CN103833416A - Preparation method of lanthanum nickelate conductive film by chemical solution deposition - Google Patents

Preparation method of lanthanum nickelate conductive film by chemical solution deposition Download PDF

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CN103833416A
CN103833416A CN201410021232.5A CN201410021232A CN103833416A CN 103833416 A CN103833416 A CN 103833416A CN 201410021232 A CN201410021232 A CN 201410021232A CN 103833416 A CN103833416 A CN 103833416A
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lanio
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CN103833416B (en
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高俊萍
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Abstract

The invention relates to a preparation method of a lanthanum nickelate conductive film by chemical solution deposition, belonging to the technical field of microelectronic manufacture. The step mainly includes the preparation of LaNiO3 sol, comprising: preparing a LaNiO3 gel film on a substrate by using a dipping Czochralski method or a spin-coating method, then drying the gel film to form a LaNiO3 gel dry film; transferring the substrate coated with the LaNiO3 gel dry film to a quartz tube heating furnace, performing thermolysis in a mixed atmosphere of H2O and O2; finally putting the thermolyzed gel dry film and the substrate into a quartz tube sintering furnace, performing high temperature calcining in the mixed atmosphere of H2O and O2, so as to form the conductive film on the substrate. The conductive film formed by the method has lower resistivity.

Description

A kind of chemical solution deposition preparation method of nickel acid lanthanum conductive film
Technical field
The present invention relates to the technology of preparing of the conductive film that microelectronic material and devices field use, be specifically related to a kind of nickel acid lanthanum LaNiO 3the preparation method of conductive film.
Background technology
Aspect microelectronic device, the conductive film with certain electroconductibility has important application prospect.Be no matter the bottom electrode that other films of service are used, or as the core component of device conduction current, even, as the special well heater of some component, the film with suitable conductivity has played keying action.In these conductive films, take inorganic thin film and metallic film as main.Metallic film has good resistivity, but because easily oxidized, thereby affects the life-span of device; Although inorganic thin film resistivity is not as metallic film, because it is corrosion-resistant, high temperature resistant, and resistance to oxidation, thereby there is good thermostability and chemical stability.In inorganic thin film, mainly contain transparent conductive film as ITO, ATO etc., have good electric conductivity, are usually used in the bottom electrode thin film layer of optics.An other class inorganic conductive film is perovskite structural material, such as LaNiO 3, YBa 2cu 3o 7-x, La 0.5sr 0.5coO 3deng material, it is nontransparent black inorganic materials.They have good resistivity, and and ferroelectric, the similar perovskite structure of piezoelectric membrane, thereby make them in ferroelectric storage, the devices field such as energy storage have important application.
At present, preparation LaNiO 3, YBa 2cu 3o 7-x, La 0.5sr 0.5coO 3mainly contain the in-situ deposition techniques such as pulsed laser deposition (PLD), magnetron sputtering method (MS), metal-organic chemical vapor deposition equipment method (MOCVD) Deng the method for film, also have the chemical solution deposition (CSD) of metal organic-matter chemical liquid phase deposition (MOD) and sol-gel method (Sol ~ Gel) isotonic deposition.Wherein, first three plants in-situ deposition technique, without follow-up annealing thermal treatment, but all needs to relate to expensive vacuum apparatus; And CSD method belongs to chemical method masking technique, equipment is simple, and is easy to control the stoichiometric ratio of metal ion, is easy to prepare large area film, therefore gets more and more people's extensive concerning.
But compared with the in-situ deposition technique such as PLD, MS, MOCVD, the electric conductivity of the prepared film of the CSD method of dystopy deposition often has certain gap.How to improve LaNiO 3deng the quality of film, particularly its resistivity is the problem that CSD method must solve.
Summary of the invention
The object of this invention is to provide a kind of chemical solution deposition preparation method of nickel acid lanthanum conductive film.It is prepared by simple solution, and the thermal treatment process of follow-up optimization, can obtain the LaNiO that resistivity is less 3conductive film.
