CN110310888A - A kind of p-type nano transition metal oxides film and its preparation method and application - Google Patents
A kind of p-type nano transition metal oxides film and its preparation method and application Download PDFInfo
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- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 55
- 230000004048 modification Effects 0.000 claims abstract description 47
- 238000012986 modification Methods 0.000 claims abstract description 47
- 230000008595 infiltration Effects 0.000 claims abstract description 26
- 238000001764 infiltration Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 230000008707 rearrangement Effects 0.000 claims description 18
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002159 nanocrystal Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012827 research and development Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 93
- 229910000480 nickel oxide Inorganic materials 0.000 description 35
- 239000010409 thin film Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000011112 polyethylene naphthalate Substances 0.000 description 10
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02656—Special treatments
- H01L21/02664—Aftertreatments
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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Abstract
The invention proposes a kind of p-type nano transition metal oxides films and its preparation method and application.Transition metal oxide film is subjected to surface modification and infiltration cleaning, obtains the p-type nano transition metal oxides film that p-type characteristic is enhanced.The present invention combines the process of infiltration cleaning by surface modification treatment, other than it can enhance hole conduction performance, the uniformity and compactness of film can also be improved, for prepare high-flatness film have the effect of it is fairly obvious, compared to the mode of Traditional dopant and high temperature sintering, implementation is simpler, and as a result repeatability is more preferable.P-type nano transition metal oxides film obtained, has wide range of applications, and has positive promote meaning to the research and development of Efficient devices.
Description
Technical field
The present invention relates to semiconductive thin film fields, and in particular to a kind of p-type nano transition metal oxides film and its system
Preparation Method and application.
Background technique
Compared to organic transport materials, transition metal oxide has many advantages, such as that mobility is high, stability is good, in semiconductor
Application in devices field especially organic thin film cells, Organic Light Emitting Diode (OLED) and light emitting diode with quantum dots (QLED)
It is very extensive, substantially increase the service life of device.However, the p-type transition metal oxide of Solution processing techniques preparation is thin
The hole-conductive performance of film is not ideal enough, has seriously affected the luminescent properties of device.For this case, current conventional method
The enhancing of transition metal oxide film p-type characteristic, but the work of both methods are realized generally by doping and high temperature sintering
Skill is complex, realizes that difficulty is big.It is therefore proposed that a kind of more simple, strong operability, aoxidizes for nano transition metal
The method of object film p-type characteristic enhancing is of great significance, and p-type transition metal oxide film is to height according to made from this method
The research and development of effect device has positive promote meaning.
Summary of the invention
Present invention aims to solve the deficiencies of the prior art, and provides a kind of a kind of p-type nano transition metal oxides film and
Preparation method and application.
To achieve the goals above, the following technical solution is employed by the present invention:
A kind of preparation method of p-type nano transition metal oxides film is provided, comprising the following steps:
Step 1: being coated on as film raw material by solwution method using transition metal oxide nano particle dispersion
Nano-crystal film is made on anode substrate, measures nano-crystal film thickness d；
Step 2: carrying out UV ozone or oxygen plasma surface modification treatment to nano-crystal film；
Step 3: carrying out rearrangement processing to the modified film in surface, it is thin that the p-type nano transition metal oxides are made
Film, when d is less than 15nm, resetting number of processes is 1 time, and when d is not less than 15nm and is less than 85nm, resetting number of processes is
log2(d/10)+1 round up after integer value number, when d be not less than 85nm when, reset number of processes be 5 times；
The rearrangement processing is specifically includes the following steps: the modified film in surface is soaked in nonpolar solvent, leaching
It takes out after 1~10s of profit, is then soaked in polar solvent again, taken out after infiltrating 1~10s, remove surface solvent, then use
Surface modification treatment is carried out with surface modifying treatment identical in step 2.
By the method for surface modification treatment, gap oxygen atom is effectively introduced, the gold of high-valence state is generated in induced crystal
Belong to atom (such as Ni2+→Ni3+), to make to form acceptor level in film, it is poor to improve p-type transition metal oxide electric conductivity
This case.But under general surface modification treatment (such as UV ozone, oxygen plasma) technique, sphere of action is only surface
Several nanometers, content of the oxygen interstitial atom from surface to internal depth position are gradually reduced, thus the p-type doping of film entirety
With apparent gradient distribution.Based on this case, the present invention proposes to clean under conditions of surface is modified in conjunction with infiltration
Technique assembling again for nano particle on micro-scale may be implemented, the rearrangement of nano particle can be real by the infiltration of solution
Existing p-type doping is uniformly distributed.Therefore, the present invention can change the oxygen atom component inside transition metal oxide film, and
The change of the valence state of metal and oxygen, generates more acceptor levels in energy level in film, also can preferably improve oxygen interstitial atom
Depth profiles uniformity, the P-type conductivity energy of enhanced film on the whole.
Preferably, in step 1, the transition metal oxide nano particle is molybdenum trioxide (MoO3), nickel oxide
(NiO), tungstic acid (WO3), vanadic anhydride (V2O5) and cuprous oxide (Cu2One of O).
Preferably, in step 1, the particle size of the transition metal oxide nano particle is 2~10nm.
Preferably, in step 1, the solwution method is spray coating method, spin-coating method, czochralski method, transfer impact system and inkjet printing
One of method.
Preferably, the anode substrate is fluorine-doped tin oxide (FTO) glass, tin indium oxide (ITO) glass, polyimides
(PI)/FTO, polyethylene terephthalate (PET)/FTO, polyethylene naphthalate (PEN)/FTO, PI/ITO,
One of PET/ITO and PEN/ITO flexible substrates.
Preferably, the nano-crystal film with a thickness of 10~100nm.
Preferably, the nonpolar solvent is one of normal octane, n-hexane, toluene, chlorobenzene and chloroform, polar solvent
For one of ethyl alcohol, methanol and isopropanol.
Preferably, the processing time of the surface modification treatment is 10~100min.
It is obtained the present invention also provides a kind of p-type nano transition metal oxides film according to made from the above method
The film p-type characteristic significantly increases, and applying has huge prospect in photoelectric field and flexible wearing electronic field, to high hole
Concentration injection and high hole mobility sull show in numerous photoelectric devices especially hull cell, flexible LED, flexibility
Application in battery, has a very important significance.
The invention has the benefit that the present invention combines the process of infiltration cleaning by surface modification treatment, in addition to
It can enhance outside hole conduction performance, moreover it is possible to the uniformity and compactness for improving film, for preparing high-flatness film with ten
Divide apparent effect, compared to the mode of Traditional dopant and high temperature sintering, implementation is simpler, and as a result repeatability is more preferable.System
The p-type nano transition metal oxides film obtained, has wide range of applications, there is positive rush to the research and development of Efficient devices
Into meaning.
Detailed description of the invention
Fig. 1 is the preparation flow of p-type transition metal oxide film in the present invention；
Fig. 2 is the specific preparation flow of the p-type transition metal oxide film in embodiment 2；
Fig. 3 is the nano NiO film of the embodiment of the present invention 2, reference examples 1 and the preparation of reference examples 2 in hole transport device
J-V curve characterized in structure.
Specific embodiment
Clear, complete description is carried out below with reference to technical effect of the embodiment to design and generation of the invention, with
It is completely understood by the purpose of the present invention, scheme and effect.It should be noted that in the absence of conflict, the reality in the application
The feature applied in example and embodiment can be combined with each other.
Embodiment 1:
A kind of p-type nano transition metal oxides film, preparation flow as shown in Figure 1, specifically includes the following steps:
(1) spray coating method is used, the MoO for being 2nm by particle size3Dispersion liquid is sprayed on FTO glass, prepares MoO3Film,
Film thickness is 10nm；
(2) by FTO/MoO3Film is placed in UV ozone equipment, carry out first time surface modification treatment, processing the time be
10min；
(3) FTO/MoO for crossing surface modification treatment3Film carries out 1 rearrangement processing, and aimed thin film is made.At rearrangement
The specific steps of reason are as follows: the FTO/MoO for crossing surface modification treatment3Film is initially positioned in normal octane solvent, infiltration cleaning 1s,
It then takes out and is placed in ethyl alcohol, infiltration cleaning 1s removes surface solvent after taking-up with 50 DEG C of heating methods；It is subsequently placed in ultraviolet smelly
Surface modification treatment is carried out in oxygen equipment, the processing time is 10min.
