CN102730741A - Preparation method of high-purity P-type CuAlO2 powder - Google Patents

Abstract

The invention discloses a preparation method of a high-purity P-type CuAlO2 powder, comprising the following steps of: fully mixing copper oxide and alumina, grinding, sintering at 1200 DEG C, cooling to room temperature, placing into a dilute acid solution, fully stirring, fully carrying out dilute acid processing, flushing by the use of deionized water, and drying to obtain the blue grey high-purity P-type CuAlO2 powder. The method provided by the invention requires low purity of the reaction materials, adopts commonly-used experiment devices, requires simple operational process and short preparation period without repeatedly sintering, requires low cost and has high efficiency.

Description

A kind of high-purity P-shaped CuAlO 2The preparation method of powder

Technical field

The invention belongs to the oxide semiconductor material field, be specifically related to a kind of high-purity P-shaped CuAlO ₂The preparation method of powder.

Background technology

As important a member in the naturally occurring P type transparent conductive oxide (TCO), CuAlO ₂Have fine application prospect in fields such as solar cell, FPD, also paid close attention to widely and studying aspect theoretical and the experiment.The CuAlO that in the past prepared ₂Powder contains the existence of impurity such as a certain amount of CuO mostly, and this preparation process then can obtain the CuAlO of based on very high purity ₂Powder.

Existing C uAlO ₂Powder preparation method mainly contains sol-gel method, hydrothermal method and solid state reaction etc.Wherein, solid state reaction is simple because of having operating process, need not advantage such as expensive vacuum experiment equipment and is extensively adopted.Raw materials used in the existing solid state reaction method mainly is Cu ₂O (or CuO) and Al ₂O ₃(or Al (OH) ₃), thorough mixing grinds by a certain percentage, puts into lehre sintering processes repeatedly between 1100-1200 degree centigrade then, finally obtains required powder sample.Owing to lack purification process process usually among the existing preparation method, so existing C uAlO to sample ₂Powder preparation method causes occurring in the product impurity such as initial reactant that do not react of minute quantity easily, thereby the purity of final product is decreased.

Summary of the invention

To the defective that exists among the above existing preparation method, the present invention proposes a kind of high-purity P-shaped CuAlO ₂The preparation method of powder may further comprise the steps:

1) with cupric oxide and aluminum oxide after the ball milling thorough mixing grinds, in 1200 degrees centigrade of following sintering 10 hours, the speed with 3 centigrade per minutes was cooled to 800 degrees centigrade then, naturally cools to room temperature again;

2) add excessive dilute acid soln, fully stir;

3) through washing and filtering, drying repeatedly, obtain said high-purity P-shaped CuAlO ₂Powder.

Wherein, before the said step 3), through filtration, deionized water rinsing, repeated multiple times repeating step 2).

Wherein, said cupric oxide and alumina molar ratio are 2:1.

Since usually to the requirement of sample purity than higher (for example; For the unnecessary interference of despumation) to the subsequent experimental measuring result; Seem particularly important so remove the process of impurity, do not propose the method that a kind of ideal is removed impurity as yet among the existing so far preparation method.

Among the present invention, utilize dilute acid soln can with this reaction in remove CuAlO ₂Other impurity beyond the powder (used reactant cupric oxide, aluminum oxide and the impurity that possibly introduce because material purity is not enough etc. when comprising the preparation sample) reaction, with its dissolving, and not can with products C uAlO ₂The powder reaction can reach the effect that ideal is removed impurity in the reaction system.In order to remove impurity fully fully, among this preparation method, add excessive dilute acid soln first, treat fully reaction after, after filtration, step such as deionized water rinsing, change dilute acid soln, repeated multiple times is removed impurity.

Preparing method of the present invention is not high to the purity requirement of reaction raw materials, and used plant and instrument is common retort furnace, need not expensive vacuum device, and operating process is simple, and preparation cycle is short, need not sintering repeatedly, and cost is low, and efficient is high.

In the inventive method, handle, can remove the impurity such as CuO that possibly exist in the sample, thereby obtain high-purity sample through dilute acid soln.

In order fully to remove the impurity that institute might contain, and avoid agents useful for same to remain in the product, in the inventive method, the time that diluted acid is handled is wanted sufficiently long, and deionized water rinsing wants thorough.

Adopt high-purity P-shaped CuAlO of the present invention ₂The final sample purity that obtains of the preparation method of powder is high.

Compare with more existing preparing methods; Mainly added the process of removing those impurity such as initial reactant that possibly fully not react among the preparation method of the present invention; This point is vital (because the height of sample purity can produce directly influence to the subsequent experimental measurement, thereby final experiment conclusion being produced interference) for obtaining high-purity final sample.XRD result shows, takes the inventive method to remove the method for impurity, can obtain the single-phase sample of based on very high purity, thereby has effectively solved in the experiment in the past owing to initial reactant does not fully react a difficult problem that appears in the final sample.

Description of drawings

Shown in Figure 1 for utilizing the CuAlO of preparing method's gained of the present invention ₂The XRD spectra of powder.

Embodiment

In conjunction with following specific embodiment and accompanying drawing, the present invention is done further detailed description.The process of embodiment of the present invention, condition, reagent, experimental technique etc. except that the following content of mentioning specially, are the universal knowledege and the common practise of this area, and the present invention does not have special limiting content.

Embodiment 1

At first take by weighing cupric oxide that an amount of mol ratio is 2:1 (CuO) and aluminum oxide (Al ₂O ₃) powder, make its thorough mixing and further porphyrize through 10 hours ball millings; The corundum crucible that the reaction raw materials that ball milling is good is packed into and cleaned up is put retort furnace into and in air ambient, is begun sintering, 1200 degrees centigrade of insulations 10 hours, after the first subsequently speed with 3 centigrade per minutes cools to 800 degrees centigrade, naturally cools to room temperature.

After the sintered product taking-up, put into the dilute hydrochloric acid solution that excessive concentration is 1mol/L, fully stir so that it fully contacts with dilute acid soln, to remove the impurity such as CuO that do not react that wherein possibly exist.Treat that dilute acid soln and sintered product fully react,, add the dilute hydrochloric acid solution that excessive concentrations is 1mol/L once more, so remove the process of impurity repeatedly through filtration, deionized water rinsing.When through staticly settling after a while, in sintered product, add dilute acid soln, and solution is colourless and do not exist till white floss (it be the product of the aluminum ion hydrolysis) existence.Dilute acid soln in the present embodiment can also adopt other can remove the impurity (the reactant cupric oxide, the aluminum oxide that comprise preparation) in the reaction system, and can dissolved product CuAlO ₂The dilute acid soln of powder or reagent, the concentration of dilute acid soln gets final product with the purpose that can realize above-mentioned removal impurity.

In the inventive method, preferably adopt dilute acid soln to carry out impurity and handle (though CuAlO ₂Powder also is insoluble to basic soln; But basic soln is unfavorable for removing impurity equally); So can remove the impurity that possibly exist and can not have influence on final product again, related mainly is the reaction of diluted acid dissolved oxygen thing class, this reaction product mainly be can be water-soluble salt; This reaction is simple and easy to control, also can not introduce other new impurity that are difficult to remove.

The sintered product that will pass through the processing of removal impurity is through filtering, use repeatedly deionized water rinsing, and the diluted acid that removal wherein maybe be remaining etc. are to avoid introducing other impurity.The throw out of washes clean is put into loft drier, and in 120 degrees centigrade of dryings 12 hours, gained pewter powder promptly was high-purity CuAlO ₂Powder.

Shown in Figure 1 for through to utilizing the CuAlO of this preparation method gained ₂The XRD spectra of sample, visible from figure, the final sample of preparation gained has only the CuAlO of pure phase ₂, wherein do not have CuO and Al ₂O ₃And the dephasigns such as other impurity that possibly exist in the reactant.This shows that the product purity that present method prepares is high.

Purity requirement to reaction raw materials among this preparation method is not high, and used plant and instrument is exactly a common retort furnace and need not expensive vacuum device etc., and operating process is simple, and preparation cycle is short, need not sintering repeatedly, and cost is low, and efficient is high.

Protection content of the present invention is not limited to above embodiment.Under spirit that does not deviate from inventive concept and scope, variation and advantage that those skilled in the art can expect all are included among the present invention, and are protection domain with the appending claims.

Claims (3)

1. high-purity P-shaped CuAlO ₂The preparation method of powder is characterized in that, may further comprise the steps:

1) with cupric oxide and aluminum oxide through ball milling thorough mixing, porphyrize, in 1200 degrees centigrade of following sintering, the speed with 3 centigrade per minutes is cooled to 800 degrees centigrade then, naturally cools to room temperature again;

2) add in the excessive dilute acid soln, fully stir;

3) through washing and filtering, drying repeatedly, obtain said high-purity P-shaped CuAlO ₂Powder.

2. preparation method as claimed in claim 1 is characterized in that, before the said step 3), through filtration, deionized water rinsing, repeated multiple times repeating step 2).

3. preparation method as claimed in claim 1 is characterized in that, said cupric oxide and alumina molar ratio are 2:1.

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