CN103342380A - Physical preparation method of nano-lead and cadmium sulfide material - Google Patents
Physical preparation method of nano-lead and cadmium sulfide material Download PDFInfo
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Abstract
The invention relates to a physical preparation method of nano-material lead and cadmium sulfide. The physical preparation method comprises the following steps of: taking a mixture of high-purity cadmium, lead and sulfur element powder as a raw material, and sealing in a ball milling tank, wherein the molar ratio of the sum of the cadmium and the lead to the sulfur is (1 plus or minus 0.1): (1 plus or minus 0.1), the molar ratio of the cadmium to the lead is an any value from 0 to 1, and ball mills with different diameters can be simultaneously arranged in the ball milling tank. The physical preparation method disclosed by the invention has the beneficial effects that the prepared lead and cadmium sulfide nano-crystal has uniform chemical components and single structure, the lattice constant and energy gap of the synthesized nano-crystal can be continuously adjusted, and the energy gap can be continuously tuned from near-infrared (1060nm) to mid-infrared (2638nm). The physical preparation method disclosed by the invention has the advantages of simple preparation process, easiness in obtaining the raw material, cheap price, environmental friendliness, capability of realizing large-batch production and the like.
Description
Technical field
The invention belongs to the preparation field of nano material, that be specifically related to is a kind of nano material lead sulfide cadmium (Cd
1-xPb
xS) physical preparation method.
Background technology
In the past twenty years, the potential of the optical property that relies on owing to its unique size of semiconductor nano and widespread use obtains more and more people's concern.Come alloy to change into ternary alloy with the material of binary semiconductor and can form the new class semi-conductor, the lattice parameter of this based semiconductor, energy gap width and other physical function parameters can reach continuous tuning by the variation of chemical ingredients in specific scope.
In recent years, PbS receives very big concern.Very narrow (the E of PbS transition band-gap energy
g=0.27eV), exciton Bohr radius big (18nm) has the scholar by chemical process it to be changed into the adjustable ternary semiconductor of energy gap with other binary sulfide alloy, has reached at the energy gap of wide wavelength region and has regulated.As recently, the optics that the membrane structure of lead sulfide cadmium nanocrystal and mixing demonstrates and photoelectric properties adjustability advantage and obtained vast concern.Yet the solubleness of two kinds of sulfide (CdS and PbS) is very low under room temperature and normal pressure, CdS as wurtzite structure is about 0.017% in the solubleness of the PbS of rock salt structure, form sosoloid among the PbS and at room temperature a large amount of CdS are dissolved in, be infeasible from the thermodynamics angle, because when it might be in metastable state under the conventional preparation condition, solidify.To the metastable state Cd by quenching, high temperature solid-state reactions preparation
1-xPb
xS anneals, with the Cd that is made by chemical bath deposition method
1-xPb
xThe S film is the same, can cause being separated as the thermodynamics expection.Cd by the wet chemical method preparation
1-xPb
xThe S nanocrystal is positioned at the near-infrared wavelength zone at x=0.3～1 time emission peak, and it is very little to be accompanied by the variation of variation energy gap amount of x.In addition, the Cd for preparing by wet chemistry method
1-xPb
xThe lattice parameter of S nanocrystal changes and changes along with the x value hardly, shows the Cd of chemical process preparation
1-xPb
xS nanocrystal composition heterogeneity does not form the Cd of phase structure
1-xPb
xS is nanocrystalline.So take a kind of physical method of replacement to prepare that the single alloy lead sulfide cadmium of surface clean and chemical constitution is nanocrystalline to seem particularly important, mechanical alloying a kind of physical method of producing cleaning surfaces in batches and forming single semiconductor nanocrystal that comes to this.
Summary of the invention
The problems referred to above to be solved by this invention are to provide a kind of physical method at above-mentioned prior art---the mechanical alloying method, form the ternary Cd that gets final product synthetic surface cleaning, homogeneous composition by the conditioned reaction thing
1-xPb
xThe S nanocrystal, synthetic nanocrystalline lattice parameter and energy gap are all adjustable continuously, its energy gap can by near infrared (860nm) continuous tuning in infrared (2638nm), and chemical composition is even, structure is single.
