CN101767810B - Method for preparing CuAlO2 powder - Google Patents

Abstract

The invention discloses a method for preparing CuAlO2 powder. The method comprises the steps of: firstly, adding monohydrate copper acetate into ethylene glycol to obtain solution A; secondly, adding aluminum nitrate nonahydrate into the solution A and adjusting the pH value to 2.0 to 4.0 to prepare uniform solution B of a precursor; drying the solution B in a drying box to obtain dried gel and grinding the dried gel by agate into fine powder for later use; putting the fine dried gel in a muffler to calcine the fine dried gel for 3 to 5 hours at the temperature of between 1,100 and 1,200 DEG C and naturally cooling the product to room temperature along with the muffler to obtain the CuAlO2 powder. In the invention, the CuAlO2 powder is prepared by a solution method. The method has the advantages of low preparation cost, simple operation and short reaction period; and no expensive vacuum device is used in the whole preparation process, so the method can effectively prepare the CuAlO2 powder at low cost.

Description

A kind of CuAlO＜sub〉2＜/sub〉preparation method of powder

Technical field:

The present invention relates to a kind of p type transparent conductive oxide (TCO) preparation methods, be specifically related to a kind of CuAlO ₂The preparation method of powder.

Background technology

CuAlO ₂It is p type transparent conductive oxide (TCO) material, directly and indirect band gap be respectively 1.8 and 3.5eV, has delafossite structure, owing in visible-range, have high transparency (broad-band gap) and specific conductivity, be widely used in solar cell, plane demonstration, specific function window coating and other photoelectric device field.(Z.Deng, X.Zhu, R.Tao, W.Dong, X.Fang, Synthesisof CuAlO2 ceramics using sol-gel, Mater.Lett.61 (2007) 686-689.) appearance of TCO opened up the frontier of opto-electronic device research, but the scarcity relatively of p type TCO has seriously restricted the exploitation and the application of transparent oxide semiconductor (TOS) related device, has hindered TCO to the research and development based on semi-conductor full impregnated Mingguang City electrical part of p-n junction.People such as Kawazoe had delivered about P type electrically conducting transparent CuAlO in 1997 ₂The research report of film (Hiroshi Kawazoe, MasahiroYasukawa, Hiroyuki HyodoP-type electrical conduction in transparentthin films of CuAlO ₂Nature, 1997,389 (30): 939 ~ 942), CuAlO so far ₂Become hot research in recent years as a kind of natural p type TCO.

Up to now, many investigators use diverse ways to prepare CuAlO ₂Powder comprises solid reaction process (Banerjee AN, Maity R, Chattopadhyay KK.Mater Lett2003; 58:10-3.), ion exchange method (Dloczik L, Tomn Y, Konenkamp R, Lux-Steiner MC, Dittrich TH.Thin Solids Films 2004; 451-452:116-119.), hydrothermal method (Shahriari DY, Barnabe A, Mason TO, Poeppelmeier KR.Inorg Chem2001; 40:5734-5.), sol-gel method (Deng Z, Zhu X, Tao R, DongW, Fang X.Mater Lett 2007; 61:686-689.), chemical Vapor deposition process (Y.Luo, Appl.Phys.Lett.76 (2000) 3959. for H.Gong, Y.Wang) etc.Above method or higher to equipment requirements, complicated operation and cost height perhaps are exactly complex process, and the cycle is long, poor repeatability etc.

Summary of the invention

The object of the present invention is to provide a kind of not only raw material cheap and easy to get, preparation cost is low, and CuAlO simple to operate, that reaction time is short ₂The preparation method of powder.

For achieving the above object, the technical solution used in the present invention is:

Step 1: at first will be mixed with Cu in the analytically pure water venus crystals adding ethylene glycol ²⁺Concentration is the blue clear solution of 0.1mol/L～0.5mol/L, and gained solution is designated as A;

Step 2: in A solution, add analytically pure nine water aluminum nitrates then, feasible (Cu ²⁺): (Al ³⁺The mol ratio of)=1: 1, and constantly stirring adds molar fraction and is 0.5%～1.0% HCOOH reagent simultaneously, and stirring and regulating pH value down is 2.0～4.0, formation uniform precursor solution B;

Step 3: above-mentioned B solution is put into loft drier at 80 ℃～120 ℃ dry 8h～12h, make it form xerogel, with stand-by behind the xerogel usefulness agate mortar porphyrize;

Step 4: the xerogel of porphyrize is put into retort furnace at 1100～1200 ℃, and calcining 3～5h cools to room temperature with the furnace, promptly obtains CuAlO ₂Powder.

Adopt solution method to prepare CuAlO ₂Powder, this method not only preparation cost is low, and simple to operate, reaction time is short, and whole process of preparation need not expensive vacuum device, obtains CuAlO so this method can low-cost high-efficiency ₂Powder.

Description of drawings

The CuAlO that Fig. 1 prepares for the present invention ₂The X-ray diffraction of powder (XRD) collection of illustrative plates.

The CuAlO that Fig. 2 prepares for the present invention ₂The scanning electron microscope of powder (SEM) photo.

Embodiment

Embodiment 1:

Step 1: at first will be mixed with Cu in the analytically pure water venus crystals adding ethylene glycol ²⁺Concentration is the blue clear solution of 0.2mol/L, and gained solution is designated as A;

Step 2: in A solution, add analytically pure nine water aluminum nitrates then, feasible (Cu ²⁺): (Al ³⁺The mol ratio of)=1: 1, and constantly stirring adds molar fraction and is 0.6% HCOOH reagent simultaneously, and stirring and regulating pH value down is 3.0, and formation uniform precursor solution solution is designated as B;

Step 3: above-mentioned B solution is put into loft drier at 120 ℃ of dry 8h, make it form xerogel, with stand-by behind the xerogel usefulness agate mortar porphyrize;

Step 4: the xerogel of porphyrize is put into retort furnace at 1200 ℃, and calcining 3h cools to room temperature with the furnace, promptly obtains CuAlO ₂Powder.

CuAlO with gained ₂Powder finds that with Japanese D/max2000PC x-ray diffractometer analytic sample of science product is the CuAlO that JCPDS is numbered 35-1401 ₂(Fig. 1).This sample is observed with the JSM-6390A type scanning electronic microscope (Fig. 2) that Japanese JEOL company produces, from the prepared as can be seen CuAlO of photo ₂Powder is a spherical particle.

Embodiment 2:

Step 1: at first will be mixed with Cu in the analytically pure water venus crystals adding ethylene glycol ²⁺Concentration is the blue clear solution of 0.1mol/L, and gained solution is designated as A;

Step 2: in A solution, add analytically pure nine water aluminum nitrates then, feasible (Cu ²⁺): (Al ³⁺The mol ratio of)=1: 1, and constantly stirring adds molar fraction and is 0.5% HCOOH reagent simultaneously, and stirring and regulating pH value down is 2.0, and formation uniform precursor solution solution is designated as B;

Step 3: above-mentioned B solution is put into loft drier at 80 ℃ of dry 12h, make it form xerogel, with stand-by behind the xerogel usefulness agate mortar porphyrize;

Step 4: the xerogel of porphyrize is put into retort furnace at 1100 ℃, and calcining 5h cools to room temperature with the furnace, promptly obtains CuAlO ₂Powder.

Embodiment 3:

Step 1: at first will be mixed with Cu in the analytically pure water venus crystals adding ethylene glycol ²⁺Concentration is the blue clear solution of 0.4mol/L, and gained solution is designated as A;

Step 2: in A solution, add analytically pure nine water aluminum nitrates then, feasible (Cu ²⁺): (Al ³⁺The mol ratio of)=1: 1, and constantly stirring adds molar fraction and is 0.8% HCOOH reagent simultaneously, and stirring and regulating pH value down is 4.0, and formation uniform precursor solution solution is designated as B;

Step 3: above-mentioned B solution is put into loft drier at 100 ℃ of dry 10h, make it form xerogel, with stand-by behind the xerogel usefulness agate mortar porphyrize;

Step 4: the xerogel of porphyrize is put into retort furnace at 1130 ℃, and calcining 4h cools to room temperature with the furnace, promptly obtains CuAlO ₂Powder.

Embodiment 4:

Step 1: at first will be mixed with Cu in the analytically pure water venus crystals adding ethylene glycol ²⁺Concentration is the blue clear solution of 0.5mol/L, and gained solution is designated as A;

Step 2: in A solution, add analytically pure nine water aluminum nitrates then, feasible (Cu ²⁺): (Al ³⁺The mol ratio of)=1: 1, and constantly stirring adds molar fraction and is 1.0% HCOOH reagent simultaneously, and stirring and regulating pH value down is 4.0, and formation uniform precursor solution solution is designated as B;

Step 3: above-mentioned B solution is put into loft drier at 90 ℃ of dry 11h, make it form xerogel, with stand-by behind the xerogel usefulness agate mortar porphyrize;

Step 4: the xerogel of porphyrize is put into retort furnace at 1170 ℃, and calcining 4h cools to room temperature with the furnace, promptly obtains CuAlO ₂Powder.

Claims (1)

1. CuAlO ₂The preparation method of powder is characterized in that:

Step 1: at first will be mixed with CU in the analytically pure water venus crystals adding ethylene glycol ²⁺Concentration is the blue clear solution of 0.1mol/L～0.5mol/L, and gained solution is designated as A;

Step 2: in A solution, add analytically pure nine water aluminum nitrates then, feasible (Cu ²⁺): (Al ³⁺The mol ratio of)=1: 1, and constantly stirring adds molar fraction and is 0.5%～1.0% HCOOH reagent simultaneously, and stirring and regulating pH value down is 2.0～4.0, formation uniform precursor solution B;

Step 3: above-mentioned B solution is put into loft drier at 80 ℃～120 ℃ dry 8h～12h, make it form xerogel, with stand-by behind the xerogel usefulness agate mortar porphyrize;

Step 4: the xerogel of porphyrize is put into retort furnace at 1100～1200 ℃, and calcining 3～5h cools to room temperature with the furnace, promptly obtains CuAlO ₂Powder.

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