CN103833416B - A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel - Google Patents
A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel Download PDFInfo
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- CN103833416B CN103833416B CN201410021232.5A CN201410021232A CN103833416B CN 103833416 B CN103833416 B CN 103833416B CN 201410021232 A CN201410021232 A CN 201410021232A CN 103833416 B CN103833416 B CN 103833416B
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Abstract
The present invention relates to a kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel in microelectronic manufacturing technology field, its step mainly includes LaNiO3The preparation of colloidal sol, then using dip-coating method or spin coating method, prepares LaNiO on substrate3Gel mould, then gel mould is dried to form LaNiO3Gel dry film；Then it will be covered with LaNiO3The substrate of gel dry film is transferred in quartz tube type heating furnace, in H-2O、O2Thermally decomposed under mixed atmosphere；Finally by the gel dry film after thermal decomposition, it is put into together with its substrate in quartz tube type sintering furnace, in H2O、O2High-temperature calcination is carried out under mixed atmosphere, conductive film is finally formed on substrate.The resistivity of the conductive film of this method formation is lower.
Description
Technical field
The present invention relates to the technology of preparing of microelectronic material and the conductive film of devices field, and in particular to a kind of nickel acid
Lanthanum LaNiO3The preparation method of conductive film.
Background technology
In terms of microelectronic component, the conductive film with certain electric conductivity has important application prospect.Either take
It is engaged in the hearth electrodes of other films, or it is special as the core component of device conducts electric current, or even as some parts
Heater, the film with suitable conductivity serves key effect.In these conductive films, with inorganic thin film and metal foil
Based on film.Metallic film has excellent resistivity, but because being oxidized easily, so as to influence the life-span of device；Inorganic thin film
Although resistivity is not so good as metallic film, because its corrosion-resistant, high temperature resistant, and resistance to oxidation, so that with good heat endurance
And chemical stability.In inorganic thin film, mainly there are transparent conductive film such as ITO, ATO etc., with good conductance, be usually used in
The hearth electrode film layer of optics.Other class inorganic conductive film is perovskite structural material, such as LaNiO3,
YBa2Cu3O7-x, La0.5Sr0.5CoO3It is nontransparent black inorganic material Deng material.They have excellent resistivity, and
The perovskite structure similar with ferroelectricity, piezoelectric membrane, so that they store in ferroelectricity, the devices field such as energy storage has important
Application.
At present, LaNiO is prepared3, YBa2Cu3O7-x, La0.5Sr0.5CoO3Method Deng film mainly has pulsed laser deposition
The in-situ deposition techniques such as method (PLD), magnetron sputtering method (MS), metal-organic chemical vapor deposition equipment method (MOCVD), also there is gold
Belong to the chemical solution deposition of organic-matter chemical liquid phase deposition (MOD) and sol-gal process (Sol ~ Gel) isotonic deposition
Method (CSD).Wherein, first three in-situ deposition technique, without follow-up annealing heat-treats, but is required to be related to expensive
Vacuum equipment；And CSD methods belong to chemical method masking technique, equipment is simple, and the stoichiometric proportion of easily controllable metal ion,
Easily prepared large area film, therefore get more and more people's extensive concerning.
But compared with the in-situ deposition technique such as PLD, MS, MOCVD, the conduction of the film prepared by the CSD methods of dystopy deposition
Rate often has certain gap.How LaNiO is improved3 Deng the quality of film, particularly its resistivity is that CSD methods have to solution
The problem of.
The content of the invention
It is an object of the invention to provide a kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel.It passes through simple
Solution prepare, and the Technology for Heating Processing subsequently optimized, you can obtain the smaller LaNiO of resistivity3Conductive film.