The present invention solves the problems of the technologies described above the technical scheme that adopts: the preparation method of Nano lead sulfide cadmium material includes following steps:
1) mixture with high purity cadmium, lead and element sulphur powder is sealed in the ball grinder as starting material, wherein the mol ratio of cadmium and plumbous sum and sulphur is (1 ± 0.1): (1 ± 0.1), and the mol ratio of cadmium and lead is any value from 0 to 1, ball milling of the different diameter size of packing into simultaneously in the ball grinder;
2) ball grinder after will sealing is placed in the glove box, opens the ball milling cover then, is full of rare gas element in ball grinder, to remove the oxygen in the starting material;
3) ball grinder of good seal is installed on the ball milling grinding machine begins ball milling, make the element powders mechanical alloy change into required semiconductor compound or nanocrystalline;
4) in the different timed interval of ball milling, ball grinder is placed in the glove box, extracts the powder of a small amount of ball milling to carry out structure and optical performance test.
Press such scheme, the molecular formula of described Nano lead sulfide cadmium is Cd
1-xPb
xS, wherein x=0～1.
Press such scheme, the energy gap of described Nano lead sulfide cadmium can change to 860nm from the 2638nm continuous tuning.
Press such scheme, the purity of described high purity cadmium is 99.9%, plumbous purity be 99.9% and the purity of sulphur be 99.9%.
Press such scheme, the sub-diameter of described ball milling is the 2-12 millimeter, and ball milling is set at 1:1～30:1 with raw-material mass ratio.
Press such scheme, described ball mill is the SPEX8000 of U.S. SPEX SpamplePrep company.
Press such scheme, the described ball milling time of step 3) is 0.5-40 hour.
Structural evolution at different ball milling time ball-milled powder is observed by Rigaku powder x-ray diffraction and JEOL2100F high resolution transmission electron microscope (HRTEM).UV3600 ultraviolet-visible-infrared spectrometer that the spectrum of ball-milled powder is to use day island proper Tianjin company to have ISR3100 integrating sphere annex is tested.
Beneficial effect of the present invention is: the nanocrystalline chemical composition of prepared lead sulfide cadmium is even, structure is single, and synthetic nanocrystalline lattice parameter and energy gap are all adjustable continuously, its energy gap can by near infrared (1060nm) continuous tuning in infrared (2638nm).Because its excellent photoelectric performance, but can become a kind of photoelectric device material of practicability, as can be used for fields such as infrared acquisition, infrared remote sensing, infrared sensing.In addition, the present invention has that preparation technology is simple, raw material is easy to get and low price, belong to environmentally friendly type, and can realize advantage such as production in enormous quantities.
Description of drawings
Fig. 1 is the Cd of embodiment 2 gained
0.5Pb
0.5The XRD figure spectrum of S nanocrystalline powder;
Fig. 2 is the Cd of embodiment gained
1-xPb
xThe XRD figure spectrum of S nanocrystalline powder; X=0.5 among the x=0.6 among the x=0.7 among the x=0.8 among the x=0.9 among the x=1 among Fig. 2 (a), Fig. 2 (b), Fig. 2 (c), Fig. 2 (d), Fig. 2 (e), Fig. 2 (f);
Fig. 3 is the Cd of embodiment 2 gained
0.5Pb
0.5The TEM collection of illustrative plates of S nanocrystalline powder;
Fig. 4 is the Cd of embodiment 2 gained
0.5Pb
0.5The HRTEM collection of illustrative plates of S nanocrystalline powder;
Fig. 5 is the Cd of embodiment gained
1-xPb
xThe infrared absorption spectrum of S nanocrystalline powder, x=1 among Fig. 5 (a) wherein, x=0.5 among the x=0.6 among the x=0.7 among the x=0.8 among the x=0.9 among Fig. 5 (b), Fig. 5 (c), Fig. 5 (d), Fig. 5 (e), Fig. 5 (f);
Fig. 6 is the Cd of the present invention's preparation
1-xPb
xRelation between the lattice parameter of S nanocrystalline powder and energy gap and the chemical constitution.
