CN107591488A - Multi-metal oxygen cluster compound metal complex oxide, its preparation method and application - Google Patents
Multi-metal oxygen cluster compound metal complex oxide, its preparation method and application Download PDFInfo
- Publication number
- CN107591488A CN107591488A CN201610533046.9A CN201610533046A CN107591488A CN 107591488 A CN107591488 A CN 107591488A CN 201610533046 A CN201610533046 A CN 201610533046A CN 107591488 A CN107591488 A CN 107591488A
- Authority
- CN
- China
- Prior art keywords
- compound
- metal
- oxygen cluster
- cluster compound
- metal oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Photovoltaic Devices (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a kind of multi-metal oxygen cluster compound metal complex oxide, its preparation method and application.The multi-metal oxygen cluster compound metal complex oxide includes：At least one multi-metal oxygen cluster compound；At least one metal oxide；And at least one solvent, to cooperatively form stable and uniform dispersion with each component in the compound.The compound can be used as electrode interface decorative material to be applied in organic electro-optic device.The raw material sources of compound of the present invention are extensive, it is easily prepared, cost is cheap, the stability of ink prepared by the compound is good, and it can deposit and form film, the film can be as the cushion of organic optoelectronic device, and it can effectively adjust the contact performance between organic active layer and electrode, and then improve the performance of organic optoelectronic device, and the device formed shows lower film thickness dependence, so as to reduce the technological requirement prepared to device, be advantageous to improve the yields of device.
Description
Technical field
Present invention relates particularly to a kind of multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and application,
Such as the purposes in organic optoelectronic device is prepared, belong to organic photoelectric and organic solar batteries field.
Background technology
Organic electro-optic device have it is flexible, light, inexpensive, be easy to using volume to volume printing method large area prepare etc. it is excellent
Point, wherein by taking organic solar batteries as an example, including just putting and be inverted two kinds of structures.Compared to the battery device for just putting structure,
The device of inverted structure avoids the metal electrode using low work content, generally possesses more preferable environmental stability, is more suitable for big face
Product printing prepares, more potential obtains high efficiency battery device.At present, battery floor interface in inverse organic solar cell
Layer, organic active layer are prepared using solwution method, and top electrode also can use the method for printing to realize, but hole transmission layer is adopted more
Prepared with the method for vacuum evaporation, complex operation, cost is higher.Therefore, the whole soln of organic solar batteries device is realized
Method prepare, seek can solution method prepare hole mobile material just become very urgent.
There are two kinds of polymer and metal oxide for hole transmission layer is currently used.Wherein, it polymerize species PEDOT:
For PSS because having higher a transparency and electric conductivity, the controllability of good technique processability and work function turns into most normal at present
Hole mobile material.But due to commercialized PEDOT:PSS is difficult directly to be deposited on organic work by the method for spin coating
Property layer surface, and PEDOT:PSS acidity and hygroscopicity can largely influence the stability of device.
Thus find alternative PEDOT:PSS hole transport class material is an important research of organic solar batteries
Direction, have more document report in recent years and hole mobile material is prepared using solwution method.Wherein metal oxide (nanoparticle
Son) it is the wide a kind of hole transport layer material of research, such as：MoO3, V2O5, WO3Deng.Wherein, MoO3With nontoxic and Gao Gong
A kind of hole mobile material that the characteristics of function is the most frequently used and effect is best.But these metal oxide nanoparticles
The problems such as difference between batch, surface trap and carrier density are relatively low generally be present.In addition to metal oxide, multi-metal oxygen cluster
(POM) also can be as the buffer electrode layer of solar cell.POM is to be connected by transition metal ions by oxygen atom to be formed
A kind of multi-metal oxygen cluster compound, have the advantages that material is cheap, easily prepare, stability is high, modifiability is strong.For example, Zhu etc.
The phosphomolybdic acid (PMA) of structure with Keggin is directly spin-coated on hole of the organic active layer surface as inverse organic solar cell
Transport layer, effectively increase PTB7:PC71The efficiency of BM devices.But because POM easy crystallinity is molten to substrate and presoma
Liquid is very sensitive.In addition, work function when as hole transmission layer to be present relatively low (4.6eV) for currently used metal oxide,
The shortcomings that being unfavorable for hole injection.
The content of the invention
It is a primary object of the present invention to provide a kind of multi-metal oxygen cluster compound-metal oxide compounds, its preparation
Method and application, to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The embodiments of the invention provide a kind of multi-metal oxygen cluster compound-metal oxide compounds, it is included：
At least one multi-metal oxygen cluster compound；
At least one metal oxide；
And at least one solvent, to cooperatively form stable homogeneous dispersion with each component in the compound
System.