The technical solution adopted in the present invention is as follows：A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel,
It is characterized in that comprising the following steps：
1）By nickel acetate dissolving in organic solvent, complexing agent is added, by stirring 1 ~ 3 hour, obtained after settled solution,
Lanthanum nitrate powder is added, continues to stir to clarify, LaNiO is obtained3Colloidal sol；The LaNiO3Nickel acetate in colloidal sol, lanthanum nitrate,
Complexing agent, the mol ratio of organic solvent are 1:（1.2~1.4）:（2~5）:（20~40）；
2）By step 1）The LaNiO of preparation3Colloidal sol, using dip-coating method or spin coating method, is prepared on substrate
LaNiO3Gel mould, then will be covered with LaNiO3The substrate of gel mould dries 5 ~ 20min at a temperature of 100 ~ 150 DEG C, makes
LaNiO3Gel mould is dried to form LaNiO3Gel dry film；
3）It will be covered with LaNiO3The substrate of gel dry film is transferred in quartz tube type heating furnace, in H2O、O2Under mixed atmosphere
Thermally decomposed；The H2O、O2In mixed atmosphere, H2O percent by volume be 1.3 ~ 8vol%, during thermal decomposition, with 5 ~ 10 DEG C/
Min speed cools to room temperature with the furnace after being warming up to 380 ~ 420 DEG C, 5 ~ 10min of insulation；
4）By step 3）Gel dry film after thermal decomposition, is put into quartz tube type sintering furnace together with its substrate, in H2O、O2It is mixed
Close and carry out high-temperature calcination under atmosphere；The H2O、O2In mixed atmosphere, H2O percent by volume is 1.3 ~ 8vol%；High-temperature calcination
When, cool to room temperature with the furnace after being warming up to 700 ~ 750 DEG C, 30 ~ 100min of insulation with 5 ~ 10 DEG C/min speed, the shape on substrate
Into conductive film.
To increase the thickness of conductive film, in step 4）Preceding repeat step 2）~3）1 ~ 5 time.
Above-mentioned H2O、O2The implementation method of mixed atmosphere is as follows：Oxygen is serially connected by 2 ~ 3, temperature is adjustable,
Equipped with liquid H2O vessel, H2O is by evaporation or by O2Bring out to form H2O、O2Mixed gas, then by H2O、O2Gaseous mixture
Body is passed through in quartz tube type heating furnace and quartz tube type sintering furnace.
In the present invention, the organic solvent can be ethylene glycol monomethyl ether, ethanol or methanol.The complexing agent can be propionic acid or third
Olefin(e) acid.The substrate can be lanthanum aluminate（LAO）, strontium titanates（SrTiO3）Monocrystal chip or single crystalline Si substrate.
The beneficial effects of the invention are as follows：
1）The present invention improves La content, makes its excess, and reduce in follow-up heat treatment process causes because of thermal decomposition
La, Ni element ratio it is unbalance；Dephasign NiO generation is avoided in the conductive film finally obtained.
2）Oxygen vacancy concentration can cause the change of LNO band structures in conductive film, the increase of Lacking oxygen can cause LNO from
Conductor is transitioned into semiconductor even insulator, and the present invention uses vapor and oxygen in the heat treatment of gel dry film and calcination process
The mixed atmosphere of gas, can reduce the increase degree of conductive film oxygen defect, its oxygen vacancy concentration is than dry oxygen, dry nitrogen, wet nitrogen
The oxygen vacancy concentration of prepared sample is low in gas atmosphere, and the resistivity of gained conductive film can be lower, and the order of magnitude is up to 10-4
Ω·cm。
Brief description of the drawings
Fig. 1 is LaNiO on LAO substrates that the embodiment of the present invention 1 is prepared3The XRD of conductive film.
Fig. 2 is LaNiO on LAO substrates that the embodiment of the present invention 1 is prepared3The XRD of conductive film.
Fig. 3 is LaNiO on the LAO substrates of the preparation of the embodiment of the present invention 13The Si substrates that conductive film is prepared with embodiment 2
Upper LaNiO3The SEM comparison diagrams of conductive film.
Fig. 4 is wet oxygen atmosphere and dry oxygen, dry nitrogen, wet nitrogen gas on the Si substrates of the preparation of the embodiment of the present invention 2
The LaNiO prepared under atmosphere3The comparison diagram of conductive film resistivity.
Embodiment
Embodiment 1
A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel, its step is as follows：
1）Using nickel acetate as raw material, nickel acetate is dissolved in ethylene glycol monomethyl ether, addition acrylic acid is complexing agent, prepares Ni
Solution.Ni solution was obtained after settled solution by stirring 1.5 hours, is added lanthanum nitrate powder, is continued to stir to clarify, and was obtained
LaNiO3Colloidal sol, the LaNiO3Nickel acetate, lanthanum nitrate, acrylic acid, the mol ratio of ethylene glycol monomethyl ether are 1 in colloidal sol: 1.3: 2:
30。
2）By step 1）The LaNiO of preparation3Colloidal sol, using dip-coating method, LaNiO is prepared on LAO monocrystal chips3It is solidifying
Glued membrane, then will be covered with LaNiO3The substrate of gel mould dries 10min at a temperature of 150 DEG C, makes LaNiO3Gel mould is dried
Form LaNiO3Gel dry film.
3）By step 2）What is obtained carries LaNiO3The LAO monocrystal chips of gel dry film are transferred in quartz tube type heating furnace,
The moist oxygen containing certain water vapour is passed through, in H2O、O2Thermally decomposed under mixed atmosphere, wherein, the H2O、O2Gaseous mixture
In atmosphere, H2O percent by volume is 1.3 ~ 5vol%.During thermal decomposition, 400 DEG C, insulation are warming up to 10 DEG C/min speed
After 10min, heat-treatment furnace is closed, and closes gas, the substrate with gel dry film cools to room temperature with the furnace.
4）Repeat the above steps 2）、3）Totally 5 times, make LaNiO3Gel dry film is constantly thickened.
5）By step 4）Gel dry film after thermal decomposition, is put into quartz tube type sintering furnace together with its LAO monocrystal chip,
H2O、O2High-temperature calcination is carried out under mixed atmosphere, the H2O、O2Mixed atmosphere and the present embodiment step 3）The mode and H of middle acquisition2O
Percent by volume it is identical；During high-temperature calcination, cooled to the furnace after being warming up to 700 DEG C, insulation 60min with 10 DEG C/min speed
Room temperature, you can obtain the LaNiO that thickness on LAO monocrystal chips is 800nm3Conductive film, resistivity is up to 1.5 × 10-5Ω·cm。
Above-mentioned H2O、O2The implementation method of mixed atmosphere is as follows：Oxygen is serially connected by 2, temperature is adjustable, dress
There is liquid H2O vessel, H2O is by evaporation or by O2Bring out to form H2O、O2Mixed gas, then by H2O、O2Mixed gas
It is passed through in quartz tube type heating furnace and quartz tube type sintering furnace.
Fig. 1 is LaNiO on LAO substrates that the embodiment of the present invention 1 is prepared3The XRD of conductive film, shows conductive thin
Film is the pure LaNiO of polycrystalline No yield point3Phase film, exists without other dephasigns.
Fig. 2 is LaNiO on LAO substrates that the embodiment of the present invention 1 is prepared3The XRD of conductive film, shows film
（00l）The pure LaNiO of c-axis growth3Phase film.
Embodiment 2
A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel, its step is as follows：
1）Using nickel acetate as raw material, nickel acetate is dissolved in ethylene glycol monomethyl ether, addition acrylic acid is complexing agent, prepares Ni
Solution, Ni solution was obtained after settled solution by stirring 3 hours, added lanthanum nitrate powder, continued to stir clarification, you can obtain
LaNiO3Nickel acetate, lanthanum nitrate, acrylic acid, the mol ratio of ethylene glycol monomethyl ether are 1 in colloidal sol, the colloidal sol:1.3: 2:40.
2）By step 1）The LaNiO of preparation3Colloidal sol, using spin coating method, LaNiO is prepared on Si monocrystal chips3Gel
Film, then will be covered with LaNiO3The substrate of gel mould dries 10min at a temperature of 100 DEG C, makes LaNiO3Gel mould dries shape
Into LaNiO3Gel dry film.
3）By step 2）What is obtained carries LaNiO3The Si substrates of gel dry film are transferred in quartz tube type heating furnace, are passed through and are contained
The moist oxygen of certain water vapour, in H2O、O2It is lower in mixed atmosphere to be thermally decomposed, H in control mixed atmosphere2O volume hundred
Divide than being 2 ~ 6vol%.During thermal decomposition, it is increased to after 400 DEG C, insulation 10min, is closed at heat with 5 ~ 10 DEG C/min heating rate
Stove is managed, and closes gas, the substrate with gel dry film cools to room temperature with the furnace.
4）Repeat the above steps 2,3 for totally 5 times, make LaNiO3Gel dry film is thickened.
5）By step 4）Gel dry film after thermal decomposition, its Si monocrystal chip of UNICOM is put into quartz tube type sintering furnace,
H2O、O2High-temperature calcination is carried out under mixed atmosphere, the H2O、O2Mixed atmosphere and the present embodiment step 3）The mode and H of middle acquisition2O
Percent by volume it is identical；During high-temperature calcination, cooled to the furnace after being warming up to 700 DEG C, insulation 100min with 5 DEG C/min speed
Room temperature, you can obtain the LaNiO that thickness on Si monocrystal chips is 800nm3Conductive film, resistivity is up to 3.0 × 10-4Ω·cm。
Above-mentioned H2O、O2The implementation method of mixed atmosphere is as follows：Oxygen is serially connected by 3, temperature is adjustable, dress
There is liquid H2O vessel, H2O is by evaporation or by O2Bring out to form H2O、O2Mixed gas, then by H2O、O2Mixed gas
It is passed through in quartz tube type heating furnace and quartz tube type sintering furnace.
Fig. 3 is the LaNiO on LAO substrates prepared by the embodiment of the present invention 13The Si bases that conductive film is prepared with embodiment 2
LaNiO on piece3In the SEM comparison diagrams of conductive film, figure（a）For the LaNiO on LAO monocrystal chips3Conductive film,（a）For
LaNiO on single crystalline Si substrate3Conductive film, contrast picture shows the LaNiO on LAO substrates3Conductive film is more fine and close flat
It is whole, so as to show lower resistivity.
Fig. 4 is the LaNiO prepared under wet oxygen atmosphere on single crystalline Si substrate prepared by patent Example 2 of the present invention3
The LaNiO prepared under conductive film, with dry oxygen, wet nitrogen, dry nitrogen different atmosphere3The contrast of the resistivity of conductive film,
Show the LaNiO prepared under wet oxygen atmosphere3Conductive film has lower resistivity.
Embodiment 3
A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel, its step is as follows：
1）Using nickel acetate as raw material, by nickel acetate dissolving in ethanol, addition propionic acid is complexing agent, prepares Ni solution.Ni
Solution was obtained after settled solution by stirring 1 hour, added lanthanum nitrate powder, continued to stir clarification, you can obtain LaNiO3It is molten
Nickel acetate, lanthanum nitrate, propionic acid, the mol ratio of ethanol are 1 in glue, the colloidal sol:1.2: 2:40.
2）By step 1）The LaNiO of preparation3Colloidal sol, using spin coating method, LaNiO is prepared on LAO monocrystal chips3It is solidifying
Glued membrane, then will be covered with LaNiO3The substrate of gel mould dries 10min at a temperature of 120 DEG C, makes LaNiO3Gel mould is dried
Form LaNiO3Gel dry film.
3）By step 2）What is obtained carries LaNiO3The LAO monocrystal chips of gel dry film are transferred in quartz tube type heating furnace,
The moist oxygen containing certain water vapour is passed through, in H2O、O2Thermally decomposed under mixed atmosphere, H in control mixed gas2O body
Product percentage is 5 ~ 8vol%.During thermal decomposition, it is increased to 5 ~ 10 DEG C/min heating rate after 400 DEG C, insulation 10min, close
Heat-treatment furnace is closed, and closes gas, the substrate with gel dry film cools to room temperature with the furnace.
4）Repeat the above steps 2,3 for totally 3 times, make LaNiO3Gel dry film is thickened.
5）By step 4）Gel dry film after thermal decomposition, is put into quartz tube type sintering furnace together with LAO monocrystal chips,
H2O、O2High-temperature calcination is carried out under mixed atmosphere, the H2O、O2Mixed atmosphere and the present embodiment step 3）The mode and H of middle acquisition2O
Percent by volume it is identical；During high-temperature calcination, cooled to the furnace after being warming up to 700 DEG C, insulation 60min with 5 DEG C/min speed
Room temperature, you can obtain the LaNiO that thickness on LAO monocrystal chips is 500nm3Conductive film, resistivity is up to 5 × 10-4Ω·cm。
Above-mentioned H2O、O2The implementation method of mixed atmosphere is as follows：Oxygen is serially connected by 2, temperature is adjustable, dress
There is liquid H2O vessel, H2O is by evaporation or by O2Bring out to form H2O、O2Mixed gas, then by H2O、O2Mixed gas
It is passed through in quartz tube type heating furnace and quartz tube type sintering furnace.
Embodiment 4
A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel, comprises the following steps：
1）Using nickel acetate as raw material, by nickel acetate dissolving in methyl alcohol, complexing agent propionic acid is added, prepare Ni solution.Ni is molten
Liquid obtains after settled solution by stirring 2.5 hours, adds lanthanum nitrate powder, continue to stir to clarify, and obtains LaNiO3It is molten
Glue；The LaNiO3Nickel acetate, lanthanum nitrate, propionic acid, the mol ratio of methanol are 1 in colloidal sol: 1.4:5: 40.
2）By step 1）The LaNiO of preparation3Colloidal sol, using dip-coating method, prepares LaNiO on strontium titanate monocrystal chip3
Gel mould, then will be covered with LaNiO3The substrate of gel mould dries 5min at a temperature of 100 DEG C, makes LaNiO3Gel mould is done
Dry formation LaNiO3Gel dry film.
3）By step 2）What is obtained carries LaNiO3The strontium titanate monocrystal chip of gel dry film is transferred to quartz tube type heating furnace
In, the moist oxygen containing certain water vapour is passed through, in H2O、O2Thermally decomposed under mixed atmosphere, H in control mixed atmosphere2O's
Percent by volume is 6 ~ 8vol%.During thermal decomposition, cooled to the furnace after being warming up to 420 DEG C, insulation 5min with 5 DEG C/min speed
Room temperature.
4）Repeat the above steps 2）、3）2 times, make LaNiO3Gel dry film is constantly thickened.
5）By step 4）Gel dry film after thermal decomposition, is put into quartz tube type sintering furnace together with its substrate, in H2O、O2It is mixed
Close and carry out high-temperature calcination under atmosphere, the H2O、O2With the present embodiment step 3 in mixed atmosphere）The mode and H of middle acquisition2O volume
Percentage is identical；During high-temperature calcination, room temperature is cooled to the furnace after being warming up to 700 DEG C, insulation 30min with 5 DEG C/min speed, i.e.,
The LaNiO that thickness on substrate of strontium titanate is 300nm can be obtained3Conductive film, resistivity is up to 7.1 × 10-4Ω·cm。
Above-mentioned H2O、O2The implementation method of mixed atmosphere is as follows：Oxygen is serially connected by 3, temperature is adjustable, dress
There is liquid H2O vessel, H2O is by evaporation or by O2Bring out to form H2O、O2Mixed gas, then by H2O、O2Mixed gas
It is passed through in quartz tube type heating furnace and quartz tube type sintering furnace.
Embodiment 5
A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel, comprises the following steps：
1）Using nickel acetate as raw material, nickel acetate is dissolved in ethylene glycol monomethyl ether, complexing agent propionic acid is added, Ni is prepared molten
Liquid.Ni solution was obtained after settled solution by stirring 3 hours, is added lanthanum nitrate powder, is continued to stir to clarify, and was obtained
LaNiO3Colloidal sol, the LaNiO3Nickel acetate, lanthanum nitrate, propionic acid, the mol ratio of ethylene glycol monomethyl ether are 1 in colloidal sol: 1.2: 4:
20。
2）By step 1）The LaNiO of preparation3Colloidal sol, using dip-coating method, LaNiO is prepared on LAO monocrystal chips3It is solidifying
Glued membrane, then will be covered with LaNiO3The substrate of gel mould dries 20min at a temperature of 150 DEG C, makes LaNiO3Gel mould is dried
Form LaNiO3Gel dry film.
3）By step 2）What is obtained carries LaNiO3The LAO substrates of gel dry film are transferred in quartz tube type heating furnace, it is passed through
Moist oxygen containing certain water vapour, in H2O、O2Thermally decomposed under mixed atmosphere, H in control mixed atmosphere2O volume hundred
Divide than being 1.3 ~ 3vol%.During thermal decomposition, it is warming up to 8 DEG C/min speed after 380 DEG C, insulation 8min, closes heat-treatment furnace,
And gas is closed, the substrate with gel dry film cools to room temperature with the furnace.
4）By step 3）Gel dry film after thermal decomposition, is put into quartz tube type sintering furnace together with its substrate, in H2O、O2It is mixed
Close and carry out high-temperature calcination under atmosphere, the H2O、O2Mixed atmosphere and the present embodiment step 3）The mode and H of middle acquisition2O volume hundred
Divide than identical；During high-temperature calcination, room is cooled to the furnace after being warming up to 730 ~ 750 DEG C, insulation 100min with 8 DEG C/min speed
Temperature, you can obtain the LaNiO that the thickness on LAO substrates is 500nm3Conductive film, resistivity is up to 4.5 × 10-4Ω·cm。
Above-mentioned H2O、O2The implementation method of mixed atmosphere is as follows：Oxygen is serially connected by 2, temperature is adjustable, dress
There is liquid H2O vessel, H2O is by evaporating into O2In, then by H2O、O2Mixed gas is passed through quartz tube type heating furnace and stone
In English pipe type sintering furnace.
Embodiment 6
A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel, comprises the following steps：
1）Using nickel acetate as raw material, by nickel acetate dissolving in ethanol, complexing agent acrylic acid is added, prepare Ni solution.Ni
Solution obtains after settled solution by stirring 2.5 hours, adds lanthanum nitrate powder, continue to stir to clarify, and obtains LaNiO3
Colloidal sol, the LaNiO3Nickel acetate, lanthanum nitrate, acrylic acid, the mol ratio of ethanol are 1 in colloidal sol: 1.2:5:30.
2）By step 1）The LaNiO of preparation3Colloidal sol, using spin coating method, in SrTiO3LaNiO is prepared on monocrystal chip3
Gel mould, then will be covered with LaNiO3The substrate of gel mould dries 10min at a temperature of 120 DEG C, makes LaNiO3Gel mould is done
Dry formation LaNiO3Gel dry film.
3）By step 2）What is obtained carries LaNiO3The SrTiO of gel dry film3Monocrystal chip is transferred to quartz tube type heating furnace
In, the moist oxygen containing certain water vapour is passed through, in H2O、O2Thermally decomposed under mixed atmosphere, control H2O、O2Mixed atmosphere
In, H2O percent by volume is 1.3 ~ 8vol%.During thermal decomposition, 400 DEG C are warming up to 5 ~ 10 DEG C/min speed, 5min is incubated
Afterwards, heat-treatment furnace is closed, and closes gas, the substrate with gel dry film cools to room temperature with the furnace.
4）By step 3）Gel dry film after thermal decomposition, is put into quartz tube type sintering furnace together with its substrate, in H2O、O2It is mixed
Close and carry out high-temperature calcination under atmosphere, the H2O、O2Mixed atmosphere and the present embodiment step 3）The mode and percent by volume of middle acquisition
It is identical；During high-temperature calcination, room temperature is cooled to the furnace after being warming up to 750 DEG C, insulation 30min with 5 ~ 10 DEG C/min speed, you can
Obtain SrTiO3Thickness is 200nm LaNiO on monocrystal chip3Conductive film, resistivity is up to 8 × 10-4Ω·cm。
Above-mentioned H2O、O2The implementation method of mixed atmosphere is as follows：Oxygen is serially connected by 2, temperature is adjustable, dress
There is liquid H2O vessel, H2O is by evaporating into O2In, then by H2O、O2Mixed gas is passed through quartz tube type heating furnace and stone
In English pipe type sintering furnace.
Embodiment 7
A kind of chemical solution deposition preparation method of the sour lanthanum conductive film of nickel, comprises the following steps：
1）Using nickel acetate as raw material, nickel acetate is dissolved in organic solvent ethylene glycol monomethyl ether, propionic acid is added and is used as complexing
Agent, prepares Ni solution.Ni solution was obtained after settled solution by stirring 1 hour, added lanthanum nitrate powder, continued to stir extremely
Clarification, obtains LaNiO3Colloidal sol, the LaNiO3Nickel acetate, lanthanum nitrate, complexing agent, the mol ratio of organic solvent are 1 in colloidal sol:
1.3:2:20。
2）By step 1）The LaNiO of preparation3Colloidal sol, using spin coating method, LaNiO is prepared on single crystalline Si substrate3Gel
Film, then will be covered with LaNiO3The substrate of gel mould dries 10min at a temperature of 100 DEG C, makes LaNiO3Gel mould dries shape
Into LaNiO3Gel dry film.
3）It will be covered with LaNiO3The substrate of gel dry film is transferred in quartz tube type heating furnace, in H2O、O2Under mixed atmosphere
Thermally decomposed；The H2O、O2In mixed atmosphere, H2O percent by volume is 5vol%, during thermal decomposition, with 5 DEG C/min speed
Rate cools to room temperature with the furnace after being warming up to 380 DEG C, insulation 10min.
4）Repeat the above steps 2）、3）4 times, make LaNiO3Gel dry film is constantly thickened.
5）By step 4）Gel dry film after thermal decomposition, is put into quartz tube type sintering furnace together with its substrate, in H2O、O2It is mixed
Close and carry out high-temperature calcination under atmosphere, the H2O、O2Mixed atmosphere and the present embodiment step 3）The mode and H of middle acquisition2O volume hundred
Divide than identical；During high-temperature calcination, room temperature is cooled to the furnace after being warming up to 700 DEG C, insulation 80min with 10 DEG C/min speed, can
Obtain the LaNiO that thickness is 640nm3Conductive film, resistivity is up to 6.3 × 10-4Ω·cm。
Above-mentioned H2O、O2The implementation method of mixed atmosphere is as follows：By oxygen and vapor, mixing match is good in proportion, then will
Mixed gas is passed through in quartz tube type heating furnace and quartz tube type sintering furnace.
The LaNiO of the present invention3The chemical solution preparation method of conductive film, in solution preparation process, with the addition of excess
La elements, so as to avoid follow-up because of the loss of La caused by heat treatment, thus pure LaNiO can be obtained3The film of phase.Heat
The atmosphere with strong oxidizing property, the i.e. oxygen atmosphere containing vapor are employed in processing procedure.Reduce because of high-temperature heat treatment
Cause LaNiO3The loss of oxygen content, has further raising than the film resiativity under simple air, or oxygen.Prepared
LaNiO3The resistivity of film, when thickness reaches 800nm, can reach 10 on si substrates-4Ω cm, in LAO monocrystalline bases
10 are can reach on piece-5Ω·cm。
The invention is not limited in above-described embodiment, on the basis of technical scheme disclosed by the invention, the skill of this area
Art personnel are according to disclosed technology contents, it is not necessary to which performing creative labour just can make one to some of which technical characteristic
A little to replace and deform, these are replaced and deformed within the scope of the present invention.
