CN103952764B - The heterojunction structure rod-like nano crystalline substance of a kind of gold and silver indium selenium and synthetic method thereof - Google Patents
The heterojunction structure rod-like nano crystalline substance of a kind of gold and silver indium selenium and synthetic method thereof Download PDFInfo
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Abstract
The heterojunction structure rod-like nano crystalline substance of a kind of gold and silver indium selenium and synthetic method thereof, relate to nanocrystalline.Described gold is Au AgInSe with the heterojunction structure rod-like nano crystalline substance of silver indium selenium2Heterojunction structure rod-like nano is brilliant, with Au nano-particle as head end, and other end growth AgInSe2The heterojunction structure of nanometer rods.Triphenylphosphine auric chloride, silver nitrate and indium chloride are mixed with oleyl amine, evacuation, logical nitrogen, after intensification reacting by heating, obtain bolarious nanogold particle and mantoquita and the oleyl amine coordination compound mixed solution of indium salts；Selenium powder is joined in oleyl amine, evacuation, logical nitrogen, after intensification reacting by heating, obtain the oleyl amine solution of the transparent selenium of rufous；The oleyl amine solution of prepared selenium is injected into nanogold particle and mantoquita and the oleyl amine coordination compound mixed solution of indium salts, keeps heated and stirred, obtain the turbid solution of grey black, reheat reaction, centrifugal, after gained precipitation is cleaned, obtain golden brilliant with the heterojunction structure rod-like nano of silver-colored indium selenium.
Description
Technical field
The present invention relates to nanocrystalline, the heterojunction structure rod-like nano crystalline substance especially relating to a kind of gold and silver indium selenium (is designated as Au-
AgInSe2) and synthetic method.
Background technology
Solar energy as the most promising regenerative resource, have reserves huge, without geographical restrictions, clean renewable etc.
Advantage.Under the trend that global energy requirements increases day by day, the research of solar energy and applying has in long-range energy strategy
Critical role.And in the effectively utilization of solar energy, the most extensive and the most great-hearted field is photovoltaic generation, and its operation principle is just
It is to utilize the photovoltaic effect of quasiconductor to convert solar energy into be available for the wide variety of electric energy of the mankind.Nanoscale science and technology
Development, provides necessary theory and technology deposit for exploitation novel solar battery.Such as, with CuInSe2For the I-represented
It is high that III-VI2 chalcopyrite type cpd just has photoelectric transformation efficiency, and stable performance, capability of resistance to radiation character can cause research by force
The concern of personnel, and excited the research enthusiasm of scientist.
As a kind of I-III-VI2Ternary semiconductor material, AgInSe2(Eg=1.19eV) be a kind of absorption coefficient of light high,
The suitable photoelectric conversion material of good stability, energy gap.So, we select AgInSe2Semi-conducting material as Ag base
Construct Au-AgInSe2Heterojunction structure.But, major part research at present is also confined to body phase and thin-film material, homogeneous nanometer
Yardstick AgInSe2The most less (the M.T.Ng of relevant report of preparation and performance study；C.B.Boothroyd；J.J.Vittal
Hybrid One-Pot Synthesis of New-Phase AgInSe2Nanorods[J].J.Am.Chem.Soc.,2006,
128,7118.).It addition, in noble metal-semiconductor compound structure, metal part can improve separation of charge effect, strengthen half
The light of conductor absorbs, thus improves photocatalysis property and the light capture rate (R.Costi of quasiconductor；A.E.Saunders；
E.Elmalem；A.Salant；U.BaninVisible Light-Induced Charge Retention and
Photocatalysis with Hybrid CdSe-Au Nanodumbbells[J].Nano Lett.,2008,8,2982.)。
Simultaneously in metal-semiconductor heterojunction structure, metal can be effectively improved the separation effect of the photo-generate electron-hole pair of semi-conducting material
Rate, and then improve the electricity conversion of semi-conducting material.Meanwhile, metal such as Au or Ag is owing to having surface plasma
Resonance effect, may greatly strengthen near field and absorb, and the light i.e. strengthening semi-conducting material absorbs, and therefore this research has important
Research and application prospect.
Summary of the invention
The heterojunction structure that it is an object of the invention to provide the relatively simple a kind of gold of processing step and silver indium selenium bar-shaped is received
Rice crystalline substance and synthetic method thereof.
Described gold is Au-AgInSe with the heterojunction structure rod-like nano crystalline substance of silver indium selenium2Heterojunction structure rod-like nano is brilliant, with Au
Nano-particle is head end, other end growth AgInSe2The heterojunction structure of nanometer rods.
The synthetic method that described gold is brilliant with the heterojunction structure rod-like nano of silver indium selenium, comprises the following steps:
1) triphenylphosphine auric chloride, silver nitrate and indium chloride being mixed with oleyl amine, evacuation, logical nitrogen, the heating that heats up is anti-
Ying Hou, obtains bolarious nanogold particle and mantoquita and the oleyl amine coordination compound mixed solution of indium salts；
2) selenium powder is joined in oleyl amine, evacuation, logical nitrogen, after intensification reacting by heating, obtain the transparent selenium of rufous
Oleyl amine solution；
3) by step 2) in the oleyl amine solution of selenium for preparing be injected into step 1) nanogold particle and mantoquita and the indium that obtain
The oleyl amine coordination compound mixed solution of salt, keeps heated and stirred, obtains the turbid solution of grey black；
4) by step 3) the turbid solution reacting by heating for preparing, centrifugal, after gained precipitation is cleaned, obtain golden with silver-colored indium selenium
Heterojunction structure rod-like nano brilliant.
In step 1) in, described triphenylphosphine auric chloride, silver nitrate, indium chloride can be (10～64) mg with the proportioning of oleyl amine
: (11～44) mg: (14～56) mg: 10mL；The vacuum of described evacuation is smaller than-0.1MPa；The temperature of described logical nitrogen
Can be 80 DEG C；The condition of described intensification reacting by heating can be to rise after temperature rises to 130 DEG C and maintains reacting by heating 10min～2h again
To 180 DEG C of constant temperature 10min～2h.
In step 2) in, described selenium powder can be (11～44) mg: 10mL with the proportioning of oleyl amine；The vacuum of described evacuation
It is smaller than-0.1MPa；The temperature of described logical nitrogen can be 80 DEG C；The temperature of described intensification reacting by heating can be 180 DEG C, heats up
The time of reacting by heating can be 1～5h.
In step 3) in, described implant operation is preferably in step 1) 180 DEG C of constant temperature 10min～2h of thermostat temperature and step
2) 180 DEG C of constant temperature 1h～5h of thermostat temperature are carried out at the end of simultaneously.
In step 4) in, the temperature of described reacting by heating can be 200～260 DEG C, and the time of reacting by heating can be 0.5h；Institute
Stating cleaning can use dehydrated alcohol to clean at least 3 times with normal hexane, and described dehydrated alcohol can be 1: 1 with the volume ratio of normal hexane.
The present invention is with triphenylphosphine auric chloride, silver nitrate, indium chloride and elemental selenium for reactant, and oleyl amine is reaction dissolvent,
By the nano-particle of previously prepared gold, and the oleyl amine solution of high-temperature digestion selenium is injected into the silver salt containing gold nano grain, indium
In the mixed solution of salt oleyl amine coordination compound, beneficially selenium and golden nanometer particle forms certain interaction force, then high temperature injects
To having dissolved the oleyl amine solution of silver nitrate and indium chloride, the most at high temperature reaction preparation Au-AgInSe2Heterojunction structure is bar-shaped to be received
Meter Jing.
The present invention has the prominent advantages that: 1) utilizes simple effective method to prepare first and is compounded with noble metal and half
The Au-AgInSe of conductor2Heterojunction structure rod-like nano is brilliant, and this material is conducive to improving the opto-electronic conversion performance of material, too
Sun can battery, the field such as photocatalysis has potential application prospect；2) Ag is utilized to form Au-Ag in the growth of Au nano grain surface
Alloy, rises high-temperature after adding selenium source, constructs Au nano-particle and Ag base semiconductor material (AgInSe further2) compound
Structure.3) select the microalloying of the most established gold nano grain and silver, further promote club shaped structure
Formed, thus avoid the situation of the respectively nucleating growth biphase with silver indium selenium of gold when low temperature injects.4) this synthetic method system letter
Single, reaction need not add stabilizer or surfactant, product is more single；5) synthesizer of the present invention is simple, preparation
Mild condition, workable, reaction efficiency is high, and favorable reproducibility has bigger synthesis application prospect.
Accompanying drawing explanation
Fig. 1 is Au-AgInSe2Low amplification scanning electron microscope (SEM) figure that heterojunction structure rod-like nano is brilliant.
Fig. 2 is Au-AgInSe2High-amplification-factor transmission electron microscope (TEM) figure that heterojunction structure rod-like nano is brilliant.
Fig. 3 is Au-AgInSe2The EDX energy spectrogram that heterojunction structure rod-like nano is brilliant.
Fig. 4 is Au-AgInSe2The X-ray powder diffraction figure that heterojunction structure rod-like nano is brilliant.
Fig. 5 is Au-AgInSe2Nanocrystalline structure composition characterizes: (a) angle of elevation annular dark-scanning transmission charge pattern
(HAADF-STEM) figure；(b), (c), (d), (e) figure (a) single nanocrystalline corresponding Surface scan distribution diagram of element (Au, Ag, Se,
In)。
Fig. 6 is Au-AgInSe2The x-ray photoelectron spectroscopy fine scanning spectrogram of the Ag3d in nanocrystalline.
Fig. 7 is Au-AgInSe2The x-ray photoelectron spectroscopy fine scanning spectrogram of the In3d in nanocrystalline.
Fig. 8 is Au-AgInSe2The x-ray photoelectron spectroscopy fine scanning spectrogram of the Se3d in nanocrystalline.In fig. 8,
Curve 1 refers to test the initial data peak of gained；Line 3 and curve 4 that curve 2 obtains after referring to operate swarming are intended again
It is combined into the data peak after a peak；Curve 3 draws Se3d after referring to be fitted spectral line5/2Peak value is 54.2eV；Curve
4 refer to spectral line is fitted after draw Se3d3/2Peak value is 55.0eV；Curve 5 refers to the peak of substrate.
Fig. 9 is Au-AgInSe2The x-ray photoelectron spectroscopy fine scanning spectrogram of the Au4f in nanocrystalline.
Detailed description of the invention
The invention will be further described to combine accompanying drawing below by embodiment.
Embodiment 1
(1) in glove box operate, in 50mL three neck round bottom, weigh add 32mg triphenylphosphine auric chloride,
22mg silver nitrate, 28mg indium chloride, and after measuring the oleyl amine mixing of 10mL, after three-necked bottle is positioned over magnetic force heating stirrer
In, left side side pipe jointing temp is popped one's head in, and middle mouth connects reflux condensing tube, and right side connects anti-mouth plug, and magnetic agitation limit, limit is warming up to 80 DEG C
Evacuation leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time, the system vacuum of making reaches-0.1MPa, then
Be heated to 130 DEG C, and isothermal reaction 0.5h in a nitrogen atmosphere, after be continuously heating to 180 DEG C, keep constant temperature 10min.
(2) in 50mL three neck round bottom, adding 22mg selenium powder and 10mL oleyl amine, room temperature ultrasonic disperse 10min, by three
Neck bottle is positioned in magnetic force heating stirrer, and two side pipes jointing temp probe respectively and anti-mouth plug, middle mouth connects reflux condensing tube, limit
Magnetic agitation limit is warming up to 80 DEG C of evacuation and leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time makes system true
Reciprocal of duty cycle reaches-0.1MPa, is heated to 180 DEG C, and isothermal reaction 1h the most in a nitrogen atmosphere.
(3), after ensureing that in step (1), reaction completes with reaction in step (2) simultaneously, the solution in step (2) is utilized gas
Pressure reduction is injected in the solution of step (1), and maintains 180 DEG C of reaction 10min.
(4) after step (3) has been reacted, it is reheated to 220 DEG C, and isothermal reaction 0.5h.
(5), after reaction terminates, solution is directly centrifuged, gained precipitation again with dehydrated alcohol and normal hexane (volume ratio is 1:
1) mixed liquor cyclic washing is centrifuged 3 times, obtains Au-AgInSe2Nanocrystalline.
The nanocrystalline pattern that as seen from Figure 1 prepared by this method is relatively uniform, and productivity is higher.And one can be entered from Fig. 2
Step determines the nanocrystalline club shaped structure that is of preparation, and length is about at 200-500nm, and diameter is probably at 60-120nm, and dispersibility
Preferably.The elementary composition of heterojunction structure is analyzed by electron spectrum (EDX) as seen from Figure 3, illustrates to deposit in heterojunction structure
At Ag, tetra-kinds of elements of In, Se, Au.Fig. 4 X powder diffraction data can be seen that the gold and silver indium selenium that product comprises pure phase, in figure
Main diffraction peak 25.64,41.93,42.78,49.77,60.72,68.34 ° of AgInSe corresponding respectively to tetragonal phase structure2
(JCPDSNo.35-1099) (112), (220), (204), (312), (400), (316) crystal face.Additionally, diffraction peak in
38.24,44.44,64.64,77.62, the 81.78 different crystal face (JCPDS that can correspond respectively to standard cube center of area Au
No.04-0784), thus we may determine that products therefrom is Au and AgInSe2Composite construction.Can spectrogram by the EDX of Fig. 5
Can be seen that the head end of product based on Au element, and mainly comprises Ag along the nanometer rods of head end growth, tri-kinds of units of In, Se
Element, this may indicate that product is with Au nano-particle as head end, other end growth AgInSe2The heterojunction structure of nanometer rods.By scheming
6, the valence state of product is characterized by the x-ray photoelectron spectroscopy fine scanning spectrogram of Fig. 7, Fig. 8, Fig. 9, and Ag3d finely sweeps
Retouch spectrum, it can be seen that Ag3d5/2Peak value be 368.1eV, with document report AgInSe2In Ag+Match.In3d's is fine
Scanning spectrum, In3d5/2Peak value be 445.0eV, with AgInSe2In In3+It is consistent.The fine scanning spectrum of Se3d, is carried out spectral line
Matching can draw Se3d5/2Peak value be 54.2eV, with AgInSe2In Se2-It is consistent.The fine scanning spectrum of Au4f, Au4f7/2
Peak value be 84.3eV, with document report Au0Matching and further demonstrating product is Au-AgInSe2Nanocrystalline.
Embodiment 2
(1) in glove box operate, in 50mL three neck round bottom, weigh add 10mg triphenylphosphine auric chloride,
11mg silver nitrate, 28mg indium chloride, and after measuring the oleyl amine mixing of 10mL, after three-necked bottle is positioned over magnetic force heating stirrer
In, left side side pipe jointing temp is popped one's head in, and middle mouth connects reflux condensing tube, and right side connects anti-mouth plug, and magnetic agitation limit, limit is warming up to 80 DEG C
Evacuation leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time, the system vacuum of making reaches-0.1MPa, then
Be heated to 130 DEG C, and isothermal reaction 10min in a nitrogen atmosphere, after be continuously heating to 180 DEG C, keep constant temperature 2h.
(2) in 50mL three neck round bottom, adding 11mg selenium powder and 10mL oleyl amine, room temperature ultrasonic disperse 10min, by three
Neck bottle is positioned in magnetic force heating stirrer, and two side pipes jointing temp probe respectively and anti-mouth plug, middle mouth connects reflux condensing tube, limit
Magnetic agitation limit is warming up to 80 DEG C of evacuation and leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time makes system true
Reciprocal of duty cycle reaches-0.1MPa, is heated to 180 DEG C, and isothermal reaction 1h the most in a nitrogen atmosphere.
(3), after ensureing that in step (1), reaction completes with reaction in step (2) simultaneously, the solution in step (2) is utilized gas
Pressure reduction is injected in the solution of step (1), and maintains 180 DEG C of reaction 10min.
(4) after step (3) has been reacted, it is reheated to 200 DEG C, and isothermal reaction 5h.
(5), after reaction terminates, solution is directly centrifuged, gained precipitation again with dehydrated alcohol and normal hexane (volume ratio is 1:
1) mixed liquor cyclic washing is centrifuged 3 times, obtains Au-AgInSe2Nanocrystalline.
Embodiment 3
(1) in glove box operate, in 50mL three neck round bottom, weigh add 32mg triphenylphosphine auric chloride,
22mg silver nitrate, 28mg indium chloride, and after measuring the oleyl amine mixing of 10mL, after three-necked bottle is positioned over magnetic force heating stirrer
In, left side side pipe jointing temp is popped one's head in, and middle mouth connects reflux condensing tube, and right side connects anti-mouth plug, and magnetic agitation limit, limit is warming up to 80 DEG C
Evacuation leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time, the system vacuum of making reaches-0.1MPa, then
Be heated to 130 DEG C, and isothermal reaction 2h in a nitrogen atmosphere, after be continuously heating to 180 DEG C, keep constant temperature 10min.
(2) in 50mL three neck round bottom, adding 22mg selenium powder and 10mL oleyl amine, room temperature ultrasonic disperse 10min, by three
Neck bottle is positioned in magnetic force heating stirrer, and two side pipes jointing temp probe respectively and anti-mouth plug, middle mouth connects reflux condensing tube, limit
Magnetic agitation limit is warming up to 80 DEG C of evacuation and leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time makes system true
Reciprocal of duty cycle reaches-0.1MPa, is heated to 180 DEG C, and isothermal reaction 5h the most in a nitrogen atmosphere.
(3), after ensureing that in step (1), reaction completes with reaction in step (2) simultaneously, the solution in step (2) is utilized gas
Pressure reduction is injected in the solution of step (1), and maintains 180 DEG C of reaction 10min.
(4) after step (3) has been reacted, it is reheated to 240 DEG C, and isothermal reaction 0.5h.
(5), after reaction terminates, solution is directly centrifuged, gained precipitation again with dehydrated alcohol and normal hexane (volume ratio is 1:
1) mixed liquor cyclic washing is centrifuged 3 times, obtains Au-AgInSe2Nanocrystalline.
Embodiment 4
(1) in glove box operate, in 50mL three neck round bottom, weigh add 64mg triphenylphosphine auric chloride,
30mg silver nitrate, 28mg indium chloride, and after measuring the oleyl amine mixing of 10mL, after three-necked bottle is positioned over magnetic force heating stirrer
In, left side side pipe jointing temp is popped one's head in, and middle mouth connects reflux condensing tube, and right side connects anti-mouth plug, and magnetic agitation limit, limit is warming up to 80 DEG C
Evacuation leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time, the system vacuum of making reaches-0.1MPa, then
Be heated to 130 DEG C, and isothermal reaction 0.5h in a nitrogen atmosphere, after be continuously heating to 180 DEG C, keep constant temperature 10min.
(2) in 50mL three neck round bottom, adding 44mg selenium powder and 10mL oleyl amine, room temperature ultrasonic disperse 10min, by three
Neck bottle is positioned in magnetic force heating stirrer, and two side pipes jointing temp probe respectively and anti-mouth plug, middle mouth connects reflux condensing tube, limit
Magnetic agitation limit is warming up to 80 DEG C of evacuation and leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time makes system true
Reciprocal of duty cycle reaches-0.1MPa, is heated to 180 DEG C, and isothermal reaction 2h the most in a nitrogen atmosphere.
(3), after ensureing that in step (1), reaction completes with reaction in step (2) simultaneously, the solution in step (2) is utilized gas
Pressure reduction is injected in the solution of step (1), and maintains 180 DEG C of reaction 1h.
(4) after step (3) has been reacted, it is reheated to 260 DEG C, and isothermal reaction 2h.
(5), after reaction terminates, solution is directly centrifuged, gained precipitation again with dehydrated alcohol and normal hexane (volume ratio is 1:
1) mixed liquor cyclic washing is centrifuged 3 times, obtains Au-AgInSe2Nanocrystalline.
Embodiment 5
(1) in glove box operate, in 50mL three neck round bottom, weigh add 32mg triphenylphosphine auric chloride,
11mg silver nitrate, 14mg indium chloride, and after measuring the oleyl amine mixing of 10mL, after three-necked bottle is positioned over magnetic force heating stirrer
In, left side side pipe jointing temp is popped one's head in, and middle mouth connects reflux condensing tube, and right side connects anti-mouth plug, and magnetic agitation limit, limit is warming up to 80 DEG C
Evacuation leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time, the system vacuum of making reaches-0.1MPa, then
Be heated to 130 DEG C, and isothermal reaction 0.5h in a nitrogen atmosphere, after be continuously heating to 180 DEG C, keep constant temperature 10min.
(2) in 50mL three neck round bottom, adding 11mg selenium powder and 10mL oleyl amine, room temperature ultrasonic disperse 10min, by three
Neck bottle is positioned in magnetic force heating stirrer, and two side pipes jointing temp probe respectively and anti-mouth plug, middle mouth connects reflux condensing tube, limit
Magnetic agitation limit is warming up to 80 DEG C of evacuation and leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time makes system true
Reciprocal of duty cycle reaches-0.1MPa, is heated to 180 DEG C, and isothermal reaction 1h the most in a nitrogen atmosphere.
(3), after ensureing that in step (1), reaction completes with reaction in step (2) simultaneously, the solution in step (2) is utilized gas
Pressure reduction is injected in the solution of step (1), and maintains 180 DEG C of reaction 10min.
(4) after step (3) has been reacted, it is reheated to 240 DEG C, and isothermal reaction 2h.
(5), after reaction terminates, solution is directly centrifuged, gained precipitation again with dehydrated alcohol and normal hexane (volume ratio is 1:
1) mixed liquor cyclic washing is centrifuged 3 times, obtains Au-AgInSe2Nanocrystalline.
Embodiment 6
(1) in glove box operate, in 50mL three neck round bottom, weigh add 32mg triphenylphosphine auric chloride,
22mg silver nitrate, 28mg indium chloride, and after measuring the oleyl amine mixing of 10mL, after three-necked bottle is positioned over magnetic force heating stirrer
In, left side side pipe jointing temp is popped one's head in, and middle mouth connects reflux condensing tube, and right side connects anti-mouth plug, and magnetic agitation limit, limit is warming up to 80 DEG C
Evacuation leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time, the system vacuum of making reaches-0.1MPa, then
Be heated to 130 DEG C, and isothermal reaction 0.5h in a nitrogen atmosphere, after be continuously heating to 180 DEG C, keep constant temperature 0.5h.
(2) in 50mL three neck round bottom, adding 22mg selenium powder and 10mL oleyl amine, room temperature ultrasonic disperse 10min, by three
Neck bottle is positioned in magnetic force heating stirrer, and two side pipes jointing temp probe respectively and anti-mouth plug, middle mouth connects reflux condensing tube, limit
Magnetic agitation limit is warming up to 80 DEG C of evacuation and leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time makes system true
Reciprocal of duty cycle reaches-0.1MPa, is heated to 180 DEG C, and isothermal reaction 1h the most in a nitrogen atmosphere.
(3), after ensureing that in step (1), reaction completes with reaction in step (2) simultaneously, the solution in step (2) is utilized gas
Pressure reduction is injected in the solution of step (1), and maintains 180 DEG C of reaction 0.5h.
(4) after step (3) has been reacted, it is reheated to 240 DEG C, and isothermal reaction 2h.
(5), after reaction terminates, solution is directly centrifuged, gained precipitation again with dehydrated alcohol and normal hexane (volume ratio is 1:
1) mixed liquor cyclic washing is centrifuged 3 times, obtains Au-AgInSe2Nanocrystalline.
Embodiment 7
(1) in glove box operate, in 50mL three neck round bottom, weigh add 32mg triphenylphosphine auric chloride,
22mg silver nitrate, 28mg indium chloride, and after measuring the oleyl amine mixing of 10mL, after three-necked bottle is positioned over magnetic force heating stirrer
In, left side side pipe jointing temp is popped one's head in, and middle mouth connects reflux condensing tube, and right side connects anti-mouth plug, and magnetic agitation limit, limit is warming up to 80 DEG C
Evacuation leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time, the system vacuum of making reaches-0.1MPa, then
Be heated to 130 DEG C, and isothermal reaction 10min in a nitrogen atmosphere, after be continuously heating to 180 DEG C, keep constant temperature 1h.
(2) in 50mL three neck round bottom, adding 22mg selenium powder and 10mL oleyl amine, room temperature ultrasonic disperse 10min, by three
Neck bottle is positioned in magnetic force heating stirrer, and two side pipes jointing temp probe respectively and anti-mouth plug, middle mouth connects reflux condensing tube, limit
Magnetic agitation limit is warming up to 80 DEG C of evacuation and leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time makes system true
Reciprocal of duty cycle reaches-0.1MPa, is heated to 180 DEG C, and isothermal reaction 2h the most in a nitrogen atmosphere.
(3), after ensureing that in step (1), reaction completes with reaction in step (2) simultaneously, the solution in step (2) is utilized gas
Pressure reduction is injected in the solution of step (1), and maintains 180 DEG C of reaction 10min.
(4) after step (3) has been reacted, it is reheated to 220 DEG C, and isothermal reaction 2h.
(5), after reaction terminates, solution is directly centrifuged, gained precipitation again with dehydrated alcohol and normal hexane (volume ratio is 1:
1) mixed liquor cyclic washing is centrifuged 3 times, obtains Au-AgInSe2Nanocrystalline.
Embodiment 8
(1) in glove box operate, in 50mL three neck round bottom, weigh add 26mg triphenylphosphine auric chloride,
22mg silver nitrate, 28mg indium chloride, and after measuring the oleyl amine mixing of 10mL, after three-necked bottle is positioned over magnetic force heating stirrer
In, left side side pipe jointing temp is popped one's head in, and middle mouth connects reflux condensing tube, and right side connects anti-mouth plug, and magnetic agitation limit, limit is warming up to 80 DEG C
Evacuation leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time, the system vacuum of making reaches-0.1MPa, then
Be heated to 130 DEG C, and isothermal reaction 0.5h in a nitrogen atmosphere, after be continuously heating to 180 DEG C, keep constant temperature 10min.
(2) in 50mL three neck round bottom, adding 22mg selenium powder and 10mL oleyl amine, room temperature ultrasonic disperse 10min, by three
Neck bottle is positioned in magnetic force heating stirrer, and two side pipes jointing temp probe respectively and anti-mouth plug, middle mouth connects reflux condensing tube, limit
Magnetic agitation limit is warming up to 80 DEG C of evacuation and leads to nitrogen repetitive operation 3 times, and at least 10min of each pumpdown time makes system true
Reciprocal of duty cycle reaches-0.1MPa, is heated to 180 DEG C, and isothermal reaction 1h the most in a nitrogen atmosphere.
(3), after ensureing that in step (1), reaction completes with reaction in step (2) simultaneously, the solution in step (2) is utilized gas
Pressure reduction is injected in the solution of step (1), and maintains 180 DEG C of reaction 10min.
(4) after step (3) has been reacted, it is reheated to 200 DEG C, and isothermal reaction 2h.
(5), after reaction terminates, solution is directly centrifuged, gained precipitation again with dehydrated alcohol and normal hexane (volume ratio is 1:
1) mixed liquor cyclic washing is centrifuged 3 times, obtains Au-AgInSe2Nanocrystalline.
The present invention is in a nitrogen atmosphere, with triphenylphosphine auric chloride, silver nitrate, indium chloride and elemental selenium for reactant,
Oleyl amine is reaction dissolvent, and the method using high temperature to inject has prepared Au-AgInSe2Heterogeneous structural nano is brilliant.Ag is utilized to exist
The growth of Au nano grain surface forms Au-Ag alloy, rises high-temperature, construct Au nano-particle and Ag further after adding selenium source
Base semiconductor material (AgInSe2) composite construction.Use high temperature to inject simultaneously and avoid gold and silver indium selenium when low temperature injects
The situation of biphase nucleating growth respectively.
Claims (6)
1. the synthetic method that a gold is brilliant with the heterojunction structure rod-like nano of silver indium selenium, it is characterised in that described gold and silver indium selenium
Heterojunction structure rod-like nano crystalline substance is Au-AgInSe2Heterojunction structure rod-like nano is brilliant, and with Au nano-particle as head end, the other end is raw
Long AgInSe2The heterojunction structure of nanometer rods；
Described synthetic method comprises the following steps:
1) triphenylphosphine auric chloride, silver nitrate and indium chloride are mixed with oleyl amine, evacuation, logical nitrogen, after intensification reacting by heating,
Obtain bolarious nanogold particle and silver salt and the oleyl amine coordination compound mixed solution of indium salts；Described triphenylphosphine auric chloride, nitric acid
Silver, indium chloride are (10～64) mg with the proportioning of oleyl amine: (11～44) mg: (14～56) mg: 10mL；Described intensification reacting by heating
Condition be to rise to 180 DEG C of constant temperature 10min～2h again after temperature rises to 130 DEG C and maintains reacting by heating 10min～2h；
2) selenium powder is joined in oleyl amine, evacuation, logical nitrogen, after intensification reacting by heating, obtain the oleyl amine of the transparent selenium of rufous
Solution；Described selenium powder is (11～44) mg: 10mL with the proportioning of oleyl amine；
3) by step 2) in the oleyl amine solution of selenium for preparing be injected into step 1) nanogold particle that obtains and silver salt and indium salts
Oleyl amine coordination compound mixed solution, keeps heated and stirred, obtains the turbid solution of grey black；
4) by step 3) the turbid solution reacting by heating for preparing, centrifugal, after gained precipitation is cleaned, obtain the different of golden and silver-colored indium selenium
Matter structure rod-like nano is brilliant.
The synthetic method that a kind of gold the most as claimed in claim 1 is brilliant with the heterojunction structure rod-like nano of silver indium selenium, it is characterised in that
In step 1) and 2) in, the vacuum of described evacuation is less than-0.1MPa.
The synthetic method that a kind of gold the most as claimed in claim 1 is brilliant with the heterojunction structure rod-like nano of silver indium selenium, it is characterised in that
In step 1) and 2) in, the temperature of described logical nitrogen is 80 DEG C.
The synthetic method that a kind of gold the most as claimed in claim 1 is brilliant with the heterojunction structure rod-like nano of silver indium selenium, it is characterised in that
In step 2) in, the temperature of described intensification reacting by heating is 180 DEG C, and the time of intensification reacting by heating is 1～5h.
The synthetic method that a kind of gold the most as claimed in claim 1 is brilliant with the heterojunction structure rod-like nano of silver indium selenium, it is characterised in that
In step 3) in, described implant operation is in step 1) 180 DEG C of constant temperature 10min～2h of thermostat temperature and step 2) thermostat temperature
180 DEG C of constant temperature 1h～5h are carried out at the end of simultaneously.
The synthetic method that a kind of gold the most as claimed in claim 1 is brilliant with the heterojunction structure rod-like nano of silver indium selenium, it is characterised in that
In step 4) in, the temperature of described reacting by heating is 200～260 DEG C, and the time of reacting by heating is 0.5h；Described cleaning uses nothing
Water-ethanol cleans at least 3 times with normal hexane, and described dehydrated alcohol is 1: 1 with the volume ratio of normal hexane.
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