CN107540402A - A kind of preparation method of porous calcium copper titanate film - Google Patents

Abstract

The invention discloses a kind of porous CaCu 3 Ti 4 O CaCu₃Ti₄O₁₂（Abbreviation CCTO）The preparation method of film, this method is with nickel acid lanthanum LaNiO₃（Abbreviation LNO）For cushion, on the substrate of LNO coverings, CCTO wet films are coated using solution chemical processes；By heat treatment, the CCTO films with loose structure are obtained.The present invention can prepare the CCTO thin-film materials that loose structure is presented in surface topography under the process conditions of lower cost, be had broad application prospects in fields such as porous ceramics, high density energy storages without template.

Description

A kind of preparation method of porous calcium copper titanate film

Technical field

The invention belongs to technical field of inorganic non-metal material preparation, more particularly to a kind of system of calcium copper titanate film material Preparation Method, the method for referring to prepare porous calcium copper titanate film on various substrates by solution chemical processes.

Technical background

The development of porous ceramics starts from 1870s, is merely possible to bacteriological filter and uranium purification material initial stage To use.As material prepares horizontal continuous improvement and the variation of technique, various plastics on new materials, high-performance porous ceramics material Material continuously emerges, and its application field and scope also expand and developed continuous.Due to the covalent bond and complicated ions of porous ceramics The bonding of key and the crystal structure of complexity, have the characteristics of high temperature resistant, corrosion-resistant and heat endurance is good.Also, work as fluid stream During through hole, porous ceramic film material surfaces externally and internally can produce various physical chemistry effects（Such as capillary siphonic effect）. Porous ceramics possesses the crowds such as density is low, permeability is high, specific surface area is big, corrosion-resistant, low-thermal conductivity and high temperature resistant due to it More good characteristics, cause the highest attention of whole world material circle.This material is widely used in catalyst carrier, and industry is dirty Numerous aspects such as water process, melted metal filtering, vehicle maintenance service, thermal and sound insulating materials.With the development of science and technology, it is more The application of hole ceramics expands to electronic applications, field of Environment Protection, biochemical field, field of medical materials and aviation field etc. again.

With Information technology industry and electronics, electric power related industries fast development, there is high-k and low dielectric to damage The electron ceramic material of consumption, become the focus of industry concern.Such material is mainly used in the production of high power capacitor, because And require that it has the characteristics of in light weight, energy storage density is high, stability is strong, this require material to have density is small, dielectric constant Big characteristic.2000 or so, scientist was found that CaCu₃Ti₄O₁₂(abbreviation CCTO) material, this material have very high Dielectric constant, relatively low loss and higher heat endurance, cause the extensive concern of people.Its good combination property, make It is expected to be applied in the electrode components such as high density energy storage, high dielectric capacitor.Reported at present in document CCTO ceramic materials prepare use solid reaction process, sintering temperature is from 850 DEG C to more than 1000 DEG C, and constant temperature time is from several small Up to tens hours.There is larger energy waste in solid reaction process, do not meet the strategic trend of national sustainable development. The preparation of CCTO films mainly has physical method（Pulsed laser deposition, magnetron sputtering etc.）And chemical method（Sol-gel process Deng）.Wherein, the cost of chemical method is cheap, and annealing temperature is relatively low（750℃）, processing step is relatively simple and easily operated, is A kind of method for preparing CCTO films of convenience and high-efficiency.

Although CCTO has high dielectric constant, but meet the needs of high density energy storage, but above method preparation CCTO materials are fine and close polycrystalline ceramics, and surface topography has no obvious special construction, can not meet device/apparatus weight Gently, the small requirement of density.And the preparation of porous membrane at present, the method filled mostly using template or organic polymer pellets, Need to remove removing template and filler using the process procedure such as corrosion or sintering, add the complexity of technique.

The content of the invention

The purpose of the present invention is to be directed to problems of the prior art, proposes one kind without template or filler, you can Prepare the method that the calcium copper titanate film material of porous pattern is presented in surface.

To achieve the above object, the concrete technical scheme that the present invention uses is as follows：

A, by either physically or chemically covering one layer of nickel acid lanthanum LaNiO on substrate₃Cushion, the buffer layer thickness 10~ 30nm；

B, the configuration of CaCu 3 Ti 4 O precursor solution

Take copper nitrate Cu (NO₃)₂, calcium nitrate Ca (NO₃)₂Solid is 3 in molar ratio:1 ratio is dissolved in ethylene glycol monomethyl ether, Heating stirring 1~6 hour, is allowed to form homogeneous solution in 30~80 DEG C of water-baths；According still further to Ca:Ti atomic molars are than 1:4 ratio Example measures butyl titanate and the acetylacetone,2,4-pentanedione of identical molal quantity adds solution, small in 30~80 DEG C of stirred in water bath heating 1~8 When, it is allowed to form homogeneous solution, is finally made into 0.01~0.1mol/L of concentration CaCu 3 Ti 4 O precursor solution；

C, porous calcium copper titanate film is prepared

Using the mode such as spin-coating or lifting film, CaCu 3 Ti 4 O presoma is coated on the substrate with nickel acid lanthanum cushion Solution, obtain CaCu 3 Ti 4 O wet film；Three-stage heat treatment is carried out in quick anneal oven：First paragraph, during 140~200 DEG C of temperature It is long 180~360 seconds；Second segment, 360~420 DEG C of temperature duration 180~360 seconds；3rd section, 650~850 DEG C of durations of temperature 180~600 seconds, one layer of porous calcium copper titanate film is obtained, repeats the coating-heat treatment process, obtains multilayer metatitanic acid Copper calcium porous membrane；Its pore diameter range is between 40~200nm.

Compared with prior art, the method have the characteristics that：(1) calcium copper titanate film obtained is loose structure；(2) Without template or filler in calcium copper titanate film growth course；(3) aperture controllable of porous calcium copper titanate film.

Brief description of the drawings

Fig. 1 is the AFM figures of the nickel acid lanthanum buffer-layer surface of embodiment 1；

Fig. 2 is the AFM figures of the porous calcium copper titanate film of embodiment 1；

Fig. 3 is the altitude scale figure of AFM figures shown in Fig. 1；

Fig. 4 is the cross section curve figure of the porous calcium copper titanate film of embodiment 1.

Embodiment

Embodiment 1

A, the selection and cleaning of substrate

Using<100>Heavily doped silicon substrate, substrate ethanol and deionized water are ultrasonically treated 20 minutes, place into rapid thermal treatment dress Put, carry out two sections of annealing：First paragraph, 200 DEG C of duration 200s of temperature；Second segment, 400 DEG C of duration 200s of temperature.

B, prepared by nickel acid lanthanum cushion

Weigh lanthanum nitrate La (NO₃)₃·6H₂3.2 grams of O solids, according to La:Ni atomic molars are than 1:1 ratio weighs nickel acetate C₄H₆O₄Ni·4H₂O solids, alcohol solvent is added, heated 3 hours or so in 40 DEG C of stirred in water bath, obtain concentration 0.1mol/ L nickel acid lanthanum homogeneous solution.A period of time is stood, no precipitation can be used.

Clean silicon substrate is placed in sol evenning machine, 4000 revs/min of rotating speed is set, using above-mentioned nickel acid lanthanum solution in silicon One layer of nickel acid lanthanum wet film is coated on substrate；It is put into rapid thermal process apparatus and carries out three sections of heat treatments：First paragraph, during 180 DEG C of temperature It is long 240 seconds；Second segment, 380 DEG C of temperature duration 240 seconds；3rd section, 700 DEG C of temperature duration 300 seconds, you can one thickness of growth The nickel acid lanthanum cushion that about 10 nanometers of degree.From accompanying drawing 1, nickel acid lanthanum surfacing, in the absence of obvious hole.

C, the configuration of CaCu 3 Ti 4 O precursor solution

Copper nitrate Cu (NO are weighed respectively₃)₂With calcium nitrate Ca (NO₃)₂0.3542 gram and 1.0872 grams of solid dissolves in ethylene glycol monomethyl ether Solvent, heating stirring 1 hour or so, is allowed to form homogeneous solution in 40 DEG C of water-baths.Butyl titanate and acetylacetone,2,4-pentanedione are measured again Each 0.9 milliliter of addition solution, heats 2 hours or so in 40 DEG C of stirred in water bath, is allowed to form homogeneous solution, is finally made into dense Spend 0.05mol/L CaCu 3 Ti 4 O solution.

D, porous calcium copper titanate film is prepared

Silicon chip with nickel acid lanthanum cushion is placed on sol evenning machine, setting speed 4000r/min, 20 seconds time, coats titanium Sour copper calcium solution, obtain CaCu 3 Ti 4 O wet film.Three-stage heat treatment is carried out in quick anneal oven：First paragraph, 180 DEG C of temperature Duration 240 seconds；Second segment, 380 DEG C of temperature duration 240 seconds；3rd section, 700 DEG C of temperature duration 300 seconds, obtain one layer of metatitanic acid Copper calcium porous membrane, above-mentioned coating-heat treatment process is repeated, obtain two layers of CaCu 3 Ti 4 O porous membrane（See accompanying drawing 2）, thickness is about 40 nanometers, about 120 nanometers of maximum diameter of hole（See accompanying drawing 4）.

Embodiment 2

A, the selection and cleaning of substrate

Using quartz glass as substrate.Substrate ethanol and deionized water are ultrasonically treated 20 minutes, are dried up with high pure nitrogen.

B, prepared by nickel acid lanthanum cushion

Cleaned quartz glass substrate is fixed on the sample tray of impulse laser deposition system.Deposit cavity is evacuated to 10^-5Below Pa；The oxygen that purity is not less than 99.999% is passed through, cavity air pressure maintains 5Pa；Sample tray is heated to 700^oC； Pulse laser ablation nickel acid lanthanum target, laser frequency 5Hz；After laser shutdown, cavity oxygen pressure is promoted to 100Pa, is incubated 30 points Clock, obtain the nickel acid lanthanum cushion of about 10 nanometers of thickness.

C, the configuration of CaCu 3 Ti 4 O precursor solution

By calcium nitrate Ca (NO₃)₂, copper nitrate Cu (NO₃)₂By Ca:Cu atomic molars are than 1:3 are dissolved in ethylene glycol monomethyl ether, and heating is stirred Mix and be allowed to form homogeneous solution.According still further to Ca:Ti atomic molars are than 1:4 acetylacetone,2,4-pentanediones for measuring butyl titanate and equivalent add molten Liquid, heated 2 hours or so in 40 DEG C of stirred in water bath, be allowed to form homogeneous solution, be finally made into concentration 0.05mol/L titanium Sour copper calcium precursor solution.

D, porous calcium copper titanate film is prepared

Substrate with nickel acid lanthanum cushion is placed on sol evenning machine, setting speed 6000r/min, 20 seconds spin coating times, applied CaCu 3 Ti 4 O solution is covered, obtains CaCu 3 Ti 4 O wet film.Three segmented mode heat treatments are carried out in quick anneal oven：First paragraph, temperature 180 DEG C of durations 240 seconds；Second segment, 380 DEG C of temperature duration 240 seconds；3rd section, 750 DEG C of temperature duration 300 seconds, obtain one Layer CaCu 3 Ti 4 O porous membrane, repeats above-mentioned coating-heat treatment process, obtains multilayer CaCu 3 Ti 4 O porous membrane.

Claims (1)

1. a kind of preparation method of porous calcium copper titanate film, it is characterised in that this method includes step in detail below：

A, by either physically or chemically covering one layer of nickel acid lanthanum LaNiO on substrate₃Cushion, the buffer layer thickness 10~ 30nm；

B, the configuration of CaCu 3 Ti 4 O precursor solution

Take copper nitrate Cu (NO₃)₂, calcium nitrate Ca (NO₃)₂Solid is dissolved in ethylene glycol monomethyl ether for 3 ︰ 1 ratio in molar ratio, 30 Heating stirring 1~6 hour, is allowed to form homogeneous solution in~80 DEG C of water-baths；According still further to ratio of the Ca ︰ Ti atomic molars than 1 ︰ 4 The acetylacetone,2,4-pentanedione for measuring butyl titanate and identical molal quantity adds solution, is heated 1~8 hour in 30~80 DEG C of stirred in water bath, It is allowed to form homogeneous solution, is finally made into 0.01~0.1mol/L of concentration CaCu 3 Ti 4 O precursor solution；

C, porous calcium copper titanate film is prepared

Using the mode such as spin-coating or lifting film, CaCu 3 Ti 4 O presoma is coated on the substrate with nickel acid lanthanum cushion Solution, obtain CaCu 3 Ti 4 O wet film；Three-stage heat treatment is carried out in quick anneal oven：First paragraph, during 140~200 DEG C of temperature It is long 180~360 seconds；Second segment, 360~420 DEG C of temperature duration 180~360 seconds；3rd section, 650~850 DEG C of durations of temperature 180~600 seconds, one layer of porous calcium copper titanate film is obtained, repeats the coating-heat treatment process, obtains multilayer metatitanic acid Copper calcium porous membrane；Its pore diameter range is between 40~200nm.