Claims (5)
1. the chemical solution deposition preparation method of the sour lanthanum conductive film of a kind of nickel, it is characterised in that comprise the following steps：
1）By nickel acetate dissolving in organic solvent, complexing agent is added, by stirring 1 ~ 3 hour, obtained after settled solution, then add
Enter lanthanum nitrate powder, continue to stir to clarify, obtain LaNiO3Colloidal sol；The LaNiO3Nickel acetate, lanthanum nitrate, complexing in colloidal sol
Agent, the mol ratio of organic solvent are 1:（1.2~1.4）:（2~5）:（20~40）；
2）By step 1）The LaNiO of preparation3Colloidal sol, using dip-coating method or spin coating method, prepares LaNiO on substrate3It is solidifying
Glued membrane, then will be covered with LaNiO3The substrate of gel mould dries 5 ~ 20min at a temperature of 100 ~ 150 DEG C, makes LaNiO3Gel
Film is dried to form LaNiO3Gel dry film；
3）It will be covered with LaNiO3The substrate of gel dry film is transferred in quartz tube type heating furnace, in H2O、O2Carried out under mixed atmosphere
Thermal decomposition；The H2O、O2In mixed atmosphere, H2O percent by volume is 1.3 ~ 8vol%, during thermal decomposition, with 5 ~ 10 DEG C/min's
Speed cools to room temperature with the furnace after being warming up to 380 ~ 420 DEG C, 5 ~ 10min of insulation；H2O、O2The implementation method of mixed atmosphere is as follows：
Oxygen is serially connected by 2 ~ 3, temperature is adjustable, equipped with liquid H2O vessel, H2O is by evaporation or by O2Bring out
Form H2O、O2Mixed gas, then by H2O、O2Mixed gas is passed through in quartz tube type heating furnace；
4）By step 3）Gel dry film after thermal decomposition, is put into quartz tube type sintering furnace together with its substrate, in H2O、O2Gaseous mixture
High-temperature calcination is carried out under atmosphere；The H2O、O2In mixed atmosphere, H2O percent by volume is 1.3 ~ 8vol%；During high-temperature calcination, with
5 ~ 10 DEG C/min speed cools to room temperature with the furnace after being warming up to 700 ~ 750 DEG C, 30 ~ 100min of insulation, is formed and led on substrate
Conductive film；H2O、O2The implementation method of mixed atmosphere is as follows：Oxygen is serially connected by 2 ~ 3, temperature is adjustable, be equipped with
Liquid H2O vessel, H2O is by evaporation or by O2Bring out to form H2O、O2Mixed gas, then by H2O、O2Mixed gas is led to
Enter in quartz tube type sintering furnace.
2. the chemical solution deposition preparation method of the sour lanthanum conductive film of nickel according to claim 1, it is characterised in that in step
Rapid 4）Preceding repeat step 2）~3）1 ~ 5 time.
3. the chemical solution deposition preparation method of the sour lanthanum conductive film of nickel according to claim 1 or 2, it is characterised in that
The organic solvent is ethylene glycol monomethyl ether, ethanol or methanol.
4. the chemical solution deposition preparation method of the sour lanthanum conductive film of nickel according to claim 1 or 2, it is characterised in that
The complexing agent is propionic acid or acrylic acid.
5. the chemical solution deposition preparation method of the sour lanthanum conductive film of nickel according to claim 1 or 2, it is characterised in that
The substrate is lanthanum aluminate, strontium titanate monocrystal chip or single crystalline Si substrate.
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| CN106702327B (en) * | 2017-01-10 | 2019-10-11 | 河北大学 | A kind of optimization method of ultra-thin lanthanum nickelate thin film electronic transport performance |
| CN108417847B (en) * | 2018-01-31 | 2021-04-09 | 浩发环保科技（深圳）有限公司 | Titanium-based lanthanum nickelate electrode and preparation method thereof |
| CN108511112B (en) * | 2018-04-03 | 2020-02-11 | 沈阳航空航天大学 | Lanthanum nickelate conductive film and preparation method and application thereof |
| CN112670087A (en) * | 2020-12-09 | 2021-04-16 | 南京邮电大学 | Ferroelectric film capacitor applied to ferroelectric memory |
| CN112877676A (en) * | 2021-01-14 | 2021-06-01 | 中国科学院上海硅酸盐研究所 | Preparation method of epitaxial growth lanthanum nickelate and lanthanum strontium manganese oxygen film |
| CN114086118B (en) * | 2021-11-09 | 2023-07-14 | 电子科技大学长三角研究院(湖州) | Self-supporting flexible film and preparation method thereof |
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