CN106025071A - Rare earth doped metal oxide nanometer material and preparation method and application thereof - Google Patents
Rare earth doped metal oxide nanometer material and preparation method and application thereof Download PDFInfo
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- CN106025071A CN106025071A CN201610362857.7A CN201610362857A CN106025071A CN 106025071 A CN106025071 A CN 106025071A CN 201610362857 A CN201610362857 A CN 201610362857A CN 106025071 A CN106025071 A CN 106025071A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- 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 relates to a rare earth doped metal oxide nanometer material and a preparation method and application thereof. Specifically, the nanometer material comprises a metal oxide and rare earth elements doped in the metal oxide, the metal oxide is a semiconductor material, and in terms of total weight of the nanometer material, the doping amount of the rare earth elements is 0.5wt% to 5wt%. The invention also discloses the preparation method and application of the nanometer material. A clad layer (or coating) prepared from the nanometer material is applied into a solar cell as an interface layer, ideal electricity property of an obtained solar cell device can be realized, and absorption and utilization for near infrared photons are realized, so that the photoelectric conversion efficiency of the solar cell is improved.
Description
Technical field
The present invention relates to Material Field, more particularly to rare earth doping metal oxide-based nanomaterial and preparation thereof
Methods and applications.
Background technology
In solaode, the main path of energy loss includes: one, photon energy loss, it includes shortwave
Long high-energy photons is owing to energy is more than quasiconductor band gap, and energy unnecessary after vitalizing semiconductor can be with heat energy
Loss, and the energy photons of long wavelength cannot can not be absorbed and lose by vitalizing semiconductor due to energy；
Two, electricity loss, this is mostly derived from battery the Carrier recombination between each layer and each layer.Wherein, organic
Solar cell semiconductor, due to its Exciton Confined, is generally of bigger energy bandgaps, therefore its light absorbed
Wavelet length is shorter, the energy loss that therefore cannot be caused by absorption due to the substantial amounts of long wavelength photons of solar spectrum
Especially prominent.
Utilize and change changing the short wavelength region to solar cell sensitivity in long wavelength photons in optical frequency, be expected to
Realize the solaode utilization to near-infrared photon.Therefore, utilize and change in optical frequency at organic solar electricity
Pond carries out spectral operation near-infrared photon is used there is actual meaning, be that one can be effective
Improve the potential method of cell photoelectric conversion efficiency, especially in the situation being used in combination the engineerings such as condenser
Under.Boundary layer electrical properties suitably can be regulated and controled additionally, rear-earth-doped, to improve battery device performance.
Utilize optical frequency up-conversion to absorb near infrared light, increase the spectral response width of solaode, also
Can apply in other type solar cells such as silica-based, thin film and organic inorganic hybridization.In known method
In, upper conversion layer is placed in outside battery device.But up-conversion is placed on solar-electricity as function interface
Inside pond, have not been reported.
Summary of the invention
It is an object of the invention to provide and a kind of have the rare earth of transfer characteristic in excellent electrical properties and optical frequency concurrently
Metal oxide semiconductor of doping and its preparation method and application.
A first aspect of the present invention, it is provided that a kind of rare earth doping metal oxide-based nanomaterial, described nanometer material
Material comprises metal-oxide and the rare earth element being doped in described metal-oxide, and described metal-oxide is half
Conductor material, and based on the gross weight of described nano material, the doping of described rare earth element is 0.5-5wt
%.
In another preference, form the metallic element of described metal-oxide selected from lower group: Mo, V, W, Ti,
Zn, Ni or a combination thereof；And/or
Described rare earth element is selected from lower group: Yb, Er, Ho, Tm, Eu or a combination thereof.
In another preference, described metal-oxide is selected from lower group: molybdenum oxide, vanadium oxide, tungsten oxide, oxygen
Change titanium, zinc oxide, nickel oxide or a combination thereof.
In another preference, based on the gross weight of described nano material, the doping of described rare earth element is 0.8
-3.5wt%, preferably 1-3wt%, more preferably 1.2-2.5wt%, most preferably 1.3-1.6wt%, most preferably
Ground 2-2.4wt%.
In another preference, the particle diameter of described nano material is 5-500nm, preferably 8-300nm, more preferably
Ground 10-200nm, most preferably 50-100nm.
In another preference, the particle diameter of described nano material is 5-100nm, preferably 10-60nm, more preferably
15-60nm。
In another preference, described nano material is crystal.
In another preference, described nano material, under near infrared light excites, has i.e. upper turn of anti-Stokes
Change fluorescent emission.
In another preference, described nano material, under ultraviolet excitation, has Stokes fluorescent emission.
A second aspect of the present invention, it is provided that the preparation method of nano material described in a kind of first aspect present invention,
Described method comprises the steps:
A-1) provide the first mixed solution, described first mixed solution comprise the first solvent and be dissolved in therein for
Form the salt of the metallic element of metal-oxide, for the salt of rare earth element of the described metal-oxide that adulterates；
A-2) heating abovementioned steps gained mixed solution, obtains presoma precipitate；
A-3) calcine described presoma precipitate, obtain nano material described in first aspect present invention.
In another preference, in step a-2) further comprise the steps of: before
A-2-00) the second mixed solution, described second mixed solution is provided to comprise the second solvent and are dissolved in therein sinking
Shallow lake agent；
A-2-01) under agitation, mix described first mixed solution and described second mixed solution, obtain
Three mixed solutions.
In another preference, described precipitant is hydroxide.
In another preference, described hydroxide be selected from lower group: sodium hydroxide, potassium hydroxide, barium hydroxide,
Or a combination thereof.
In another preference, described first solvent and described second solvent may be the same or different, separately
Selected from lower group: water, alcohols or a combination thereof.
In another preference, described alcohols is selected from lower group: methanol, ethanol, propanol, butanol or a combination thereof.
In another preference, described salt is selected from lower group: ammonium salt, acetate, halogenated acetic acids salt or a combination thereof.
In another preference, the pH of described first mixed solution is 2-6, preferably 2.5-4.5, preferably 3.
In another preference, step a-2) treatment temperature of described heat treated is 30-120 DEG C；And/or
Step a-2) process time of described heat treated is 0.5-3 hour；And/or
Step a-3) treatment temperature of described calcination processing is 600-800 DEG C；And/or
Step a-3) process time of described calcination processing is 2-6 hour.
In another preference, step a-2) treatment temperature of described heat treated is 40-80 DEG C.
In another preference, step a-2) process time of described heat treated is 0.8-2 hour.
In another preference, step a-3) treatment temperature of described calcination processing is 650-720 DEG C.
In another preference, step a-3) process time of described calcination processing is 3-5 hour.
In another preference, in step a-3) before the most optionally include step:
A-3-00) centrifugal treating abovementioned steps products therefrom；
A-3-01) abovementioned steps products therefrom is cleaned.
In another preference, cleanout fluid used by described cleaning is selected from lower group: water, alcohols or a combination thereof.
In another preference, described centrifugal treating and described clean cycle are carried out, and cycle-index is 2-5 time,
Preferably 3-4 time.
A third aspect of the present invention, it is provided that a kind of solaode, described solaode include anode layer,
Active layer and negative electrode layer,
I) there is hole transport boundary layer between described anode layer and described active layer, the most described negative electrode layer and
There is electric transmission boundary layer between described active layer, and described hole transport boundary layer is by first aspect present invention institute
State nano material to make, and the most described electric transmission boundary layer is by nano material described in first aspect present invention
Make；Or
Ii) there is electric transmission boundary layer between described anode layer and described active layer, the most described negative electrode layer and
There is hole transport boundary layer between described active layer, and described electric transmission boundary layer is by first aspect present invention institute
State nano material to make, and the most described hole transport boundary layer is by nano material described in first aspect present invention
Make.
In another preference, form the material of described anode layer selected from lower group: ITO, FTO, Ag, Au or
A combination thereof.
In another preference, form the material of described active layer selected from lower group: P3HT, PCE-10, PCE-11,
PC61BM、PC71BM or a combination thereof.
In another preference, the thickness of described active layer is 50-300nm, preferably 100-200nm.