The technical solution adopted in the present invention is as follows: a kind of chemical solution deposition preparation method of nickel acid lanthanum conductive film, is characterized in that comprising the steps:
1) nickel acetate is dissolved in organic solvent, adds complexing agent, through stirring 1 ~ 3 hour, obtain after settled solution, then add lanthanum nitrate powder, continue to stir to clarify, obtain LaNiO 3colloidal sol; Described LaNiO 3in colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, complexing agent, organic solvent is 1:(1.2 ~ 1.4): (2 ~ 5): (20 ~ 40);
2) LaNiO being prepared by step 1) 3colloidal sol, adopts dip-coating method or spin coating method, prepares LaNiO on substrate 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 5 ~ 20min at the temperature of 100 ~ 150 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film;
3) will be coated with LaNiO 3the substrate of gel dry film proceeds in quartz tube type process furnace, at H- 2o, O 2under mixed atmosphere, carry out thermolysis; Described H- 2o, O 2in mixed atmosphere, H- 2the volume percent of O is 1.3 ~ 8vol%, when thermolysis, is warming up to 380 ~ 420 ℃ with the speed of 5 ~ 10 ℃/min, after insulation 5 ~ 10min, cools to room temperature with the furnace;
4) by the gel dry film after step 3) thermolysis, put into quartz tube type sintering oven together with its substrate, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination; Described H- 2o, O 2in mixed atmosphere, H- 2the volume percent of O is 1.3 ~ 8vol%; When high-temperature calcination, be warming up to 700 ~ 750 ℃ with the speed of 5 ~ 10 ℃/min, after insulation 30 ~ 100min, cool to room temperature with the furnace, on substrate, form conductive film.
For increasing the thickness of conductive film, repeating step 2 before step 4)) ~ 3) 1 ~ 5 time.
Above-mentioned H 2o, O 2the implementation method of mixed atmosphere is as follows: by oxygen by 2 ~ 3 mutually series connection, that temperature is adjustable, liquid H is housed 2the vessel of O, H 2o is by evaporation or by O 2bring out and form H 2o, O 2mixed gas, then by H 2o, O 2mixed gas passes in quartz tube type process furnace and quartz tube type sintering oven.
In the present invention, described organic solvent can be ethylene glycol monomethyl ether, ethanol or methyl alcohol.Described complexing agent can be propionic acid or vinylformic acid.Described substrate can be lanthanum aluminate (LAO), strontium titanate (SrTiO 3) monocrystal chip or single crystalline Si substrate.
The invention has the beneficial effects as follows:
1) the present invention has improved the content of La, make it excessive, has reduced the unbalance of the La causing because of thermolysis in follow-up heat treatment process, Ni element ratio; In the final conductive film obtaining, avoid the generation of dephasign NiO.
2) in conductive film, oxygen vacancy concentration can cause the variation of LNO energy band structure, the increase in oxygen room can cause LNO to be transitioned into even isolator of semi-conductor from conductor, and the present invention adopts the mixed atmosphere of water vapour and oxygen in the thermal treatment of gel dry film and calcination process, can reduce the increase degree of conductive film oxygen defect, its oxygen vacancy concentration is lower than the oxygen vacancy concentration of prepared sample in dry oxygen, dry nitrogen, wet nitrogen atmosphere, the resistivity of gained conductive film can be lower, and the order of magnitude can reach 10 -4Ω cm.
Accompanying drawing explanation
Fig. 1 is LaNiO on the LAO substrate for preparing of the embodiment of the present invention 1 3the XRD figure of conductive film.
Fig. 2 is LaNiO on the LAO substrate for preparing of the embodiment of the present invention 1 3the XRD figure of conductive film.
Fig. 3 is LaNiO on the LAO substrate prepared of the embodiment of the present invention 1 3laNiO on Si substrate prepared by conductive film and embodiment 2 3the SEM comparison diagram of conductive film.
Fig. 4 is the LaNiO preparing under wet oxygen atmosphere and dry oxygen on the Si substrate prepared of the embodiment of the present invention 2, dry nitrogen, wet nitrogen atmosphere 3the comparison diagram of conductive film resistivity.
Embodiment
Embodiment 1
A chemical solution deposition preparation method for nickel acid lanthanum conductive film, its step is as follows:
1) take nickel acetate as raw material, nickel acetate is dissolved in ethylene glycol monomethyl ether, adding vinylformic acid is complexing agent, preparation Ni solution.Ni solution, through stirring 1.5 hours, obtains after settled solution, adds lanthanum nitrate powder, continues to stir to clarify, and obtains LaNiO 3colloidal sol, described LaNiO 3in colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, vinylformic acid, ethylene glycol monomethyl ether is 1:1.3:2:30.
2) LaNiO being prepared by step 1) 3colloidal sol, adopts dip-coating method, on LAO monocrystal chip, prepares LaNiO 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 10min at the temperature of 150 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film.
3) by step 2) obtain with LaNiO 3the LAO monocrystal chip of gel dry film proceeds in quartz tube type process furnace, passes into the moist oxygen containing certain water vapor, at H- 2o, O 2under mixed atmosphere, carry out thermolysis, wherein, described H- 2o, O 2in mixed atmosphere, H- 2the volume percent of O is 1.3 ~ 5vol%.When thermolysis, be warming up to 400 ℃ with the speed of 10 ℃/min, after insulation 10min, close heat treatment furnace, and close gas, cool to room temperature with the furnace with the substrate of gel dry film.
4) repeat above-mentioned steps 2), 3) totally 5 times, make LaNiO 3gel dry film constantly thickens.
5), by the gel dry film after step 4) thermolysis, put into quartz tube type sintering oven together with its LAO monocrystal chip, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination, this H 2o, O 2the mode and the H-that in mixed atmosphere and the present embodiment step 3), obtain 2the volume percent of O is identical; When high-temperature calcination, be warming up to 700 ℃ with the speed of 10 ℃/min, after insulation 60min, cool to room temperature with the furnace, can obtain the LaNiO that on LAO monocrystal chip, thickness is 800nm 3conductive film, resistivity reaches 1.5 × 10 -5Ω cm.
Above-mentioned H 2o, O 2the implementation method of mixed atmosphere is as follows: by oxygen by 2 mutually series connection, that temperature is adjustable, liquid H is housed 2the vessel of O, H 2o is by evaporation or by O 2bring out and form H 2o, O 2mixed gas, then by H 2o, O 2mixed gas passes in quartz tube type process furnace and quartz tube type sintering oven.
Fig. 1 is LaNiO on the LAO substrate for preparing of the embodiment of the present invention 1 3the XRD figure of conductive film, shows that conductive film is the pure LaNiO of polycrystalline without orientation 3phase film, exists without other dephasigns.
Fig. 2 is LaNiO on the LAO substrate for preparing of the embodiment of the present invention 1 3the XRD figure of conductive film, shows the pure LaNiO that film (00l) c-axis is grown 3phase film.
Embodiment 2
A chemical solution deposition preparation method for nickel acid lanthanum conductive film, its step is as follows:
1) take nickel acetate as raw material, nickel acetate is dissolved in ethylene glycol monomethyl ether, adding vinylformic acid is complexing agent, preparation Ni solution, Ni solution, through stirring 3 hours, obtains after settled solution, adds lanthanum nitrate powder, continues to stir clarification, can obtain LaNiO 3colloidal sol, in described colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, vinylformic acid, ethylene glycol monomethyl ether is 1:1.3:2:40.
2) LaNiO being prepared by step 1) 3colloidal sol, adopts spin coating method, on Si monocrystal chip, prepares LaNiO 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 10min at the temperature of 100 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film.
3) by step 2) obtain with LaNiO 3the Si substrate of gel dry film proceeds in quartz tube type process furnace, passes into the moist oxygen containing certain water vapor, at H- 2o, O 2under in mixed atmosphere, carry out thermolysis, control H-in mixed atmosphere 2the volume percent of O is 2 ~ 6vol%.When thermolysis, be elevated to 400 ℃ with the temperature rise rate of 5 ~ 10 ℃/min, after insulation 10min, close heat treatment furnace, and close gas, cool to room temperature with the furnace with the substrate of gel dry film.
4) repeat above-mentioned steps 2,3 totally 5 times, make LaNiO 3gel dry film thickens.
5), by the gel dry film after step 4) thermolysis, its Si monocrystal chip of UNICOM is put into quartz tube type sintering oven, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination, this H 2o, O 2the mode and the H-that in mixed atmosphere and the present embodiment step 3), obtain 2the volume percent of O is identical; When high-temperature calcination, be warming up to 700 ℃ with the speed of 5 ℃/min, after insulation 100min, cool to room temperature with the furnace, can obtain the LaNiO that on Si monocrystal chip, thickness is 800nm 3conductive film, resistivity reaches 3.0 × 10 -4Ω cm.
Above-mentioned H 2o, O 2the implementation method of mixed atmosphere is as follows: by oxygen by 3 mutually series connection, that temperature is adjustable, liquid H is housed 2the vessel of O, H 2o is by evaporation or by O 2bring out and form H 2o, O 2mixed gas, then by H 2o, O 2mixed gas passes in quartz tube type process furnace and quartz tube type sintering oven.
Fig. 3 is the on-chip LaNiO of LAO prepared by the embodiment of the present invention 1 3the on-chip LaNiO of Si prepared by conductive film and embodiment 2 3the SEM comparison diagram of conductive film, in figure, (a) is the LaNiO on LAO monocrystal chip 3conductive film, (a) is the on-chip LaNiO of single crystalline Si 3conductive film, contrast picture shows the on-chip LaNiO of LAO 3conductive film is more fine and close smooth, thereby shows lower resistivity.
Fig. 4 is that the single crystalline Si prepared of patent working example 2 of the present invention is on-chip, the LaNiO preparing under wet oxygen atmosphere 3conductive film, with the LaNiO preparing under dry oxygen, wet nitrogen, dry nitrogen different atmosphere 3the contrast of the resistivity of conductive film, shows the LaNiO preparing under wet oxygen atmosphere 3conductive film has lower resistivity.
Embodiment 3
A chemical solution deposition preparation method for nickel acid lanthanum conductive film, its step is as follows:
1) take nickel acetate as raw material, nickel acetate is dissolved in ethanol, adding propionic acid is complexing agent, preparation Ni solution.Ni solution, through stirring 1 hour, obtains after settled solution, adds lanthanum nitrate powder, continues to stir clarification, can obtain LaNiO 3colloidal sol, in described colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, propionic acid, ethanol is 1:1.2:2:40.
2) LaNiO being prepared by step 1) 3colloidal sol, adopts spin coating method, on LAO monocrystal chip, prepares LaNiO 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 10min at the temperature of 120 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film.
3) by step 2) obtain with LaNiO 3the LAO monocrystal chip of gel dry film proceeds in quartz tube type process furnace, passes into the moist oxygen containing certain water vapor, at H- 2o, O 2under mixed atmosphere, carry out thermolysis, control H-in mixed gas 2the volume percent of O is 5 ~ 8vol%.When thermolysis, be elevated to 400 ℃ with the temperature rise rate of 5 ~ 10 ℃/min, after insulation 10min,, close heat treatment furnace, and close gas, cool to room temperature with the furnace with the substrate of gel dry film.
4) repeat above-mentioned steps 2,3 totally 3 times, make LaNiO 3gel dry film thickens.
5) by the gel dry film after step 4) thermolysis, put into quartz tube type sintering oven together with LAO monocrystal chip, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination, this H 2o, O 2the mode and the H-that in mixed atmosphere and the present embodiment step 3), obtain 2the volume percent of O is identical; When high-temperature calcination, be warming up to 700 ℃ with the speed of 5 ℃/min, after insulation 60min, cool to room temperature with the furnace, can obtain the LaNiO that on LAO monocrystal chip, thickness is 500nm 3conductive film, resistivity reaches 5 × 10 -4Ω cm.
Above-mentioned H 2o, O 2the implementation method of mixed atmosphere is as follows: by oxygen by 2 mutually series connection, that temperature is adjustable, liquid H is housed 2the vessel of O, H 2o is by evaporation or by O 2bring out and form H 2o, O 2mixed gas, then by H 2o, O 2mixed gas passes in quartz tube type process furnace and quartz tube type sintering oven.
Embodiment 4
A chemical solution deposition preparation method for nickel acid lanthanum conductive film, comprises the steps:
1) take nickel acetate as raw material, nickel acetate is dissolved in methyl alcohol, add complexing agent propionic acid, preparation Ni solution.Ni solution, through stirring 2.5 hours, obtains after settled solution, then adds lanthanum nitrate powder, continues to stir to clarify, and obtains LaNiO 3colloidal sol; Described LaNiO 3in colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, propionic acid, methyl alcohol is 1:1.4:5:40.
2) LaNiO being prepared by step 1) 3colloidal sol, adopts dip-coating method, prepares LaNiO on strontium titanate monocrystal chip 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 5min at the temperature of 100 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film.
3) by step 2) obtain with LaNiO 3the strontium titanate monocrystal chip of gel dry film proceeds in quartz tube type process furnace, passes into the moist oxygen containing certain water vapor, at H- 2o, O 2under mixed atmosphere, carry out thermolysis, control H-in mixed atmosphere 2the volume percent of O is 6 ~ 8vol%.When thermolysis, be warming up to 420 ℃ with the speed of 5 ℃/min, after insulation 5min, cool to room temperature with the furnace.
4) repeat above-mentioned steps 2), 3) 2 times, make LaNiO 3gel dry film constantly thickens.
5) by the gel dry film after step 4) thermolysis, put into quartz tube type sintering oven together with its substrate, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination, this H- 2o, O 2in mixed atmosphere with the present embodiment step 3) in the mode and the H-that obtain 2the volume percent of O is identical; When high-temperature calcination, be warming up to 700 ℃ with the speed of 5 ℃/min, after insulation 30min, cool to room temperature with the furnace, can obtain the LaNiO that on substrate of strontium titanate, thickness is 300nm 3conductive film, resistivity reaches 7.1 × 10 -4Ω cm.
Above-mentioned H 2o, O 2the implementation method of mixed atmosphere is as follows: by oxygen by 3 mutually series connection, that temperature is adjustable, liquid H is housed 2the vessel of O, H 2o is by evaporation or by O 2bring out and form H 2o, O 2mixed gas, then by H 2o, O 2mixed gas passes in quartz tube type process furnace and quartz tube type sintering oven.
Embodiment 5
A chemical solution deposition preparation method for nickel acid lanthanum conductive film, comprises the steps:
1) take nickel acetate as raw material, nickel acetate is dissolved in ethylene glycol monomethyl ether, add complexing agent propionic acid, preparation Ni solution.Ni solution, through stirring 3 hours, obtains after settled solution, adds lanthanum nitrate powder, continues to stir to clarify, and obtains LaNiO 3colloidal sol, described LaNiO 3in colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, propionic acid, ethylene glycol monomethyl ether is 1:1.2:4:20.
2) LaNiO being prepared by step 1) 3colloidal sol, adopts dip-coating method, on LAO monocrystal chip, prepares LaNiO 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 20min at the temperature of 150 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film.
3) by step 2) obtain with LaNiO 3the LAO substrate of gel dry film proceeds in quartz tube type process furnace,, pass into the moist oxygen containing certain water vapor, at H- 2o, O 2under mixed atmosphere, carry out thermolysis, control H-in mixed atmosphere 2the volume percent of O is 1.3 ~ 3vol%.When thermolysis, be warming up to 380 ℃ with the speed of 8 ℃/min, after insulation 8min, close heat treatment furnace, and close gas, cool to room temperature with the furnace with the substrate of gel dry film.
4) by the gel dry film after step 3) thermolysis, put into quartz tube type sintering oven together with its substrate, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination, this H 2o, O 2the mode and the H-that in mixed atmosphere and the present embodiment step 3), obtain 2the volume percent of O is identical; When high-temperature calcination, be warming up to 730 ~ 750 ℃ with the speed of 8 ℃/min, after insulation 100min, cool to room temperature with the furnace, can obtain the LaNiO that thickness is 500nm on LAO substrate 3conductive film, resistivity reaches 4.5 × 10 -4Ω cm.
Above-mentioned H 2o, O 2the implementation method of mixed atmosphere is as follows: by oxygen by 2 mutually series connection, that temperature is adjustable, liquid H is housed 2the vessel of O, H 2o enters O by evaporation 2in, then by H 2o, O 2mixed gas passes in quartz tube type process furnace and quartz tube type sintering oven.
Embodiment 6
A chemical solution deposition preparation method for nickel acid lanthanum conductive film, comprises the steps:
1) take nickel acetate as raw material, nickel acetate is dissolved in ethanol, add complexing agent vinylformic acid, preparation Ni solution.Ni solution, through stirring 2.5 hours, obtains after settled solution, then adds lanthanum nitrate powder, continues to stir to clarify, and obtains LaNiO 3colloidal sol, described LaNiO 3in colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, vinylformic acid, ethanol is 1:1.2:5:30.
2) LaNiO being prepared by step 1) 3colloidal sol, adopts spin coating method, at SrTiO 3on monocrystal chip, prepare LaNiO 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 10min at the temperature of 120 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film.
3) by step 2) obtain with LaNiO 3the SrTiO of gel dry film 3monocrystal chip proceeds in quartz tube type process furnace, passes into the moist oxygen containing certain water vapor, at H- 2o, O 2under mixed atmosphere, carry out thermolysis, control H- 2o, O 2in mixed atmosphere, H- 2the volume percent of O is 1.3 ~ 8vol%.When thermolysis, be warming up to 400 ℃ with the speed of 5 ~ 10 ℃/min, after insulation 5min, close heat treatment furnace, and close gas, cool to room temperature with the furnace with the substrate of gel dry film.
4) by the gel dry film after step 3) thermolysis, put into quartz tube type sintering oven together with its substrate, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination, this H 2o, O 2mixed atmosphere is identical with the mode and the volume percent that obtain in the present embodiment step 3); When high-temperature calcination, be warming up to 750 ℃ with the speed of 5 ~ 10 ℃/min, after insulation 30min, cool to room temperature with the furnace, can obtain SrTiO 3the LaNiO that on monocrystal chip, thickness is 200nm 3conductive film, resistivity reaches 8 × 10 -4Ω cm.
Above-mentioned H 2o, O 2the implementation method of mixed atmosphere is as follows: by oxygen by 2 mutually series connection, that temperature is adjustable, liquid H is housed 2the vessel of O, H 2o enters O by evaporation 2in, then by H 2o, O 2mixed gas passes in quartz tube type process furnace and quartz tube type sintering oven.
Embodiment 7
A chemical solution deposition preparation method for nickel acid lanthanum conductive film, comprises the steps:
1) take nickel acetate as raw material, nickel acetate is dissolved in organic solvent ethylene glycol monomethyl ether, add propionic acid as complexing agent, preparation Ni solution.Ni solution, through stirring 1 hour, obtains after settled solution, then adds lanthanum nitrate powder, continues to stir to clarify, and obtains LaNiO 3colloidal sol, described LaNiO 3in colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, complexing agent, organic solvent is 1:1.3:2:20.
2) LaNiO being prepared by step 1) 3colloidal sol, adopts spin coating method, on single crystalline Si substrate, prepares LaNiO 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 10min at the temperature of 100 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film.
