CN101774822B

CN101774822B - Method for preparing CuAlO2 film with microwave hydrothermal process

Info

Publication number: CN101774822B
Application number: CN2009102188673A
Authority: CN
Inventors: 黄剑锋; 李抗; 曹丽云; 吴建鹏
Original assignee: Shaanxi University of Science and Technology
Current assignee: Shaanxi University of Science and Technology
Priority date: 2009-10-30
Filing date: 2009-10-30
Publication date: 2012-02-15
Anticipated expiration: 2029-10-30
Also published as: CN101774822A

Abstract

The invention relates to a method for preparing a CuAlO2 film with a microwave hydrothermal process, which comprises the following steps that: copper acetate monohydrate is firstly added into ethylene glycol to obtain solution A; the pH value is adjusted to be 2.0 to 4.0 after aluminum nitrate nonahydrate is added into the solution A to form uniform precursor solution B; solution B is poured into a hydrothermal reaction kettle, and a silicon substrate is steeped in the solution B; the hydrothermal reaction kettle is sealed to be arranged inside a MDS-8 temperature-pressure dual-control microwave hydrothermal reaction instrument; the temperature control mode or the pressure control mode is selected, and the reaction kettle is naturally cooled to the room temperature after the reaction; the hydrothermal reaction kettle is opened, the silicon substrate is taken out to be washed for many times respectively by deionized water, absolute ethyl alcohol or isopropanol and then to be dried to obtain the CuAlO2 film. The CuAlO2 film is prepared with the microwave hydrothermal method. Not only the preparation cost is low, the operation is simple, and the reaction period is short, but also the purity of the product is high, the development of the crystal particles is complete, the granular distribution is uniform, the shape is controllable, and the calcination treatment is not required. The CuAlO2 film which is produced by the preparation method is uniform and compact and has strong binding force.

Description

A kind of microwave-hydrothermal method prepares CuAlO 2The method of film

Technical field

The present invention relates to the preparation method of a kind of p type transparent conductive oxide (TCO) film, be specifically related to a kind of microwave-hydrothermal method and prepare CuAlO ₂The method of film.

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 that with the p-n junction are semi-conductor full impregnated Mingguang City electrical part on basis.People such as Kawazoe had delivered about P type electrically conducting transparent CuAlO in 1997 ₂The RR of film (Hiroshi Kawazoe; MasahiroYasukawa, Hiroyuki HyodoP-type electrical conduction in transparentthin films of CuAlO2Nature, 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 successfully to prepare CuAlO ₂Film comprises magnetron sputtering method (A.N.Banerjee, S.Kundoo; K.K.Chattopadhyay; Thin SolidFilms 440 (2003) 5-10), 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 (H.Gong; Y.Wang, Y.Luo, Appl.Phys.Lett.76 (2000) 3959.), pulsed laser deposition (M.Neumann-Spallart; S.P.Pai, R.Pinto Thin Solid Films 515 (2007) 8641-8644) etc.Above method or higher to equipment requirements, complicated operation and cost are high, perhaps are exactly complex process, and the cycle is long, poor repeatability etc.

Summary of the invention

The objective of the invention is to propose that a kind of not only preparation cost is low, simple to operate, reaction time is short, and product purity is high, crystal grain is grown complete, even particle size distribution, controllable shapes and do not need a kind of microwave-hydrothermal method of calcination processing to prepare CuAlO ₂The method of film.

For achieving the above object, the technical scheme that the present invention adopts is:

Step 1: at first with being mixed with Cu in the analytically pure water venus crystals adding terepthaloyl moietie 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 x 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: B solution is poured in the hydrothermal reaction kettle, and compactedness is controlled at 50-80%; Silicon substrate is placed in the hydrothermal reaction kettle, is dipped in the B solution; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode or pressure control pattern to react; The hydrothermal temperature of said temperature controlling mode is controlled at 100-200 ℃, and the hydro-thermal pressure-controlling of pressure control pattern naturally cools to room temperature at 0.5MPa-4.0MPa behind the reaction 10min-90min;

Step 4: open hydrothermal reaction kettle, take out silicon substrate, adopt deionized water, absolute ethyl alcohol or washed with isopropyl alcohol for several times then respectively, promptly get CuAlO 60 ℃ of vacuum-dryings ₂Film.

Silicon substrate of the present invention soaked 5 minutes in volumetric concentration is 20% HF solution earlier before being rotated in hydrothermal reaction kettle, used washed with de-ionized water, carried out ultrasonic cleaning with ethanolic soln then.

The present invention adopts microwave-hydrothermal method to prepare CuAlO ₂Film.Since microwave-hydrothermal method be adopt microwave field as thermal source carry out hydro-thermal synthetic method (Wang Yongzai. Chinese Journal of Inorganic Chemistry; 2007; 23:1055-1058), it is fast that microwave heating has speed, advantages such as no thermograde; Not only preparation cost is low, simple to operate, reaction time is short, and product purity is high, crystal grain is grown complete, even particle size distribution, controllable shapes and do not need calcination processing.The CuAlO that makes by preparation method of the present invention ₂Film even compact, bonding force are strong.

Description of drawings

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

Embodiment

Embodiment 1:

Step 1: at first with being mixed with Cu in the analytically pure water venus crystals adding terepthaloyl moietie 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 x and is 0.5% HCOOH reagent simultaneously, and stirring and regulating pH value down is 2.0, formation uniform precursor solution B;

Step 3: is to soak 5 minutes in 20% the HF solution silicon substrate in volumetric concentration, uses washed with de-ionized water, carries out ultrasonic cleaning with ethanolic soln then, gets B solution then and pours in the hydrothermal reaction kettle, and compactedness is controlled at 60%; Silicon substrate after the ultrasonic cleaning is placed in the hydrothermal reaction kettle, is dipped in the B solution; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, hydrothermal temperature is controlled at 100 ℃, naturally cools to room temperature behind the reaction 90min;

Embodiment 2:

Step 1: at first with being mixed with Cu in the analytically pure water venus crystals adding terepthaloyl moietie 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 x and is 0.6% HCOOH reagent simultaneously, and stirring and regulating pH value down is 3.0, formation uniform precursor solution B;

Step 3: is to soak 5 minutes in 20% the HF solution silicon substrate in volumetric concentration, uses washed with de-ionized water, carries out ultrasonic cleaning with ethanolic soln then, gets B solution then and pours in the hydrothermal reaction kettle, and compactedness is controlled at 50%; Silicon substrate after the ultrasonic cleaning is placed in the hydrothermal reaction kettle, is dipped in the B solution; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react; Hydrothermal temperature is controlled at 200 ℃, naturally cools to room temperature behind the reaction 10min;

Embodiment 3:

Step 1: at first with being mixed with Cu in the analytically pure water venus crystals adding terepthaloyl moietie 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 x and is 0.8% HCOOH reagent simultaneously, and stirring and regulating pH value down is 4.0, formation uniform precursor solution B;

Step 3: is to soak 5 minutes in 20% the HF solution silicon substrate in volumetric concentration, uses washed with de-ionized water, carries out ultrasonic cleaning with ethanolic soln then, gets B solution then and pours in the hydrothermal reaction kettle, and compactedness is controlled at 70%; Silicon substrate after the ultrasonic cleaning is placed in the hydrothermal reaction kettle, is dipped in the B solution; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react; Hydrothermal temperature is controlled at 160 ℃, naturally cools to room temperature behind the reaction 50min;

Embodiment 4:

Step 1: at first with being mixed with Cu in the analytically pure water venus crystals adding terepthaloyl moietie 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 x and is 1.0% HCOOH reagent simultaneously, and stirring and regulating pH value down is 4.0, formation uniform precursor solution B;

Step 3: is to soak 5 minutes in 20% the HF solution silicon substrate in volumetric concentration, uses washed with de-ionized water, carries out ultrasonic cleaning with ethanolic soln then, gets B solution then and pours in the hydrothermal reaction kettle, and compactedness is controlled at 80%; Silicon substrate after the ultrasonic cleaning is placed in the hydrothermal reaction kettle, is dipped in the B solution; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select the pressure control pattern to react; The hydro-thermal pressure-controlling of pressure control pattern naturally cools to room temperature at 0.5MPa behind the reaction 80min;

Embodiment 5:

Step 1: at first with being mixed with Cu in the analytically pure water venus crystals adding terepthaloyl moietie ²⁺Concentration is the blue clear solution of 0.3mol/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 x and is 0.7% HCOOH reagent simultaneously, and stirring and regulating pH value down is 3.0, formation uniform precursor solution B;

Step 3: is to soak 5 minutes in 20% the HF solution silicon substrate in volumetric concentration, uses washed with de-ionized water, carries out ultrasonic cleaning with ethanolic soln then, gets B solution then and pours in the hydrothermal reaction kettle, and compactedness is controlled at 65%; Silicon substrate after the ultrasonic cleaning is placed in the hydrothermal reaction kettle, is dipped in the B solution; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select the pressure control pattern to react; The hydro-thermal pressure-controlling of pressure control pattern naturally cools to room temperature at 2.0MPa behind the reaction 40min;

Embodiment 6:

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 x and is 0.9% HCOOH reagent simultaneously, and stirring and regulating pH value down is 2.0, formation uniform precursor solution B;

Step 3: is to soak 5 minutes in 20% the HF solution silicon substrate in volumetric concentration, uses washed with de-ionized water, carries out ultrasonic cleaning with ethanolic soln then, gets B solution then and pours in the hydrothermal reaction kettle, and compactedness is controlled at 75%; Silicon substrate after the ultrasonic cleaning is placed in the hydrothermal reaction kettle, is dipped in the B solution; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select the pressure control pattern to react; The hydro-thermal pressure-controlling of pressure control pattern naturally cools to room temperature at 4.0MPa behind the reaction 20min;

Referring to Fig. 1, with the CuAlO of gained ₂Film finds that with Japanese D/max2000PC x-ray diffractometer analytic sample of science product is the CuAlO that JCPDS is numbered 35-1401 ₂

Claims

1. a microwave-hydrothermal method prepares CuAlO ₂The method of film is characterized in that:

2. microwave-hydrothermal method according to claim 1 prepares CuAlO ₂The method of film is characterized in that: described silicon substrate soaked 5 minutes in volumetric concentration is 20% HF solution earlier before being positioned over hydrothermal reaction kettle, used washed with de-ionized water, carried out ultrasonic cleaning with ethanolic soln then.