CN104532346A - Self-doping localized surface plasma resonance Cu(3-x)P nanocrystalline and preparation method thereof - Google Patents
Self-doping localized surface plasma resonance Cu(3-x)P nanocrystalline and preparation method thereof Download PDFInfo
- Publication number
- CN104532346A CN104532346A CN201510023547.8A CN201510023547A CN104532346A CN 104532346 A CN104532346 A CN 104532346A CN 201510023547 A CN201510023547 A CN 201510023547A CN 104532346 A CN104532346 A CN 104532346A
- Authority
- CN
- China
- Prior art keywords
- preparation
- nanocrystalline
- reaction
- tms
- surface plasma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
-
- 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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Abstract
The invention discloses a self-doping localized surface plasma resonance Cu(3-x)P nanocrystalline and a preparation method thereof. Specifically, the method disclosed by the invention comprises three steps including preparation of a copper precursor, synthesis of Cu(3-x)P nanocrystalline and high-temperature heating aftertreatment; and the Cu(3-x)P nanocrystalline of which the size is 5.3-44.2nm and the localized surface plasma resonance absorption peak is adjustable within a range from 1,390 to 1,710nm, can be obtained by controlling the reaction conditions, the C band (1,530-1,565nm) and L band (1,565-1,625nm) of optical communication are just covered, and the intensity of resonance absorption can be controlled through high-temperature heating so that the material has tremendous application prospect in terms of optical communication and pulse lasers.
Description
Technical field
The present invention relates to technical field of function materials, be specifically related to a kind of auto-doping local surface plasma resonance Cu
3-xp is nanocrystalline and preparation method thereof.
Background technology
When light to by the nano particle that precious metal is formed time, if the body vibration frequency of incident photon frequency and noble metal nano particles conduction electron matches, this nano particle will produce very strong sorption to photon energy, local surface plasma resonance will occur.There is the nanocrystalline of local surface plasma resonance (LSPR:Localized Surface Plasmon Resonance) effect in opto-electronic device, data storage, microscope, solar cell and bio-sensing etc., have huge application prospect.
For research at present the most widely precious metals species (gold and silver, copper), its free carrier concentration is very large, and plasmon absorption peak is in visible-range mostly.Meanwhile, for a given metal nanoparticle, its chemical constitution and pattern are fixed, and local surface plasma resonance frequency is difficult to significantly regulate and control, and which greatly limits applying of surface plasma body resonant vibration.2009, Clemens Burda seminar Late Cambrian Cu
2-xthe nanocrystalline absorption near infrared region of S comes from its local surface plasma resonance and absorbs, and 2011, A. Paul Alivisatos seminar discussed Cu in detail
2-xthe LSPR Forming Mechanism that S is nanocrystalline.Have a large amount of about Cu subsequently
2-xs, Cu
2-xthe LSPR Quality Research of Se is all from testing and confirming that the LSPR of this type of semiconductor material comes from Cu atom and lacks the auto-doping caused in theory.More meaningfully, the concentration of this auto-doping regulates and controls easily through the disappearance degree of regulation and control Cu atom, and this provides possibility near infrared is applied to the LSPR of mid infrared region.
At present, the system of most study is all based on Cu
2-xx(X=S, Se, Te), and rare about Cu
3-xthe research report of P system.Synthesize Cu the earliest
3-xwhen P is nanocrystalline, use tri octyl phosphine as presoma, with copper nanocrystallite or cuprous chloride presoma at high temperature (>300 DEG C) react, but Cu prepared by this method
3-xp is nanocrystalline does not observe local surface plasma resonance phenomenon.2013, phosphine gas was passed in the oleyl amine solution of cuprous chloride by Narayan Pradhan seminar, has synthesized the Cu with LSPR effect first
3-xp nanocrystalline material, its LSPR absorption peak is within the scope of 1800-2100nm.But the phosphine gas used in the method has hypertoxic and wayward.Therefore, find a kind of effectively, the Cu that controls of low toxicity and being easy to
3-xthe synthetic method of P nanocrystalline material has become the focus of this area research and development.
Summary of the invention
In order to solve the problems of the prior art, the object of the present invention is to provide a kind of auto-doping local surface plasma resonance Cu
3-xp is nanocrystalline and preparation method thereof.
To achieve these goals, the present invention adopts following technical scheme:
A kind of auto-doping local surface plasma resonance Cu
3-xthe preparation method that P is nanocrystalline, it comprises the following steps:
1) α-benzoinoxime, trialkyl phosphine and oleyl amine are joined in reaction vessel, stir at 50 ~ 150 DEG C and vacuumize, until α-benzoinoxime dissolves completely, reaction solution bubble-free and be clear shape, obtain copper presoma, the mol ratio of wherein said α-benzoinoxime and trialkyl phosphine is 1:2 ~ 6;
2) in reaction vessel, pass into rare gas element, and be adjusted to the design temperature of 60 ~ 180 DEG C, by three (TMS) phosphine ((TMS)
3p) and octadecylene mix in the copper presoma obtained in rear fast transfer to step 1), and continue reaction 5 ~ 30 minutes, the mol ratio of wherein said three (TMS) phosphines and α-benzoinoxime is 1 ~ 8:12;
3) after completion of the reaction, reaction solution is down to room temperature, by acetone precipitation, the centrifugal aftertreatment discarding upper liquid and vacuum and drain, obtains auto-doping local surface plasma resonance Cu
3-xp is nanocrystalline.
Preferably, α-benzoinoxime described in step 1) be selected from cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide any one, preferred cuprous chloride or cupric chloride, more preferably cuprous chloride.
Preferably, trialkyl phosphine described in step 1) be selected from tributylphosphine, three amyl group phosphines, three hexyl phosphines, three heptyl phosphines, tri octyl phosphine any one, preferred tri octyl phosphine or tributylphosphine, more preferably tri octyl phosphine.
Preferably, carry out at being stirred in 100 DEG C described in step 1).
Preferably, step 2) described in rare gas element be selected from nitrogen, helium, neon any one, preferred nitrogen.
Preferably, step 2) described in design temperature be 60,90,120,150 or 180 DEG C, preferably 120 DEG C.
Preferably, step 2) described in reaction time be 10 minutes.
Preferably, according to the purity requirement of actual production, acetone precipitation described in step 3) can be repeated, centrifugally discard upper liquid and vacuum is drained.
Preferably, according to nanocrystalline concrete pattern requirement, in step 2) described in reacted after, and before step 3) is carried out, temperature risen to 300 DEG C and continue reaction for some time, described time and step 2) described in time of reacting identical.
On the other hand, the present invention also provides the auto-doping local surface plasma resonance prepared according to above-mentioned preparation method Cu
3-xp is nanocrystalline, and its local surface plasma resonance absorption peak is adjustable within the scope of 1390 ~ 1710nm, is of a size of 5.3 ~ 44.2nm, and thickness is about 5nm, and pattern is hexagon or disc, is dissolvable in water in normal hexane, chloroform, toluene equal solvent.
Compared with prior art, the present invention of technique scheme is adopted to have following advantages:
(1) phosphine gas of severe toxicity has been replaced to lower and more manageable liquid phosphorus presoma three (TMS) phosphine of a kind of toxicity by the present invention, reduces the operational risk of practitioner, makes reaction process more controlled, easy;
(2) the present invention (such as 60 DEG C) can prepare the Cu having local surface plasma resonance and absorb at quite low temperatures
3-xp is nanocrystalline, reduces temperature of reaction and danger;
(3) the present invention is mainly through regulating the ratio of cuprous chloride and tri octyl phosphine, the ratio regulating cuprous chloride and three (TMS) phosphine and these three kinds of modes of heat aftertreatment to Cu
3-xthe position at size, shape characteristic and local surface plasmon absorption peak that P is nanocrystalline regulates and controls, and successfully prepares the Cu that size uniformity is controlled
3-xp is nanocrystalline, its local surface plasma resonance absorption peak is adjustable within the scope of 1390-1710nm, just in time cover C-band (1530-1565nm) and the L-band (1565-1625nm) of optical communication, and the intensity of resonance absorption also can be regulated and controled by heat, this material is made to have huge application prospect in optical communication and pulsed laser;
(4) Cu
3-xp is nanocrystalline as a kind of novel auto-doping local surface plasma resonance material, extends the scope of this special performance material, for direction has been widened in further mechanism and applied research.
Accompanying drawing explanation
Fig. 1 is the Cu that CuCl and TOP synthesizes under different ratios condition
3-xthe uv-visible absorption spectra figure that P is nanocrystalline, wherein the mol ratio of CuCl and TOP is respectively 1:2,1:3,1:4,1:5 and 1:6, and temperature of reaction is 120 DEG C, CuCl and (TMS)
3the mol ratio of P is 6:1.
Fig. 2 is the Cu that CuCl and TOP synthesizes under different ratios condition
3-xthe transmission electron microscope picture that P is nanocrystalline, wherein the mol ratio of CuCl and TOP is respectively 1:3,1:4,1:5 and 1:6, and temperature of reaction is 120 DEG C, CuCl and (TMS)
3the mol ratio of P is 6:1.
Fig. 3 is the Cu synthesized under differential responses temperature condition
3-xthe uv-visible absorption spectra figure that P is nanocrystalline, wherein temperature of reaction is 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, 180 DEG C respectively, and the mol ratio of CuCl and TOP is 1:4, CuCl and (TMS)
3the mol ratio of P is 6:1.
Fig. 4 is the Cu synthesized under differential responses temperature condition
3-xthe transmission electron microscope picture that P is nanocrystalline, wherein temperature of reaction is 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, 180 DEG C respectively, and the mol ratio of CuCl and TOP is 1:4, CuCl and (TMS)
3the mol ratio of P is 6:1.
Fig. 5 is CuCl and (TMS)
3the Cu that P synthesizes under different ratios condition
3-xthe uv-visible absorption spectra figure that P is nanocrystalline, wherein CuCl and (TMS)
3the mol ratio of P is 12:1,6:1,3:1,1.5:1, and the mol ratio of CuCl and TOP is 1:4, and temperature of reaction is 120 DEG C.
Fig. 6 is CuCl and (TMS)
3the Cu that P synthesizes under different ratios condition
3-xthe transmission electron microscope picture that P is nanocrystalline, wherein CuCl and (TMS)
3the mol ratio of P is 12:1,6:1,3:1,1.5:1, and the mol ratio of CuCl and TOP is 1:4, and temperature of reaction is 120 DEG C.
Fig. 7 is the Cu that CuCl and TOP synthesizes under different ratios condition
3-xthe nanocrystalline uv-visible absorption spectra figure again after 300 DEG C of heating of P, wherein the mol ratio of CuCl and TOP is respectively 1:2,1:3,1:4,1:5 and 1:6, and temperature of reaction is 120 DEG C, CuCl and (TMS)
3the mol ratio of P is 6:1.
Fig. 8 is the Cu that CuCl and TOP synthesizes under different ratios condition
3-xthe nanocrystalline transmission electron microscope picture again after 300 DEG C of heating of P, wherein the mol ratio of CuCl and TOP is respectively 1:2,1:3,1:4,1:5 and 1:6, and temperature of reaction is 120 DEG C, CuCl and (TMS)
3the mol ratio of P is 6:1.
Fig. 9 is the Cu synthesized under differential responses temperature condition
3-xthe nanocrystalline uv-visible absorption spectra figure again after 300 DEG C of heating of P, wherein temperature of reaction is 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, 180 DEG C respectively, and the mol ratio of CuCl and TOP is 1:4, CuCl and (TMS)
3the mol ratio of P is 6:1.
Figure 10 is the Cu synthesized under differential responses temperature condition
3-xthe nanocrystalline transmission electron microscope picture again after 300 DEG C of heating of P, wherein temperature of reaction is 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, 180 DEG C respectively, and the mol ratio of CuCl and TOP is 1:4, CuCl and (TMS)
3the mol ratio of P is 6:1.
Embodiment
Hereafter will make further instructions the present invention with specific embodiment by reference to the accompanying drawings.
Embodiment 1: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 444mg(1.2mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 1, transmission electron microscope as shown in Figure 2 for its UV-Vis absorption spectrum.
Embodiment 2: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 666mg(1.8mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 1, its transmission electron microscope picture as shown in Figure 2 for its UV-Vis absorption spectrum.
Embodiment 3: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 1, its transmission electron microscope picture as shown in Figure 2 for its UV-Vis absorption spectrum.
Embodiment 4: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 1110mg(3.0mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 1, its transmission electron microscope picture as shown in Figure 2 for its UV-Vis absorption spectrum.
Embodiment 5: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 1332mg(3.6mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 1, its transmission electron microscope picture as shown in Figure 2 for its UV-Vis absorption spectrum.
Embodiment 6: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 60 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 3, its transmission electron microscope picture as shown in Figure 4 for its UV-Vis absorption spectrum.
Embodiment 7: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5 mL oleyl amines join in 25mL there-necked flask, stir and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 90 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 3, its transmission electron microscope picture as shown in Figure 4 for its UV-Vis absorption spectrum.
Embodiment 8: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5 mL oleyl amines join in 25mL there-necked flask, stir and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 150 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 3, its transmission electron microscope picture as shown in Figure 4 for its UV-Vis absorption spectrum.
Embodiment 9: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5 mL oleyl amines join in 25mL there-necked flask, stir and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 180 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 3, its transmission electron microscope picture as shown in Figure 4 for its UV-Vis absorption spectrum.
Embodiment 10: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5 mL oleyl amines join in 25mL there-necked flask, stir and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 125mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.05mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 5, its transmission electron microscope picture as shown in Figure 6 for its UV-Vis absorption spectrum.
Embodiment 11: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 500mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.2mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 5, its transmission electron microscope picture as shown in Figure 6 for its UV-Vis absorption spectrum.
Embodiment 12: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 1000mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.4mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 5, its transmission electron microscope picture as shown in Figure 6 for its UV-Vis absorption spectrum.
Embodiment 13: disc auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 666mg(1.8mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes, then temperature is risen to 300 DEG C and react 10 minutes again;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 7, its transmission electron microscope picture as shown in Figure 8 for its UV-Vis absorption spectrum.
Embodiment 14: disc auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes, then temperature is risen to 300 DEG C and react 10 minutes again;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 7, its transmission electron microscope picture as shown in Figure 8 for its UV-Vis absorption spectrum.
Embodiment 15: disc auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg cuprous chloride (0.6mmol), 1110mg(3.0mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes, then temperature is risen to 300 DEG C and react 10 minutes again;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 7, its transmission electron microscope picture as shown in Figure 8 for its UV-Vis absorption spectrum.
Embodiment 16: disc auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 1332mg(3.6mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes, then temperature is risen to 300 DEG C and react 10 minutes again;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 7, its transmission electron microscope picture as shown in Figure 8 for its UV-Vis absorption spectrum.
Embodiment 17: disc auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 60 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes, then temperature is risen to 300 DEG C and react 10 minutes again;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 9, its transmission electron microscope picture as shown in Figure 10 for its UV-Vis absorption spectrum.
Embodiment 18: disc auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 90 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes, then temperature is risen to 300 DEG C and react 10 minutes again;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 9, its transmission electron microscope picture as shown in Figure 10 for its UV-Vis absorption spectrum.
Embodiment 19: disc auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 150 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes, then temperature is risen to 300 DEG C and react 10 minutes again;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 9, its transmission electron microscope picture as shown in Figure 10 for its UV-Vis absorption spectrum.
Embodiment 20: disc auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 180 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes, then temperature is risen to 300 DEG C and react 10 minutes again;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline, and as shown in Figure 9, its transmission electron microscope picture as shown in Figure 10 for its UV-Vis absorption spectrum.
Embodiment 21: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 102mg(0.6mmol) cupric chloride, 888mg(2.4mmol) tri octyl phosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline.
Embodiment 22: hexagon auto-doping local surface plasma resonance Cu
3-xthe preparation that P is nanocrystalline.
1) preparation of copper presoma: by 60mg(0.6mmol) cuprous chloride, 486mg(2.4mmol) tributylphosphine and 5mL oleyl amine join in 25mL there-necked flask, stirs and vacuumize 1 hour, obtain copper presoma at 100 DEG C, stand-by;
2) in there-necked flask, passing into nitrogen, and adjust the temperature to 120 DEG C, is (TMS) of 10% by 250mg mass concentration
3p hexane solution (wherein (TMS)
3the consumption of P is about 0.1mmol) and 1mL octadecylene mix and after vacuum drains normal hexane, be injected into fast in above-mentioned copper presoma with syringe, and continue reaction 10 minutes;
3) after completion of the reaction, room temperature is down in airbath, adds acetone to reaction solution and becomes muddy, after centrifuge, discard upper liquid; Use n-hexane dissolution again, centrifugal after adding acetone, discard upper liquid.The product obtained is drained under vacuo, in glove box, preserves the Cu existed with black solid form
3-xp is nanocrystalline.
Claims (10)
1. an auto-doping local surface plasma resonance Cu
3-xthe preparation method that P is nanocrystalline, it comprises the following steps:
1) α-benzoinoxime, trialkyl phosphine and oleyl amine are joined in reaction vessel, stir at 50 ~ 150 DEG C and vacuumize, until α-benzoinoxime dissolves completely, reaction solution bubble-free and be clear shape, obtain copper presoma, the mol ratio of wherein said α-benzoinoxime and trialkyl phosphine is 1:2 ~ 6;
2) in reaction vessel, rare gas element is passed into, and be adjusted to the design temperature of 60 ~ 180 DEG C, three (TMS) phosphines and octadecylene are mixed in the copper presoma obtained in rear fast transfer to step 1), and continuing reaction 5 ~ 30 minutes, the mol ratio of wherein said three (TMS) phosphines and α-benzoinoxime is 1 ~ 8:12;
3) after completion of the reaction, reaction solution is down to room temperature, by acetone precipitation, the centrifugal aftertreatment discarding upper liquid and vacuum and drain, obtains auto-doping local surface plasma resonance Cu
3-xp is nanocrystalline.
2. preparation method according to claim 1, is characterized in that, α-benzoinoxime described in step 1) be selected from cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide any one.
3. preparation method according to claim 1, is characterized in that, trialkyl phosphine described in step 1) be selected from tributylphosphine, three amyl group phosphines, three hexyl phosphines, three heptyl phosphines, tri octyl phosphine any one.
4. preparation method according to claim 1, is characterized in that, carries out at being stirred in 100 DEG C described in step 1).
5. preparation method according to claim 1, is characterized in that, step 2) described in rare gas element be selected from nitrogen, helium, neon any one.
6. preparation method according to claim 1, is characterized in that, step 2) described in design temperature be 60,90,120,150 or 180 DEG C.
7. preparation method according to claim 1, is characterized in that, step 2) described in reaction time be 10 minutes.
8. preparation method according to claim 1, is characterized in that, repeats acetone precipitation described in step 3), centrifugally discards upper liquid and vacuum is drained.
9. preparation method according to claim 1, it is characterized in that, in step 2) described in reacted after, and before step 3) is carried out, temperature risen to 300 DEG C and continue reaction for some time, described time and step 2) described in time of reacting identical.
10. the auto-doping local surface plasma resonance Cu for preparing of preparation method according to any one of claim 1 to 9
3-xp is nanocrystalline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510023547.8A CN104532346B (en) | 2015-01-16 | 2015-01-16 | A kind of auto-dope local surface plasma resonance Cu3‑xP is nanocrystalline and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510023547.8A CN104532346B (en) | 2015-01-16 | 2015-01-16 | A kind of auto-dope local surface plasma resonance Cu3‑xP is nanocrystalline and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104532346A true CN104532346A (en) | 2015-04-22 |
| CN104532346B CN104532346B (en) | 2017-11-28 |
Family
ID=52847958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510023547.8A Active CN104532346B (en) | 2015-01-16 | 2015-01-16 | A kind of auto-dope local surface plasma resonance Cu3‑xP is nanocrystalline and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104532346B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078114B (en) * | 2019-05-16 | 2021-06-18 | 苏州大学 | Metal oxide nanocrystalline with localized surface plasma resonance absorption and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851498A (en) * | 2010-06-08 | 2010-10-06 | 济南大学 | Method for converting water solubility for reducing biotoxicity of luminous quantum dot synthesized by organic phase |
-
2015
- 2015-01-16 CN CN201510023547.8A patent/CN104532346B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851498A (en) * | 2010-06-08 | 2010-10-06 | 济南大学 | Method for converting water solubility for reducing biotoxicity of luminous quantum dot synthesized by organic phase |
Non-Patent Citations (3)
| Title |
|---|
| GOUTAM MANNA等: "Semiconducting and Plasmonic Copper Phosphide Platelets", 《ANGEW. CHEM. INT. ED.》 * |
| LUCA DE TRIZIO等: "Size-Tunable, Hexagonal Plate-like Cu3P and Janus-like Cu-Cu3P Nanocrystals", 《ACSNANO》 * |
| MD HOSNAY MOBAROK等: "Phase-Pure Crystalline Zinc Phosphide Nanoparticles: Synthetic Approaches and Characterization", 《CHEM. MATER.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104532346B (en) | 2017-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107934916B (en) | Preparation method of stable lead-free all-inorganic double perovskite A2 BB' X6 nanocrystal | |
| Muthuswamy et al. | Facile synthesis of germanium nanoparticles with size control: microwave versus conventional heating | |
| Wang et al. | Alternative synthesis of CuFeSe2 nanocrystals with magnetic and photoelectric properties | |
| Jiang et al. | Elemental solvothermal reaction to produce ternary semiconductor CuInE2 (E= S, Se) nanorods | |
| Xie et al. | Tuning and locking the localized surface plasmon resonances of CuS (covellite) nanocrystals by an amorphous CuPd x S shell | |
| US7892519B2 (en) | Rapid synthesis and size control of chalcopyrite-based semi-conductor nanoparticles using microwave irradiation | |
| Ye et al. | Controllable emission bands and morphologies of high-quality CsPbX 3 perovskite nanocrystals prepared in octane | |
| Atkins et al. | An efficient microwave-assisted synthesis method for the production of water soluble amine-terminated Si nanoparticles | |
| CN108546994A (en) | A kind of two phosphide atom crystal of two-dimentional three selenizing and its preparation method and application | |
| CN104894635A (en) | Size-controlled copper antimony sulfur nano crystal material and preparation method thereof | |
| CN105565379B (en) | Cu3SbS4The controllable method for preparing of nanocrystalline material | |
| Singh et al. | Selective phase transformation of wurtzite Cu2ZnSn (SSe) 4 (CZTSSe) nanocrystals into zinc-blende and kesterite phases by solution and solid state transformations | |
| CN101857265A (en) | Method for preparing metal sulfide nanocrystalline | |
| CN105540663A (en) | Controllable preparation method of CuSbS2 nanocrystalline material | |
| Zao et al. | Convenient synthesis of silver nanoplates with adjustable size through seed mediated growth approach | |
| Li et al. | Simple continuous-flow synthesis of Cu–In–Zn–S/ZnS and Ag–In–Zn–S/ZnS core/shell quantum dots | |
| Flynn et al. | Continuous flow mesofluidic synthesis of Cu2ZnSnS4 nanoparticle inks | |
| Mandal et al. | Molecular Precursors for CdS Nanoparticles: Synthesis and Characterization of Carboxylate− Thiourea or− Thiosemicarbazide Cadmium Complexes and Their Decomposition | |
| Yarur Villanueva et al. | Binary Cu2–x S Templates Direct the Formation of Quaternary Cu2ZnSnS4 (Kesterite, Wurtzite) Nanocrystals | |
| CN104532346A (en) | Self-doping localized surface plasma resonance Cu(3-x)P nanocrystalline and preparation method thereof | |
| Chang et al. | Investigate the reacting flux of chemical bath deposition by a continuous flow microreactor | |
| CN106830052B (en) | The preparation method and products obtained therefrom of three-dimensional flower-shaped nano zinc oxide material | |
| WO2013185453A1 (en) | Method for preparing monoclinic ga2s3 crystal and use in optics thereof | |
| Xun et al. | Hydrothermal synthesis of complex fluorides NaHoF4 and NaEuF4 with fluorite structures under mild conditions | |
| Kreider et al. | Two-step continuous-flow synthesis of CuInSe 2 nanoparticles in a solar microreactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |