CN115028192B - Method for synthesizing indium oxide semiconductor nanocrystals based on organic phosphine compound - Google Patents
Method for synthesizing indium oxide semiconductor nanocrystals based on organic phosphine compound Download PDFInfo
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 72
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 239000004054 semiconductor nanocrystal Substances 0.000 title claims abstract description 14
- -1 phosphine compound Chemical class 0.000 title claims description 30
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims description 28
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims description 23
- 239000002159 nanocrystal Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 229910052738 indium Inorganic materials 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 150000003003 phosphines Chemical class 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 37
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- LEGGANXCVQPIAI-UHFFFAOYSA-N 4-methyl-octanoic acid Chemical compound CCCCC(C)CCC(O)=O LEGGANXCVQPIAI-UHFFFAOYSA-N 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- PTLIZOFGXLGHSY-UHFFFAOYSA-N dibutylphosphane Chemical compound CCCCPCCCC PTLIZOFGXLGHSY-UHFFFAOYSA-N 0.000 claims description 3
- BYYQOWAAZOHHFN-UHFFFAOYSA-N dioctylphosphane Chemical compound CCCCCCCCPCCCCCCCC BYYQOWAAZOHHFN-UHFFFAOYSA-N 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- JMOLZNNXZPAGBH-UHFFFAOYSA-N hexyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCC JMOLZNNXZPAGBH-UHFFFAOYSA-N 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 60
- 229910052786 argon Inorganic materials 0.000 description 30
- 238000004627 transmission electron microscopy Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000003446 ligand Substances 0.000 description 10
- 238000004847 absorption spectroscopy Methods 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 8
- 238000006136 alcoholysis reaction Methods 0.000 description 7
- 238000007098 aminolysis reaction Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 239000013110 organic ligand Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000001706 (4R)-4-methyloctanoic acid Substances 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- ZDVNRCXYPSVYNN-UHFFFAOYSA-K di(tetradecanoyloxy)indiganyl tetradecanoate Chemical compound [In+3].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O ZDVNRCXYPSVYNN-UHFFFAOYSA-K 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- AYRCLEBEKHDPTF-UHFFFAOYSA-K decanoate indium(3+) Chemical compound C(CCCCCCCCC)(=O)[O-].[In+3].C(CCCCCCCCC)(=O)[O-].C(CCCCCCCCC)(=O)[O-] AYRCLEBEKHDPTF-UHFFFAOYSA-K 0.000 description 2
- FCMXICIJDIVQKW-UHFFFAOYSA-K di(butanoyloxy)indiganyl butanoate Chemical compound [In+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O FCMXICIJDIVQKW-UHFFFAOYSA-K 0.000 description 2
- UYQMZBMJAYEKPO-UHFFFAOYSA-K di(octadecanoyloxy)indiganyl octadecanoate Chemical compound [In+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UYQMZBMJAYEKPO-UHFFFAOYSA-K 0.000 description 2
- BDOFFEYJSIJAFH-UHFFFAOYSA-K dodecanoate;indium(3+) Chemical compound [In+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BDOFFEYJSIJAFH-UHFFFAOYSA-K 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- UEEZVGJDCXOJSH-UHFFFAOYSA-K hexadecanoate indium(3+) Chemical compound [In+3].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O UEEZVGJDCXOJSH-UHFFFAOYSA-K 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 229950004531 hexyldecanoic acid Drugs 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- HBVDRGWGIYKRFQ-UHFFFAOYSA-K indium(3+);octanoate Chemical compound [In+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HBVDRGWGIYKRFQ-UHFFFAOYSA-K 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- OARDBPIZDHVTCK-UHFFFAOYSA-N 2-butyloctanoic acid Chemical compound CCCCCCC(C(O)=O)CCCC OARDBPIZDHVTCK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- WHTDKDNWUFDEBX-UHFFFAOYSA-N CCCCCC(C)(C)C(C)(C)C(=O)O Chemical compound CCCCCC(C)(C)C(C)(C)C(=O)O WHTDKDNWUFDEBX-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GBHRVZIGDIUCJB-UHFFFAOYSA-N hydrogenphosphite Chemical class OP([O-])[O-] GBHRVZIGDIUCJB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a method for synthesizing indium oxide semiconductor nanocrystals based on organic phosphine compounds, which comprises the steps of adding fatty carboxylic acid indium precursors and solvents into a container, exhausting materials in an inert gas atmosphere, maintaining the protection of inert gas, adding 2-20 times of organic phosphine compounds into the solution, heating to 200-280 ℃, keeping for 10-60 minutes, stopping the reaction, cooling the obtained solution, purifying to obtain indium oxide nanocrystals, and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation and application, and particularly relates to a method for synthesizing indium oxide semiconductor nanocrystals based on organic phosphonates.
Background
Indium oxide is a novel n-type semiconductor material, has a wider forbidden bandwidth and higher catalytic activity, and has wide application in the aspects of photoelectricity, gas sensitivity, catalysis and the like.
The nanocrystalline is a semiconductor material with the size in the nanoscale range and quantum confinement effect, and has the advantages of adjustable band gap, good light absorption capacity, abundant surface reaction sites, easy surface modification and the like.
The traditional method for preparing the indium oxide nanocrystalline is mainly carried out by a magnetron sputtering or pyrolysis mode, and has high reaction temperature, harsh reaction conditions and high cost. In addition, the surface of the generated indium oxide nanocrystalline is provided with a long-chain organic ligand, so that the carrier transport capacity of the indium oxide nanocrystalline is influenced, and the ligand on the surface of the indium oxide nanocrystalline needs to be removed by a subsequent treatment method when the indium oxide nanocrystalline is applied to the field of photoelectricity.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a method for synthesizing indium oxide semiconductor nanocrystals based on organic phosphine compounds.
The invention is realized by the following technical scheme:
the invention discloses a method for synthesizing indium oxide nano semiconductor nanocrystals based on organic phosphine compounds, which utilizes the catalysis of the organic phosphine compounds to generate the indium oxide nano semiconductor nanocrystals.
As a further improvement, the method according to the invention comprises in particular the following steps:
1) Adding an indium aliphatic carboxylate precursor and a solvent into a container;
2) Exhausting the materials in the step 1) under the inert gas atmosphere and maintaining the inert gas protection;
3) Adding 2-20 times of organic phosphine compound into the solution in the step 2), heating to 200-280 ℃, keeping for 10-60 minutes, stopping the reaction, cooling the obtained solution, and purifying to obtain the indium oxide nanocrystalline. (lower than the temperature required for conventional hydrolysis to produce indium oxide nanocrystals.)
As a further improvement, the indium fatty carboxylate precursor in step 1) of the present invention is a linear indium fatty carboxylate or a branched indium fatty acid carboxylate.
As a further improvement, the fatty carboxylic acid indium precursor of the present invention is indium acetate, or indium butyrate, or indium caproate, or indium caprylate, or indium caprate, or indium laurate, or indium myristate, or indium palmitate, or indium stearate, or indium eicosanate, or indium isooctanoate, or indium 4-methyloctanoate, or indium 2-hexyldecanoate, or 2-ethylhexanoate, or a mixture of indium acetate and butyric acid, or a mixture of indium acetate and caproic acid, or a mixture of indium acetate and caprylic acid, or a mixture of indium acetate and capric acid, or a mixture of indium acetate and lauric acid, or a mixture of indium acetate and myristic acid, or a mixture of indium acetate and palmitic acid, or a mixture of indium acetate and stearic acid, or a mixture of indium acetate and isooctanoic acid, or a mixture of indium acetate and 4-methyloctanoic acid, or a mixture of indium acetate and 2-hexyldecanoic acid, or a mixture of indium acetate and 2-ethylhexanoic acid.
As a further improvement, the exhaust time in the step 2) is 5-15 minutes.
As a further improvement, the organic phosphine compound in step 3) according to the present invention is tributylphosphine, or trioctylphosphine, or triphenylphosphine, or dibutylphosphine, or dioctylphosphine, or diphenylphosphine.
As a further improvement, in the step 3) of the invention, the obtained indium oxide nanocrystalline is spherical or flower-shaped or tetrapod-shaped nanocrystalline, and the size is 2-10nm.
The beneficial effects of the invention are as follows:
1) The invention can reduce the reaction temperature and the reaction time for preparing the indium oxide nanocrystalline and save energy.
2) The invention discovers a reaction mechanism for generating semiconductor nanocrystals based on the catalysis of organic phosphonates.
3) The invention provides a novel synthesis method for preparing indium oxide nanocrystals based on organic phosphonates.
4) The preparation method provided by the invention can greatly reduce the preparation temperature of the indium oxide nanocrystalline, and can adjust the size and the morphology of the indium oxide nanocrystalline to synthesize indium oxide nanocrystalline with different sizes and different morphologies, such as flower-like or dot-like shapes.
5) The invention has pushing effect on reducing the energy consumption of the preparation of the indium oxide semiconductor and developing a novel photoelectric device based on the metal oxide semiconductor nanocrystalline.
6) The surface of the indium oxide nanocrystalline generated by the method is mainly provided with short-chain neutral organic phosphine ligands, and compared with the indium oxide nanocrystalline with long-chain organic ligands generated by the existing aminolysis and alcoholysis methods, the indium oxide nanocrystalline has higher carrier transport capacity, and when the indium oxide nanocrystalline is applied to the photoelectric field, the step of ligand exchange can be omitted, so that the process flow is simplified.
Drawings
FIG. 1 is a TEM image of indium oxide nanocrystals prepared in examples 1 to 6;
FIG. 2 is a graph showing the absorption spectrum of the indium oxide nanocrystal prepared in example 1 of the present invention during synthesis;
FIG. 3 is a graph showing the absorption spectrum during the synthesis of the indium oxide nanocrystal prepared in example 2 of the present invention;
FIG. 4 is a graph showing the absorption spectrum during the synthesis of the indium oxide nanocrystal prepared in example 3 of the present invention;
FIG. 5 is a graph showing the absorption spectrum of the indium oxide nanocrystal prepared in example 5 of the present invention during synthesis;
FIG. 6 is a TEM image of the indium oxide nanocrystal prepared in example 7;
FIG. 7 is a graph showing the absorption spectrum during synthesis of indium oxide nanocrystals prepared from a control group based on example 2 without the addition of an organophosphonate;
FIG. 8 is a TEM image of indium oxide nanocrystals prepared from a control group based on example 2 without the addition of an organic phosphine compound;
Detailed Description
The invention discloses a method for synthesizing indium oxide nano semiconductor nanocrystals based on organic phosphine compounds, which is to generate the indium oxide nano semiconductor nanocrystals by utilizing the catalysis of the organic phosphine compounds, and specifically comprises the following steps:
1) Adding an indium aliphatic carboxylate precursor and a solvent into a container;
the fatty acid indium precursor is linear fatty acid indium carboxylate or branched fatty acid indium carboxylate; the fatty carboxylic acid indium precursor is indium acetate, or indium butyrate, or indium caproate, or indium caprylate, or indium caprate, or indium laurate, or indium myristate, or indium palmitate, or indium stearate, or indium eicosanate, or indium isooctanoate, or indium 4-methyloctanoate, or indium 2-hexylcaprate, or 2-ethylhexanoate, or a mixture of indium acetate and butyric acid, or a mixture of indium acetate and caproic acid, or a mixture of indium acetate and capric acid, or a mixture of indium acetate and lauric acid, or a mixture of indium acetate and myristic acid, or a mixture of indium acetate and palmitic acid, or a mixture of indium acetate and stearic acid, or a mixture of indium acetate and eicosanoic acid, or a mixture of indium acetate and isooctanoic acid, or a mixture of indium acetate and 4-methyloctanoic acid, or a mixture of indium acetate and 2-hexylcaproic acid, or a mixture of indium acetate and 2-ethylhexanoic acid.
2) Exhausting the materials in the step 1) for 5-15 minutes in an inert gas atmosphere and maintaining the inert gas protection;
3) Adding 2-20 times of organic phosphine compound into the solution in the step 2), heating to 200-280 ℃, keeping for 10-60 minutes, stopping the reaction, cooling the obtained solution, and purifying to obtain the indium oxide nanocrystalline. The reaction temperature is lower than the temperature required by the traditional hydrolysis to generate indium oxide nanocrystalline.
The organic phosphine compound is tributylphosphine, trioctylphosphine, triphenylphosphine, dibutylphosphine, dioctylphosphine, or diphenylphosphine; the obtained indium oxide nanocrystalline is spherical, flower-shaped or tetrapod-shaped nanocrystalline, and the size is 2-10nm.
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1: method for synthesizing indium oxide nanocrystalline by utilizing organic phosphine compound
The preparation method comprises the following steps:
(1) 0.0178g of indium acetate, 3.5mL of octadecene and stirring magnet were weighed and placed in a three-necked flask;
(2) And (3) introducing argon into the material in the step (1), stirring, exhausting for 10min, and exhausting air in the three-neck flask to enable the material to be in an argon environment. Then heating to 150 ℃, and continuously introducing argon for 10-15min;
(3) And (3) injecting 0.3mLTOP into the transparent solution obtained in the step (2), heating to 230-250 ℃, maintaining argon environment for reaction for 60min, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
(4) As shown in FIG. 2, after 60min of reaction, there was a significant rise in the spectrum at 300nm, which, in combination with the TEM of FIG. 1, demonstrated that a large amount of indium oxide nanocrystals were produced.
Example 2: method for synthesizing indium oxide nanocrystalline by utilizing organic phosphine compound
The preparation method comprises the following steps:
(1) 0.0178g of indium acetate, 0.0684g of tetradecanoic acid, 3.5mL of octadecene and stirring magnet are weighed and placed in a three-necked flask;
(2) And (3) introducing argon into the material in the step (1), stirring, exhausting for 10min, and exhausting air in the three-neck flask to enable the material to be in an argon environment. Then heating to 150 ℃, and continuously introducing argon for 10-15min;
(3) And (3) injecting 0.3mLTOP into the transparent solution obtained in the step (2), heating to 230-250 ℃, maintaining argon environment for reaction for 60min, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
(4) As shown in FIG. 3, after 60min of reaction, there was a significant rise in the spectrum at 300nm, which, in combination with the TEM of FIG. 1, demonstrated that a large amount of indium oxide nanocrystals were produced.
Example 3: method for synthesizing indium oxide nanocrystalline by utilizing organic phosphine compound
The preparation method comprises the following steps:
(1) 0.0178g of indium acetate, 0.0474g of 4-methyl octanoic acid and 3.5mL of octadecene and stirring magnet were weighed into a three-necked flask;
(2) And (3) introducing argon into the material in the step (1), stirring, exhausting for 10min, and exhausting air in the three-neck flask to enable the material to be in an argon environment. Then heating to 150 ℃, and continuously introducing argon for 10-15min;
(3) And (3) injecting 0.3mLTOP into the transparent solution obtained in the step (2), heating to 230-250 ℃, maintaining argon environment for reaction for 60min, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
(4) As shown in FIG. 4, after 60min of reaction, there was a significant rise in the spectrum at 300nm, which, in combination with the TEM of FIG. 1, demonstrated that a large amount of indium oxide nanocrystals were produced.
Example 4: method for synthesizing indium oxide nanocrystalline by utilizing organic phosphine compound
The preparation method comprises the following steps:
(1) 0.0178g of indium acetate, 0.0768g of 2 hexyl decanoic acid and 3.5mL of octadecene and stirring magnet were weighed into a three-necked flask;
(2) And (3) introducing argon into the material in the step (1), stirring, exhausting for 10min, and exhausting air in the three-neck flask to enable the material to be in an argon environment. Then heating to 150 ℃, and continuously introducing argon for 10-15min;
(3) And (3) injecting 0.3mLTOP into the transparent solution obtained in the step (2), heating to 230-250 ℃, maintaining argon environment for reaction for 60min, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
Example 5: method for synthesizing indium oxide nanocrystalline by utilizing organic phosphine compound
The preparation method comprises the following steps:
(1) 0.0178g of indium acetate, 0.0474g of tetramethyl octanoic acid, 3.5mL of octadecene and stirring rod were weighed into a three-necked flask;
(2) And (3) introducing argon into the material in the step (1), stirring, exhausting for 10min, and exhausting air in the three-neck flask to enable the material to be in an argon environment. Then heating to 150 ℃, and continuously introducing argon for 10-15min;
(3) And (3) injecting 0.3mLTBP into the transparent solution obtained in the step (2), heating to 230-250 ℃, maintaining argon environment for reaction for 60min, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
(4) As shown in FIG. 5, after 60min of reaction, there was a significant rise in the spectrum at 300nm, which, in combination with the TEM of FIG. 1, demonstrated that a large amount of indium oxide nanocrystals were produced.
Example 6: method for synthesizing indium oxide nanocrystalline by utilizing organic phosphine compound
The preparation method comprises the following steps:
(1) 0.0178g of indium acetate, 0.0684g of tetradecanoic acid, 3.5mL of octadecene and stirring magnet are weighed and placed in a three-necked flask;
(2) And (3) introducing argon into the material in the step (1), stirring, exhausting for 10min, and exhausting air in the three-neck flask to enable the material to be in an argon environment. Then heating to 150 ℃, and continuously introducing argon for 10-15min;
(3) And (3) injecting 0.3mLTBP into the transparent solution obtained in the step (2), heating to 230-250 ℃, maintaining argon environment for reaction for 60min, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
(3) And (3) injecting 0.3mLTOP into the transparent solution obtained in the step (2), heating to 230-250 ℃, maintaining argon environment for reaction for 60min, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
Example 7: method for synthesizing indium oxide nanocrystalline by utilizing organic phosphine compound
The preparation method comprises the following steps:
(1) 0.0627g of synthesized indium myristate, 3.5mL of octadecene and stirring magnet are weighed and placed in a three-necked flask;
(2) And (3) introducing argon into the material in the step (1), stirring, exhausting for 10min, exhausting air in the three-neck flask, and removing the material from the argon environment. Then heating to 150 ℃, and continuously introducing argon for 10-15min;
(3) And (3) injecting 0.3mLTOP into the transparent solution obtained in the step (2), heating to 230-250 ℃, reacting for 60min in the environment, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
(3) And (3) injecting 0.3mLTOP into the transparent solution obtained in the step (2), heating to 230-250 ℃, maintaining argon environment for reaction for 60min, and cooling. The generation of indium oxide nanocrystals can be demonstrated by absorption spectroscopy and Transmission Electron Microscopy (TEM).
(4) According to a transmission electron microscope TEM image, the indium oxide nanocrystalline synthesized by the synthesized fatty acid salt has more regular morphology and has no flower aggregation phenomenon.
Example 8: comparison
(1) Based on case 2, under the condition that the rest conditions are unchanged, a control experiment is carried out, the control group is not added with TOP and reacts for 20min, the absorption spectrum is shown in fig. 7, the absorption spectrum of the experimental group 2 without TOP is shown in a dotted line and is almost zero, the TEM is shown in fig. 8, the combination of the TEM and the illustration shows that no indium oxide nanocrystalline is generated, the absorption spectrum of case 2 is a solid line, the absorption spectrum is obviously raised, and the combination of the TEM and the illustration shows that a large amount of indium oxide nanocrystalline is generated in case 2 in combination with fig. 3. This comparative experiment demonstrates that tertiary progenitor organophosphonates can react to form indium oxide nanocrystals.
In the prior art, the reaction temperature and the reaction time of the alcoholysis test method (1) and the aminolysis test method (2) are compared with those of the preparation method of the phosphino solution
| Test method of alcoholysis (1) | Aminolysis test method (2) | The preparation method of the invention | |
| Minimum reaction temperature | 270℃ | 290℃ | 230℃ |
| Reaction time | 3 hours | About 2 hours | 1 hour |
(1) Test method of alcoholysis: 0.1mmol of indium acetate, 0.3mmol of tetradecanoic acid and 5g of octadecene are added into a 25ml three-necked flask, the temperature is raised to 250 ℃ in an argon environment, then 0.25g (0.3 mmol) of n-decanol is added, and the temperature is raised to 270 ℃ to react for 3 hours, so that punctiform indium oxide nanocrystalline can be generated.
(2) Experimental procedure for aminolysis: 0.4mmol indium acetate +0.55ml (70%) oleylamine + 0.6ml (90%) oleic acid dissolved with 7ml (> 99%) hexadecane was added to a 25ml three-necked flask, and the solution was warmed to 110 ℃ under vacuum for a period of time to make it pale green, then warmed to 120 ℃ for 1 hour, the solution was gradually changed to pale yellow, then warmed to 290 ℃ at a rate of 10min/°c, and then maintained for 35min.
(3) As can be seen from the comparison, the phosphinolysis mode applied by the patent can greatly reduce the temperature and time required by the reaction, thereby achieving the purpose of saving energy.
In the prior art, the alcoholysis test method (1) and the aminolysis test method (2) are compared with the main surface ligand of the preparation method of the phosphino solution
| Alcoholysis of | Aminolysis of | Phosphine decomposition | |
| Primary surface ligands | Long chain organic ligands | Long chain organic ligands | Neutral organophosphine ligands, short chain |
In applications in the photovoltaic field, long-chain organic ligands on the surface of indium oxide nanocrystals produced by alcoholysis and aminolysis reduce their carrier transport capacity, so that further ligand exchange treatments are generally required to remove the long-chain ligands from the surface. In the phosphine solution method in the patent, the surface of the phosphine solution method is mainly short-chain organophosphorus ligand due to different reaction mechanisms, so that the phosphine solution method has higher carrier transport capacity, and the step of ligand exchange can be omitted.
Finally, it should also be noted that the above list is merely a specific example of the invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible, and all modifications which can be directly derived or suggested to a person skilled in the art from the disclosure of the present invention should be considered as the protection scope of the present invention.
Claims (3)
1. The method for synthesizing the indium oxide semiconductor nanocrystals based on the organic phosphine compound is characterized in that the indium oxide semiconductor nanocrystals are generated by using the catalysis of the organic phosphine compound; the method specifically comprises the following steps:
1) Adding an indium aliphatic carboxylate precursor and a solvent into a container;
2) Exhausting the materials in the step 1) under the inert gas atmosphere and maintaining the inert gas protection;
3) Adding 2-20 times of organic phosphine compound into the solution in the step 2), heating to 200-280 ℃, keeping for 10-60 minutes, stopping the reaction, cooling the obtained solution, and purifying to obtain indium oxide nanocrystalline;
the organic phosphine compound in the step 3) is tributylphosphine, trioctylphosphine, dibutylphosphine, dioctylphosphine or diphenyl phosphine;
the fatty carboxylic acid indium precursor is a mixture of indium acetate and butyric acid, or a mixture of indium acetate and caproic acid, or a mixture of indium acetate and caprylic acid, or a mixture of indium acetate and capric acid, or a mixture of indium acetate and lauric acid, or a mixture of indium acetate and myristic acid, or a mixture of indium acetate and palmitic acid, or a mixture of indium acetate and stearic acid, or a mixture of indium acetate and eicosanoic acid, or a mixture of indium acetate and isooctanoic acid, or a mixture of indium acetate and 4-methyl caprylic acid, or a mixture of indium acetate and 2-hexyl capric acid, or a mixture of indium acetate and 2-ethyl caproic acid.
2. The method for synthesizing indium oxide semiconductor nanocrystals based on an organic phosphonate compound as recited in claim 1, wherein the degassing time in step 2) is 5 to 15 minutes.
3. The method for synthesizing indium oxide semiconductor nanocrystals based on organic phosphine compounds according to claim 1, wherein the indium oxide nanocrystals obtained in step 3) are spherical or flower-like or tetrapod-like nanocrystals having a size of 2 to 10nm.
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