Embodiment
Below in conjunction with preparation example and the collection of illustrative plates of sample, the present invention is further illustrated.
The preparation method of Nano lead sulfide cadmium material includes following steps:
1) mixture with high purity cadmium, lead and element sulphur powder is sealed in the ball grinder as starting material, wherein the mol ratio of cadmium and plumbous sum and sulphur is (1 ± 0.1): (1 ± 0.1), and the mol ratio of cadmium and lead is any value from 0 to 1, ball milling of the different diameter size of packing into simultaneously in the ball grinder;
2) ball grinder after will sealing is placed in the glove box, opens the ball milling cover then, is full of rare gas element in ball grinder, to remove the oxygen in the starting material;
3) ball grinder of good seal is installed on the ball milling grinding machine begins ball milling, make the element powders mechanical alloy change into required semiconductor compound or nanocrystalline;
4) in the different timed interval of ball milling, ball grinder is placed in the glove box, extracts the powder of a small amount of ball milling to carry out structure and optical performance test.
Press such scheme, the molecular formula of described Nano lead sulfide cadmium is Cd
1-xPb
xS, wherein x=0～1.
Press such scheme, the energy gap of described Nano lead sulfide cadmium can change to 860nm from the 2638nm continuous tuning.
Press such scheme, the purity of described high purity cadmium is 99.9%, plumbous purity be 99.9% and the purity of sulphur be 99.9%.
Press such scheme, the sub-diameter of described ball milling is the 2-12 millimeter, and ball milling is set at 1:1～30:1 with raw-material mass ratio.
Press such scheme, described ball mill is the SPEX8000 of U.S. SPEX SpamplePrep company.
Press such scheme, the described ball milling time of step 3) is 0.5-40 hour.
The ternary semiconductor lead sulfide cadmium (Cd that is combined to by mechanical alloy
1-xPb
xS) compound or nanocrystalline has tunable energy gap, and its absorption spectrum can change near infrared region by the mid infrared region continuous tuning; And along with variation (x=0～1), its crystalline structure of its chemical constitution are also adjustable continuously, namely its lattice is along with the increase of Pb content is expanded continuously.
Embodiment 1
It is nanocrystalline that mechanical alloying method prepares CdS, be x=0, stoichiometric ratio by CdS claims sample, for avoiding Cd excessive, then the atomic ratio of Cd and S is set to 0.46:0.54, distinguish weighing Elements C d and each 11.2371g of S powder and 3.7628g then, the error of weighing is ± 0.0002g, the purity of high purity cadmium and sulphur is same under the 99.9%(), place in the ball grinder that is placed with different diameter sizes of balls mill respectively load weighted sample and sealing, the sub-diameter of described ball milling is the 2-12 millimeter, ball milling is set at 1:1～10:1 with raw-material mass ratio, be placed on and open the ball milling cover in the glove box, in ball grinder, be full of rare gas element 30 minutes, to remove the oxygen in the starting material, take out the sealing back, be loaded on the ball mill (SPEX8000) of U.S. SPEX SpamplePrep company and carry out ball milling, ball milling 1～40h, it is nanocrystalline to make the element powder generate single-phase CdS by the mechanical alloying complete reaction; The different timed interval at ball milling is placed at ball grinder in the glove box, extracts the powder of a small amount of ball milling to carry out structure and optical performance test, to avoid oxidation.