Embodiment 2:
A kind of p-type nano transition metal oxides film, preparation flow as shown in Figure 1, detailed process as shown in Fig. 2,
Specifically includes the following steps:
(1) spin-coating method is used, the NiO dispersion liquid that particle size is 4nm is spin-coated on ito glass, NiO film is prepared,
Film thickness is 20nm；
(2) ITO/NiO film is placed in UV ozone equipment, carry out first time surface modification treatment, processing the time be
20min；
(3) the ITO/NiO film for crossing surface modification treatment carries out 2 rearrangements processing, and aimed thin film is made.Rearrangement processing
Specific steps are as follows: the ITO/NiO film that surface modification treatment is crossed is initially positioned in n-hexane solvent, infiltration cleaning 2s, with
It takes out and is placed in methanol afterwards, infiltration cleaning 2s removes surface solvent after taking-up with 50 DEG C of heating methods；It is subsequently placed in UV ozone
Surface modification treatment is carried out in equipment, the processing time is 20min.
Embodiment 3:
A kind of p-type nano transition metal oxides film, preparation flow as shown in Figure 1, specifically includes the following steps:
It (1) the use of czochralski method is the WO of 5nm with particle size in PI/FTO flexible substrates3Dispersion liquid as stoste,
Lifting preparation WO3Film, film thickness 40nm；
(2) by PI/FTO/WO3Film is placed in oxygen plasma apparatus, first time surface modification treatment is carried out, when processing
Between be 40min；
(3) PI/ITO/WO for crossing surface modification treatment3Film carries out 3 rearrangements processing, and aimed thin film is made.It resets
The specific steps of processing are as follows: the PI/ITO/WO for crossing surface modification treatment3Film is initially positioned in toluene solvant, infiltration cleaning
4s then takes out and is placed in isopropanol, and infiltration cleaning 4s removes surface solvent after taking-up with 50 DEG C of heating methods；It is subsequently placed in
Surface modification treatment is carried out in oxygen plasma apparatus, the processing time is 20min.
Embodiment 4:
A kind of p-type nano transition metal oxides film, preparation flow as shown in Figure 1, specifically includes the following steps:
(1) using transfer impact system, the V for being 8nm by particle size2O5Dispersion liquid is spin-coated in PET/FTO flexible substrates,
Prepare V2O5Film, film thickness 80nm；
(2) by PET/FTO/V2O5Film is placed in oxygen plasma apparatus, carries out first time surface modification treatment, processing
Time is 80min；
(3) PET/FTO/V for crossing surface modification treatment2O5Film carries out 4 rearrangements processing, and aimed thin film is made.It resets
The specific steps of processing are as follows: the PET/FTO/V for crossing surface modification treatment2O5Film is initially positioned in chlorobenzene solvent, infiltration cleaning
8s then takes out and is placed in ethyl alcohol, and infiltration cleaning 8s removes surface solvent after taking-up with 50 DEG C of heating methods；It is subsequently placed in purple
Surface modification treatment is carried out in outer ozone devices, the processing time is 80min.
Embodiment 5:
A kind of p-type nano transition metal oxides film, preparation flow as shown in Figure 1, specifically includes the following steps:
(1) ink-jet printing is used, the Cu for being 10nm by particle size2O dispersion liquid is spin-coated on PEN/FTO flexible substrates
On, prepare Cu2O film, film thickness 100nm；
(2) by PEN/FTO/Cu2O film is placed in oxygen plasma apparatus, carries out first time surface modification treatment, processing
Time is 100min；
(3) PEN/FTO/Cu for crossing surface modification treatment2O film carries out 5 rearrangements processing, and aimed thin film is made.Weight
Arrange the specific steps of processing are as follows: the PEN/FTO/Cu for crossing surface modification treatment2O film is initially positioned in chloroform solvent, infiltration
10s is cleaned, then takes out and is placed in methanol, infiltration cleaning 10s removes surface solvent after taking-up with 50 DEG C of heating methods；Then
It is placed in UV ozone equipment and carries out surface modification treatment, the processing time is 100min.
