus monocrystalline (BP).Fig. 4 exhibition
The perspective view of BP, the orthogonal black phosphorus monocrystalline that rule visible in detail has cause overlapping layer by layer, while this feature also table are shown
The black phosphorus monocrystalline quality with higher of preparation is illustrated.Visually observe it is also seen that, without other crystalline residues in addition to black phosphorus,
Not only ingredient is pure for these crystal, but also crystallinity is high.
Fig. 5 show the eds figure of black phosphorus monocrystalline.The a part for extracting the surface BP carries out elemental analysis, and discovery has individual P
Element composition, then without other elements, represent prepare BP purity it is higher, further demonstrate and prepared the black of high quality
Phosphorus.
Fig. 6 be black phosphorus monocrystalline solution UV-visible absorption spectrum and black phosphorus monocrystalline solution thereon illustration, it is ultraviolet-
What visible absorption spectra figure was shown the linear absorption of black phosphorus monocrystalline solution, the photo of black phosphorus monocrystalline solution show black phosphorus monocrystalline
Black is presented in solution.
Embodiment 2
The black phosphorus single crystal preparation black phosphorus quantum dot prepared using embodiment 1:
Black phosphorus monocrystalline prepared by Example 1, is placed in mortar and is fully ground into powder, weighs the ground black phosphorus monocrystalline of 30mg
Powder is dissolved in 30ml N-Methyl pyrrolidone, obtains solution A up to being completely dissolved within magnetic agitation 2 hours；Take 6 beakers
1,2,3,4,5,6 are respectively labeled as, the N-Methyl pyrrolidone of the NaOH and 35ml of 400mg, magnetic force are separately added into beaker
Stirring 2 hours, obtains B solution, is denoted as solution B respectively1、B2、B3、B4、B5、B6；The molten of 4ml is separately added into six B solutions
Liquid A stir 12 hours after be transferred in the reaction kettle of 6 50ml, be put into high temperature furnace, heated respectively at 160 DEG C 4h, 8h, 12h,
16h,20h,24h,32h.After system is cooled to room temperature, gained reaction solution is centrifuged, 600 revs/min, is centrifuged 15 minutes.It protects
Supernatant is stayed, obtains being dissolved in the black phosphorus quantum dot in N-Methyl pyrrolidone.As shown in Figure 7 and Figure 8, with the reaction time
Extend, the size of black phosphorus quantum dot gradually becomes smaller and shape is more and more uniform.
Fig. 9 is the UV-visible absorption spectrum and black phosphorus quantum dot solution photo for reacting 20h sample black phosphorus quantum dot
Illustration, what UV-visible absorption spectrum was shown the linear absorption of black phosphorus quantum dot solution, the photo of black phosphorus quantum dot solution
Show that yellow is presented in black phosphorus quantum dot solution.
The embodiment of the above, only presently preferred embodiments of the present invention, is only used to explain the present invention, not limit
The scope of the present invention processed to those of ordinary skill in the art certainly can be according to skill disclosed in this specification
Art content, makes other embodiments easily by way of replacing or changing, therefore all in the principle of the present invention and technique item
The changes and improvements etc. that part is done, should be included in scope of the present invention patent.
Claims (6)
1. a kind of preparation method of orthogonal black phosphorus crystal, which comprises the following steps:
A. quartz ampoule is taken, firing 3 at the place 5~10cm of the quartzy nozzle of distance with acetylene torch rifle is in angular distribution and to quartz
The point of pipe inner recess；
B. it is cooled down in the natural environment to quartz ampoule, argon gas is full of into quartz ampoule；Then by red phosphorus, simple substance Sn, simple substance I2It is packed into
In quartz ampoule, and it is put into quartzy column sealing into quartz ampoule, quartz ampoule is vacuumized, when vacuum degree reaches 1pa, with acetylene fire
Flame rifle is fired against the position where quartz column, until being fully sealed, the red phosphorus, simple substance SnWith simple substance I2Mass ratio
For 1:2:0.52；
C. the quartz ampoule being sealed is put in single temperature zone tube furnace, the one end for having drug is placed on to the middle of tube furnace, if
Set the heating schedule of tube furnace: 700 DEG C -10h-of room temperature -10h -, 700 DEG C -10h -, 400 DEG C -5h -, 400 DEG C-room temperature,
Start single temperature zone tube furnace；Cooled down by the way of air cooling-down after completion of the reaction；
D. when single temperature zone tubular type furnace temperature is down to room temperature, quartz ampoule is taken out, black phosphorus list can be obtained in the fire end of quartz ampoule
It is brilliant.
2. a kind of preparation method of orthogonal black phosphorus crystal according to claim 1, which is characterized in that the preparation method is also
Including clean purification step, specifically: take out black phosphorus product of single crystal simultaneously be dissolved in the mixed solution of water and hydrochloric acid, stand for 24 hours after,
Removing supernatant must precipitate, and then be precipitated using milli-Q water, until pH=7 and it is washed after ultrapure clarification of water, then use nothing
Water-ethanol washing, is finally dried in vacuo under the conditions of 50 DEG C in a vacuum drying oven.
3. a kind of preparation method of orthogonal black phosphorus crystal according to claim 2, which is characterized in that the water and hydrochloric acid
Volume ratio is 1:5.
4. a kind of preparation method of orthogonal black phosphorus crystal according to claim 2, which is characterized in that black phosphorus described in every 450g
The mixed solution of monocrystalline addition 120ml water and hydrochloric acid.
5. utilizing the black phosphorus quantum dot for the black phosphorus single crystal preparation that claim 1 obtains.
6. the preparation method of black phosphorus quantum dot described in claim 5, comprising the following steps:
A. the black phosphorus monocrystalline grind into powder prepared by claim 1, and be scattered in N-Methyl pyrrolidone, magnetic agitation is straight
To being completely dissolved, solution A is obtained；The black phosphorus monocrystal of 1mg is added in the N-Methyl pyrrolidone of every 1ml；
B. it disperses NaOH in N-Methyl pyrrolidone, magnetic agitation obtains solution B up to being completely dissolved；The N- of every 7ml
The NaOH of 2mmol is added in methyl pyrrolidone；
C. solution A is added into solution B, is transferred in reaction kettle, is then placed in high temperature furnace after stirring, adds under the conditions of 160 DEG C
Hot 4h~32h is centrifuged gained reaction solution after system is cooled to room temperature, and retains supernatant, obtains being dissolved in N- methylpyrrole
Black phosphorus quantum dot in alkanone；The solution A of 4ml is added in every 35ml solution B.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110531540A (en) * | 2019-09-03 | 2019-12-03 | 山东大学 | MoTe2With the full light Terahertz modulator of Si composite construction and preparation method thereof |
| CN110627029A (en) * | 2019-10-29 | 2019-12-31 | 陕西科技大学 | Black phosphorus quantum dot/nanosheet composite material and preparation method thereof |
| CN113130795A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110531540A (en) * | 2019-09-03 | 2019-12-03 | 山东大学 | MoTe2With the full light Terahertz modulator of Si composite construction and preparation method thereof |
| CN110627029A (en) * | 2019-10-29 | 2019-12-31 | 陕西科技大学 | Black phosphorus quantum dot/nanosheet composite material and preparation method thereof |
| CN113130795A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
| CN113130795B (en) * | 2019-12-31 | 2022-09-27 | Tcl科技集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
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Application publication date: 20190416 |