Mechanical alloying method prepares Cd
0.5Pb
0.5S is nanocrystalline, i.e. x=0.5; Difference weighing Elements C d, Pb and each 4.3939g of S powder, 8.0992g and 2.5067g, the error that keeps weighing is in ± 0.0002g scope, place in the ball grinder that is placed with different diameter sizes of balls mill load weighted sample and sealing, the sub-diameter of described ball milling is the 2-12 millimeter, ball milling is set at 1:1～10:1 with raw-material mass ratio, be placed on and open the ball milling cover in the glove box, in ball grinder, be full of rare gas element 30 minutes, to remove the oxygen in the starting material, take out the sealing back, be loaded on the ball mill (SPEX8000) of U.S. SPEX SpamplePrep company and carry out ball milling, ball milling is 15 minutes respectively, 30 minutes, 60 minutes, 2 hours, 5 hours, 10 hours, 20 hours, 40 hours, to in glove box, take a sample for the sample of different ball milling time and to carry out structure and optical performance test, to avoid oxidation.Sample to different time sections carries out the XRD test respectively, and its XRD figure is composed as shown in Figure 1, and its infared spectrum is shown in Fig. 5 (f).
The Cd that Fig. 1 goes out for prepared by mechanical alloy
0.5Pb
0.5The XRD figure of S nanocrystalline powder spectrum, this figure has demonstrated that the element powder is through the structural evolution of chemical machinery alloying in whole mechanical milling process, and Fig. 1 a has shown that 30 minutes sample of ball milling has only the synthetic Cd of minority
0.5Pb
0.5S mainly be the diffraction peak of element powder, and Fig. 1 b has shown that 60 minutes sample of ball milling has generated Cd
0.5Pb
0.5S has only minority element powder still to be retained in the sample, synthetic Cd
0.5Pb
0.5S is by cubic structure and hexagonal structure coexistence.After 2 hours, the diffraction peak intensity of single-element powder continues to reduce as Fig. 1 c ball milling, and the ball milling time is more of a specified duration, and plumbous diffraction peak intensity is just more low.As Fig. 1 d, ball milling is after 5 hours, the diffraction peak completely dissolve of element powder, the product of generation is pure Cd fully
0.5Pb
0.5S sosoloid.From 2 hours to 5 hours mechanical milling process, in the wurtzite structure (100), (002), and (101), the diffracted intensity of (102) and (103) crystal face has reduced greatly.As Fig. 1 e, when ball milling reaches 10 hours, the diffraction peak completely dissolve of wurtzite structure, having obtained single cube phase, diffraction peak is from Cd
0.5Pb
0.5{ 111}, { 200}, { 220} and { the 311} crystal face of S.In 2 hours to 10 hours process of ball milling, the structure from the wurtzite structure to the rock salt structure has taken place changed mutually.As Fig. 1 g, prolong ball milling time to 40 hour, the variation of essence does not take place in nanocrystalline structure, and the sample average size of particles is estimated as about 9nm by the Scherrer formula.
Fig. 3 is 40 hours Cd of ball milling
0.5Pb
0.5The nanocrystalline TEM collection of illustrative plates that is diffused in the acetone soln of S, we can see from figure, and most nanoparticles are to be evenly dispersed in the acetone, and their size ranges are 2～8nm, can offer an explanation out single nanoparticle, and the macroparticle of 10～30nm can be observed also.The Cd of some ball millings
0.5Pb
0.5S is nanocrystalline to demonstrate poly-phenomenon, has several particles to condense together to form one by one bunch to be positioned on the copper mesh randomly.
Fig. 4 is 40 hours Cd of ball milling
0.5Pb
0.5The HRTEM collection of illustrative plates of S nanocrystal can clearly be seen lattice fringe from figure, this shows the nanocrystal well-crystallized.The about 9nm of particle A, rock salt structure; Particle B belongs to cubic structure, about 5nm; Particle C, D and F are oval-shaped, belong to rock salt structure, and its short-axis direction size is about 6～8nm; Particle F, G, H, I are rounded, for cubic structure, size is about 2～5nm.Lattice fringe all is derived from rock salt structure { 111} and { crystal face of 200}, Cd from the FFT reciprocal space
0.5Pb
0.5The S nanocrystal { the 111} spacing can be estimated as
Embodiment 3:
Mechanical alloying method prepares Cd
0.3Pb
0.7S is nanocrystalline, i.e. x=0.7; Difference weighing Elements C d, Pb and each 2.3992g of S powder, 10.3193g and 2.2813g, the error of weighing is ± 0.0002g, place in the ball grinder that is placed with different diameter sizes of balls mill load weighted sample and sealing, the sub-diameter of described ball milling is the 2-12 millimeter, ball milling is set at 1:1～10:1 with raw-material mass ratio, be placed on and open the ball milling cover in the glove box, in ball grinder, be full of rare gas element 30 minutes, to remove the oxygen in the starting material, take out the sealing back, be loaded on the ball mill (SPEX8000) of U.S. SPEX SpamplePrep company and carry out ball milling, ball milling 1～40 hour, to in glove box, take a sample for the sample of different ball milling time and to carry out structure and optical performance test, to avoid oxidation, namely obtain Cd
0.3Pb
0.7S is nanocrystalline.Its infared spectrum is shown in Fig. 5 (d), and its XRD figure spectrum is shown in Fig. 2 (d).
Embodiment 4:
Mechanical alloying method prepares Cd
0.1Pb
0.9S is nanocrystalline, i.e. x=0.9; Difference weighing Elements C d, Pb and each 0.7337g of S powder, 12.1730g and 2.0931g, the error of weighing is ± 0.0002g, place in the ball grinder that is placed with different diameter sizes of balls mill load weighted sample and sealing, the sub-diameter of described ball milling is the 2-12 millimeter, ball milling is set at 1:1～10:1 with raw-material mass ratio, be placed on and open the ball milling cover in the glove box, in ball grinder, be full of rare gas element 30 minutes, to remove the oxygen in the starting material, take out the sealing back, be loaded on the ball mill (SPEX8000) of U.S. SPEX SpamplePrep company and carry out ball milling, ball milling 1～40 hour, to in glove box, take a sample for the sample of different ball milling time and to carry out structure and optical performance test, to avoid oxidation, namely obtain Cd
0.1Pb
0.9S is nanocrystalline.Its infared spectrum is shown in Fig. 5 (b), and its XRD figure spectrum is with reference to figure 2(b) shown in.
Embodiment 5:
It is nanocrystalline that mechanical alloying method prepares PbS, i.e. x=1; Difference weighing elements Pb and each 12.9897g of S powder and 2.0102g, the error of weighing is ± 0.0002g, the purity of high purity lead is 99.9%, with load weighted sample place be placed with in the ball grinder of diameter ball milling and the sealing, the sub-diameter of described ball milling is the 2-12 millimeter, ball milling is set at 1:1～10:1 with raw-material mass ratio, be placed on and open the ball milling cover in the glove box, in ball grinder, be full of rare gas element 30 minutes, removing the oxygen in the starting material, take out the sealing back, is loaded on the ball mill (SPEX8000) of U.S. SPEX SpamplePrep company to carry out ball milling, ball milling 1～40h, it is nanocrystalline namely to obtain PbS.After ball milling is finished, ball grinder placed in the glove box take a sample, anti-oxidation.Its infared spectrum shown in Fig. 5 (a), demonstration be the semi-conductive optical type of direct gap, energy gap is 0.44～0.47eV, its XRD figure spectrum is with reference to figure 2(a) shown in.
Fig. 2 is 40 hours nanocrystal Cd of ball milling
1-xPb
xS(x=0.5～1) XRD figure spectrum as can be seen from the figure, is worked as Cd
1-xPb
xWhen the molar ratio of lead atom increases in the S nanocrystal, can be accompanied by continuous lattice dilatation.All Cd
1-xPb
xThe S nanocrystal all belongs to rock salt structure.As can be seen from the figure when the molar fraction of lead atom increased, spacing of lattice or lattice parameter can increase, thereby have greatly influenced the nanocrystalline energy band structure of ball milling, and then became the instrument of regulating semiconductor nano band gap energy in mid infrared region.
Fig. 5 is 40 hours Cd of preparation
1-xPb
xS nanocrystal near infrared and in infrared collection of illustrative plates, obviously PbS is a kind of optical type of direct gap semiconductor.For Cd
1-xPb
xOther spectrum of S (0.5＜x＜1) has one significantly to glide and a slip in the specific absorption of wavelength place band-gap energy, and this is the characteristic feature of indirect gap semiconductor optical spectra.Its energy gap can be by using (α E) at infrared region
1/2Straight line than E determines that the indirect band gap energy is by linear extrapolation slip place (aE)
1/2The edge absorbs to zero to be determined.Fig. 5 shows that specific absorption is very little when photon energy during less than band-gap energy, because these photons are not enough to excite transition of electron in valence band to conduction band.When photon energy during greater than band-gap energy, specific absorption can be earlier slowly growth show unexpected increase then, slowly the specific absorption that increases is derived from indirect band gap, the unexpected surge of specific absorption then is the transition that is derived from direct band gap.Cd
1-xPb
xViolent change takes place in the variation very sensitive and that be accompanied by chemical constitution of the nanocrystalline direct band gap energy of S, and when being increased to 1 as the atomic ratio as Pb from 0.5, the direct band gap energy can expand to mid infrared region near infrared region; The indirect band gap energy is then very slow to the reaction that chemical constitution changes.Can see also that from figure along with the increase of Cd molar fraction, energy of absorption edge is carried out blue shift to short wavelength's direction.So can be that the value of x reaches adjustable continuously from the near infrared to the mid infrared region of band-gap energy or energy of absorption edge by changing chemical constitution.
Fig. 6 has demonstrated direct band gap energy and lattice parameter to the dependence of chemical constitution, from Fig. 6 a as can be seen by changing the Pb molar fraction, can continuous tuning Cd
1-xPb
xS compound or nanocrystalline band-gap energy (energy gap), Pb content is more many, Cd
1-xPb
xThe S band-gap energy is just more little; Match to experimental data can obtain following equation: E
g(x)=1.1954+0.6421x-1.373x
2(eV), x is Cd in the formula
1-xPb
xThe molar fraction of lead among the S, E
gBe Cd
1-xPb
xS is corresponding to the energy gap of certain specific x value.For any given E
gBe worth corresponding x value, can obtain by finding the solution this equation, that is the semi-conductor of any desired energy gap of region of ultra-red, can both obtain by setting its chemical constitution x value.Fig. 6 b has shown the linear relationship between lattice parameter and the Pb molar fraction, and nonlinearities change takes place when chemical constitution changes for other physical properties such as band-gap energy.The formula of the linear relationship between lattice parameter and the Pb molar fraction is
Known that by formula when the Cd atom was replaced by the Pb atom, crystal lattices can expand, the Cd atom that is replaced by the Pb atom is more many, and lattice parameter is just more big.This lattice dilatation has changed Cd
1-xPb
xTherefore the valence band structure of S nanocrystal also is and the concentration dependent Cd of Pb
1-xPb
xThe reason that S nanocrystal band gap reduces.Since the linear relationship of lattice parameter and Pb concentration, the Cd of alloying
1-xPb
xThe lattice parameter of S mixture can reach adjustable continuously according to the molar fraction of Pb, thereby can be continuously, tuning its energy gap size accurately.So any nanocrystal at the desired band-gap energy of infrared wavelength range can pass through alloying Cd
1-xPb
xThe chemical ingredients of S compound designs.
Table 1 has been listed the Cd that several typical cases form
1-xPb
xDirect and the indirect gap value that S is nanocrystalline:
Claims (2)
1. the physical preparation method of Nano lead sulfide cadmium material, the mixture of high purity cadmium, lead and element sulphur powder is sealed in the ball grinder as starting material, wherein the mol ratio of cadmium and plumbous sum and sulphur is (1 ± 0.1): (1 ± 0.1), and the mol ratio of cadmium and lead is any value from 0 to 1, ball milling of the different diameter size of packing into simultaneously in the ball grinder; In the future the lead sulfide cadmium material of this method preparation is applied to opto-electronic device (as infrared sensor, infrared remote sensor, solar cell, infrared eye etc.) all in the claim scope of this patent, and the chemical formula of lead sulfide cadmium is Cd
1-xPb
xS(x=0～1), be a cube rock salt structure, wherein the value of chemical constitution x can change to 1 from 0, and its energy gap can change to 860nm from the 2638nm continuous tuning; Namely can be applied near infrared to infrared any infrared optoelectronic device.
2. the physical preparation method of Nano lead sulfide cadmium material according to claim 1 is characterized in that:
1) used pharmaceutical chemicals is Cd, Pb and S powder, and the total mass of element powder is 15g in the experiment, but is applied in the actual mass production processes, and its quality then is not limited to 15g, desirable any weight;
2) ratio of the mole of Cd+Pb and S meets certain proportion, and the ratio of being got in experiment is 1:1, but can come the adjusting ratio according to the material that will obtain in actual production, is not limited to 1:1, wherein the mol ratio of Cd and Pb (1-x): x(x gets 0～1 arbitrary value);
3) in experiment the quality of ball milling in the ball grinder and with the mass ratio of element powder be 1:1～30:1, the diameter of ball milling is that 2～12mm does not wait; But in actual batch production process, ball milling is not limited to this scope with the ratio of element powder quality, and the diameter of ball milling also can reselect, and is not limited thereto magnitude range;
4) when prepared in laboratory lead sulfide cadmium nano material, element powder mixture weight is got 15g, obtains the nanocrystal of uniform component in 40 hours through ball milling, but in reality is produced in batches the ball milling time be not limited only to 40 hours, desirable random time value;
5) in experiment, after the medicine weighing well, place sealing in the ball grinder, and be placed on glove box interior unlimited 30 minutes, remove the air in the medicine; But in actual production process, ball grinder not necessarily will be put into the glove box sealing; And the time that places glove box to remove air is not limited only to 30 minutes;
6) the lead sulfide cadmium nanocrystal described in the claim 2 makes by mechanical alloying (ball milling) method, used in the experimentation is the SPEX8000M ball mill of U.S. SPEX SpamplePrep company, but in actual production, be not limited only to this model ball mill device, can select the ball mill of disposable type.
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| CN107043130A (en) * | 2017-04-14 | 2017-08-15 | 武汉理工大学 | Solid solution Zinc Tungstate cadmium semiconductor nano and preparation method thereof |
| CN107119321A (en) * | 2017-04-14 | 2017-09-01 | 武汉理工大学 | Ternary semiconductor PbSnS3It is nanocrystalline and preparation method thereof |
| CN110104676A (en) * | 2019-05-17 | 2019-08-09 | 清华大学 | A method of Nano lead sulfide is converted by the lead plaster of waste lead acid battery |
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| CN103787406B (en) * | 2014-02-17 | 2015-03-18 | 河南理工大学 | Preparation method for PbS thermoelectric compound |
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| CN105776324B (en) * | 2014-12-15 | 2018-04-17 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of lead cadmium sulphur nano particle of pyridine parcel and products thereof |
| CN107043130A (en) * | 2017-04-14 | 2017-08-15 | 武汉理工大学 | Solid solution Zinc Tungstate cadmium semiconductor nano and preparation method thereof |
| CN107119321A (en) * | 2017-04-14 | 2017-09-01 | 武汉理工大学 | Ternary semiconductor PbSnS3It is nanocrystalline and preparation method thereof |
| CN110104676A (en) * | 2019-05-17 | 2019-08-09 | 清华大学 | A method of Nano lead sulfide is converted by the lead plaster of waste lead acid battery |
| CN114100784A (en) * | 2021-12-02 | 2022-03-01 | 中国电子科技集团公司第四十六研究所 | Raw material processing method for growing CdS single crystal by PVT method |
| CN114100784B (en) * | 2021-12-02 | 2023-08-22 | 中国电子科技集团公司第四十六研究所 | Raw material treatment method for growing CdS monocrystal by PVT method |
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