Embodiment 6:
A kind of p-type nano transition metal oxides film, preparation flow as shown in Figure 1, specifically includes the following steps:
(1) spin-coating method is used, the NiO dispersion liquid that particle size is 4nm is spin-coated in PI/ITO flexible substrates, is prepared
NiO film, film thickness 20nm；
(2) PI/ITO/NiO film is placed in oxygen plasma apparatus, first time surface modification treatment is carried out, when processing
Between be 20min；
(3) the PI/ITO/NiO film for crossing surface modification treatment carries out 2 rearrangements processing, and aimed thin film is made.It resets
The specific steps of processing are as follows: the PI/ITO/NiO film that surface modification treatment is crossed is initially positioned in n-hexane solvent, infiltration is clear
2s is washed, then takes out and is placed in methanol, infiltration cleaning 2s removes surface solvent after taking-up with 50 DEG C of heating methods；It is subsequently placed in
Surface modification treatment is carried out in UV ozone equipment, the processing time is 20min.
Embodiment 7:
A kind of p-type nano transition metal oxides film, preparation flow as shown in Figure 1, specifically includes the following steps:
(1) spin-coating method is used, the NiO dispersion liquid that particle size is 6nm is spin-coated in PET/ITO flexible substrates, is prepared
NiO film, film thickness 40nm；
(2) PET/ITO/NiO film is placed in oxygen plasma apparatus, carries out first time surface modification treatment, processing
Time is 40min；
(3) the PET/ITO/NiO film for crossing surface modification treatment carries out 3 rearrangements processing, and aimed thin film is made.It resets
The specific steps of processing are as follows: the PET/ITO/NiO film that surface modification treatment is crossed is initially positioned in n-hexane solvent, infiltration is clear
4s is washed, then takes out and is placed in methanol, infiltration cleaning 4s removes surface solvent after taking-up with 50 DEG C of heating methods；It is subsequently placed in
Surface modification treatment is carried out in UV ozone equipment, the processing time is 40min.
Embodiment 8:
A kind of p-type nano transition metal oxides film, preparation flow as shown in Figure 1, specifically includes the following steps:
(1) spin-coating method is used, the NiO dispersion liquid that particle size is 8nm is spin-coated in PEN/ITO flexible substrates, is prepared
NiO film, film thickness 60nm；
(2) PEN/ITO/NiO film is placed in oxygen plasma apparatus, carries out first time surface modification treatment, processing
Time is 60min；
(3) the PEN/ITO/NiO film for crossing surface modification treatment carries out 4 rearrangements processing, and aimed thin film is made.It resets
The specific steps of processing are as follows: the PEN/ITO/NiO film that surface modification treatment is crossed is initially positioned in n-hexane solvent, infiltration is clear
6s is washed, taking-up is placed in ethyl alcohol, and infiltration cleaning 6s removes surface solvent after taking-up with 50 DEG C of heating methods；It is subsequently placed in purple
Surface modification treatment is carried out in outer ozone devices, the processing time is 60min.
Reference examples 1:
This reference examples will be with both modified without surface, also without the method for infiltrating cleaning treatment, preparation p-type transition metal oxide
Film, step include:
(1) spin-coating method is used, the NiO dispersion liquid that particle size is 4nm is spin-coated on ito glass, NiO film is prepared,
Film thickness is 20nm；
(2) by ITO/NiO film heating to 50 DEG C, film surface solvent is removed, common p-type transition metal oxide is made
Film.
Reference examples 2:
This reference examples will be handled with 1 subsurface and combine 1 method for resetting processing, and preparation p-type transition metal oxide is thin
Film, step include:
(1) spin-coating method is used, the NiO dispersion liquid that particle size is 4nm is spin-coated on ito glass, NiO film is prepared,
Film thickness is 20nm；
(2) ITO/NiO film is placed in UV ozone equipment, carry out first time surface modification treatment, processing the time be
20min；
(3) the ITO/NiO film for crossing surface modification treatment carries out 1 rearrangement processing, and aimed thin film is made.Rearrangement processing
Specific steps are as follows: the ITO/NiO film that surface modification treatment is crossed is initially positioned in n-hexane solvent, infiltration cleaning 2s, with
It takes out and is placed in methanol afterwards, infiltration cleaning 2s, then be drawn off removing surface solvent with 50 DEG C of heating methods；It is subsequently placed in ultraviolet
In ozone devices, surface modification treatment is carried out again, and the processing time is 20min.
Embodiment 9:
The nano NiO film of embodiment 2, reference examples 1 and reference examples 2 preparation is applied and is surveyed in hole transport device
Examination, as shown in figure 3, hole current density J is in identical on-load voltage in identical thicknesses of layers (20nm) and device architecture
(V) under the conditions of, as UV ozone surface is modified and the increasing for number of processes of infiltration cleaning and is gradually increased, illustrate nanometer
The p-type characteristic of NiO film enhances, and hole transport performance has clear improvement.
Table 1 is the hole mobility of nano NiO film prepared by embodiment 2, reference examples 1 and reference examples 2, as shown in Table 1,
The modified processing for combining infiltration cleaning in surface is carried out to p-type nano transition metal oxides film, for enhancing the P of nano thin-film
Type characteristic has obvious effect.
The hole mobility of 1 nano NiO film of table
Claims (10)
1. a kind of preparation method of p-type nano transition metal oxides film, which comprises the following steps:
Step 1: being coated on anode by solwution method as film raw material using transition metal oxide nano particle dispersion
Nano-crystal film is made on substrate, measures nano-crystal film thickness d；
Step 2: carrying out UV ozone or oxygen plasma surface modification treatment to nano-crystal film；
Step 3: carrying out rearrangement processing to the modified film in surface, the p-type nano transition metal oxides film is made,
When d is less than 15nm, resetting number of processes is 1 time, and when d is not less than 15nm and is less than 85nm, rearrangement number of processes is log2
(d/10)+1 round up after integer value number, when d be not less than 85nm when, reset number of processes be 5 times；
Rearrangement processing specifically includes the following steps: the modified film in surface is soaked in nonpolar solvent, infiltration 1~
It takes out after 10s, is then soaked in polar solvent again, taken out after infiltrating 1~10s, remove surface solvent, then use and step
Identical surface modifying treatment carries out surface modification treatment in two.
2. the method according to claim 1, wherein in step 1, the transition metal oxide nano particle
For MoO3、NiO、WO3、V2O5And Cu2One of O.
3. the method according to claim 1, wherein in step 1, the transition metal oxide nano particle
Particle size be 2~10nm.
4. the method according to claim 1, wherein in step 1, the solwution method be spray coating method, spin-coating method,
Czochralski method, transfer one of impact system and ink-jet printing.
5. the method according to claim 1, wherein the anode substrate is FTO glass, ITO glass in step 1
One of glass, PI/FTO, PET/FTO, PEN/FTO, PI/ITO, PET/ITO and PEN/ITO flexible substrates.
6. the method according to claim 1, wherein in step 1, the nano-crystal film with a thickness of 10~
100nm。
7. the method according to claim 1, wherein in step 3, the nonpolar solvent be normal octane, just oneself
One of alkane, toluene, chlorobenzene and chloroform, polar solvent are one of ethyl alcohol, methanol and isopropanol.
8. the method according to claim 1, wherein in step 2 neutralization procedure four, the surface modification treatment
The processing time be 10~100min.
9. a kind of p-type nano transition metal oxides film, which is characterized in that the film is any one of according to claim 1~8
Method is made.
10. application of the film as claimed in claim 9 in photoelectric field and flexible wearing electronic field.
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| CN114380512A (en) * | 2022-01-21 | 2022-04-22 | 浙江大学 | Nickel oxide electrochromic film with high lithium storage capacity and preparation method and application thereof |
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