CN110527855A - preparation method of tin-germanium alloy material and tin-germanium alloy material - Google Patents
preparation method of tin-germanium alloy material and tin-germanium alloy material Download PDFInfo
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- CN110527855A CN110527855A CN201910759472.8A CN201910759472A CN110527855A CN 110527855 A CN110527855 A CN 110527855A CN 201910759472 A CN201910759472 A CN 201910759472A CN 110527855 A CN110527855 A CN 110527855A
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- 239000000956 alloy Substances 0.000 title claims abstract description 92
- 229910000927 Ge alloy Inorganic materials 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- IWTIUUVUEKAHRM-UHFFFAOYSA-N germanium tin Chemical compound [Ge].[Sn] IWTIUUVUEKAHRM-UHFFFAOYSA-N 0.000 title abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 121
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 claims abstract description 38
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims description 120
- 239000002904 solvent Substances 0.000 claims description 18
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 8
- 238000013021 overheating Methods 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 2
- 229940038384 octadecane Drugs 0.000 claims description 2
- CUDGTZJYMWAJFV-UHFFFAOYSA-N tetraiodogermane Chemical compound I[Ge](I)(I)I CUDGTZJYMWAJFV-UHFFFAOYSA-N 0.000 claims description 2
- ZRLCXMPFXYVHGS-UHFFFAOYSA-N tetramethylgermane Chemical compound C[Ge](C)(C)C ZRLCXMPFXYVHGS-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000012010 growth Effects 0.000 abstract description 6
- 238000010899 nucleation Methods 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 229910045601 alloy Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- -1 octadecylene Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical group CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- PFJFNQUFMTYCHB-UHFFFAOYSA-N C[SiH2]N[SiH3] Chemical compound C[SiH2]N[SiH3] PFJFNQUFMTYCHB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the field of nanotechnology, and particularly relates to a preparation method of a tin-germanium alloy material and the tin-germanium alloy material. The preparation method provided by the invention comprises the following steps: dispersing tin nano-particles and a germanium precursor in a reaction solvent under an inert atmosphere to obtain a mixture; and continuously heating the mixture to 60-200 ℃ for heating reaction to obtain the tin-germanium alloy material. The tin nano particles are used as the synthesis template of the tin-germanium alloy material, so that the reaction energy barrier of nucleation, crystallization and growth of the tin-germanium alloy material is greatly reduced, the tin-germanium alloy material can be prepared under the condition of heating to 60 ℃, and the quality is stable and controllable. The method is simple, is simple and convenient to operate, and is easy for large-scale production of the tin-germanium alloy material.
Description
Technical field
The invention belongs to field of nanometer technology, and in particular to a kind of preparation method and tin germanium alloy material of tin Ge alloy material
Material.
Background technique
Tin Ge alloy material near infrared region have adjustable band gap and hypotoxicity, photoelectric device, biomedical imaging,
The fields such as solar battery have important application prospect.But the crystallization temperature of germanium be higher than 300 DEG C (fusing point of tin only has 230
DEG C), the lattice dislocation between tin and germanium be more than 14% and the two compatibility lower than 1% so that the tin germanium of preparation high quality closes
There is very big challenge in gold nanocrystals.In the past more than ten years, researchers have attempted a variety of methods and regulation tin germanium are gone to close
The structure and pattern of gold, such as epitaxial growth method, pulse laser fusion method, liquid phase method, still, these methods are cumbersome, and
Generally require about 300 DEG C of pyroreaction condition.
Summary of the invention
The main purpose of the present invention is to provide a kind of preparation methods of tin Ge alloy material, to reduce reaction temperature, letter
Change operating procedure.
Another object of the present invention is to provide one kind tin Ge alloy material as made from above-mentioned preparation method.
In order to achieve the above-mentioned object of the invention, the present invention provides following specific technical solutions:
A kind of preparation method of tin Ge alloy material, comprising the following steps:
Tin nanoparticles, germanium presoma and reaction dissolvent are provided；
Under an inert atmosphere, the tin nanoparticles and the germanium presoma are dispersed in the reaction dissolvent, are obtained
Mixture；Then, the mixture persistently overheating is subjected to heating reaction to 60-200 DEG C, obtains the tin Ge alloy material.
The preparation method of tin Ge alloy material provided by the invention, the conjunction using tin nanoparticles as tin Ge alloy material
At template, the reaction energy barrier of tin Ge alloy material nucleation, crystallization and growth is greatly reduced, is allowed to be heated to 60 DEG C of condition
Under can prepare tin Ge alloy material, it is stable and controllable for quality.Method is simple, easy to operate, is easy to tin Ge alloy material
Large-scale production.
Correspondingly, the tin Ge alloy material as made from above-mentioned preparation method.
Present invention tin Ge alloy material as made from above-mentioned preparation method, have uniform alloy structure, photoelectric device,
There is very strong application potential in the fields such as biomedical imaging, solar battery.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) image of tin Ge alloy material made from embodiment 1；
Fig. 2 is high-resolution-ration transmission electric-lens (HRTEM) image of tin Ge alloy material made from embodiment 1；
Fig. 3 is the EDS distribution diagram of element of tin Ge alloy material made from embodiment 1；
Fig. 4 is the X-ray diffraction spectrogram of tin Ge alloy material made from embodiment 1；
Fig. 5 is the Raman image of X-ray diffraction spectrogram made from embodiment 1；
Fig. 6 is that the sample in differential responses stage in the preparation process of tin Ge alloy material carries out HRTEM, STEM and corresponding
The testing result of the linear scanning analysis of EDS element.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
A kind of preparation method of tin Ge alloy material, comprising the following steps:
S01, tin nanoparticles, germanium presoma and reaction dissolvent are provided；
S02, under an inert atmosphere, the tin nanoparticles and the germanium presoma are dispersed in the reaction dissolvent,
Obtain mixture；Then, the mixture persistently overheating is subjected to heating reaction to 60-200 DEG C, obtains the tin germanium alloy material
Material.
The preparation method of tin Ge alloy material provided in an embodiment of the present invention, using tin nanoparticles as tin germanium alloy material
The synthesis template of material greatly reduces the reaction energy barrier of tin Ge alloy material nucleation, crystallization and growth, is allowed in a heated condition
The tin Ge alloy material with uniform alloy structure can be prepared.Method is simple, easy to operate, is easy to tin Ge alloy material
Large-scale production.
Specifically, the tin nanoparticles are Sillim's metal particles that size reaches Nano grade, at this in step S01
In inventive embodiments, synthesis template of the tin nanoparticles as tin Ge alloy material promotes tin germanium to reduce reaction energy barrier
Nucleation, crystallization and the growth of alloy material, to prepare the tin Ge alloy material of high quality.As preferred embodiment, institute
The partial size for stating tin nanoparticles is 11-16nm, and its average grain diameter standard deviation is 6%-8%, using uniform particle diameter, small size
Tin nanoparticles as reaction raw materials, can promote the tin phase transition process nanocrystalline to tin germanium alloy, conducive to synthesis high quality
Tin Ge alloy material.
The tin nanoparticles are chosen as commercially available tin nanoparticles commodity, and conventional technical means in the art preparation can also be used
It obtains, the embodiment of the present invention is not especially limited the source of the tin nanoparticles.As preferred embodiment, the tin
The preparation of nano particle the following steps are included:
S011, tin presoma, tungsten carbonyl, oleyl amine, hexamethyldisilazane and non-coordinating solvent are provided, tin presoma and
The mass ratio of tungsten carbonyl is (40-400): the volume ratio of (10-100), oleyl amine, hexamethyldisilazane and non-coordinating solvent are
(1-10): (0.75-7.5): the mass volume ratio of (9-90), tin presoma and non-coordinating solvent is (40-400) mg:(9-90)
mL；
S012, in an inert atmosphere, by the tin presoma, the tungsten carbonyl, the oleyl amine and the hexamethyl two
Silazane is dissolved in the non-coordinating solvent, obtains mixture；Then, by the heating rate of 8-12 DEG C/min by the mixing
Object is heated to 200-220 DEG C, insulation reaction 1-120min, to which reaction solution to be cooled to room temperature to after reaction and carried out solid-liquid point
From processing, the tin nanoparticles are obtained.
More specifically, the tin presoma is for providing tin atom, preferably stannic chloride, stannous octoate, stannous sulfate
Or stannous acetate, in some embodiments, the tin presoma is selected as stannic chloride.The tungsten carbonyl is used for as reducing agent
The tin ion of reduction tin presoma is tin atom and then forms tin nanoparticles.The oleyl amine and the hexamethyldisilazane are made
For ligand, acted on by its covalent coordinate between tin atom, nucleation and growth course that can be nanocrystalline with Effective Regulation tin,
And by acting synergistically with above-mentioned tungsten carbonyl and stannic chloride, tin nanoparticles reunion can be effectively suppressed, it is equal to be conducive to acquisition size
Tin nanoparticles of the even and particle size range between 11-16nm.
The germanium presoma refers to a kind of precursor substance by reaction offer germanium atom, the including but not limited to nothing of germanium
Machine salt or the organic salt of germanium etc., it is preferred that the germanium presoma in diiodinating germanium, germanium tetraiodide and tetramethyl germanium at least
It is a kind of.In some embodiments, the germanium presoma is selected as diiodinating germanium.
The reaction dissolvent provides dicyandiamide solution for the synthesis of tin Ge alloy material, in embodiments of the present invention, described anti-
Solvent is answered to preferably comprise the non-coordinating solvent that boiling point is higher than reaction temperature (such as 60 DEG C or more), what the non-coordinating solvent referred to
It is a kind of organic reagent there is no with the lone electron pair of metal combination, as synthesis tin nanoparticles and tin Ge alloy material
Reaction dissolvent, preferably temperature higher than 200 DEG C and carbon atom number in 10 alkane, the alkene more than and less than or equal to 22
At least one of hydrocarbon, ether and aromatic compound.As preferred embodiment, the non-coordinating solvent be selected from the tetradecane,
At least one of hexadecane, octadecane, eicosane, 1- octadecylene, phenylate, benzyl oxide and atoleine.In some embodiments,
The non-coordinating solvent is selected as octadecylene.
Further, the reaction dissolvent further includes ligand and/or ligand solvent, and the ligand is mainly used for stable dispersion
Tin nanoparticles prevent tin nanoparticles from reuniting；The ligand solvent is can be molten with metal coordination containing lone electron pair
Agent, for dissolving the germanium presoma, to promote tin nanoparticles and germanium presoma to be sufficiently mixed in reaction dissolvent.As excellent
Choosing, the ligand are the mixture of oleyl amine and hexamethyldisilazane, and the ligand solvent is tertiary phosphine, in some embodiments,
The tertiary phosphine is tri-n-octyl phosphine (TOP) and/or tri-n-butyl phosphine (TBP).
Specifically, tin nanoparticles and germanium presoma are dispersed in reaction dissolvent in step S02, so that each reaction
Raw material uniformly mixes.Preferably, the molar ratio of the tin atom of the germanium atom and tin nanoparticles of germanium presoma is (73-82):
(18-27), to synthesize the tin Ge alloy material of high Ge content, thus obtained tin Ge alloy material is Sn1-xGex, wherein x
=0.73-0.82.
As an implementation, the step of tin nanoparticles and germanium presoma being dispersed in reaction dissolvent includes following step
It is rapid:
S021, tin nanoparticles are dispersed in the octadecylene containing oleyl amine and HMDS, prepare tin nanoparticles solution；
S022, germanium presoma and ligand solvent are provided, the germanium presoma is dissolved in the ligand solvent, obtain germanium
Precursor solution；
In tin nanoparticles solution prepared by S023, the germanium precursor solution injection step S021 for preparing step S022,
It is mixed well.
Further, the step of tin nanoparticles and germanium presoma being dispersed in reaction dissolvent control in an inert atmosphere into
Row, the inert gas atmosphere are selected from least one of argon atmosphere, helium atmosphere and nitrogen atmosphere, in one embodiment,
The inert gas atmosphere is selected as argon atmosphere.
The mixture persistently overheating is subjected to heating reaction to 60-200 DEG C, to synthesize tin Ge alloy material.It is heating
During reaction, germanium presoma and tin nanoparticles haptoreaction, and realize tin Ge alloy material from non-uniform nucleocapsid knot
Differentiation of the structure to uniform alloy structure.As preferred embodiment, the mixture persistently overheating is heated to 60-200 DEG C
In the step of carrying out heating reaction, the mixture is heated to 150-200 DEG C by the heating rate of 8-12 DEG C/min, is then protected
Temperature reaction 10min or more, so that the tin Ge alloy material prepared has uniform alloy structure.It is right in some test cases
The phase-change mechanism of tin to tin Ge alloy material has made further research, finds the tin Ge alloy material when temperature is warming up to 90 DEG C
For the unformed tin germanium alloy of Sn-；When temperature is warming up to 120 DEG C, for the tin germanium alloy of Sn- crystallization；When temperature is warming up to 180 DEG C
And after reacting 5h, Sn is formed1-xGexAlloy, and x=0.73-0.82, it is shown that the mixture is heated to 150-200 DEG C simultaneously
Insulation reaction 10min or more can get the tin Ge alloy material with uniform alloy structure, be obviously improved tin Ge alloy material
Quality.
Further, the mixture persistently overheating the step of heating is reacted is carried out to 60-200 DEG C to control in indifferent gas
It is carried out in atmosphere.
As preferred embodiment, to which reaction solution to be cooled to room temperature to after reaction and carried out purifies and separates processing,
With obtain high-purity the tin Ge alloy material.As an implementation, the purifies and separates processing includes: described
Precipitating reagent is added in reaction solution, then carries out that precipitating is collected by centrifugation, alternately washing/precipitating is carried out to precipitating later.Further,
The precipitating reagent is selected as that the organic solvent of the tin Ge alloy material, such as ethyl alcohol etc. can not be dissolved；Precipitating is replaced
The step of washing/precipitating, is using for example isometric n-hexane/alcohol mixeding liquid.Further, purifies and separates processing is carried out
The step of after, sintering is dried to tin Ge alloy material.
To sum up, each reaction raw materials and its amount ranges and reaction temperature of above-mentioned optimization provided in an embodiment of the present invention,
Under the conditional parameters such as time, and the comprehensive function of optimization technique, the preparation method provided through the embodiment of the present invention may make
The comprehensive performance of obtained tin Ge alloy material is optimal, bandgap range 0.51eV to 0.71eV.
Correspondingly, the tin Ge alloy material as made from above-mentioned preparation method.
Tin Ge alloy material as made from above-mentioned preparation method of the embodiment of the present invention has uniform alloy structure, in light
There is very strong application potential in the fields such as electrical part, biomedical imaging, solar battery.
As a preferred embodiment, the tin Ge alloy material is Sn1-xGex, wherein x=0.73-0.82, this
Class tin Ge alloy material has uniform alloy structure, and its bandgap range 0.51eV to 0.71eV.
As another preferred embodiment, the partial size of the tin Ge alloy material is 9-13nm.
To make, the above-mentioned implementation detail of the present invention and operation can be clearly readily appreciated by one skilled in the art and the present invention is real
The progress performance of the preparation method and tin Ge alloy material of applying a kind of tin Ge alloy material of example embodies significantly, below by way of implementation
Implementation of the invention is illustrated in example.
Embodiment 1
The present embodiment is prepared for a kind of preparation method of tin Ge alloy material, specifically includes the following steps:
1, tin nanoparticles solution is prepared
40mg stannous chloride (99% pure, the Alfa Aesar of analysis) is weighed in glove box and is put into vial, then
Oleyl amine (1mL, 70% analyzes pure, Aldrich) and octadecylene (ODE, 9mL, 90% analysis by water removal deoxygenation processing is added
It is pure, Aldrich), it is ultrasonically treated after sealing until obtaining white suspension.Then, three-necked flask is taken, 10mg carbonyl is added
Tungsten (W (CO)6, 97% analyzes pure, Alfa Aesar), suitable condenser pipe, heating mantle, thermocouple and rubber stopper are chosen, it will
Reaction unit is sealed.Then it will be vacuumized in bottle 1 hour, be then charged with Ar gas, by the suspension and 0.75mL six after ultrasound
Methyl disilazane (HMDS, 99% pure, the Aldrich of analysis) is injected into there-necked flask, is heated to by the heating rate of 10 DEG C/min
60 DEG C and holding about 10min ensure that each reaction raw materials are completely dissolved；Then, continue to be heated to by the heating rate of 10 DEG C/min
210 DEG C, solution becomes black and keeps reaction 10min, obtains tin nanoparticles solution.
2, tin Ge alloy material is synthesized
1) in glove box, the diiodinating germanium of 30mg is dissolved in the TOP solution of 2mL, germanium precursor solution is prepared.
2) in argon atmosphere, the ratio for being 81.58:18.42 according to the molar ratio of germanium atom and tin atom, by germanium forerunner
Liquid solution injects in the tin nanoparticles solution of above-mentioned steps preparation, and is heated to 180 DEG C by the heating rate of 10 DEG C/min, instead
It answers 5 hours；Later, reaction solution is cooled to room temperature rapidly with ice-water bath, the n-hexane dilute reaction solution of 12.5mL is added, then
The ethyl alcohol that 25mL is added settles tin Ge alloy material, then, alternately three times using isometric n-hexane and ethyl alcohol centrifugation purification,
The tin Ge alloy material Sn purified0.18Ge0.82, band gap 0.70-0.75eV.
The essential condition parameter of the tin Ge alloy material of embodiment 2-5 preparation being related to is as shown in table 1:
Table 1
Test case 1
Tin Ge alloy material prepared by Example 1 carries out observation analysis using transmission electron microscope, and Fig. 1 is that it is saturating
Penetrate electron microscope (TEM) image, the tin Ge alloy material regular appearance of display preparation of the embodiment of the present invention；Fig. 2 is its high score
Distinguish transmission electron microscope (HRTEM) image, it was confirmed that the tin Ge alloy material of preparation of the embodiment of the present invention is monocrystalline；Fig. 3 is its EDS member
The tin Ge alloy material of plain distribution map, display preparation of the embodiment of the present invention is mainly made of two kinds of elements of Ge and Sn.
Test case 2
The tin Ge alloy material of Example 1- embodiment 5 carries out X-ray diffraction analysis (XRD), and Fig. 4 is that its X-ray is spread out
Spectrogram is penetrated, with the increase of Ge ingredient, X-ray diffraction peak gradually deviates to high angle and tends to the standard card position of Ge for display
It sets.
The tin Ge alloy material of Example 1- embodiment 5 carries out Raman image (Raman), and Fig. 5 is its Raman image,
Increase of the display with Ge ingredient, the system blue shift of Ge-Ge optical phonon modes.
Test case 3
The sample for synthesizing the differential responses stage in tin Ge alloy material step to embodiment 1 carries out HRTEM, STEM and right
The linear scanning analysis of EDS element answered, Fig. 6 is testing result, is the unformed tin germanium alloy of Sn- when being shown in 90 DEG C, at 120 DEG C
When for Sn- crystallization tin germanium alloy, form Sn after 180 DEG C of reaction 5h0.18Ge0.82Alloy discloses tin germanium in synthesis process and closes
Evolution process of the never uniform core-shell structure of golden material to uniform alloy structure.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of tin Ge alloy material, which comprises the following steps:
Tin nanoparticles, germanium presoma and reaction dissolvent are provided；
Under an inert atmosphere, the tin nanoparticles and the germanium presoma are dispersed in the reaction dissolvent, are mixed
Object；Then, the mixture persistently overheating is subjected to heating reaction to 60-200 DEG C, obtains the tin Ge alloy material.
2. preparation method according to claim 1, which is characterized in that the germanium atom of the germanium presoma and the sijna rice
The molar ratio of the tin atom of particle is (73-82): (18-27).
3. preparation method according to claim 1, which is characterized in that carry out heating reaction the step of in, by 8-12 DEG C/
The mixture is heated to 150-200 DEG C by the heating rate of min, then insulation reaction 10min or more.
4. preparation method according to any one of claims 1 to 3, which is characterized in that the germanium presoma is selected from diiodinating
At least one of germanium, germanium tetraiodide and tetramethyl germanium；And/or
The partial size of the tin nanoparticles is 11-16nm.
5. preparation method according to any one of claims 1 to 3, which is characterized in that the reaction dissolvent includes boiling point height
In the non-coordinating solvent of reaction temperature；
The non-coordinating solvent includes carbon atom number in 10 alkane, alkene, ether and the aromatic series more than and less than or equal to 22
At least one of compound.
6. preparation method according to claim 5, which is characterized in that the reaction dissolvent further includes ligand and/or coordination
Solvent；
The ligand is the mixture of oleyl amine and hexamethyldisilazane；
The ligand solvent is tertiary phosphine.
7. preparation method according to claim 5, which is characterized in that the non-coordinating solvent be selected from the tetradecane, hexadecane,
At least one of octadecane, eicosane, 1- octadecylene, phenylate, benzyl oxide and atoleine.
8. the tin Ge alloy material as made from claim 1 to 7 described in any item preparation methods.
9. tin Ge alloy material according to claim 8, which is characterized in that the tin Ge alloy material is Sn1-xGex,
In, x=0.73-0.82.
10. tin Ge alloy material according to claim 8, which is characterized in that the partial size of the tin Ge alloy material is 9-
13nm。
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