3) will be coated with LaNiO 3the substrate of gel dry film proceeds in quartz tube type process furnace, at H- 2o, O 2under mixed atmosphere, carry out thermolysis; Described H- 2o, O 2in mixed atmosphere, H- 2the volume percent of O is 5vol%, when thermolysis, is warming up to 380 ℃ with the speed of 5 ℃/min, after insulation 10min, cools to room temperature with the furnace.
4) repeat above-mentioned steps 2), 3) 4 times, make LaNiO 3gel dry film constantly thickens.
5) by the gel dry film after step 4) thermolysis, put into quartz tube type sintering oven together with its substrate, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination, this H 2o, O 2the mode and the H-that in mixed atmosphere and the present embodiment step 3), obtain 2the volume percent of O is identical; When high-temperature calcination, be warming up to 700 ℃ with the speed of 10 ℃/min, after insulation 80min, cool to room temperature with the furnace, can obtain the LaNiO that thickness is 640nm 3conductive film, resistivity reaches 6.3 × 10 -4Ω cm.
Above-mentioned H 2o, O 2the implementation method of mixed atmosphere is as follows: oxygen and water vapour are mixed in proportion to proportioning good, then mixed gas are passed in quartz tube type process furnace and quartz tube type sintering oven.
LaNiO of the present invention 3the chemical solution preparation method of conductive film, in solution preparation process, has added excessive La element, thereby has avoided the loss of the follow-up La causing because of thermal treatment, thereby can obtain pure LaNiO 3the film of phase.In heat treatment process, adopt the atmosphere with strong oxidizing property, contained the oxygen atmosphere of water vapour.Reduce and caused LaNiO because of high-temperature heat treatment 3the loss of oxygen level, than simple air, or film resiativity under oxygen has further raising.Prepared LaNiO 3the resistivity of film in the time that thickness reaches 800nm, can reach 10 on Si substrate -4Ω cm can reach 10 on LAO monocrystal chip -5Ω cm.
The present invention is not limited to above-described embodiment; on the basis of technical scheme disclosed by the invention; those skilled in the art is according to disclosed technology contents; do not need performing creative labour just can make some replacements and distortion to some technical characterictics wherein, these replacements and distortion are all in protection scope of the present invention.

Claims (6)

1. a chemical solution deposition preparation method for nickel acid lanthanum conductive film, is characterized in that comprising the steps:
1) nickel acetate is dissolved in organic solvent, adds complexing agent, through stirring 1 ~ 3 hour, obtain after settled solution, then add lanthanum nitrate powder, continue to stir to clarify, obtain LaNiO 3colloidal sol; Described LaNiO 3in colloidal sol, the mol ratio of nickel acetate, lanthanum nitrate, complexing agent, organic solvent is 1:(1.2 ~ 1.4): (2 ~ 5): (20 ~ 40);
2) LaNiO being prepared by step 1) 3colloidal sol, adopts dip-coating method or spin coating method, prepares LaNiO on substrate 3gel-film, will be coated with LaNiO subsequently 3the substrate of gel-film is dry 5 ~ 20min at the temperature of 100 ~ 150 ℃, makes LaNiO 3the dry LaNiO that forms of gel-film 3gel dry film;
3) will be coated with LaNiO 3the substrate of gel dry film proceeds in quartz tube type process furnace, at H- 2o, O 2under mixed atmosphere, carry out thermolysis; Described H- 2o, O 2in mixed atmosphere, H- 2the volume percent of O is 1.3 ~ 8vol%, when thermolysis, is warming up to 380 ~ 420 ℃ with the speed of 5 ~ 10 ℃/min, after insulation 5 ~ 10min, cools to room temperature with the furnace;
4) by the gel dry film after step 3) thermolysis, put into quartz tube type sintering oven together with its substrate, at H 2o, O 2under mixed atmosphere, carry out high-temperature calcination; Described H- 2o, O 2in mixed atmosphere, H- 2the volume percent of O is 1.3 ~ 8vol%; When high-temperature calcination, be warming up to 700 ~ 750 ℃ with the speed of 5 ~ 10 ℃/min, after insulation 30 ~ 100min, cool to room temperature with the furnace, on substrate, form conductive film.
2. the chemical solution deposition preparation method of nickel according to claim 1 acid lanthanum conductive film, is characterized in that repeating step 2 before step 4)) ~ 3) 1 ~ 5 time.
3. the chemical solution deposition preparation method of nickel acid lanthanum conductive film according to claim 1 and 2, is characterized in that H 2o, O 2the implementation method of mixed atmosphere is as follows: by oxygen by 2 ~ 3 mutually series connection, that temperature is adjustable, liquid H is housed 2the vessel of O, H 2o is by evaporation or by O 2bring out and form H 2o, O 2mixed gas, then by H 2o, O 2mixed gas passes in quartz tube type process furnace and quartz tube type sintering oven.
4. the chemical solution deposition preparation method of nickel acid lanthanum conductive film according to claim 1 and 2, is characterized in that, described organic solvent is ethylene glycol monomethyl ether, ethanol or methyl alcohol.
5. the chemical solution deposition preparation method of nickel acid lanthanum conductive film according to claim 1 and 2, is characterized in that, described complexing agent is propionic acid or vinylformic acid.
6. the chemical solution deposition preparation method of nickel acid lanthanum conductive film according to claim 1 and 2, is characterized in that, described substrate is lanthanum aluminate, strontium titanate monocrystal chip or single crystalline Si substrate.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106702327A (en) * 2017-01-10 2017-05-24 河北大学 Optimizing method of electrical transport property of ultrathin lanthanum nickelate film
CN108417847A (en) * 2018-01-31 2018-08-17 浩发环保科技（深圳）有限公司 A kind of titanium-based nickel acid lanthanum electrode and preparation method thereof
CN108511112A (en) * 2018-04-03 2018-09-07 沈阳航空航天大学 A kind of nickel acid lanthanum conductive film and its preparation method and application
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
CN114086118A (en) * 2021-11-09 2022-02-25 电子科技大学长三角研究院(湖州) Self-supporting flexible film and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362749A (en) * 2001-12-07 2002-08-07 中国科学院上海技术物理研究所 Prepn of lanthanum nickelate-conducting metal oxide film material
CN101863679A (en) * 2009-04-14 2010-10-20 中国科学院合肥物质科学研究院 Method for preparing lanthanum nickel oxide thin-film material
CN102320670A (en) * 2011-05-27 2012-01-18 华东师范大学 Method for prepararing lanthanum nickelate conductive metal oxide film material
CN103360107A (en) * 2012-03-29 2013-10-23 中国科学院金属研究所 Gold-lanthanum nickelate composite conductive thin-film material and preparation method for same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362749A (en) * 2001-12-07 2002-08-07 中国科学院上海技术物理研究所 Prepn of lanthanum nickelate-conducting metal oxide film material
CN101863679A (en) * 2009-04-14 2010-10-20 中国科学院合肥物质科学研究院 Method for preparing lanthanum nickel oxide thin-film material
CN102320670A (en) * 2011-05-27 2012-01-18 华东师范大学 Method for prepararing lanthanum nickelate conductive metal oxide film material
CN103360107A (en) * 2012-03-29 2013-10-23 中国科学院金属研究所 Gold-lanthanum nickelate composite conductive thin-film material and preparation method for same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陆维等: "镍酸镧导电薄膜的热处理制度与电性能研究", 《功能材料与器件学报》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106702327A (en) * 2017-01-10 2017-05-24 河北大学 Optimizing method of electrical transport property of ultrathin lanthanum nickelate film
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
CN108417847A (en) * 2018-01-31 2018-08-17 浩发环保科技（深圳）有限公司 A kind of titanium-based nickel acid lanthanum electrode and preparation method thereof
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
CN108511112A (en) * 2018-04-03 2018-09-07 沈阳航空航天大学 A kind of nickel acid lanthanum conductive film and its preparation method and application
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
CN114086118A (en) * 2021-11-09 2022-02-25 电子科技大学长三角研究院(湖州) Self-supporting flexible film and preparation method thereof
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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