CN107591488B - Multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and application - Google Patents
Multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and application Download PDFInfo
- Publication number
- CN107591488B CN107591488B CN201610533046.9A CN201610533046A CN107591488B CN 107591488 B CN107591488 B CN 107591488B CN 201610533046 A CN201610533046 A CN 201610533046A CN 107591488 B CN107591488 B CN 107591488B
- Authority
- CN
- China
- Prior art keywords
- compound
- oxygen cluster
- metal
- metal oxide
- cluster compound
- 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.)
- Active
Links
Landscapes
- Photovoltaic Devices (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a kind of multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and applications.Multi-metal oxygen cluster compound-the metal oxide compounds include: 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 applied in organic electro-optic device.The raw material sources of compound of the present invention are extensive, it is easily prepared, it is low in cost, the stability of ink prepared by the compound is good, and it can deposit and form film, the film can be used as the buffer layer 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 it is formed by device and shows lower film thickness dependence, so as to reduce the technique requirement to device preparation, be conducive to the yields for improving device.
Description
Technical field
Present invention relates particularly to a kind of multi-metal oxygen cluster compound-metal oxide compounds, preparation method and application,
Such as the purposes in organic optoelectronic device is being prepared, belong to organic photoelectric and organic solar batteries field.
Background technique
Organic electro-optic device has method large area preparation that is flexible, light, inexpensive, being easy to use roll-to-roll printing etc. excellent
Point, wherein by taking organic solar batteries as an example, including just setting and be inverted two kinds of structures.Compared to the battery device for just setting structure,
The device of inverted structure avoids the metal electrode using low work content, usually possesses better environmental stability, is more suitable for big face
Product printing preparation more potential obtains high efficiency battery device.Currently, battery floor interface in inverse organic solar cell
Layer, organic active layer are all made of solwution method preparation, and the method that printing can also be used in top electrode is realized, but hole transmission layer is adopted more
It is prepared with the method for vacuum evaporation, complicated for operation, higher cost.Therefore, the whole soln of Yao Shixian organic solar batteries device
Method preparation, seek can solution method preparation hole mobile material just become very urgent.
It is currently used for hole transmission layer to have polymer and two kinds of metal oxide.Wherein, it polymerize species PEDOT:
Because of transparency with higher and electric conductivity, the controllability of good technique processability and work function becomes at present most often PSS
Hole mobile material.But since commercialized PEDOT:PSS is difficult directly to be deposited on organic work by the method for spin coating
Property layer surface, and the acidity and hygroscopicity of PEDOT:PSS largely will affect the stability of device.
The hole transport class material for thus finding alternative PEDOT:PSS is an important research of organic solar batteries
Direction has more document report using solwution method in recent years and prepares hole mobile material.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
It is also the best a kind of hole mobile material of effect that the characteristics of function, which is the most frequently used,.But these metal oxide nanoparticles
Usually there is the problems such as difference between batch, surface trap and carrier density are lower.In addition to metal oxide, multi-metal oxygen cluster
(POM) it also can be used as the electrode buffer layer of solar battery.POM is to be formed by transition metal ions by oxygen atom connection
A kind of multi-metal oxygen cluster compound has many advantages, such as that material is cheap, easily preparation, stability height, modifiability is strong.For example, Zhu etc.
The phosphomolybdic acid (PMA) of structure with Keggin is directly spin-coated on organic active layer surface as the hole of inverse organic solar cell
Transport layer effectively increases PTB7:PC71The efficiency of BM device.But since the easy crystallinity of POM is molten to substrate and presoma
Liquid is very sensitive.In addition, that there are work functions when as hole transmission layer is lower (4.6eV) for currently used metal oxide,
The shortcomings that being unfavorable for hole injection.
Summary of the invention
The main purpose of the present invention is to provide a kind of multi-metal oxygen cluster compound-metal oxide compounds, its preparation
Method and application, to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of multi-metal oxygen cluster compound-metal oxide compounds, it includes:
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 invention also provides the method for preparing the multi-metal oxygen cluster compound-metal oxide compounds,
Comprising: the multi-metal oxygen cluster compound uniformly be mixed in solvent with metal oxide, to form the compound.
The embodiment of the invention also provides the purposes of the multi-metal oxygen cluster compound-metal oxide compounds.
For example, it includes multi-metal oxygen cluster compound-metals the embodiment of the invention provides a kind of compound ink
Complex oxide.
For example, the embodiment of the invention also provides the methods for preparing the compound ink comprising: by multi-metal oxygen cluster
Object is closed uniformly to mix in solvent with metal oxide and form the compound ink.
For example, the embodiment of the invention also provides multi-metal oxygen cluster compound-metal oxide compounds or institutes
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 invention also provides by the multi-metal oxygen cluster compound-metal oxide compounds or
The film that the compound ink is formed.
For example, the embodiment of the invention also provides the methods for preparing the film comprising: at least select coating and/or
Mode of printing carries out at film forming the multi-metal oxygen cluster compound-metal oxide compounds or the compound ink
Reason, to form the film.
For example, it includes the films the embodiment of the invention also provides a kind of device.The device includes 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, raw material sources are extensive, are easy to make
It is standby, it is low in cost；
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, can effectively be filled in multi-metal oxygen cluster chemical combination
In gap between object, 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. nationality can be used as organic light by the film that multi-metal oxygen cluster compound-metal oxide compounds of the present invention are formed
The buffer layer of electronic device effectively adjusts the contact performance between organic active layer and electrode, and then improves organic optoelectronic device
The performance of part；
4. nationality is had by the compound Hole-injecting Buffer Layer for Improvement that multi-metal oxygen cluster compound-metal oxide compounds of the present invention are formed
Better film forming and higher stability, and material is cheap, easy to operate, and experimental repeatability is good, can be more in technique
Good combination printing prepares organic electro-optic device；
5. nationality is shown by the organic electro-optic device that multi-metal oxygen cluster compound-metal oxide compounds of the present invention are formed
Lower film thickness dependence is conducive to the yields for improving device so as to reduce the technique requirement to device preparation.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of solar battery in the embodiment of the present invention 1；
Fig. 2 a- Fig. 2 d is P3HT:PC in the embodiment of the present invention 1 respectively61BM film, P3HT:PC61BM/PMA film,
P3HT:PC61BM/MoO3Film, P3HT:PC61BM/PMA:MoO3The AFM of film schemes；
Fig. 3 a is in the embodiment of the present invention 1 respectively with PMA, MoO3、PMA:MoO3, vapor deposition MoO3(e-MoO3) it is used as anode
The P3HT:PC of decorative layer61The J-V curve graph of BM system solar battery；
Fig. 3 b is in the embodiment of the present invention 1 respectively with PMA, MoO3、PMA:MoO3, vapor deposition MoO3(e-MoO3) it is used as anode
The P3HT:PC of decorative layer61The EQE curve graph of BM system solar battery.
Specific embodiment
In view of the deficiencies in the prior art, and improve the urgent demand of organic electro-optic device stability, inventor's warp
It studies for a long period of time and largely practices, be able to propose technical solution of the present invention.It as follows will be to the technical solution, its implementation process and original
Reason etc. is further explained.
The one aspect of the embodiment of the present invention provides a kind of multi-metal oxygen cluster compound-metal oxide compounds,
Include:
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, the two mass ratio is 1:10~3:2.
More preferred, the concentration of the compound is 0.5-20mg/mL, especially preferably 3-6mg/mL.
One of preferably, the multi-metal oxygen cluster compound is at least selected from containing any one in molybdenum, tungsten, vanadium
Or two or more combined multi-metal oxygen cluster compounds, but not limited to this.
It is further preferred that the multi-metal oxygen cluster compound also may include have phosphorus, silicon, germanium, in 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 oxygen cluster compound, Lindqvist type multi-metal oxygen cluster compound or two
Kind or more combination, 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 where individualism, and the size after reunion is
200-400nm。
As being preferably implemented one of case, the metal oxide is at least selected from the oxide of molybdenum, the oxide of vanadium, tungsten
Oxide, the oxide of nickel, the oxide of zinc, any one or two kinds and two or more combinations in titanyl compound, but
It is without being limited thereto.
Wherein, the metal oxide is preferably nano particle, can be obtained by commercially available approach, and industry can also be used
Appropriate method known to boundary is produced.
Wherein, the metal oxide is preferably dimensioned to be 5-50nm.
For example, in some more specific embodiments, 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 obtains
Obtain metal oxide mixture.In some embodiments, the metal or its oxide powder may include: molybdenum, vanadium,
Tungsten, nickel, zinc, the powder of titanium and above-mentioned metal oxide, but not limited to this.In some embodiments, the solvent can
To include: water, methanol, ethyl alcohol, 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, is added under hydrogen peroxide room temperature and is reacted acquisition in 20-30 hours
's.
(b) by above-mentioned metal oxide mixture through pervaporation solvent, dissolution, ultrasonic disperse, centrifuge separation multi step strategy,
Obtain the metal oxide dispersion of required alcohol phase or water phase.To prepare the MoO of ethyl alcohol dispersion3For ink: first will be anti-
Resulting mixture is answered to stand, reaction vessel lower layer is the complete black molybdenum powder of unreacted, and upper layer is the blue oxygen that reaction obtains
Change molybdenum ethanol solution.Upper layer blue supernatant is pipetted with liquid-transfering gun, is spin-dried on a rotary evaporator, removes solvent, then with ethyl alcohol weight
New dissolution, is then centrifuged for, discards precipitating, obtain the MoO of stable dispersion3Nanometer ink.
In some embodiments, the solvent includes water, any one or two or more combinations in Organic Alcohol.
Further, the Organic Alcohol include methanol, ethyl alcohol, 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.
More preferably, the solvent further includes secondary organic solvent, such as acetone, chloroform, toluene, dimethylbenzene, front three
Benzene, chlorobenzene, any one or two or more combinations in dichloro-benzenes, 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 the preparation multi-metal oxygen cluster compound-metal oxide
The method for closing object comprising: the multi-metal oxygen cluster compound is uniformly mixed in solvent with metal oxide and forms institute
State compound.
The one aspect of the embodiment of the present invention additionally provides a kind of compound ink, and it includes the multi-metal oxygen cluster chemical combination
Object-metal oxide compounds.
The embodiment of the invention also provides the methods for preparing the compound ink comprising: by multi-metal oxygen cluster compound
It is uniformly mixed in solvent with metal oxide and forms the compound ink.
In some more preferred embodiments, 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 is scattered in solvent and forms multi-metal oxygen cluster compound solution or dispersion
Liquid,
Metal oxide dispersion is uniform by the mass ratio of setting with multi-metal oxygen cluster compound solution or dispersion liquid
Mixing, to form the compound ink.
Wherein, the solvent may include water, methanol, ethyl alcohol, normal propyl alcohol, in isopropanol any one or it is 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
It is mixed according to certain volume ratio, i.e. acquisition mixed ink.
With PMA-MoO3It may include: to disperse PMA in steam again to form the in isopropanol for the preparation of compound ink
One system, by the MoO of different volumes3Ethanol solution is injected into the aqueous isopropanol of PMA, is mixed and is obtained by ultrasonic disperse
PMA-MoO3Compound ink.
The one aspect 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 aspect of the embodiment of the present invention additionally provides compound by the multi-metal oxygen cluster compound-metal oxide
The film that object or the compound ink are formed.
Correspondingly, the one aspect of the embodiment of the present invention additionally provides the method for preparing the film comprising: at least select
With coating and/or mode of printing to the multi-metal oxygen cluster compound-metal oxide compounds or the compound ink
Film process are carried out, the film is formed.
For example, can select coating and/or mode of printing that the compound ink is applied in substrate, formed described thin
Film.
In certain embodiments, the coating and/or mode of printing include that spin-coating, blade coating, ink-jet are beaten
Print, silk-screen printing, any one or two or more combinations in intaglio printing mode.
The one aspect of the embodiment of the present invention additionally provides a kind of device, and it includes the films.Described device includes
Organic optoelectronic device, such as organic luminescent device, organic photovoltaic battery with electric light and light transfer characteristic etc..
The present invention is formed described and uniformly mixing the solution of multi-metal oxygen cluster compound with metal oxide ink
Compound can reduce the agglomeration of multi-metal oxygen cluster compound, while metal oxide nanoparticles can be effectively filled in
In gap 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 can also play adjusting 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, effectively improves the performance of device.
In compound of the invention, compound ink especially of the invention, the selection of solvent needs to combine multi-metal oxygen
Requirement of dispersion performance and subsequent thin film deposition process of the cluster compound in different solvents to solvent carries out comprehensive selection.
For example, being ITO/ZnO/P3HT:PC in preparation structure61BM/PMA:MoO3The inverted organic solar batteries of/Al
When, in order to avoid spin coating anode modification layer PMA:MoO3Destruction of the solvent to optically active layer in the process, solvent need to avoid using
Chlorobenzene, dichloro-benzenes equal solvent.
In another example being ITO/TiO in preparation structure2/PVSK(CH3NH3PbX3,NH2CH=NH2PbX3, X=Cl, Br, I)/
PMA:MoO3When the perovskite battery of/Al, since perovskite thin film meets water decomposition, therefore the ink must be anhydrous system, and
The alcohol of butanol, propyl alcohol class also has certain destructiveness to perovskite thin film, so when configuring the ink in addition to requiring PMA points
It is dispersed in except anhydrous methanol, ethyl alcohol or methanol, ethyl alcohol and butanol mixed solvent, also requires MoO3It cannot be dispersed in water, so
PMA:MoO in the system3It is dispersed in dehydrated alcohol.
For another example being ITO/PMA:MoO in structure3/PVSK(CH3NH3PbX3,NH2CH=NH2PbX3, X=Cl, Br, I)/
PCBM/Al or ITO/PMA:MoO3/P3HT:PC61BM/MoO3In the system of/Al, because of PMA:MoO3Directly in ITO (oxidation
Indium tin) prepared by surface, therefore there is no solvents to the destruction problem of primer, and it also therefore can be according to printing technology
The stability of demand and ink selects 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 may include: that the multi-metal oxygen cluster chemical combination is deposited on organic active layer by the modes such as being coated with or printing
Object-metal oxide compounds or the compound ink, to form organic photovoltaic devices or organic electroluminescence device
Hole-injecting Buffer Layer for Improvement.
In some embodiments, the film of the invention can also be deposited directly to various other 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.
Since multi-metal oxygen cluster compound-metal oxide compounds provided by the present invention are evenly dispersed in a solvent,
It therefore, can be preferably between metal oxide and multi-metal oxygen cluster compound using in 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 gap among, therefore the compactness and uniformity of complex thin film can be improved, improves the surface smoothness of laminated film.
Compared with conventional hole cushioning layer material, the compound Hole-injecting Buffer Layer for Improvement of the invention and show better film forming and
Higher stability, and material is cheap, easy to operate, and experimental repeatability is good, and printing system can be preferably combined in technique
Standby organic electro-optic device.
Below by way of several embodiments and in conjunction with the attached drawing technical solution that present invention be described in more detail.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 process of compound ink includes:
(1) preparation of PMA ink: 3mg tri- is taken to be hydrated phosphomolybdic acid (H3PO4·12MoO3·3H2O, PMA) powder, it is added
1mL steams isopropanol again, and ultrasound arrives the PMA ink that weight concentration is 3mg/mL to being completely dispersed；
(2)MoO3The preparation of ink: taking 250mg molybdenum powder in the single-necked flask for filling 10mL ethyl alcohol, then stirring is added
The hydrogenperoxide steam generator of 0.5mL 30%, reaction solution gradually become navy blue by black, react for 24 hours under room temperature.After standing 4h, take
Upper solution is spin-dried on a rotary evaporator, removes solvent, then re-dissolved with 10mL ethyl alcohol.Then under 4000rpm revolving speed
It is centrifuged 10min, discards precipitating, obtains the MoO that concentration is 6mg/mL3Nanometer ink；
(3)PMA:MoO3The preparation of compound ink: the MoO for the PMA ink and 6mg/mL that concentration is 1mg/mL is taken3Ink is pressed
It is mixed according to different volume ratios, PMA:MoO can be obtained in ultrasound3Compound ink.
2. corresponding PMA:MoO3The preparation process 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: as shown in Figure 1, institute for the preparation process of the inversion device of anode modification layer
Stating and being inverted the structure of device includes ITO cathode, ZnO cathodic modification layer, P3HT:PC61BM photoactive layer, PMA:MoO3Anode modification
Layer, Al anode.Respectively with PMA, MoO3、PMA:MoO3, vapor deposition MoO3For anode modification layer, preparation structure ITO/ZnO/P3HT:
PC61BM/ anode modification layer/Al inverted structure device.PMA ink, PMA:MoO3Ink, MoO3Ink is all made of 3500rpm
Spin coating 1min.Fig. 2 a- Fig. 2 d is please referred to, from the AFM of film figure it can be seen that pure PMA ink is in P3HT:PC61It is formed on BM film
Island shape film, 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 particle is improved, to obtain PMA:MoO3Film it is thick
Rugosity is 6.30nm.
The performance parameter of the J-V curve of Fig. 3 a- Fig. 3 b, EQE curve and table 1 is please referred to again it is found that 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 of device are obviously improved.
With PMA, MoO in 1 embodiment 1 of table3、PMA:MoO3、e-MoO3P3HT:PC as anode modification layer61BM system
The device parameter performance of solar battery
Embodiment 2PMA:MoO3Application of the composite layer in perovskite battery
1. the PMA:MoO3The preparation process of compound ink includes:
(1) preparation of PMA ink: 1-5mg tri- is taken to be hydrated phosphomolybdic acid (H3PO4·12MoO3·3H2O, PMA) powder, it is added
1mL isopropanol, ultrasound arrive the PMA ink that weight concentration is 1-5mg/mL to being completely dispersed；
(2)PMA:MoO3The preparation of compound ink: PMA ink and MoO are taken3Ink is mixed by 1:1 volume ratio, and ultrasound is
A series of PMA:MoO can be obtained3Compound 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 are as follows: ITO/PMA:MoO3/PVSK/PCBM/Al.Device parameter performance are as follows: VOC=0.84V, JSC=17.5mA/
cm2, FF=0.61, PCE=8.97%.Illustrate PMA:MoO3Composite layer can be used 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 ink: 1-5mg phosphotungstic acid hydrate (H is taken3PO4·12WO3·H2O, PWA) powder, it is added
1mL isopropanol, ultrasound arrive the PWA ink that weight concentration is 1-5mg/mL to being completely dispersed；
(2)PWA:MoO3The preparation of compound ink: PWA ink and MoO are taken3Ink is mixed by the volume ratio of 5:1-1:5,
A series of PWA:MoO can be obtained in ultrasound3Compound 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 are as follows: ITO/PWA:MoO3/PVSK/PCBM/Al.PWA ink and MoO3The optimal volume ratio of ink is 1:2, device
Performance parameter are as follows: VOC=0.87V, JSC=16.8mA/cm2, FF=0.63, PCE=9.21%.Illustrate PWA:MoO3Composite layer 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 are obviously improved.
Embodiment 4PWA:V2O5The preparation of compound ink and the application in perovskite battery
(1) preparation of PWA ink: 1-5mg phosphotungstic acid hydrate (H is taken3PO4·12WO3·H2O, PWA) powder, it is added
1mL isopropanol, ultrasound arrive the PWA ink that weight concentration is 1-5mg/mL to being completely dispersed；
(2)PWA:V2O5The preparation of compound ink: PWA ink and V are taken2O5Ink is mixed by the volume ratio of 5:1-1:5,
A series of PWA:V can be obtained in ultrasound2O5Compound 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 are as follows: ITO/PWA:V2O5/PVSK/PCBM/Al.PWA ink and V2O5The optimal volume ratio of ink is 1:2, device
Performance parameter are as follows: VOC=0.87V, JSC=17.8mA/cm2, FF=0.65, PCE=10.06%.Illustrate PWA:V2O5Composite layer
It can be used 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 are obviously improved.
It should be noted that various raw materials, process conditions, device material and structural parameters used by embodiment as above etc.
It is more typical example, but is verified by inventor's a large number 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 technical effect.
It is pointed out that the technical concepts and features of above-described embodiment only to illustrate the invention, it is ripe its object is to allow
The personage for knowing technique cans understand the content of the present invention and implement it accordingly, and protection model of the invention can not be limited with this
It encloses.Any equivalent change or modification in accordance with the spirit of the invention should be covered by the protection scope of the present invention.
Claims (20)
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, the multi-metal oxygen cluster compound is at least selected from containing any one in molybdenum, vanadium
Kind or two or more combined multi-metal oxygen cluster compounds, the multi-metal oxygen cluster compound also include phosphorus, silicon, germanium,
Any one in arsenic or two or more combinations, alternatively, the multi-metal oxygen cluster compound includes metal polyacid and/or gold
Belong to the salt of polyacid, size of the multi-metal oxygen cluster compound after reunion is 200-400nm；
At least one metal oxide, the metal oxide are at least selected from the oxidation of the oxide of molybdenum, the oxide of vanadium, tungsten
Object, the oxide of nickel, zinc oxide in any one or two kinds and two or more combinations, the ruler of the metal oxide
Very little is 5-50nm；
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: described multiple
Closing the mass ratio of multi-metal oxygen cluster compound and metal oxide in object is 1:10~3:2.
3. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1 or 2, it is characterised in that: described
The concentration of compound is 0.5-20mg/mL.
4. multi-metal oxygen cluster compound-metal oxide compounds according to claim 3, it is characterised in that: described multiple
The concentration for closing object is 3-6mg/mL.
5. multi-metal oxygen cluster compound-metal oxide compounds according to claim 4, it is characterised in that: described more
Metal oxygen cluster compound include Keggin-type multi-metal oxygen cluster compound, Wells-Dawson type multi-metal oxygen cluster compound,
Any one in Lindqvist type multi-metal oxygen cluster compound or two or more combinations.
6. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1, it is characterised in that: described molten
Agent includes water, any one or two or more combinations in Organic Alcohol.
7. multi-metal oxygen cluster compound-metal oxide compounds according to claim 6, it is characterised in that: described to have
Machine alcohol includes methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, ethylene glycol, any one in glycol monoethyl ether
Or two or more combination.
8. multi-metal oxygen cluster compound-metal oxide compounds according to claim 6 or 7, it is characterised in that: described
Solvent further includes secondary organic solvent, the secondary organic solvent include acetone, chloroform, toluene, dimethylbenzene, trimethylbenzene, chlorobenzene,
Any one in dichloro-benzenes or two or more combinations.
9. multi-metal oxygen cluster compound-metal oxide compounds according to claim 1, it is characterised in that: described multiple
Conjunction object is homogeneous (uniform) fluid shape dispersion.
10. the preparation method of multi-metal oxygen cluster compound-metal oxide compounds of any of claims 1-9,
It is characterised by comprising: multi-metal oxygen cluster compound is uniformly mixed in solvent with metal oxide and is formed described compound
Object.
11. a kind of compound ink, it is characterised in that include multi-metal oxygen cluster compound-of any of claims 1-9
Metal oxide compounds.
12. the preparation method of compound ink as claimed in claim 11, characterized by comprising: by multi-metal oxygen cluster compound with
Metal oxide uniformly mixes in solvent, to form the compound ink.
13. the preparation method of compound ink according to claim 12, characterized by comprising:
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, to be formed described compound
Ink.
14. the preparation method of the 2 or 13 compound inks according to claim 1, it is characterised in that: the solvent includes water, first
Alcohol, ethyl alcohol, normal propyl alcohol, any one or two or more combinations in isopropanol.
15. multi-metal oxygen cluster compound-metal oxide compounds of any of claims 1-9 or claim 13
The compound ink is in preparing the purposes in modifying interface material or organic electro-optic device.
16. by multi-metal oxygen cluster compound-metal oxide compounds of any of claims 1-9 or claim
The film that compound ink is formed described in 11.
17. the preparation method of film described in claim 16, characterized by comprising: at least select coating and/or mode of printing
To described in multi-metal oxygen cluster compound-metal oxide compounds of any of claims 1-9 or claim 11
Compound ink carry out film process, to form the film.
18. the preparation method of 7 films according to claim 1, it is characterised in that: the coating and/or mode of printing include
Spin-coating, blade coating, inkjet printing, silk-screen printing, any one or two or more combinations in intaglio printing mode.
19. a kind of device, it is characterised in that include the film described in claim 16.
20. device according to claim 19, 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 CN107591488A (en) | 2018-01-16 |
| CN107591488B true 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113061220B (en) * | 2021-06-03 | 2021-09-21 | 北京石油化工学院 | Heteropoly acid mixtures and their use |
| CN113410392B (en) * | 2021-06-24 | 2022-11-22 | 上海大学 | Non-fullerene organic solar cell and preparation method thereof |
Citations (4)
| 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 |
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474977A (en) * | 1991-08-26 | 1995-12-12 | Uop | Catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks |
| CN101307148B (en) * | 2008-07-10 | 2010-12-15 | 中国科学院化学研究所 | Composite discolored thin film, method for preparing same and applications |
| CN103943365B (en) * | 2014-04-25 | 2016-08-24 | 中南大学 | A kind of preparation method of DSSC modification light anode |
| 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 (4)
| 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 |
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 12-Phosphormolibdic acid doped polyaniline–V2O5 composite;O.Yu.Posudievsky et al;《Synthetic Metals》;20040412;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107591488A (en) | 2018-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Giussi et al. | Practical use of polymer brushes in sustainable energy applications: interfacial nanoarchitectonics for high-efficiency devices | |
| CN105778619B (en) | Compound ink of polymer-nano-metal-oxide and the preparation method and application thereof | |
| CN105098073B (en) | Metal oxide-conducting polymer -ol composition, preparation method and application | |
| KR101176716B1 (en) | Water Dispersible Polypyrroles Made with Polymeric Acid Colloids for Electronics Applications | |
| Wang et al. | Inkjet-printed full-color matrix quasi-two-dimensional perovskite light-emitting diodes | |
| CN107591488B (en) | Multi-metal oxygen cluster compound-metal oxide compounds, its preparation method and application | |
| Ruscello et al. | Nanocomposite of nickel oxide nanoparticles and polyethylene oxide as printable hole transport layer for organic solar cells | |
| TW200539195A (en) | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof | |
| CN106611818B (en) | Polymer-multi-metal oxygen cluster compound composite material, preparation method and application | |
| WO2016095828A1 (en) | Polymer-metal compound composite ink and preparation method and use thereof | |
| US9856388B2 (en) | Titanium dioxide nano particle modified by surface stabilizer, titanium dioxide nano ink comprising the same, solar cell employing the same, and producing method of the same | |
| CN107629642A (en) | The adjustable polymer composites of work content, its preparation method and application | |
| CN109904329A (en) | Knife coating structure of modified efficient perovskite solar cell and preparation method | |
| CN108417717A (en) | A kind of fast preparation method of flexible solar battery | |
| Im et al. | Improved stability of interfacial energy-level alignment in inverted planar perovskite solar cells | |
| KR101023021B1 (en) | Inverted organic solar cell and method for manufacturing thereof | |
| KR20090109357A (en) | Formation Method of Hybrid Solar Cell | |
| CN114634732B (en) | Two-dimensional material water-based ink and preparation method and application thereof | |
| CN112071988A (en) | Preparation method of full-screen printing perovskite solar cell | |
| US10020449B2 (en) | Composition for anode buffer layer of organic thin film solar cell and organic thin film solar cell | |
| CN117241642A (en) | Two-dimensional peroxide optimized modified three-dimensional perovskite film and preparation method and application thereof | |
| CN108075041B (en) | Flexible composite electrode, preparation method and application thereof | |
| KR101023020B1 (en) | Inverted transparent organic solar cell and method for manufacturing thereof | |
| CN108258122A (en) | A kind of transparent conductive material and preparation method thereof | |
| CN103965591A (en) | Forming method of optoelectronic devices, particularly of inverted-type OPV cells |
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 |