The embodiment of the present invention additionally provides the method for preparing the multi-metal oxygen cluster compound-metal oxide compounds,
It includes：The multi-metal oxygen cluster compound is uniformly mixed in solvent with metal oxide, so as to form the compound.
The embodiment of the present invention additionally provides the purposes of the multi-metal oxygen cluster compound-metal oxide compounds.
For example, the embodiments of the invention provide a kind of compound ink, it includes described multi-metal oxygen cluster compound-metal
Complex oxide.
For example, the embodiment of the present invention additionally provides the method for preparing the compound ink, it includes：By multi-metal oxygen cluster
Compound uniformly mixes in solvent with metal oxide and forms the compound ink.
For example, the embodiment of the present invention additionally provides described multi-metal oxygen cluster compound-metal oxide compounds or institute
Compound ink is stated in preparing the purposes in modifying interface material (such as electrode interface decorative material) or organic electro-optic device.
For example, the embodiment of the present invention additionally provide by described multi-metal oxygen cluster compound-metal oxide compounds or
The film that described compound ink is formed.
For example, the embodiment of the present invention additionally provides the method for preparing the film, it includes：At least from coating and/or
Mode of printing is carried out at film forming to described multi-metal oxygen cluster compound-metal oxide compounds or described compound ink
Reason, so as to form the film.
For example, the embodiment of the present invention additionally provides a kind of device, it includes described film.Described device is included but not
It is limited to organic optoelectronic device.
Compared with prior art, advantages of the present invention at least that：
1. multi-metal oxygen cluster compound-metal oxide compounds provided by the invention, its raw material sources is extensive, is easy to make
Standby, cost is cheap；
2. multi-metal oxygen cluster compound-metal oxide compounds provided by the invention can reduce multi-metal oxygen cluster compound
Agglomeration, while use metal oxide be preferably nano particle, it can effectively be filled in multi-metal oxygen cluster chemical combination
In space between thing, so the compactness and uniformity of film can be improved, the surface smoothness of film is improved, reduces boundary
The surface roughness of face decorative layer；
3. the film that nationality is formed by multi-metal oxygen cluster compound-metal oxide compounds of the present invention can be used as organic light
The cushion of electronic device, the contact performance between organic active layer and electrode is effectively adjusted, and then improve organic optoelectronic device
The performance of part；
4. the compound Hole-injecting Buffer Layer for Improvement that nationality is formed by multi-metal oxygen cluster compound-metal oxide compounds of the present invention has
The stability of more preferable film forming and Geng Gao, and material is cheap, simple to operate, and experimental repeatability is good, can be more in technique
Good combination printing prepares organic electro-optic device；
5. the organic electro-optic device that nationality is formed by multi-metal oxygen cluster compound-metal oxide compounds of the present invention is shown
Lower film thickness dependence, so as to reduce the technological requirement prepared to device, be advantageous to improve the yields of device.
Brief description of the drawings
Fig. 1 is a kind of structural representation of solar cell in the embodiment of the present invention 1；
Fig. 2 a- Fig. 2 d are P3HT in the embodiment of the present invention 1 respectively:PC61BM films, P3HT:PC61BM/PMA films,
P3HT:PC61BM/MoO3Film, P3HT:PC61BM/PMA:MoO3The AFM figures of film；
Fig. 3 a are respectively with PMA, MoO in the embodiment of the present invention 13、PMA:MoO3, evaporation MoO3(e-MoO3) it is used as anode
The P3HT of decorative layer:PC61The J-V curve maps of BM system solar cells；
Fig. 3 b are respectively with PMA, MoO in the embodiment of the present invention 13、PMA:MoO3, evaporation MoO3(e-MoO3) it is used as anode
The P3HT of decorative layer:PC61The EQE curve maps of BM system solar cells.
Embodiment
In view of the deficiencies in the prior art, and improve the urgent demand of organic electro-optic device stability, inventor's warp
Study for a long period of time and largely put into practice, be able to propose technical scheme.As follows will be to the technical scheme, its implementation process and original
Reason etc. is further explained.
The one side of the embodiment of the present invention provides a kind of multi-metal oxygen cluster compound-metal oxide compounds, its
Comprising：
At least one multi-metal oxygen cluster compound；
At least one metal oxide；
And at least one solvent, to cooperatively form stable homogeneous dispersion with each component in the compound
System.
Wherein, the mass ratio of multi-metal oxygen cluster compound and metal oxide is any ratio in the compound, as excellent
One of case study on implementation is selected, both mass ratioes are 1:10~3:2.
More preferable, the concentration of the compound is 0.5-20mg/mL, especially preferably 3-6mg/mL.
One of preferably, any one of the multi-metal oxygen cluster compound at least in containing molybdenum, tungsten, vanadium
Or the multi-metal oxygen cluster compound of two or more combinations, but not limited to this.
It is further preferred that the multi-metal oxygen cluster compound can also include in phosphorus, silicon, germanium, arsenic any one or
The two or more combination of person, but not limited to this.
One of preferably, the multi-metal oxygen cluster compound include Keggin-type multi-metal oxygen cluster compound,
Any one in Wells-Dawson type multi-metal oxygens cluster compound, Lindqvist type multi-metal oxygen cluster compounds or two
The combination of the kind above, but not limited to this.
One of preferably, the multi-metal oxygen cluster compound includes the salt of metal polyacid and/or metal polyacid.
Wherein, the multi-metal oxygen cluster compound is easy to reunite in the case of individualism, and the size after reunion is
200-400nm。
As being preferable to carry out one of case, the metal oxide is at least selected from the oxide of molybdenum, the oxide of vanadium, tungsten
Any one in oxide, the oxide of nickel, the oxide of zinc, titanyl compound or two kinds and two or more combinations, but
Not limited to this.
Wherein, the metal oxide is preferably nano particle, and it can be obtained by approach purchased in market, can also use industry
Appropriate method is produced known to boundary.
Wherein, the metal oxide is preferably dimensioned to be 5-50nm.
For example, in some more specific embodiment, the preparation method of the metal oxide nanoparticles includes：
(a) using metal or metal oxide powder as raw material, and hydrogen peroxide progress oxidation reaction is added in a solvent and is obtained
Obtain metal oxide mixture.In certain embodiments, described metal or its oxide powder can include：Molybdenum, vanadium,
Tungsten, nickel, zinc, the oxide of the powder of titanium and above-mentioned metal, but not limited to this.In certain embodiments, described solvent can
With including：Water, methanol, ethanol, propyl alcohol, isopropanol, but not limited to this.In some more typical embodiments, molybdenum oxide is received
Rice grain is synthesized by using molybdenum powder as raw material, in alcohol solvent, add hydrogen peroxide normal temperature under reaction 20-30 hours obtain
's.
(b) above-mentioned metal oxide mixture is passed through into evaporation solvent, dissolving, ultrasonic disperse, centrifugation multi step strategy,
Obtain the metal oxide dispersion of required alcohol phase or aqueous phase.To prepare the scattered MoO of ethanol3Exemplified by ink：First will be anti-
The mixture of gained is answered to stand, reaction vessel lower floor is the complete black molybdenum powder of unreacted, and upper strata is the blue oxygen that reaction obtains
Change molybdenum ethanol solution.Upper strata blue supernatant is pipetted with liquid-transfering gun, is spin-dried on a rotary evaporator, removes solvent, then with ethanol weight
New dissolving, is then centrifuged for, discards precipitation, obtain the MoO of stable dispersion3Nanometer ink.
In some embodiments, the solvent includes any one in water, Organic Alcohol or two or more combinations.
Further, the Organic Alcohol include methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, ethylene glycol,
Any one in glycol monoethyl ether or two or more combinations, but not limited to this.
It is more highly preferred to, the solvent also includes secondary organic solvent, such as acetone, chloroform, toluene, dimethylbenzene, front three
Any one in benzene, chlorobenzene, dichloro-benzenes or two or more combinations, but not limited to this.
In some embodiments, the compound is preferably homogeneous (uniform) fluid shape dispersion, and is considered as a kind of ink
Water.
It is multiple that the another aspect of the embodiment of the present invention additionally provides multi-metal oxygen cluster compound-metal oxide described in preparing
The method of compound, it includes：The multi-metal oxygen cluster compound is uniformly mixed with metal oxide in solvent and forms institute
State compound.
The one side of the embodiment of the present invention additionally provides a kind of compound ink, and it includes described multi-metal oxygen cluster chemical combination
Thing-metal oxide compounds.
The embodiment of the present invention additionally provides the method for preparing the compound ink, and it includes：By multi-metal oxygen cluster compound
Uniformly mixed in solvent with metal oxide and form the compound ink.
In some more preferred embodiment, the preparation method includes：
By metal oxide dispersion in forming metal oxide dispersion in solvent,
Multi-metal oxygen cluster compound is dissolved in and/or be scattered in solvent and forms multi-metal oxygen cluster compound solution or scattered
Liquid,
Metal oxide dispersion is uniform by the mass ratio of setting with multi-metal oxygen cluster compound solution or dispersion liquid
Mixing, so as to form the compound ink.
Wherein, the solvent can be including any one in water, methanol, ethanol, normal propyl alcohol, isopropanol or two or more
Combination, but not limited to this.
In certain embodiments, multi-metal oxygen cluster compound solution or dispersion liquid are pressed with metal oxide dispersion
Mixed according to certain volume ratio, that is, obtain mixed ink.
With PMA-MoO3Exemplified by the preparation of compound ink, it can include：PMA is scattered in steam again the is formed in isopropanol
One system, by the MoO of different volumes3Ethanol solution is injected into PMA aqueous isopropanol, is mixed and obtained by ultrasonic disperse
PMA-MoO3Compound ink.
The one side of the embodiment of the present invention additionally provide the multi-metal oxygen cluster compound-metal oxide compounds in
The purposes in modifying interface material and organic optoelectronic device is prepared, such as is modified as electrode interface in organic optoelectronic device
The purposes of material.
The one side of the embodiment of the present invention additionally provides compound by described multi-metal oxygen cluster compound-metal oxide
The film that thing or described compound ink are formed.
Accordingly, the one side of the embodiment of the present invention additionally provides the method for preparing the film, and it includes：At least select
With coating and/or mode of printing to described multi-metal oxygen cluster compound-metal oxide compounds or described compound ink
Film process are carried out, form the film.
For example, can select coating and/or mode of printing that described compound ink is applied in substrate, formed described thin
Film.
In certain embodiments, the coating and/or mode of printing are beaten including spin-coating, scraper for coating, ink-jet
Any one in print, silk-screen printing, intaglio printing mode or two or more combinations.
The one side of the embodiment of the present invention additionally provides a kind of device, and it includes described film.Described device includes
Organic optoelectronic device with electric light and light transfer characteristic, such as organic luminescent device, organic photovoltaic battery etc..
Described in the present invention is formed by the way that the solution of multi-metal oxygen cluster compound is uniformly mixed with metal oxide ink
Compound, the agglomeration of multi-metal oxygen cluster compound can be reduced, while metal oxide nanoparticles can be effectively filled in
In space between multi-metal oxygen cluster compound, so the compactness and uniformity of complex thin film can be improved, boundary is reduced
The surface roughness of face decorative layer.Simultaneously, metal oxide may also function as regulation multi-metal oxygen cluster in compound interface layer
The work function of compound, and then change the function of the application performance of photoelectric device.
Wherein, the surface work content of laminated film can be realized by adjusting the compositely proportional between compound.This is compound
Contact performance between film and organic active layer is good, is effectively improved the performance of device.
In the compound of the present invention, the particularly compound ink of the present invention, the selection of solvent needs to combine multi-metal oxygen
Requirement of dispersive property and subsequent thin film deposition process of the cluster compound in different solvents to solvent carries out comprehensive selection.
For example, it is ITO/ZnO/P3HT in preparation structure:PC61BM/PMA:MoO3/ Al inverted organic solar batteries
When, in order to avoid spin coating anode modification layer PMA:MoO3During destruction of the solvent to optically active layer, solvent need to avoid using
Chlorobenzene, dichloro-benzenes equal solvent.
In another example it is ITO/TiO in preparation structure2/PVSK(CH3NH3PbX3,NH2CH=NH2PbX3, X=Cl, Br, I)/
PMA:MoO3During/Al perovskite battery, because perovskite thin film meets water decomposition, therefore the ink must be anhydrous system, and
Butanol, the alcohol of propyl alcohol class also have certain destructiveness to perovskite thin film, so when configuring the ink except requiring PMA points
It is dispersed in outside absolute methanol, ethanol or methanol, ethanol and butanol mixed solvent, also requires MoO3It can not be dispersed in water, so
PMA in the system:MoO3It is dispersed in absolute ethyl alcohol.
For another example it is ITO/PMA in structure:MoO3/PVSK(CH3NH3PbX3,NH2CH=NH2PbX3, X=Cl, Br, I)/
PCBM/Al or ITO/PMA:MoO3/P3HT:PC61BM/MoO3In/Al system, because PMA:MoO3Directly in ITO (oxidations
Indium tin) prepared by surface, therefore destruction problem of the solvent to primer is not present, and also therefore can be according to typography
The stability of demand and ink, select multi-solvents.
In some more specific case study on implementation, a kind of multi-metal oxygen cluster compound-metal oxide compound buffer layer
Preparation method can include：Described multi-metal oxygen cluster chemical combination is deposited on organic active layer by the mode such as being coated with or printing
Thing-metal oxide compounds or described compound ink, so as to form organic photovoltaic devices or organic electroluminescence device
Hole-injecting Buffer Layer for Improvement.
In certain embodiments, the film of the invention can also be deposited directly to other various substrate surfaces, wherein
The base material can include but is not limited to：Glass, plastics, paper and sheet metal, such as：Stainless steel, aluminium foil etc..
Because multi-metal oxygen cluster compound-metal oxide compounds provided by the present invention are dispersed in a solvent,
Therefore, can be preferably between metal oxide and multi-metal oxygen cluster compound using in the film prepared by the compound
It is mixed to form uniform laminated film.Simultaneously metal oxide nanoparticles can effectively be filled in multi-metal oxygen cluster compound it
Between space among, therefore the compactness and uniformity of complex thin film can be improved, improve the surface smoothness of laminated film.
Than conventional hole cushioning layer material, the compound Hole-injecting Buffer Layer for Improvement of the invention and show more preferable film forming and
Higher stability, and material is cheap, simple to operate, and experimental repeatability is good, and printing system can be preferably combined in technique
Standby organic electro-optic device.
Technical scheme is further described below by way of some embodiments and with reference to accompanying drawing.It is however, selected
Embodiment be merely to illustrate the present invention, and do not limit the scope of the invention.
Embodiment 1PMA:MoO3The preparation of compound ink and the application in organic photovoltaic devices
1. the PMA:MoO3The preparation technology of compound ink includes：
(1) preparation of PMA inks：3mg tri- is taken to be hydrated phosphomolybdic acid (H3PO4·12MoO3·3H2O, PMA) powder, add
1mL steams isopropanol again, ultrasound obtains the PMA inks that weight concentration is 3mg/mL to being completely dispersed；
(2)MoO3The preparation of ink：250mg molybdenum powders are taken in the single-necked flask for filling 10mL ethanol, stirs, then adds
0.5mL 30% hydrogenperoxide steam generator, reaction solution gradually become navy blue by black, react 24h under normal temperature.After standing 4h, take
Upper solution is spin-dried on a rotary evaporator, removes solvent, then dissolved again with 10mL ethanol.Then under 4000rpm rotating speeds
10min is centrifuged, discards precipitation, obtains the MoO that concentration is 6mg/mL3Nanometer ink；
(3)PMA:MoO3The preparation of compound ink：Concentration is taken as 1mg/mL PMA inks and 6mg/mL MoO3Ink is pressed
Mixed according to different volume ratios, ultrasound can obtain PMA:MoO3Compound ink.
2. corresponding PMA:MoO3The preparation technology of laminated film includes：By universal methods such as spin coating, blade coatings by the PMA:
MoO3Compound ink is coated on base material, forms the laminated film after drying.
3. with PMA:MoO3Laminated film includes for the preparation technology of the inversion device of anode modification layer：As shown in figure 1, institute
Stating the structure of inversion device includes ITO negative electrodes, ZnO cathodic modification layers, P3HT:PC61BM photoactive layers, PMA:MoO3Anode modification
Layer, Al anodes.Respectively with PMA, MoO3、PMA:MoO3, evaporation MoO3For anode modification layer, preparation structure ITO/ZnO/P3HT:
PC61BM/ anode modification layers/Al inverted structure device.PMA inks, PMA:MoO3Ink, MoO3Ink uses 3500rpm
Spin coating 1min.Fig. 2 a- Fig. 2 d are referred to, from the AFM figures of film it can be seen that pure PMA inks are in P3HT:PC61Formed on BM films
Island shape film, its isolated island size about 100nm, this is mainly the reunion from PMA, therefore the roughness of film is very big, about
8.84nm.And PMA and MoO3It is compound so that the agglomeration of PMA particles is improved, so as to obtain PMA:MoO3Film it is thick
Rugosity is 6.30nm.
The performance parameter for referring to Fig. 3 a- Fig. 3 b J-V curves, EQE curves and table 1 again is understood, with PMA:MoO3It is multiple
The device performance for closing anode modification layer is better than with independent PMA and independent MoO3As the device of anode modification layer, especially compared to
PMA is the device of anode modification layer, and the open-circuit voltage and short circuit current and fill factor, curve factor of device are obviously improved.
With PMA, MoO in the embodiment 1 of table 13、PMA:MoO3、e-MoO3P3HT as anode modification layer:PC61BM systems
The device parameter performance of solar cell
Embodiment 2PMA:MoO3Application of the composite bed in perovskite battery
1. the PMA:MoO3The preparation technology of compound ink includes：
(1) preparation of PMA inks：1-5mg tri- is taken to be hydrated phosphomolybdic acid (H3PO4·12MoO3·3H2O, PMA) powder, add
1mL isopropanols, ultrasound obtain the PMA inks that weight concentration is 1-5mg/mL to being completely dispersed；
(2)PMA:MoO3The preparation of compound ink：Take PMA inks and MoO3Ink presses 1:1 volume ratio mixes, and ultrasound is
It can obtain a series of PMA:MoO3Compound ink.
2. with PMA:MoO3For the preparation and performance test of the perovskite battery of anode modification layer：Perovskite in the present embodiment
The structure of battery is：ITO/PMA:MoO3/PVSK/PCBM/Al.Device parameter performance is：VOC=0.84V, JSC=17.5mA/
cm2, FF=0.61, PCE=8.97%.Illustrate PMA:MoO3Composite bed can be as the anode modification layer of perovskite battery.
Embodiment 3PWA:MoO3The preparation of compound ink and the application in perovskite battery
(1) preparation of PWA inks：Take 1-5mg phosphotungstic acid hydrates (H3PO4·12WO3·H2O, PWA) powder, add
1mL isopropanols, ultrasound obtain the PWA inks that weight concentration is 1-5mg/mL to being completely dispersed；
(2)PWA:MoO3The preparation of compound ink：Take PWA inks and MoO3Ink presses 5:1-1:5 volume ratio mixing,
Ultrasound can obtain a series of PWA:MoO3Compound ink.
2. with PWA:MoO3For the preparation and performance test of the perovskite battery of anode modification layer：Perovskite in the present embodiment
The structure of battery is：ITO/PWA:MoO3/PVSK/PCBM/Al.PWA inks and MoO3The optimal volume ratio of ink is 1:2, device
Performance parameter is：VOC=0.87V, JSC=16.8mA/cm2, FF=0.63, PCE=9.21%.Illustrate PWA:MoO3Composite bed can
Using the anode modification layer as perovskite battery.Compared to the device that PWA is anode modification layer, the open-circuit voltage of device and short circuit
Electric current and fill factor, curve factor are obviously improved.
Embodiment 4PWA:V2O5The preparation of compound ink and the application in perovskite battery
(1) preparation of PWA inks：Take 1-5mg phosphotungstic acid hydrates (H3PO4·12WO3·H2O, PWA) powder, add
1mL isopropanols, ultrasound obtain the PWA inks that weight concentration is 1-5mg/mL to being completely dispersed；
(2)PWA:V2O5The preparation of compound ink：Take PWA inks and V2O5Ink presses 5:1-1:5 volume ratio mixing,
Ultrasound can obtain a series of PWA:V2O5Compound ink.
2. with PWA:V2O5For the preparation and performance test of the perovskite battery of anode modification layer：Perovskite in the present embodiment
The structure of battery is：ITO/PWA:V2O5/PVSK/PCBM/Al.PWA inks and V2O5The optimal volume ratio of ink is 1:2, device
Performance parameter is：VOC=0.87V, JSC=17.8mA/cm2, FF=0.65, PCE=10.06%.Illustrate PWA:V2O5Composite bed
Can be as the anode modification layer of perovskite battery.Compared to the device that PWA is anode modification layer, the open-circuit voltage of device and short
Road electric current and fill factor, curve factor are obviously improved.
It should be noted that various raw materials, process conditions, device material and structural parameters etc. used by example is performed as described above
It is more typical example, but by the checking of inventor's lot of experiments, it is other different types of in those listed above
Raw material and other technological parameters etc. are also applicable, and also equal attainable cost invents claimed technique effect.
It is pointed out that the technical concepts and features of above-described embodiment only to illustrate the invention, ripe its object is to allow
Present disclosure can be understood and implement according to this by knowing the personage of technique, and the protection model of the present invention can not be limited with this
Enclose.Any equivalent change or modification in accordance with the spirit of the invention, it should all be included within the scope of the present invention.
Claims (22)
1. a kind of multi-metal oxygen cluster compound-metal oxide compounds, it is characterised in that include：
At least one multi-metal oxygen cluster compound；
At least one metal oxide；
And at least one solvent, to cooperatively form stable dispersed system with each component in the compound.
2. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1, it is characterised in that：It is described multiple
The mass ratio of multi-metal oxygen cluster compound and metal oxide is 1 in compound:10~3:2.
3. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1 or 2, it is characterised in that：It is described
The concentration of compound is 0.5-20mg/mL, preferably 3-6mg/mL.
4. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1, it is characterised in that：It is described more
The multi-metal oxygen cluster of any one or two or more combination of the metal oxygen cluster compound at least in containing molybdenum, tungsten, vanadium
Compound；Preferably, the multi-metal oxygen cluster compound also include in phosphorus, silicon, germanium, arsenic any one or it is two or more
Combination；And/or size of the multi-metal oxygen cluster compound after reunion is 200-400nm.
5. multi-metal oxygen cluster compound-metal oxide compounds according to claim 4, it is characterised in that：It is described more
Metal oxygen cluster compound include Keggin-type multi-metal oxygen cluster compound, Wells-Dawson type multi-metal oxygens cluster compound,
Any one in Lindqvist type multi-metal oxygen cluster compounds or two or more combinations.
6. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1, it is characterised in that：It is described more
Metal oxygen cluster compound includes the salt of metal polyacid and/or metal polyacid.
7. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1, it is characterised in that：The gold
Belong to oxide at least selected from the oxide of molybdenum, the oxide of vanadium, the oxide of tungsten, the oxide of nickel, the oxide of zinc, the oxygen of titanium
Any one in compound or two kinds and two or more combinations；And/or the size of the metal oxide is 5-50nm.
8. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1, it is characterised in that：It is described molten
Agent includes any one or two or more combinations in water, Organic Alcohol.
9. multi-metal oxygen cluster compound-metal oxide compounds according to claim 8, it is characterised in that：It is described to have
Machine alcohol includes any one in methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, ethylene glycol, glycol monoethyl ether
Or two or more combination.
10. multi-metal oxygen cluster compound-metal oxide compounds according to claim 8 or claim 9, it is characterised in that：Institute
Stating solvent also includes secondary organic solvent, and the secondary organic solvent includes acetone, chloroform, toluene, dimethylbenzene, trimethylbenzene, chlorine
Any one in benzene, dichloro-benzenes or two or more combinations.
11. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1, it is characterised in that：It is described multiple
Compound is homogeneous (uniform) fluid shape dispersion.
12. the preparation method of multi-metal oxygen cluster compound-metal oxide compounds any one of claim 1-11,
It is characterized in that including：Multi-metal oxygen cluster compound is uniformly mixed with metal oxide in solvent and formed described compound
Thing.
A kind of 13. compound ink, it is characterised in that comprising the multi-metal oxygen cluster compound any one of claim 1-11-
Metal oxide compounds.
14. the preparation method of compound ink as claimed in claim 13, it is characterised in that including：By multi-metal oxygen cluster compound with
Metal oxide uniformly mixes in solvent, so as to form the compound ink.
15. the preparation method of compound ink according to claim 14, it is characterised in that including：
By metal oxide dispersion in forming metal oxide dispersion in solvent,
Multi-metal oxygen cluster compound is dissolved in and/or is scattered in solvent and forms multi-metal oxygen cluster compound solution or dispersion liquid,
Metal oxide dispersion is mixed with multi-metal oxygen cluster compound solution or homogeneous dispersion, it is described compound so as to be formed
Ink.
16. the preparation method of compound ink according to claims 14 or 15, it is characterised in that：The solvent includes water, first
Any one in alcohol, ethanol, normal propyl alcohol, isopropanol or two or more combinations.
17. multi-metal oxygen cluster compound-metal oxide compounds or claim any one of claim 1-11
The 13 compound inks are in preparing the purposes in modifying interface material or organic electro-optic device.
18. will as multi-metal oxygen cluster compound-metal oxide compounds any one of claim 1-11 or right
The film for asking the compound ink described in 13 to be formed.
19. the preparation method of film described in claim 18, it is characterised in that including：At least from coating and/or mode of printing
To described in multi-metal oxygen cluster compound-metal oxide compounds any one of claim 1-11 or claim 13
Compound ink carry out film process, so as to form the film.
20. the preparation method of film according to claim 19, it is characterised in that：The coating and/or mode of printing include
Any one in spin-coating, scraper for coating, inkjet printing, silk-screen printing, intaglio printing mode or two or more combinations.
21. a kind of device, it is characterised in that include the film described in claim 18.
22. device according to claim 21, it is characterised in that：Described device includes organic optoelectronic device, described to have
Machine opto-electronic device includes organic luminescent device and/or organic photovoltaic battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610533046.9A CN107591488B (en) | 2016-07-08 | 2016-07-08 | Multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610533046.9A CN107591488B (en) | 2016-07-08 | 2016-07-08 | Multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107591488A true CN107591488A (en) | 2018-01-16 |
| CN107591488B CN107591488B (en) | 2019-08-23 |
Family
ID=61046438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610533046.9A Active CN107591488B (en) | 2016-07-08 | 2016-07-08 | Multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107591488B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061220A (en) * | 2021-06-03 | 2021-07-02 | 北京石油化工学院 | Heteropoly acid mixtures and their use |
| CN113130779A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
| CN113410392A (en) * | 2021-06-24 | 2021-09-17 | 上海大学 | Non-fullerene organic solar cell and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171727A (en) * | 1991-08-26 | 1992-12-15 | Uop | Method of preparing a catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks |
| US5474977A (en) * | 1991-08-26 | 1995-12-12 | Uop | Catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks |
| CN101307148A (en) * | 2008-07-10 | 2008-11-19 | 中国科学院化学研究所 | Composite discolored thin film, method for preparing same and applications |
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN103943365A (en) * | 2014-04-25 | 2014-07-23 | 中南大学 | Manufacturing method of dye-sensitized solar cell modified photo anode |
| CN104984766A (en) * | 2015-07-29 | 2015-10-21 | 河南师范大学 | B/POMs/TiO2 ternary composite photocatalytic material and preparation method thereof |
| CN105390293A (en) * | 2015-12-15 | 2016-03-09 | 哈尔滨工业大学 | Preparation method for dye-sensitized solar cell photo anode based on heteropolyacid SiW11Ni modified TiO2 |
| CN105575667A (en) * | 2015-12-15 | 2016-05-11 | 哈尔滨工业大学 | Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2 |
-
2016
- 2016-07-08 CN CN201610533046.9A patent/CN107591488B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171727A (en) * | 1991-08-26 | 1992-12-15 | Uop | Method of preparing a catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks |
| US5474977A (en) * | 1991-08-26 | 1995-12-12 | Uop | Catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks |
| CN101307148A (en) * | 2008-07-10 | 2008-11-19 | 中国科学院化学研究所 | Composite discolored thin film, method for preparing same and applications |
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN103943365A (en) * | 2014-04-25 | 2014-07-23 | 中南大学 | Manufacturing method of dye-sensitized solar cell modified photo anode |
| CN104984766A (en) * | 2015-07-29 | 2015-10-21 | 河南师范大学 | B/POMs/TiO2 ternary composite photocatalytic material and preparation method thereof |
| CN105390293A (en) * | 2015-12-15 | 2016-03-09 | 哈尔滨工业大学 | Preparation method for dye-sensitized solar cell photo anode based on heteropolyacid SiW11Ni modified TiO2 |
| CN105575667A (en) * | 2015-12-15 | 2016-05-11 | 哈尔滨工业大学 | Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2 |
Non-Patent Citations (1)
| Title |
|---|
| O.YU.POSUDIEVSKY ET AL: "12-Phosphormolibdic acid doped polyaniline–V2O5 composite", 《SYNTHETIC METALS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113130779A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
| CN113130779B (en) * | 2019-12-30 | 2022-08-02 | Tcl科技集团股份有限公司 | Nano material, preparation method thereof and quantum dot light-emitting diode |
| CN113061220A (en) * | 2021-06-03 | 2021-07-02 | 北京石油化工学院 | Heteropoly acid mixtures and their use |
| CN113061220B (en) * | 2021-06-03 | 2021-09-21 | 北京石油化工学院 | Heteropoly acid mixtures and their use |
| CN113410392A (en) * | 2021-06-24 | 2021-09-17 | 上海大学 | Non-fullerene organic solar cell and preparation method thereof |
| CN113410392B (en) * | 2021-06-24 | 2022-11-22 | 上海大学 | Non-fullerene organic solar cell and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107591488B (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jiang et al. | Recent advances of synthesis, properties, film fabrication methods, modifications of poly (3, 4‐ethylenedioxythiophene), and applications in solution‐processed photovoltaics | |
| Wang et al. | Large‐area organic solar cells: material requirements, modular designs, and printing methods | |
| Lawes et al. | Printing nanostructured carbon for energy storage and conversion applications | |
| Razza et al. | Research Update: Large-area deposition, coating, printing, and processing techniques for the upscaling of perovskite solar cell technology | |
| Balis et al. | Graphene and transition metal dichalcogenide nanosheets as charge transport layers for solution processed solar cells | |
| Janáky et al. | The role of (photo) electrochemistry in the rational design of hybrid conducting polymer/semiconductor assemblies: From fundamental concepts to practical applications | |
| Zi et al. | Flexible perovskite solar cells based on green, continuous roll-to-roll printing technology | |
| Parida et al. | Recent developments in upscalable printing techniques for perovskite solar cells | |
| CN105098073B (en) | Metal oxide-conducting polymer -ol composition, preparation method and application | |
| AL-Refai et al. | Polythiophene and its derivatives–Based nanocomposites in electrochemical sensing: A mini review | |
| CN105778619A (en) | Polymer-nanometer metal oxide composite ink, and preparation method and application thereof | |
| Zhao et al. | Research progress in large-area perovskite solar cells | |
| TW200539195A (en) | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof | |
| CN107591488B (en) | Multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and application | |
| KR101113658B1 (en) | Titanium Dioxide Nano Particle Modified by Surface Stabilizer, Titanium Dioxide Nano Ink Comprising the same, Solar Battery Employing the Same, and Producing Method of the Same | |
| KR101023021B1 (en) | Inverted organic solar cell and method for manufacturing thereof | |
| KR20090109357A (en) | Formation Method of Hybrid Solar Cell | |
| CN103403906A (en) | Photovoltaic cells | |
| CN106611818B (en) | Polymer-multi-metal oxygen cluster compound composite material, preparation method and application | |
| CN107629642A (en) | The adjustable polymer composites of work content, its preparation method and application | |
| Jang et al. | All-solution-processed PbS quantum dot solar modules | |
| Li et al. | Roll-to-roll micro-gravure printed P3HT: PCBM organic solar cells | |
| CN112071988B (en) | Preparation method of full-screen printing perovskite solar cell | |
| CN114634732B (en) | Two-dimensional material water-based ink and preparation method and application thereof | |
| KR101023020B1 (en) | Inverted transparent organic solar cell and method for manufacturing thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |