CN116285993B - Synthesis method of ZnSe/ZnSeTe/ZnSe spherical quantum well structure coated by blue light emission ZnS - Google Patents
Synthesis method of ZnSe/ZnSeTe/ZnSe spherical quantum well structure coated by blue light emission ZnS Download PDFInfo
- Publication number
- CN116285993B CN116285993B CN202211736273.3A CN202211736273A CN116285993B CN 116285993 B CN116285993 B CN 116285993B CN 202211736273 A CN202211736273 A CN 202211736273A CN 116285993 B CN116285993 B CN 116285993B
- Authority
- CN
- China
- Prior art keywords
- znse
- precursor solution
- znsete
- zinc
- solution
- 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.)
- Active
Links
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000001308 synthesis method Methods 0.000 title claims description 8
- 239000002243 precursor Substances 0.000 claims abstract description 127
- 239000002096 quantum dot Substances 0.000 claims abstract description 54
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052786 argon Inorganic materials 0.000 claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- 238000002347 injection Methods 0.000 claims abstract description 9
- 239000007924 injection Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 178
- 239000011701 zinc Substances 0.000 claims description 60
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 54
- 229910052725 zinc Inorganic materials 0.000 claims description 54
- 239000011669 selenium Substances 0.000 claims description 47
- 229910052711 selenium Inorganic materials 0.000 claims description 43
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229910052714 tellurium Inorganic materials 0.000 claims description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 16
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 16
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 16
- 239000005642 Oleic acid Substances 0.000 claims description 16
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 16
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 16
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 16
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 15
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 30
- 230000007547 defect Effects 0.000 abstract description 14
- 239000011258 core-shell material Substances 0.000 abstract description 8
- 150000001450 anions Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000001427 coherent effect Effects 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 238000005424 photoluminescence Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000002707 nanocrystalline material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- 229960000314 zinc acetate Drugs 0.000 description 9
- 239000004246 zinc acetate Substances 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004054 semiconductor nanocrystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
Abstract
A method for synthesizing a high-color-purity blue light emission ZnSe/ZnSeTe/ZnSe spherical quantum well structure belongs to the technical field of semiconductor nanocrystalline material synthesis and luminous display. Synthesizing ZnSe quantum dot cores by a thermal injection method under an argon environment, alternately injecting anion and cation precursors by a continuous ion layer adsorption method, and coating ZnSeTe layers on the ZnSe surfaces; and continuously and alternately injecting cations and anion precursors to synthesize the ZnSe/ZnSeTe/ZnSe spherical quantum well. The one-pot synthesis process can effectively avoid the oxidation problem caused by the quantum dot purification process; the synthesized spherical quantum well structure can effectively adjust photoluminescence emission peak positions to obtain blue light emission, and compared with the traditional method, the high color purity is maintained; the coherent strain heterostructure is formed, the lattice mismatch defect between ZnSe and ZnSeTe is reduced, the fluorescence quantum yield of the traditional core-shell structure is effectively improved, and the surface defect is modified by a thick ZnS shell layer, so that the high color purity (the half-width of a luminescence peak to 18 nm) and the high fluorescence quantum yield (more than 90%) are finally obtained.
Description
Technical Field
The invention belongs to the technical field of synthesis of semiconductor nanocrystalline materials, and particularly relates to a blue light emission ZnSe/ZnSeTe/ZnSe spherical quantum well structure with high fluorescence quantum yield and high color purity and a synthesis method thereof.
Background
When the size of the colloidal semiconductor nanocrystals is smaller than the exciton wave radius, the colloidal semiconductor nanocrystals can be subjected to quantum confinement effect, so that the forbidden band width of the colloidal semiconductor nanocrystals is related to the size; when all three dimensions are subjected to quantum confinement effects, such semiconductor nanocrystals are referred to as quantum dots. The quantum dot is an excellent luminescent material, and has the advantages of adjustable emission wavelength, high color saturation, wide color gamut, high light stability and heat stability, nearly 100% fluorescence quantum yield (Photoluminescence Quantum Yield, PLQY), low preparation cost by a solution method and the like. At present, research is relatively mature, and quantum dots with excellent performance are mainly Cd-series quantum dots; however, cd is heavy metal, and the toxicity of Cd limits further popularization and application, so that the development of the non-heavy metal quantum dots is of great significance.
The II-VI semiconductor ZnSe with the forbidden band width of 2.7eV is a potential non-heavy metal blue light emitting material. However, due to quantum confinement effects, znSe quantum dots emit peaks in the violet or deep blue bands. In order to obtain blue light emission, te is doped in ZnSe quantum dots, znSeTe alloy quantum dots are prepared, and the emission peak position can be shifted in red. Taehung Kim et al (Nature.2020, 586 (7829), 385-389) first synthesized ZnSeTe quantum dots by thermal injection, purified the quantum dots and then grown shell layers, in which HF etching of the ZnSeTe surface oxide layer and ZnCl was used 2 The finally obtained ZnSeTe core-shell quantum dot realizes blue light emission at 457nm by processing and eliminating the stacking fault, but has a fluorescence emission spectrum half-peak width reaching 36nm and lower color purity due to the uneven doping of Te and other problems.
In 2022 Sun-Hyong Lee et al (Chemical Engineering journal.2022,429, 132464) synthesized ZnSeTe core-shell quantum dots by a two-step method. When the ZnSeTe/ZnSe quantum dots are prepared by coating the ZnSe shell, the fluorescence quantum yield is increased along with the continuous increase of the thickness of the ZnSe shell because the surface defects are passivated. However, when the size of the ZnSeTe/ZnSe quantum dot reaches 9.71nm, the fluorescence quantum yield tends to be reduced, because lattice mismatch exists between heterostructures, and when the thickness of a shell layer is increased, stress between a core and the shell layer material is difficult to release, so that lattice mismatch defects are formed, and the luminous efficiency of the quantum dot is reduced. Similarly, when Eun-Pyo Jang et al (ACS Applied Materials & interfaces.2019,11, 46062-46069) prepared ZnSe/ZnS, the fluorescence quantum yield had begun to decrease when the size of the equivalent quantum dot reached-7.6 nm. Further, going back, the ZnSe/ZnS core-shell quantum dots prepared by Aqiang Wang et al (nanoscale.2015, 7, 2951-2959) obtain the highest fluorescence quantum efficiency when the diameter is 10nm, and the fluorescence quantum yield is reduced by continuously thickening the ZnS shell.
The shell layer coating the surface of the quantum dot core with a wide forbidden band can improve the quantum yield and air stability, and the thick shell layer can effectively relieve the energy transfer between the quantum dots in the compact quantum dot film, which plays a key role in the preparation of devices, but the reduction of the fluorescence quantum yield is unavoidable when the thick shell layer quantum dot is prepared by using the traditional core-shell structure, such as the above. Therefore, designing a non-traditional core-shell structure and developing a controllable synthesis method thereof to obtain blue light emission non-heavy metal quantum dots with high fluorescence quantum yield and high color purity is a problem to be solved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a blue light emission ZnSe/ZnSeTe/ZnSe spherical quantum well structure with high fluorescence quantum yield and high color purity and a synthesis method thereof, and the synthesis method uses a one-pot method, is simple compared with the traditional method, is easier to realize and avoids oxidation caused by an intermediate purification process; the quantum well structure is designed, so that mismatch defects between ZnSe and ZnSeTe are effectively reduced, the luminous peak position is continuously adjustable by regulating and controlling the thickness of the shell layer, blue light emission is realized, meanwhile, high color purity is kept, and finally, the fluorescence quantum yield and air stability of the ZnSe/ZnSeTe/ZnSe spherical quantum well structure are further improved through ZnS shell layer cladding.
In order to achieve the aim of the invention and solve the defects in the prior art, the invention adopts the following technical scheme:
a method for synthesizing a blue light emission ZnSe/ZnSeTe/ZnSe spherical quantum well structure with high fluorescence quantum yield and high color purity comprises the following steps:
(1) Synthesizing ZnSe core: mixing a zinc source, saturated fatty acid and a solvent in a three-neck flask; vacuumizing, and then introducing argon; heating to 120-150 ℃ in an argon environment to form a colloid solution, namely a zinc precursor solution;
continuously heating to 220-250 ℃ in an argon environment, then adding selenium precursor solution and preserving heat; heating to 300-320 ℃, respectively injecting a zinc precursor solution and a selenium precursor solution, and preserving heat to obtain a ZnSe nuclear quantum dot solution;
(2) Injecting a zinc precursor solution into the ZnSe quantum dot solution, simultaneously injecting a selenium precursor solution and a tellurium precursor solution, and preserving heat for 30-50min to obtain a ZnSe/ZnSeTe quantum dot solution;
in the step, the molar ratio of the zinc precursor solution, the selenium precursor solution and the tellurium precursor solution is 1:x:y, wherein 0< x <1,0< y <1-x;
(3) Injecting a zinc precursor solution into the ZnSe/ZnSeTe quantum dot solution, then injecting a selenium precursor solution and preserving heat to obtain a ZnSe/ZnSeTe/ZnSe spherical quantum well structure;
(4) Injecting a zinc precursor solution into the ZnSe/ZnSeTe/ZnSe spherical quantum well solution, then injecting a sulfur precursor solution, preserving heat for 1-2h, and coating a ZnS shell to obtain a ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure;
the selenium precursor solution, the tellurium precursor solution and the sulfur precursor solution are respectively selenium powder, tellurium powder and sublimed sulfur colloid solutions.
The injection rate of the zinc precursor solution is 20-25mL/h, the injection rate of the selenium precursor solution is 3-5mL/h, and the injection rate of the sulfur precursor solution is 3-5mL/h.
Further, the synthetic method comprises the following steps:
(1) Firstly, synthesizing ZnSe core, mixing a zinc source, saturated fatty acid and a solvent in a three-neck flask according to a molar ratio of 1-3:3-7:40-80, and vacuumizing completely at room temperature; then argon is introduced, heating is carried out under the argon environment, the temperature is raised to 120-150 ℃, a zinc precursor is formed, and vacuum is carried out for 1h at 90 ℃. Continuously heating to 220-250 ℃ in an argon environment, then injecting selenium precursor solution, and preserving heat for 30-60min; heating to 300-320 ℃, then injecting 4mL of zinc precursor solution at the rate of 24mL/h, then injecting 0.4mL of selenium precursor solution at the rate of 3mL/h, and preserving heat for 15-40min to obtain ZnSe nuclear quantum dot solution. The zinc source is one of zinc chloride, zinc oxide, anhydrous zinc acetate, zinc stearate or zinc acetylacetonate; the solvent is one or more of paraffin oil, octadecene or tri-n-octylamine. The saturated fatty acid is one of oleic acid and tetradecanoic acid; the zinc precursor solution is a colloidal solution obtained by mixing 9mmol of zinc source with 6mL of Oleic Acid (OA), 30mL of Octadecene (ODE), vacuumizing at room temperature, and then heating to 120-150 ℃ under argon atmosphere, wherein the zinc source is completely dissolved, and the zinc precursor solutions are all the following solutions; the selenium precursor solution is a colloidal solution obtained by mixing selenium powder (Se) with tri-n-butylphosphine, tri-n-octylphosphine or diphenylphosphine and completely dissolving the selenium powder, and the selenium precursor solutions are all described below.
(2) Injecting 4mL of zinc precursor solution into the ZnSe quantum dot solution at a rate of 24mL/h, then injecting selenium precursor solution and tellurium precursor solution at a rate of 3mL/h, and preserving heat for 30-50min to obtain ZnSe/ZnSeTe quantum dot solution; the molar ratio of the zinc precursor solution to the selenium precursor solution to the tellurium precursor solution is 1:x:y, wherein 0< x <1,0< y <1-x; the tellurium precursor solution is a colloidal solution obtained by mixing tellurium powder (Te) with tri-n-butylphosphine or tri-n-octylphosphine and completely dissolving the tellurium powder.
(3) Injecting 4mL of zinc precursor solution into the ZnSe/ZnSeTe quantum dot solution at the rate of 24mL/h, then injecting 0.5mL of selenium precursor solution at the rate of 3mL/h, preserving heat for 30-50min, and repeating for 1-5 times to obtain a ZnSe/ZnSeTe/ZnSe quantum well structure; the synthesis of the step can be flexibly adjusted, and the ZnSe/ZnSeTe/ZnSe spherical quantum wells with different shell layers can be obtained by repeating for different times, and the steps correspond to different emission peak positions.
(4) And (3) injecting 8mL of zinc precursor solution into the ZnSe/ZnSeTe/ZnSe quantum well solution synthesized in the step (3) at the rate of 24mL/h, then injecting 2mL of sulfur precursor solution at the rate of 3mL/h, preserving heat for 1-2h, and coating a ZnS shell layer to further improve the fluorescence quantum yield and the air stability of the ZnSe/ZnSeTe/ZnSe quantum well. The sulfur precursor solution is a colloidal solution obtained by mixing sublimed sulfur (S) with tri-n-butylphosphine or tri-n-octylphosphine and completely dissolving the sublimed sulfur.
The beneficial effects of the invention are as follows:
in the method, a ZnSe quantum dot core is synthesized by a thermal injection method under an argon environment, and then a continuous ion layer adsorption method is adopted, namely, anion and cation precursors are alternately injected according to a certain rate, and a ZnSeTe layer is coated on the ZnSe surface to form the ZnSe/ZnSeTe quantum dot; and continuously and alternately injecting cations and anion precursors to synthesize the ZnSe/ZnSeTe/ZnSe spherical quantum well.
(1) The invention adopts a one-pot method for synthesis, does not need to take out the quantum dot solution for purification in the middle, simplifies the synthesis process, and avoids the defect of oxidation introduced in the purification process. Compared with the traditional synthesis method of the quantum dot with the core-shell structure, the method is simpler, and can effectively avoid the oxidation problem caused by the quantum dot purification process
(2) The spherical quantum well structure synthesized by the invention can effectively adjust the photoluminescence emission peak position to obtain blue light emission, and compared with the traditional method, the spherical quantum well structure has high color purity; and a coherent strain heterostructure is designed, so that mismatch defects between ZnSe and ZnSeTe layers are effectively reduced, the thickness of the ZnSe outer layer can be flexibly adjusted, the luminescence peak position can be continuously adjusted, blue light emission is realized, and meanwhile, high color purity is maintained; and the fluorescence quantum yield of the traditional core-shell structure is effectively improved. The overall size of the designed quantum well structure reaches 14.98nm, and the condition of no reduction of fluorescence quantum yield is avoided, which shows that the invention successfully realizes the growth of the thick shell layer and the fluorescence quantum yield is not influenced by the lattice defect, thereby greatly improving the photochemical stability of the quantum dot; and for compact quantum dot films, the thick shell layer can effectively relieve energy transfer between adjacent quantum dots, so that the film maintains high fluorescence quantum yield (PLQY), which makes the film suitable for preparing photoelectric devices.
(3) Finally, the ZnS shell layer modifies the surface defect through the ZnS shell layer coating, so that the fluorescence quantum yield and the air stability of the ZnSe/ZnSeTe/ZnSe spherical quantum well structure are further improved. Finally, high color purity (half-width of luminescence to 18 nm) and high fluorescence quantum yield (> 90%) are obtained.
Drawings
FIG. 1 is an Abs-PL profile of ZnSe/ZnSeTe/ZnSe spherical quantum wells of varying ZnSe outer thickness.
FIG. 2 is a high resolution TEM image of ZnSe/ZnSeTe/ZnSe spherical quantum wells.
The size distribution of ZnSe/ZnSeTe/ZnSe spherical quantum wells in FIG. 3.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
(1) Firstly, a ZnSe core is synthesized, and zinc acetate (Zn (Ac) 2 ) Mixing Oleic Acid (OA) and Octadecene (ODE) in a molar ratio of 1:4:40 in a three-neck flask, and pumping and inflating 3 times at room temperature to ensure that the vacuum pumping is complete; argon is then introduced, and the temperature is raised to 120 ℃ under the argon environment, so as to form zinc precursor, and vacuum is pumped at 90 ℃ for 1h. Continuously heating to 230 ℃ in an argon environment, rapidly injecting 0.5mL of selenium precursor solution when the temperature reaches 230 ℃, and preserving the temperature for 30min at 230 ℃; heating to 300 ℃, then injecting 4mL of zinc precursor solution at a rate of 24mL/h, then injecting 0.4mL of selenium precursor solution at a rate of 3mL/h, and preserving heat for 20min to obtain ZnSe nuclear quantum dot solution. The zinc precursor solution described herein was 9mmol zinc acetate (Zn (Ac) 2 ) Mixing with 6mL of Oleic Acid (OA) and 30mL of Octadecene (ODE), pumping and inflating for 3 times at room temperature, then heating to 120 ℃ under argon atmosphere, and completely dissolving zinc acetate to obtain a colloidal solution, wherein the zinc precursor solutions are all the following solutions; the selenium precursor solution is a colloidal solution obtained by mixing 8mmol of selenium powder (Se) with 8mL of tri-n-octylphosphine and completely dissolving the selenium powder, and the selenium precursor solutions are all described below.
(2) Injecting 4mL of zinc precursor solution into the ZnSe quantum dot solution at a rate of 24mL/h, then simultaneously injecting 0.5mL of selenium precursor solution and 1mL of tellurium precursor solution at a rate of 3mL/h, and preserving heat for 30min to obtain ZnSe/ZnSeTe quantum dot solution; the molar ratio of the zinc precursor solution to the selenium precursor solution to the tellurium precursor solution is 1:0.5:0.015; the tellurium precursor solution is a colloidal solution obtained by mixing 0.12mmol tellurium powder (Te) with 8mL tri-n-octyl phosphine and completely dissolving the tellurium powder.
(3) 4mL of zinc precursor solution is injected into the ZnSe/ZnSeTe quantum dot solution at the rate of 24mL/h, then 0.5mL of selenium precursor solution is injected at the rate of 3mL/h, and the temperature is kept for 40min, so that the ZnSe/ZnSeTe/ZnSe spherical quantum well structure is obtained.
(4) And (3) injecting 8mL of zinc precursor solution into the ZnSe/ZnSeTe/ZnSe spherical quantum well solution synthesized in the step (3) at the rate of 24mL/h, then injecting 2mL of sulfur precursor solution at the rate of 3mL/h, and carrying out heat preservation for 1h to coat a ZnS shell layer, thereby further improving the fluorescence quantum yield and the air stability of the ZnSe/ZnSeTe/ZnSe quantum well. The sulfur precursor solution described herein was a colloidal solution obtained by mixing 8mmol of sublimed sulfur (S) with 8mL of tri-n-octylphosphine, and completely dissolving the sublimed sulfur.
Example 2
(1) Firstly, a ZnSe core is synthesized, and zinc acetate (Zn (Ac) 2 ) Mixing Oleic Acid (OA) and Octadecene (ODE) in a molar ratio of 1:6:50 in a three-neck flask, and pumping and inflating 3 times at room temperature to ensure that the vacuum pumping is complete; argon is then introduced, and the temperature is raised to 120 ℃ under the argon environment, so as to form zinc precursor, and vacuum is pumped at 90 ℃ for 1h. Continuously heating to 230 ℃ in an argon environment, injecting 0.5mL of selenium precursor solution when the temperature reaches 230 ℃, and preserving the temperature for 30min at 230 ℃; heating to 300 ℃, then injecting 4mL of zinc precursor solution at a rate of 24mL/h, then injecting 0.4mL of selenium precursor solution at a rate of 3mL/h, and preserving heat for 20min to obtain ZnSe nuclear quantum dot solution. The zinc precursor solution described herein was 9mmol zinc acetate (Zn (Ac) 2 ) Mixing with 6mL of Oleic Acid (OA) and 30mL of Octadecene (ODE), pumping and inflating for 3 times at room temperature, then heating to 120 ℃ under argon atmosphere, and completely dissolving zinc acetate to obtain a colloidal solution, wherein the zinc precursor solutions are all the following solutions; the selenium precursor solution is a colloidal solution obtained by mixing 8mmol of selenium powder (Se) with 8mL of tri-n-octylphosphine and completely dissolving the selenium powder, and the selenium precursor solutions are all described below.
(2) Injecting 4mL of zinc precursor solution into the ZnSe quantum dot solution at a rate of 24mL/h, then injecting 0.5mL of selenium precursor solution and 0.5mL of tellurium precursor solution at a rate of 3mL/h, and preserving heat for 30min to obtain ZnSe/ZnSeTe quantum dot solution; the molar ratio of the zinc precursor solution to the selenium precursor solution to the tellurium precursor solution is 1:0.5:0.015; the tellurium precursor solution is a colloidal solution obtained by mixing 0.24mmol tellurium powder (Te) with 8mL tri-n-octyl phosphine and completely dissolving the tellurium powder.
(3) 4mL of zinc precursor solution is injected into the ZnSe/ZnSeTe quantum dot solution at the rate of 24mL/h, then 0.5mL of selenium precursor solution is injected at the rate of 3mL/h, the temperature is kept for 40min, and the process is repeated twice, so that the ZnSe/ZnSeTe/ZnSe spherical quantum well structure is obtained.
(4) And (3) injecting 8mL of zinc precursor solution into the ZnSe/ZnSeTe/ZnSe spherical quantum well solution synthesized in the step (3) at the rate of 24mL/h, then injecting 2mL of sulfur precursor solution at the rate of 3mL/h, and carrying out heat preservation for 1h to coat a ZnS shell layer, thereby further improving the fluorescence quantum yield and the air stability of the ZnSe/ZnSeTe/ZnSe spherical quantum well. The sulfur precursor solution described herein was a colloidal solution obtained by mixing 8mmol of sublimed sulfur (S) with 8mL of tri-n-octylphosphine, and completely dissolving the sublimed sulfur.
Example 3
(1) Firstly, a ZnSe core is synthesized, and zinc acetate (Zn (Ac) 2 ) Mixing Oleic Acid (OA) and Octadecene (ODE) in a molar ratio of 1:4:40 in a three-neck flask, and pumping and inflating 3 times at room temperature to ensure that the vacuum pumping is complete; argon is then introduced, and the temperature is raised to 120 ℃ under the argon environment, so as to form zinc precursor, and vacuum is pumped at 90 ℃ for 1h. Continuously heating to 230 ℃ in an argon environment, injecting 0.5mL of selenium precursor solution when the temperature reaches 230 ℃, and preserving the temperature for 30min at 230 ℃; heating to 300 ℃, then injecting 4mL of zinc precursor solution at a rate of 24mL/h, then injecting 0.4mL of selenium precursor solution at a rate of 3mL/h, and preserving heat for 30min to obtain ZnSe nuclear quantum dot solution. The zinc precursor solution described herein was 9mmol zinc acetate (Zn (Ac) 2 ) Mixing with 6mL of Oleic Acid (OA) and 30mL of Octadecene (ODE), pumping and inflating for 3 times at room temperature, then heating to 120 ℃ under argon atmosphere, and completely dissolving zinc acetate to obtain a colloidal solution, wherein the zinc precursor solutions are all the following solutions; the selenium precursor solution is a colloidal solution obtained by mixing 8mmol of selenium powder (Se) with 8mL of tri-n-octylphosphine and completely dissolving the selenium powder, and the selenium precursor solutions are all described below.
(2) Injecting 4mL of zinc precursor solution into the ZnSe quantum dot solution at a rate of 24mL/h, then injecting 0.5mL of selenium precursor solution and 2mL of tellurium precursor solution at a rate of 3mL/h, and preserving heat for 30min to obtain ZnSe/ZnSeTe quantum dot solution; the molar ratio of the zinc precursor solution to the selenium precursor solution to the tellurium precursor solution is 1:0.5:0.03; the tellurium precursor solution is a colloidal solution obtained by mixing 0.12mmol tellurium powder (Te) with 8mL tri-n-octyl phosphine and completely dissolving the tellurium powder.
(3) 4mL of zinc precursor solution is injected into the ZnSe/ZnSeTe quantum dot solution at the rate of 24mL/h, then 0.5mL of selenium precursor solution is injected at the rate of 3mL/h, the temperature is kept for 40min, and the above operation is repeated twice, so that the ZnSe/ZnSeTe/ZnSe spherical quantum well structure is obtained.
(4) And (3) injecting 8mL of zinc precursor solution into the ZnSe/ZnSeTe/ZnSe spherical quantum well solution synthesized in the step (3) at the rate of 24mL/h, then injecting 2mL of sulfur precursor solution at the rate of 3mL/h, and carrying out heat preservation for 1h to coat a ZnS shell layer, thereby further improving the fluorescence quantum yield and the air stability of the ZnSe/ZnSeTe/ZnSe quantum well. The sulfur precursor solution described herein was a colloidal solution obtained by mixing 8mmol of sublimed sulfur (S) with 8mL of tri-n-octylphosphine, and completely dissolving the sublimed sulfur.
The ultraviolet-visible spectrophotometer and the F-380 fluorescence spectrophotometer are adopted to measure samples, the absorption spectrum and the photoluminescence spectrum are obtained, the thickness of the outer layer ZnSe is adjusted in the embodiment 1 and the embodiment 2, the continuous adjustment of the luminescence peak position of the quantum well structure is realized, the increase of the thickness of the ZnSe shell layer can not cause the rapid decrease of the fluorescence quantum yield, and the designed quantum well structure can keep good coherent strain between interfaces, alternately inject cations and anions, slowly grow the shell layer and well release the stress between the interfaces.
Fig. 2 is a high resolution TEM image of a quantum well structure from which it can be seen that the lattice thereof has no stacking fault defect but an ordered atomic arrangement. The size distribution is shown in fig. 3, the overall size of the designed quantum well structure reaches-14.98 nm, and no decrease in fluorescence quantum yield occurs, which indicates that the invention successfully realizes thick-shell layer growth and no lattice defect is generated to influence the fluorescence quantum yield.
Finally, the surface defect of the quantum well structure is modified by coating the ZnS shell layer, so that the quantum yield and the air stability of the quantum well structure are further improved, and finally, the high color purity (PL half-peak width-18 nm) and the high fluorescence quantum yield (> 90%) are obtained.
Claims (8)
1. The synthesis method of the ZnSe/ZnSeTe/ZnSe spherical quantum well structure coated by blue light emitting ZnS is characterized by comprising the following steps:
(1) Synthesizing ZnSe core: mixing a zinc source, saturated fatty acid and a solvent in a three-neck flask; vacuumizing, and then introducing argon; heating to 120-150 ℃ in an argon environment to form a colloid solution, namely a zinc precursor solution;
continuously heating to 220-250 ℃ in an argon environment, then adding selenium precursor solution and preserving heat; heating to 300-320 ℃, respectively injecting a zinc precursor solution and a selenium precursor solution, and preserving heat to obtain a ZnSe nuclear quantum dot solution;
(2) Injecting a zinc precursor solution into the ZnSe quantum dot solution, simultaneously injecting a selenium precursor solution and a tellurium precursor solution, and preserving heat for 30-50min to obtain a ZnSe/ZnSeTe quantum dot solution;
in the step, the molar ratio of the zinc precursor solution, the selenium precursor solution and the tellurium precursor solution is 1:x:y, wherein 0< x <1,0< y <1-x;
(3) Injecting a zinc precursor solution into the ZnSe/ZnSeTe quantum dot solution, then injecting a selenium precursor solution and preserving heat to obtain a ZnSe/ZnSeTe/ZnSe spherical quantum well structure;
(4) Injecting a zinc precursor solution into the ZnSe/ZnSeTe/ZnSe quantum well solution, then injecting a sulfur precursor solution, preserving heat for 1-2h, and coating a ZnS shell to obtain a ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure;
the selenium precursor solution, the tellurium precursor solution and the sulfur precursor solution are respectively selenium powder, tellurium powder and sublimed sulfur colloid solutions.
2. The method for synthesizing the blue light emitting ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure according to claim 1, which is characterized in that: the injection rate of the zinc precursor solution is 20-25mL/h, the injection rate of the selenium precursor solution is 3-5mL/h, and the injection rate of the sulfur precursor solution is 3-5mL/h.
3. The method for synthesizing the blue light emitting ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure according to claim 1, which is characterized in that: the zinc source in the step (1) is one of zinc chloride, zinc oxide, anhydrous zinc acetate, zinc stearate or zinc acetylacetonate.
4. The method for synthesizing the blue light emitting ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure according to claim 1, which is characterized in that: the solvent in the step (1) is one or more of paraffin oil, octadecene or tri-n-octylamine.
5. The method for synthesizing the blue light emitting ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure according to claim 1, which is characterized in that: the saturated fatty acid in the step (1) is one of oleic acid and tetradecanoic acid.
6. The method for synthesizing the blue light emitting ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure according to claim 1, which is characterized in that: the molar ratio of the zinc source, the saturated fatty acid and the solvent in the step (1) is as follows: 1-3:3-7:40-80.
7. The method for synthesizing the blue light emitting ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure according to claim 1, which is characterized in that:
the selenium precursor solution is a colloidal solution of selenium powder dissolved in tri-n-butyl phosphine, tri-n-octyl phosphine or diphenyl phosphine;
the tellurium precursor solution is a colloid solution of tellurium powder dissolved in tri-n-butyl phosphine or tri-n-octyl phosphine;
the sulfur precursor solution is a colloidal solution of sublimed sulfur dissolved in tri-n-butyl phosphine or tri-n-octyl phosphine.
8. The method for synthesizing the blue light emitting ZnS coated ZnSe/ZnSeTe/ZnSe spherical quantum well structure according to claim 1, which is characterized in that: repeating the step (3) for 1-5 times, and obtaining ZnSe/ZnSeTe/ZnSe spherical quantum wells with different shell thicknesses corresponding to different emission peak positions according to different repetition times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211736273.3A CN116285993B (en) | 2022-12-31 | 2022-12-31 | Synthesis method of ZnSe/ZnSeTe/ZnSe spherical quantum well structure coated by blue light emission ZnS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211736273.3A CN116285993B (en) | 2022-12-31 | 2022-12-31 | Synthesis method of ZnSe/ZnSeTe/ZnSe spherical quantum well structure coated by blue light emission ZnS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116285993A CN116285993A (en) | 2023-06-23 |
| CN116285993B true CN116285993B (en) | 2024-01-12 |
Family
ID=86827630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211736273.3A Active CN116285993B (en) | 2022-12-31 | 2022-12-31 | Synthesis method of ZnSe/ZnSeTe/ZnSe spherical quantum well structure coated by blue light emission ZnS |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116285993B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964529A (en) * | 2019-11-25 | 2020-04-07 | 南昌航空大学 | Preparation method of ZnSe/CdSe/ZnSe trap quantum dots with high fluorescence yield |
| CN111218284A (en) * | 2018-11-23 | 2020-06-02 | 纳晶科技股份有限公司 | Core-shell quantum dot, preparation method thereof and electronic device |
-
2022
- 2022-12-31 CN CN202211736273.3A patent/CN116285993B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111218284A (en) * | 2018-11-23 | 2020-06-02 | 纳晶科技股份有限公司 | Core-shell quantum dot, preparation method thereof and electronic device |
| CN110964529A (en) * | 2019-11-25 | 2020-04-07 | 南昌航空大学 | Preparation method of ZnSe/CdSe/ZnSe trap quantum dots with high fluorescence yield |
Non-Patent Citations (1)
| Title |
|---|
| Sun-Hyoung Lee.Heterostructural tailoring of blue ZnSeTe quantum dots toward high-color purity and high-efficiency electroluminescence.《Chemical Engineering Journal》.2021,第429卷全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116285993A (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20170118248A (en) | Group III-V/Zinc Chalcogenide Alloyed Semiconductor Quantum Dots | |
| CN110028970B (en) | Preparation method of CdZnSe/CdSe/ZnSe green light quantum dots | |
| CN111971367B (en) | Red light-emitting quantum dot with light-emitting wavelength and small half-value width for high-color-purity display screen and preparation method thereof | |
| US20110175030A1 (en) | Preparing large-sized emitting colloidal nanocrystals | |
| Li et al. | Chemical synthesis and applications of colloidal metal phosphide nanocrystals | |
| US20110175054A1 (en) | Device containing large-sized emitting colloidal nanocrystals | |
| KR20190055390A (en) | MANUFACTURING METHOD OF InP/ZnS CORE/SHELL QUATUM DOTS | |
| JP7202352B2 (en) | Quantum dot and method for manufacturing quantum dot | |
| Mu et al. | Recent progress and future prospects on halide perovskite nanocrystals for optoelectronics and beyond | |
| Sun et al. | Physical origins of high photoluminescence quantum yield in α-CsPbI3 nanocrystals and their stability | |
| US11242483B2 (en) | Quantum dot | |
| CN116285993B (en) | Synthesis method of ZnSe/ZnSeTe/ZnSe spherical quantum well structure coated by blue light emission ZnS | |
| CN108630814B (en) | Core-shell structure colloid nanosheet, QLED device and preparation method | |
| CN111218283B (en) | Alloy quantum dot capable of remarkably inhibiting Auger recombination and preparation and application thereof | |
| Solov’ev et al. | Metamorphic InAs/InGaAs/InAlAs quantum wells with submonolayer InSb insertions emitted in the mid-infrared spectral range | |
| KR101958088B1 (en) | Manufacturing method of core/shell multi-layered structure semiconductor nanoparticles | |
| JP2012144587A (en) | Method for manufacturing compound semiconductor particle | |
| Cheng et al. | Near‐Unity Quantum Yield ZnSeTe Quantum Dots Enabled by Controlling Shell Growth for Efficient Deep‐Blue Light‐Emitting Diodes | |
| CN110616068A (en) | Particles and method for producing same | |
| CN109423287B (en) | Preparation method of core-shell structure nanocrystal | |
| KR20200069488A (en) | Method for forming quantum dots having concentration gradient type buffer layer | |
| KR102103009B1 (en) | Method for producing a quantum dot nanoparticles, Quantum dot nanoparticles prepared by the method, Quantum dot nanoparticles having a core-shell structure, and Light emitting element | |
| CN115161015B (en) | Metal/quasi two-dimensional perovskite nanocrystalline composite film and preparation method thereof | |
| TWI843173B (en) | Semiconductor quantum dots and method for making the same | |
| CN116162458B (en) | Method for regulating forming path of magic cluster/quantum dot and application of method for preparing magic cluster and quantum dot |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |