CN101870458B - Preparation methods of multi-element metal chalcogen compound, target and coating material - Google Patents
Preparation methods of multi-element metal chalcogen compound, target and coating material Download PDFInfo
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- CIEIRSLXYJFLEF-SBYNAHCQSA-N C/C=C(\C=C/C(N)=C)/N Chemical compound C/C=C(\C=C/C(N)=C)/N CIEIRSLXYJFLEF-SBYNAHCQSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N Nc1cc(N)ccc1 Chemical compound Nc1cc(N)ccc1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N Nc1ccccc1N Chemical compound Nc1ccccc1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to preparation methods of a multi-element metal chalcogen compound, a target and a coating material. The preparation method of the multi-element metal chalcogen compound comprises the following steps of: synthesizing an elementary substance powder selected from forming elements at normal pressure with a liquid phase synthesis method, wherein the used organic solvent in the synthesis process is an aromatic amines compound with a boiling point higher than 240 DEG C and pH value of 7-10, and thereby producing a copper-indium-gallium-selenium element compound through chelation reactions at high temperature. The compound can be particularly applied to the solar energy field of semiconductor films, can be directly coated into a film and sputtered to a film through producing a target, the selenylation process is unneeded, the production procedure can be reduced, the consistency of the film components is improved, and the product yield and the efficiency are enhanced.
Description
Technical field
The present invention relates to the preparation method of a kind of methods of multi-element metal chalcogen compound and target and coated material; And be particularly related to a kind of nano-powder and be applied to the compound semiconductor thin film solar field this methods of multi-element metal chalcogen compound; Can be with direct coating film forming of this compound and forming sputtering film; Need not to carry out again the selenizing process, thereby reduced production sequence, improved production capacity efficient.
Background technology
In recent years; Copper-indium-gallium-selenium compound semiconductor thin-film solar cell (Copper Indium Galliumdiselenide Solar Cell; Hereinafter to be referred as the CIGS solar cell) from development in 1997 so far; It is 19.9% (american energy institute (NREL) delivered in 2008) that battery efficiency is brought up to best battery efficiency by about 6% (University of Maine proposition); And have high-level efficiency and can stablize the advantage of using for a long time,, and for example can be applicable in power station, the building materials etc. so its range of application also therefore and diversified.
The CIGS solar cell is meant that the composition that absorbs outside sunlight wavelength and then produce the active coating (Active layer) of electric current is Cu (In
1-xGa
x) Se
2Solar cell.Because of having reached 19.9%, its cell photoelectric efficient gets most of the attention; This high-quality CIGS (Cu, In, Ga, Se) film; Be to adopt high vacuum multi-source copper steam-plating (Cu), indium (In), gallium (Ga) and selenium (Se) element of etc.ing altogether traditionally, simultaneously substrate applied 500-600 ℃ high temperature generation chemical reaction chemical combination and form.This vapor deposition ratio juris does, in same vacuum cavity, inserts copper, indium, gallium, four kinds of vapor deposition source of selenium, controls its vaporator rate respectively, and four kinds of elements are deposited on the substrate simultaneously, and substrate is applied high temperature carries out chemical combination, to form this CIGS film.Yet; This method is because material use efficiency is not high enough, the uniform film thickness degree is good inadequately, mixture homogeneity differs, substrate needs problems such as heat; Cause that yield is not good, material and result such as equipment cost increases, the production size can't be amplified, and then influence its productivity.
Except being total to evaporation coating technique; Adopt the single sputtered target material copper-indium-gallium alloy (hereinafter to be referred as the CIG alloy) or the metal precursor of employing preplating binary alloy in addition; Form CIG (Cu, In, Ga) film, under hot environment, feed selenium steam or Selenium hydride (H then
2Se) gas or hydrogen sulfide (H
2S) gas carries out selenizing or sulfidation, generates the method for CIGS film.Yet; Selenizing or sulfidation are a complicated and technology consuming time, not only need very high technological temperature, also can increase the technology cost and reduce throughput rate; The more important thing is that the device levels that is adopted also need improve and increase equipment cost owing to used hypertoxicity gas Selenium hydride.
In addition; In order to improve material use efficiency, to enhance productivity and the production size; Can also adopt plating method (Electrodeposition), chemical Vapor deposition process (Chemical Vapor Deposition), spraying method process methodes such as (Spray Deposition); Yet these methods are all because of factor such as battery efficiency is not good, material use efficiency is not good or the crystallization crystalline phase is not good, and influence its productivity.
Moreover; Adopt printing ink coating method (Ink-jet printing) can improve material use efficiency and production size; But problems such as it still is subject to, and battery efficiency is low, thin film preparation process need at high temperature feed hydrogen reducing and feed the hydrogen selenide gas selenizing, the thin film crystallization crystalline phase is not good or the printing ink manufacturing is difficult for, working condition is harsh as need under high temperature and high pressure environment, to synthesize or flow process is numerous and diverse, and influence its productivity.
Hence one can see that, and the compound method of CIGS nano-powder comprises following several kinds of modes:
Carmalt et al.
(1)Propose to adopt metal halide and the metal chalcogenide element compound that contains sodium to replace synthesis method (Solution phase metathesis synthesis), precursor reflux reaction in 72 hours in toluene is obtained with liquid phase.
Schulz et al.
(2)Proposition is with cuprous iodide (CuI), indium iodide (InI
3), gallium iodide (GaI
3) and sodium selenide (Na
2Se) being dissolved in the pyridine reaction obtains.
Malik et al.
(3)Propose heat and penetrate synthesis method (Hot injection method), with cuprous chloride (CuCl) and indium chloride (InCl
3) be dissolved in the tri octyl phosphine (trioctylphosphine) (hereinafter to be referred as TOP) and form metal complexes; TOPO (trioctylphosphine oxide) (hereinafter to be referred as TOPO) reinjects; Reinjecting obtains two copper indium diselenide (hereinafter to be referred as CIS) in 330 ℃ selenizing tri octyl phosphine (trioctylphosphine selenide) (hereinafter to be referred as TOPSe) reaction, but this method only can generate the CIS ternary compound and contain selenkupfer (Cu
2Se) and Indium sesquioxide (In
2O
3) wait by product, be difficult for purifying.
Pyrolysis method (Pyrolysis) is prepared (PPh earlier
3)
2CuIn (SePh)
4Metal complexes sprays cracking with it then and obtains the CIS powder in hot environment.
Grisaru et al.
(4)Propose microwave-assisted synthesis method (Microwave-assisted synthesis), precursors such as cuprous chloride, indium powder and selenium powder are dissolved in the terepthaloyl moietie, apply the microwave energy cracking, reaction obtains CIS, but still contains the selenkupfer by product, is difficult for purifying.
Li et al.
(5)Solution heating method (Solvothermal) is proposed, with cupric chloride (CuCl
2), indium chloride and selenium powder be dissolved in quadrol (ethylenediamine) and the DIETHANOL AMINE (diethylamine), in autoclave (Autoclave), reaction is more than 15 hours under high temperature and high pressure environment, reaction obtains the CIS powder.Jianget al.
(6)Further change precursor into simple substance by halogenide.Chun YG et al.
(7)Further obtain the CIGS powder with elemental copper, indium, gallium, selenium are synthetic, have only this method can't mass production because of being subject to reaction conditions with this method.
Take a broad view of technique scheme, what have can only generate ternary compound, and the synthesis condition that needs HTHP that has and be not suitable for mass production has halide-ions in the product that has, and for producing and the assembly demand, all can't cooperate.
Reference:
1.Carmalt?C，Morrision?D，Parkin?I.1998.Journal?of?Materials?Chemistry?8：2209-2211
2.Schulz?DL，Curtis?CJ，Ginley?DS.2000.United?States?Patent?No.612740
3.Malik?MA，O’Brien?P，Revaparasadu?N.1999.Advanced?Materials?11：1441-1444
4.Grisaru?H，Palchik?O，Gedanken?A，Palchik?V，Slifkin?MA，Weiss?AM.2003.Inorganic?Chemistry?42：7148-7155
5.Li?B，Xie?Y，Huang?JX，Qian?YT.1999.Advanced?Materials11：1456-1459
6.Jiang?Y，Wu?Y，Mo?X，Yu?WC，Xie?Y，Qian?YT.Inorganic?Chemistry39：2964
7.Chun?YG，Kim?KH，Yoon?KH.2005.Thin?Solid?Films?480：46-49
Summary of the invention
Defective in view of existing in the prior art the purpose of this invention is to provide a kind of preparation method, and this method can be carried out under atmospheric pressure environments; But mass production goes out to have the CIGS powder of nano-scale; Method is simple, and preparation cost is low, and not halogen-containing ion; And can be according to the preparation needs; Change the atomic ratio of copper, indium, gallium, selenium in this material within the specific limits arbitrarily, thereby improved the efficient of battery component, and through using this material can produce the printing ink of material composition homogeneous and stability and the quality of forming film that sputtered target material has improved the preparation process.
In order to accomplish the present invention; From the result that contriver of the present invention studies, recognize; Through research to synthesis condition and aromatic series or the synthetic wedding agent of heteroaromatic aminated compounds (chemical classification is arylamines (arylamine)); And have high boiling point, weakly alkaline and have the aromatic amine compounds wedding agent of sequestering power through use, building-up reactions is carried out under atmospheric pressure conditions, produce not halogen-containing in a large number ionic high-purity C IGS powder.
The present invention is according to above-mentioned cognition; The preparation method of the nano-powder of a kind of methods of multi-element metal chalcogen compound (Chalcogenide) is proposed, wherein, with pure element material powders such as copper, indium, gallium, selenium; Place the organic solvent heating to carry out combination reaction, temperature of reaction is controlled at more than 240 ℃; Wherein, said organic solvent possesses boiling point at least and is higher than 240 ℃ and is the weakly alkaline characteristic of 7-10 with pH value.
Methods of multi-element metal chalcogen compound nano-powder of the present invention can be pressed into sputtered target material through high temperature sintering.Sputtered target material of the present invention; Through the sedimentary CIGS film of sputtering process, each position component homogeneous, and component does not change with the sputter time; It is controlled to make the thin film preparation process condition reach composition; And do not need to pass through the selenizing process again, reach the purpose that reduces production unit cost, release selenizing material cost, component homogeneous, yield raising, and improved the productivity of CIGS thin-film solar cells greatly.
Description of drawings
Fig. 1 is the preparing method's of an a kind of methods of multi-element metal chalcogen compound provided by the invention schema.
The XRD figure of the compound powder that Fig. 2 obtains for the method that adopts embodiment 1.
The SEM figure of Fig. 3 after for the method coating film forming that adopts embodiment 2.
Fig. 4 schemes for the SEM of the solid powder that the method that adopts embodiment 2 obtains.
The XRD figure of the solid powder that Fig. 5 obtains for the method that adopts embodiment 2.
Nomenclature
100 step 110 steps
120 step 130 steps
140 steps
Embodiment
Fig. 1 is the preparing method's of a kind of methods of multi-element metal chalcogen compound provided by the invention (Chalcogenide) a schema.This preparation method comprises the steps: in step 100, uses at least one container.In step 110; Directly with in copper, phosphide element, the gallium element at least a (for example; The combination of copper Cu, indium In, gallium Ga, copper Cu and indium In, copper Cu and gallium Ga, indium In and gallium Ga or copper Cu and indium In and gallium Ga) is placed in this container with sulfur family element (for example, sulphur S, selenium Se or tellurium Te); This copper, this phosphide element, this gallium element are used as initiator for using element state simple substance.In step 120, provide at least a boiling point to be higher than 240 ℃ and pH value weakly alkaline organic solvent for 7-10, this organic solvent is poured in the said vesse, be used as reaction solvent.Perhaps, at least a and sulfur family element in copper, phosphide element, the gallium element directly is placed in the container that fills organic solvent.In step 130,, and carry out building-up reactions with copper, phosphide element, gallium element, sulfur family element material uniform mixing such as (are example with selenium).This organic solvent and above-mentioned element are heated to temperature of reaction, and with synthetic methods of multi-element metal chalcogen compound, wherein, said temperature of reaction is more than 240 ℃.In step 140, comprise the step that this methods of multi-element metal chalcogen compound is lowered the temperature, separates out, filters, cleaned and dries, to form the nano-powder of this methods of multi-element metal chalcogen compound.The present invention can synthesize CIGS (Cu, In, Ga, the Se) powder with nano-scale under normal pressure.The employed organic solvent of this building-up reactions is not limited to a kind of, can be the mixture of at least two kinds of solvents.According to quaternary metal chalcogenide element compound provided by the invention, its structural formula is Cu
x(In
1-yGa
y) Se
z, wherein 0.8≤x≤1.2,0≤y≤1.0 and 1.6≤z≤2.4.According to binary provided by the invention or ternary metal sulfur family element compound, its structural formula is respectively In
2Se
3, (In, Ga)
2Se
3, Ga
2Se
3, CuSe or Cu
2Se.
Said organic solvent can be aromatic amine compound or aromatic diamine compounds, and its chemical structural formula is respectively shown in following formula (a)-Shi (e):
Wherein:
Said organic solvent can be the aromatic amine compound, shown in (a), wherein, said R ' and R " can be independently selected from Wasserstoffatoms, aromatic base, carbonatoms respectively and be a kind of in the amino of 1-5 and the hydroxyalkyl that carbonatoms is 1-5.Said aromatic amine compounds is preferably selected from one or more in pentanoic (diphenylamine), N-phenyl benzene methanamine (N-phenylbenzylamine), 2-phenylamino ethanol (2-anilinoethano1) and the N-phenylethylenediamine (N-phenylethylene-diamine);
Said organic solvent can be the aromatic amine compound; Shown in (b); Wherein, said R can be selected from a kind of in alkyl that Wasserstoffatoms, carbonatoms are 1-10, amino that carbonatoms is 1-10, alkoxyl group, itrile group and the aromatic base that carbonatoms is 1-10.Said aromatic amine compounds is preferably selected from 4-monomethylaniline, adjacent phenylaniline (2-biphenylylamine), 2-anthranilo nitrile (2-aminobenzonitrile), N; N-diethylammonium-1; 4-phenylenediamine (N; N-diethyl-1, one or more 4-phenylenediamine) and in the o-phenetidine (o-phenetidine); And
Said organic solvent can be the aromatic diamines compound, and shown in (c)-Shi (e), wherein, said R can be selected from a kind of in alkyl, itrile group and the aromatic base that Wasserstoffatoms, carbonatoms are 1-10.This aromatic diamine compounds is preferably selected from O-Phenylene Diamine (1; 2-phenylenediamine), mphenylenediamine (1; 3-phenylenediamine), Ursol D (1; 4-phenylenediamine) with the 4-methyl isophthalic acid, 3-phenylenediamine (4-methyl-1, one or more in 3-phenylenediamine).
Specifically, can prepare Cu (In according to method of the present invention
1-xGa
x) Se
2Quaternary compound nano-powder, and preparation in accordance with the present invention can also be prepared ternary compound, for example CuInSe
2, CuGaSe
2, and binary compound, for example CuSe, Cu
2-xSe and In
2Se
3Deng.Further, preparation in accordance with the present invention for sulfur family element, can adopt sulphur (S) element or tellurium (Te) element to replace selenium (Se) element.For copper family elements, can adopt silver (Ag) element to replace copper (Cu) element.For boron group element, can adopt aluminium (Al) element to replace indium (In) element and gallium (Ga) element.
In addition, methods of multi-element metal chalcogen compound nano-powder of the present invention also can be applicable to coating and printing technology and sputtering process.For instance, through this methods of multi-element metal chalcogen compound nano-powder is dispersed in the printing ink, to be formed for the coated material of coating and printing technology.Perhaps, with this methods of multi-element metal chalcogen compound nano-powder sintering and be pressed into the target that is used for sputtering process at high temperature.In other words, the present invention also provides a kind of preparation method who is used for the target of sputtering process, and said target is through being processed through high temperature sintering by the CIGS nano-powder of the component homogeneous of solution synthetic method preparation.
Pass through sputtering process; Sputtered target material of the present invention is carried out sputter; The component homogeneous at each position of CIGS film that deposition obtains; And the component at each position does not change with the sputter change of time, makes sputter-deposited thin-film technique condition reach the controlled purpose of composition, and does not need to pass through selenizing (or sulfuration) technology again; And reach reduce the production unit cost, the purpose of exempt selenizing (or sulfuration) material cost, component homogeneous, and yield be improved and improved the productivity of CIGS thin-film solar cells greatly.
Following embodiment is used for the present invention is further described in detail, but and is not used in qualification protection scope of the present invention.
Embodiment 1
The container (for example, three-necked bottle) of 500ml is heated to more than 100 ℃ or 100 ℃, feeds nitrogen, deoxygenation 1 hour dewaters.Then the gallium ingot is heated to 30 ℃, and about 0.06 mole of gallium, 0.2 mole of copper powder, 0.14 mole of indium powder and 0.5 mole of selenium powder are placed in the said vesse, and in container, mix, dissolve with 1.0 moles pentanoic (organic solvent); And with magnetite stirring 1 hour; Slowly be heated to 240 ℃, treat after the temperature-stable, reacted 24 hours; Be cooled to then below 80 ℃ or 80 ℃; Add and remove non-solvent (non-solvent) (for example, methyl alcohol or the toluene) 300ml that anhydrates, separate out, filter, use again non-solvent (non-solvent) (for example methyl alcohol or toluene) to clean black solid; The gained solid in vacuum, and oven dry 1 hour under the condition more than 50 ℃ or 50 ℃, is taken out then.Said non-solvent is meant and react with organic solvent (for example, pentanoic and Ursol D) and can dissolve each other, but do not dissolve or do not disperse the solvent of methods of multi-element metal chalcogen compound.
The XRD figure of the crystalline structure of the powder that employing X-ray diffractometer (hereinafter to be referred as XRD) analysis obtains is as shown in Figure 2, Cu (In, Ga) Se
2.5Special peak value lay respectively at 112 (27.38), 204/220 (44.88), 116/312 (53.13), 008/400 (65.2), 316/332 (71.83), 228/424 (82.81), in addition, detect simultaneously (In, Ga)
2Se
3Special peak value 110 (25.12) and (48.43), adopt elemental analyser (hereinafter to be referred as EDX) to analyze the atomic ratio of powder, the result is: the ratio of Cu/ (In+Ga) is about 1.0, Ga/ (In+Ga) ratio is about 0.3.By product (In, Ga)
2Se
3Existence be because adopt superstoichiometric selenium (Se) to cause.
Embodiment 2
The container (for example, three-necked bottle) of 500ml is heated to more than 100 ℃ or 100 ℃, feeds rare gas element (for example, nitrogen, helium or argon gas), deoxygenation 1 hour dewaters.Then the gallium ingot is heated to 30 ℃, and about 0.04 mole of gallium, 0.18 mole of copper powder, 0.16 mole of indium powder and 0.44 mole of selenium powder are placed in the said vesse, and in container, mix, dissolve, and stirred 1 hour with magnetite with 0.6 mole mphenylenediamine (organic solvent); Slowly be heated to 260 ℃, treat after the temperature-stable, placing response 24 hours is cooled to below 80 ℃ or 80 ℃ then; Add and remove the methyl alcohol 100ml that anhydrates, take out the 20ml dark solution then, drop on the sheet glass; Drying and forming-film, with electron microscope scanning (hereinafter to be referred as SEM), electron microscope photo scanning is as shown in Figure 3; Then, in above-mentioned reactant, add 160ml non-solvent (non-solvent) (for example, methyl alcohol or toluene) again; Separate out, filter, use again non-solvent (non-solvent) (for example, methyl alcohol or toluene) to clean black solid, with the solid that obtains in vacuum, and oven dry 1 hour under the condition more than 50 ℃ or 50 ℃; Take out, with SEM scanning, electron microscope photo scanning is as shown in Figure 4.
The crystalline structure of the powder that the employing XRD analysis obtains is as shown in Figure 5, Cu
0.9(In, Ga) Se
2.2Special peak value lay respectively at 112 (27.19), 204/220 (44.69), 116/312 (52.81), 008/400 (65.02), 316/332 (71.25), 228/424 (82.18); The measured impurity of collection of illustrative plates is few; Take EDX to analyze the atomic ratio of powder; The result is: the ratio of Cu/ (In+Ga) is about 0.9, and the ratio of Ga/ (In+Ga) is about 0.2.
Claims (13)
1. the preparation method of a methods of multi-element metal chalcogen compound is characterized in that, this method comprises the steps:
(1) uses at least one container;
(2) directly at least a element in copper, phosphide element, the gallium element and sulfur family element are placed in the said container, wherein said copper, phosphide element, gallium element, sulfur family element are pure element material powder;
(3) organic solvent is poured in the said container, said organic solvent is that boiling point is more than 240 ℃, and the pH value is 7 to 10 aromatic amine compounds or aromatic diamine compounds;
The chemical structural formula of said aromatic amine compounds is by shown in following formula (a) or the formula (b):
Wherein, R ' and R in the chemical formula (a) " are independently selected from Wasserstoffatoms, aromatic base, carbonatoms respectively and are a kind of in the amino of 1-5 and the hydroxyalkyl that carbonatoms is 1-5; R is selected from a kind of in alkyl that Wasserstoffatoms, carbonatoms are 1-10, amino that carbonatoms is 1-10, alkoxyl group, itrile group and the aromatic base that carbonatoms is 1-10 in the chemical formula (b);
The chemical structural formula of said aromatic diamine compounds is respectively by following formula (c), formula (d) and formula (e) expression:
Wherein, chemical formula (c) or (d) or (e) in R be selected from a kind of in alkyl, itrile group and the aromatic base that Wasserstoffatoms, carbonatoms are 1-10;
And said organic solvent and above-mentioned element are heated to temperature of reaction carry out building-up reactions, obtain methods of multi-element metal chalcogen compound, wherein, said temperature of reaction is more than 240 ℃.
2. preparation method according to claim 1, wherein, said aromatic amine compounds is selected from one or more in pentanoic, 2-phenylamino ethanol and the N-phenylethylenediamine.
3. preparation method according to claim 1, wherein, said aromatic amine compounds is selected from adjacent phenylaniline, 2-anthranilo nitrile, N, N-diethylammonium-1, at least a in the 4-phenylenediamine.
4. preparation method according to claim 1, wherein, said aromatic diamine compounds is selected from O-Phenylene Diamine, mphenylenediamine, Ursol D and 4-methyl isophthalic acid, at least a in the 3-phenylenediamine.
5. preparation method according to claim 1, wherein, said sulfur family element is selected from a kind of in element sulphur, selenium element and the tellurium element.
6. preparation method according to claim 1, wherein, the employed organic solvent of said building-up reactions is at least two kinds a mixed solvent.
7. preparation method according to claim 1, wherein, this method also comprises the step that the methods of multi-element metal chalcogen compound that obtains is lowered the temperature, separates out, filters, cleaned and dries, to form the nano-powder of this methods of multi-element metal chalcogen compound.
8. preparation method according to claim 7, wherein, said cooling step comprises said methods of multi-element metal chalcogen compound is cooled to below 80 ℃.
9. preparation method according to claim 7, wherein, the said step of separating out comprises and adds non-solvent and separate out this methods of multi-element metal chalcogen compound.
10. preparation method according to claim 7, wherein, said baking step is included in dried this methods of multi-element metal chalcogen compound more than 1 hour under vacuum, the condition more than 50 ℃.
11. a preparation method who is used for the target of sputtering process is characterized in that, this method comprises carries out the nano-powder in the claim 7 high temperature sintering and is pressed into target.
12. a preparation method who is used for the coated material of coating and printing technology is characterized in that, this method comprises the nano-powder in the claim 7 is dispersed in the printing ink, so to form coated material.
13. the preparation method of a methods of multi-element metal chalcogen compound is characterized in that, this method comprises the steps:
(1) copper family elements, boron group element, sulfur family element are mixed with organic solvent; Wherein, said copper family elements is selected from copper or silver element, and said boron group element is selected from two kinds in aluminium element, phosphide element and the gallium element; Wherein, Said copper family elements, boron group element, sulfur family element are pure element material powder, and this organic solvent is that boiling point is more than 240 ℃, and the pH value is aromatic amine compounds or the aromatic diamine compounds of 7-10;
The chemical structural formula of said aromatic amine compounds is by shown in following formula (a) or the formula (b):
Wherein, R ' and R in the chemical formula (a) " are independently selected from Wasserstoffatoms, aromatic base, carbonatoms respectively and are a kind of in the amino of 1-5 and the hydroxyalkyl that carbonatoms is 1-5; R is selected from a kind of in alkyl that Wasserstoffatoms, carbonatoms are 1-10, amino that carbonatoms is 1-10, alkoxyl group, itrile group and the aromatic base that carbonatoms is 1-10 in the chemical formula (b);
The chemical structural formula of said aromatic diamine compounds is respectively by following formula (c), formula (d) and formula (e) expression:
Wherein, chemical formula (c) or (d) or (e) in R be selected from a kind of in alkyl, itrile group and the aromatic base that Wasserstoffatoms, carbonatoms are 1-10;
And (2) be heated to temperature of reaction with this organic solvent and above-mentioned element and carry out building-up reactions, and to obtain methods of multi-element metal chalcogen compound, wherein, said temperature of reaction is more than 240 ℃.
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| CN102463349A (en) * | 2010-11-05 | 2012-05-23 | 慧濠光电科技股份有限公司 | Manufacturing method of copper-indium-gallium-selenium-sulfur five-element target material |
| CN102464305A (en) * | 2010-11-05 | 2012-05-23 | 慧濠光电科技股份有限公司 | Multi-metal sulfur group compound and manufacture method thereof |
| CN102060273A (en) * | 2010-11-05 | 2011-05-18 | 桂林理工大学 | Method for preparing I-III-VI group semiconductor material through solvothermal synthesis in constant pressure open system |
| CN102476791A (en) * | 2010-11-25 | 2012-05-30 | 马瑞新 | Method for preparing copper indium diselenide nanometer powder |
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