CN101570893B - Method for preparing semi-conductor material by regulation and control of gas slowly catalysis combined with organic molecular film - Google Patents
Method for preparing semi-conductor material by regulation and control of gas slowly catalysis combined with organic molecular film Download PDFInfo
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- CN101570893B CN101570893B CN2009100651389A CN200910065138A CN101570893B CN 101570893 B CN101570893 B CN 101570893B CN 2009100651389 A CN2009100651389 A CN 2009100651389A CN 200910065138 A CN200910065138 A CN 200910065138A CN 101570893 B CN101570893 B CN 101570893B
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Abstract
The invention belongs to the technical field of biomimetic synthesis and monomolecular film, in particular to a method for preparing a semi-conductor material by regulation and control of gas slowly catalysis combined with an organic molecular film. The semi-conductor material is AS, wherein A is Cd or Pb; thiacetamide or thiourea is taken to be mixed with aqueous solution of A salt at room temperature; after impurities on the surface of the solution are removed, chloroformic solution of PBA is dripped on the surface of the mixed solution to keep standing until surface pressure of the PBA molecular film is stabilized to 8 to 12 mN/m; hydrochloric acid or ammonia spirit is placed close to the mixed solution to be placed in a closed environment to sufficiently react, or the mixed solution isdirectly placed stand at room temperature for 6 to 9 days without any reagent to obtain the semi-conductor material. The method can prepare sulphide in different crystal forms and different types thr ough changing different catalytic gases and reaction precursors, has simple process, low requirement on equipment and low cost, and is a good method for realizing preparation and orderly arrangement of functional materials with large-scale appearance and controllable crystal forms.
Description
(1) technical field
The invention belongs to bionical synthetic and unimolecular film technical field, particularly the regulation and control of gas slowly catalyzed combination organic molecular film prepare the method for semiconductor material.
(2) background technology
By utilizing unimolecular film or LB (langmuir-Blodgett) film as template simulation biomineralization process, people study multiple mineral crystal.In recent years, PbS and CdS have been subjected to paying close attention to widely as important semiconductor material.Research and utilization eicosanoic acid unimolecular film induced growth is arranged pattern even, along the trilateral PbS crystal of (111) high preferred orientation growth; Utilize PVK as organic formwork, by regulation and control H
2Conditions such as the feeding amount of S gas, reactant concn, temperature of reaction have obtained the PbS crystal of a series of different-shapes.These researchs adopt organic molecule and polymer molecule film as organic formwork mostly, and employing feeds H mostly
2The mode of S has inevitably been brought certain environmental pollution; Simultaneously owing to only rely on the inducing action of organic molecular film, and do not make full use of the regulating and controlling effect of kinetic factor to crystal growth, make the structure of this type of material and the control measures of pattern are seemed single, cause the controllability of the pattern of this type of prepared crystalline material and structure obviously not enough.
(3) summary of the invention
The object of the present invention is to provide a kind of gas slowly catalyzed combination organic molecular film regulation and control to prepare the method for semiconductor material, to overcome pattern and the uncontrollable defective of crystal formation that existing method easily produces environmental pollution, functional materials.
The technical solution used in the present invention is as follows:
The regulation and control of gas slowly catalyzed combination organic molecular film prepare the method for semiconductor material, described semiconductor material is AS, A is Cd or Pb, getting thioacetamide or thiocarbamide mixes under room temperature with the aqueous solution of A salt, remove drip PBA behind the solution surface impurity chloroformic solution in the mixing solutions surface, it is stable to 8-12mN/m to leave standstill the surface pressure for the treatment of the PBA molecular film; Place hydrochloric acid or ammonia soln and all place fully reaction or do not place any reagent and directly under normal temperature, leave standstill and promptly got described semiconductor material in 6-9 days of closed environment in that mixing solutions is other.
If described semiconductor material is CdS, the concentration ratio preferably of the aqueous solution of thioacetamide and Cd salt is 1: 0.1-1; And carry out catalyzed reaction at the other hydrochloric acid soln of placing of mixing solutions; And preferably under closed environment, react.
If described semiconductor material is PbS, the concentration ratio preferably of the aqueous solution of thioacetamide and Pb salt is 1: 0.1-1; React at the other ammonia soln of placing of mixing solutions.
The strength of solution of thioacetamide is 0.01mol/L.If use thiocarbamide, strength of solution and consumption can carry out with reference to thioacetamide.
The concentration of the chloroformic solution of PBA is 0.1-0.5mg/mL.
This method is that the water-soluble salt solution of thioacetamide or thiocarbamide and Cd or Pb such as cadmium nitrate or lead nitrate are mixed under the room temperature situation, specifically can insert in the tetrafluoroethylene sulculus that is placed in the moisture eliminator, draw the clear film of impurity that may exist several times with syringe needle then.The PBA that the surface drips is that the amount of polyphenyl methyl aspartic acid can be through calculating, and the surface-area of this and used tetrafluoroethylene sulculus is relevant, specifically can be according to people such as Yang at J.Phys.Chem.195, and 99, the method for using among the 5500-5504 is calculated.Leave standstill in the process, allow chloroform volatilize on the one hand, on the other hand, PBA fully sprawls in solution surface and forms unitary film and obtain stable surface pressure.At other hydrochloric acid or the ammoniacal liquor placed of tetrafluoroethylene sulculus, the process that the hermetically drying device fully reacts is to allow hydrochloric acid or ammoniacal liquor volatilization be diffused into the hydrolysis of mixing solutions spatial induction thioacetamide discharge the process that sulfonium ion forms Cadmium Sulfide/lead sulfide.Standing and reacting also can obtain this type of material at normal temperatures, but more airtight catalytic environment of time will grow, and to the adjustability of pattern and structure slightly a little less than.The key of inventive point is that this kinetic control effect of hydrolysis with the inducing action of molecular film and gaseous diffusion catalysis thioacetamide or thiocarbamide combines and has realized the Modulatory character of structure and pattern.
The amount of employed hydrochloric acid and ammoniacal liquor and concentration depend on the amount of product of preparation and the size of reaction compartment, and these those skilled in the art can control and adjust voluntarily.
In the present invention, the Cadmium Sulfide that utilizes the hydrochloric acid inducing catalysis to make has the polycrystalline particle about the 70nm that obviously in order (linearity) arrange; Then the crystal formation effect is poor slightly with material that ammoniacal liquor makes; The crystal morphology that the nature hydrolysising condition obtains is equal to consistent under the hydrochloric acid catalysis situation with size.
Described lead sulfide is the 100nm left and right sides square of monocrystalline, tetragonal, the growth of (200) planar orientation under natural hydrolysis situation.Under the ammonia catalysis situation, prepare polycrystalline particle with linearly aligned 100nm.Use hydrochloric acid catalysis, obtain consistent under result and the natural hydrolysising condition.
In addition, present method can also be by the pattern of recently controlling product and the structure of thioacetamide or thiocarbamide and Pb or Cd salt in the change mixing solutions.The big more product of thioacetamide or thiocarbamide proportion is intensive more, otherwise product is sparse more, but pattern does not have difference.
As seen, the present invention is by introducing the hydrolysis of gaseous diffusion catalysis precursor, reactant concn on regulation and control solution and the interface, thereby realize dynamic (dynamical) purpose of control crystal growth, the stay in place form information that the binding molecule film provides, reach the pattern in the regulation and control mineral crystal process of growth and the purpose of structure, finally realize the pattern of inorganic crystal material and the controlled preparation of structure.Therefore the present invention can prepare different crystal forms and different types of sulfide by changing different catalytic gas and reaction precursor body, and method technology of the present invention is simple, low for equipment requirements, with low cost, be to realize the functional materials preparation of large-area pattern and crystal with controllable crystal forms and the good method of ordered arrangement.
(4) description of drawings
Fig. 1 is the low power sem photograph (SEM) of embodiment 1 product;
Fig. 2 is the low power transmission electron microscope picture (TEM) of embodiment 1 product;
Fig. 3 is the low high-resolution electron microscopy diffraction fringe figure (HREM) of embodiment 1 product;
Fig. 4 is the low power sem photograph (SEM) of embodiment 2 products;
Fig. 5 is the low power transmission electron microscope picture (TEM) of embodiment 2 products;
Fig. 6 is the low high-resolution electron microscopy diffraction fringe figure (HREM) of embodiment 2 products;
Fig. 7 is the X-ray diffractogram (XRD) of embodiment 2 products;
Fig. 8 is the low power transmission electron microscope picture (TEM) of embodiment 3 products;
Fig. 9 is the low high-resolution electron microscopy diffraction fringe figure (HREM) of embodiment 3 products;
Figure 10 is the X-ray diffractogram (XRD) of embodiment 3 products.
(5) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
(1) with 0.308g Cd (NO
3)
2.4H
2O (purity 99.9%) is dissolved in the deionized water, makes the Cd (NO of 0.001M
3)
2Solution;
(2) with 0.075g C
2H
5NS (purity 99.9%) is dissolved in the deionized water, makes the C of 0.001M
2H
5NS solution;
(3) chloroformic solution of preparation 0.3mg/ml PBA;
(4) each 40ml of solution with step (1) and step (2) preparation mixes about 23 ℃, inserts (the long-pending 35.1cm of being of solution surface in the tetrafluoroethylene sulculus that is placed in the moisture eliminator
2), draw the clear film of impurity that may exist several times with syringe needle then.The surface drips the PBA 11 μ L of step (3) preparation, leaves standstill to allow the chloroform volatilization in 30 minutes, and PBA fully sprawls the formation unitary film in solution surface, stable to surface pressure be 8mN/m.Taken advantage of 20ml 1.8%wt hydrochloric acid (20ml water adds 1ml 36%wt concentrated hydrochloric acid) other placement of tetrafluoroethylene sulculus, the hermetically drying device allows the hydrochloric acid volatilization be diffused into mixing solutions spatial induction thioacetamide hydrolysis release sulfonium ion and forms Cadmium Sulfide then.
Analytical test shows, sees Fig. 1-Fig. 3, and product is mainly by large-area class disk shape granulometric composition (Fig. 1), and size is even, and yardstick is about 70nm, and several particles are linked to be string and are the linear array (see figure 2).According to high resolution TEM (see figure 3), the Cadmium Sulfide of preparation is a polycrystalline structure.
Embodiment 2
(1) with 0.3331g Pb (NO
3)
2.4H
2O (purity 99.9%) is dissolved in the deionized water, makes the Pb (NO of 0.001M
3)
2Solution;
(2) with 0.075g C
2H
5NS (purity 99.9%) is dissolved in the deionized water, makes the C of 0.001M
2H
5NS solution;
(3) the PBA chloroformic solution of preparation 0.3mg/ml.
(4) each 40ml of solution with step (1) and step (2) preparation mixes about 23 ℃, inserts (the long-pending 35.1cm of being of solution surface in the tetrafluoroethylene sulculus that is placed in the moisture eliminator
2), draw the clear film of impurity that may exist several times with syringe needle then.The surface drips the PBA 11 μ L of step (3) preparation, leaves standstill to allow the chloroform volatilization in 30 minutes, and PBA fully sprawls the formation unitary film in solution surface, stable to surface pressure be 10mN/m.Take advantage of 200ml weak ammonia (200ml water adds the weak ammonia that 160 μ L 28%wt strong aquas are made 0.0224%w) other placement of tetrafluoroethylene sulculus, the hermetically drying device allows the ammonia volatilization be diffused into the hydrolysis of mixing solutions spatial induction thioacetamide and discharges sulfonium ion formation lead sulfide then.
Analytical test shows that the crystal big area distributes, and particle size is homogeneous comparatively, sees Fig. 4; About granular size 100nm, and particle alignment is linear, sees Fig. 5; The crystal structure degree is higher, as Fig. 6; Crystal is a polycrystalline, sees Fig. 6-7.
Embodiment 3
(1) with 0.3331g Pb (NO
3)
2.4H
2O (purity 99.9%) is dissolved in the deionized water, makes the Pb (NO of 0.001M
3)
2Solution;
(2) with 0.075g C
2H
5NS (purity 99.9%) is dissolved in the deionized water, makes the C of 0.001M
2H
5NS solution;
(3) chloroformic solution of preparation 0.3mg/ml PBA.
(4) each 40ml of solution with step (1) and step (2) preparation mixes about 23 ℃, inserts (the long-pending 35.1cm of being of solution surface in the tetrafluoroethylene sulculus that is placed in the moisture eliminator
2), draw the clear film of impurity that may exist several times with syringe needle then.The surface drips the PBA 11 μ L of step (3) preparation, be statically placed in the atmosphere thioacetamide naturally hydrolysis very slowly discharged sulfonium ion in 7 days and form lead sulfide.
Analytical test shows that the PbS crystal is square shape, and size is comparatively even, and yardstick is in 100nm left and right sides (see figure 8), and is along (200) planar orientation growth (seeing Fig. 9-10).
Embodiment 4
Use 200ml weak ammonia (200ml water adds the weak ammonia that 160 μ L 28%wt strong aquas are made 0.0224%w) to substitute hydrochloric acid and react, other are with embodiment 1, and what obtain is the film of very intensive very little granulometric composition.Ammonia concn also can change at 5 μ L-200 μ L, and the result who obtains is very little membrana granulosa, and it is fast that the big reaction of ammonia concn is carried out.
Embodiment 5
The surface drip be statically placed in behind the PBA 11 μ L of step (3) preparation in the atmosphere thioacetamide naturally hydrolysis very slowly discharged sulfonium ion in 7 days and form Cadmium Sulfide, other are with embodiment 1.The crystal morphology that obtains is equal to consistent under the hydrochloric acid catalysis situation with size.
Embodiment 6
Replace ammonia soln with the hydrochloric acid soln of 20ml 1.8%wt, other are with embodiment 2, consistent under the PbS pattern that obtains and the natural hydrolysising condition.
Claims (8)
1. the regulation and control of gas slowly catalyzed combination organic molecular film prepare the method for semiconductor material, described semiconductor material is AS, A is Cd or Pb, it is characterized in that, the solution of getting thioacetamide or thiocarbamide mixes under room temperature with the aqueous solution of A salt, remove drip PBA behind the solution surface impurity chloroformic solution in the mixing solutions surface, it is stable to 8-12mN/m to leave standstill the surface pressure for the treatment of the PBA molecular film; Place hydrochloric acid or ammonia soln and all place fully reaction or do not place any reagent and directly under normal temperature, leave standstill and promptly got described semiconductor material in 6-9 days of closed environment in that mixing solutions is other.
2. gas slowly catalyzed combination organic molecular film regulation and control as claimed in claim 1 prepare the method for semiconductor material, it is characterized in that described semiconductor material is CdS, and the concentration ratio of the aqueous solution of the solution of thioacetamide and Cd salt is 1: 0.1-1.
3. gas slowly catalyzed combination organic molecular film regulation and control as claimed in claim 2 prepare the method for semiconductor material, it is characterized in that, place closed environment fully to react.
4. gas slowly catalyzed combination organic molecular film regulation and control as claimed in claim 3 prepare the method for semiconductor material, it is characterized in that, react at the other hydrochloric acid soln of placing of mixing solutions.
5. gas slowly catalyzed combination organic molecular film regulation and control as claimed in claim 1 prepare the method for semiconductor material, it is characterized in that described semiconductor material is PbS, and the concentration ratio of the aqueous solution of the solution of thioacetamide and Pb salt is 1: 0.1-1.
6. gas slowly catalyzed combination organic molecular film regulation and control as claimed in claim 5 prepare the method for semiconductor material, it is characterized in that, react at the other ammonia soln of placing of mixing solutions.
7. regulate and control to prepare the method for semiconductor material as the described gas slowly catalyzed combination of one of claim 1-6 organic molecular film, it is characterized in that the strength of solution of thioacetamide is 0.01mol/L.
8. gas slowly catalyzed combination organic molecular film regulation and control as claimed in claim 7 prepare the method for semiconductor material, it is characterized in that the concentration of the chloroformic solution of PBA is 0.1-0.5mg/mL.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1719578A (en) * | 2005-04-29 | 2006-01-11 | 同济大学 | A kind of method for preparing IIB family semiconductor sulfuration thing nano material |
| CN1986910A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Process of preparing nano lead sulfide semiconductor particle |
| CN101429679A (en) * | 2008-11-25 | 2009-05-13 | 陕西科技大学 | Nano PbS film production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1719578A (en) * | 2005-04-29 | 2006-01-11 | 同济大学 | A kind of method for preparing IIB family semiconductor sulfuration thing nano material |
| CN1986910A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Process of preparing nano lead sulfide semiconductor particle |
| CN101429679A (en) * | 2008-11-25 | 2009-05-13 | 陕西科技大学 | Nano PbS film production method |
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