In another preference, form the material of described negative electrode layer selected from lower group: Al, Ag, Au, Ca or its
Combination.
In another preference, the thickness of described negative electrode layer is 20-200nm, preferably 60-150nm.
In another preference, form the metallic element choosing of the described metal-oxide of described electric transmission boundary layer
From lower group: Zn, Ti, Ni or a combination thereof.
In another preference, form the metallic element choosing of the described metal-oxide of described hole transport boundary layer
From lower group: Mo, V, W or a combination thereof.
In another preference, the thickness of described hole transport boundary layer is 5-150nm；And/or
The thickness of described electric transmission boundary layer is 10-100nm.
In another preference, the thickness of described hole transport boundary layer is 10-100nm, preferably 15-50nm,
More preferably 20-40nm.
In another preference, the thickness of described electric transmission boundary layer is 20-80nm, preferably 30-60nm.
In another preference, make compared to the metal-oxide of the identical type with undoped p rare earth element
Material is as electric transmission boundary layer or the solaode of hole transport boundary layer, the photoelectricity of described solaode
Conversion efficiency improves at least 5%, the most at least 20-30%, more preferably at least 40%.
A fourth aspect of the present invention, it is provided that the purposes of nano material described in a kind of first aspect present invention, is used for
Make the boundary layer of solaode.
In another preference, described solaode is selected from lower group: organic, silica-based class, thin film class, have
Machine inorganic hybridization class, dye sensitization class or a combination thereof.
A fifth aspect of the present invention, it is provided that a kind of goods, described goods comprise to be received described in first aspect present invention
Rice material or be made up of nano material described in first aspect present invention.
In another preference, described goods are selected from lower group: solaode, light emitting diode, transistor.
A sixth aspect of the present invention, it is provided that a kind of method improving solar cell photoelectric conversion efficiency, in institute
State and between the electrode of solaode and active layer, add electric transmission boundary layer and/or hole transport boundary layer, institute
State electric transmission boundary layer and/or described hole transport boundary layer comprise nano material described in first aspect present invention or
It is made up of nano material described in first aspect present invention.
In should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and below (as implemented
Example) in can be combined with each other between each technical characteristic of specifically describing, thus constitute new or preferred skill
Art scheme.As space is limited, the most tired at this state.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained MoO3: the XRD test result of Yb, Er nano material 1.
Fig. 2 is embodiment 1 gained MoO3: the SEM test result of Yb, Er nano material 1.
Fig. 3 is embodiment 1 gained MoO3: the up-conversion fluorescence of Yb, Er nano material 1 launches spectrogram, and
The absorption spectra of the organic active layer material P3HT used in embodiment 1.
Fig. 4 is the structural representation of organic solar batteries of the present invention.
Fig. 5 is embodiment 1 gained organic solar batteries 1, comparative example 1 gained organic solar batteries C1
Battery j-V curve test result with comparative example 2 gained organic solar batteries C2.
Fig. 6 is that embodiment 1 gained organic solar batteries device 1 excites lower observation at 975nm near infrared light
The up-conversion fluorescence figure arrived.
Detailed description of the invention
The present inventor is through in-depth study for a long time, by using rare earth doped semi-conductive metal oxide
Thing prepares a kind of rare earth doped metal oxide nano-material, with described nano material as raw material
Prepare gained to be applied in solaode as boundary layer, utilize electrology characteristic and the optical frequency of described boundary layer
Upper swing absorption utilizes the synergism of near-infrared photon, can realize solaode electric property lifting and
Near-infrared photon is absorbed, thus significantly improves the photoelectric transformation efficiency of solaode.At this base
On plinth, inventor completes the present invention.
Nano material
The invention provides a kind of rare earth doping metal oxide-based nanomaterial, described nano material comprises metal oxygen
Compound and the rare earth element being doped in described metal-oxide, and described metal-oxide is semi-conducting material, and
And based on the gross weight of described nano material, the doping of described rare earth element is 0.5-5wt%.
In the present invention, form the metallic element of described metal-oxide include (but being not limited to): Mo, V,
W, Ti, Zn, Ni or a combination thereof；And/or
Described rare earth element includes (but being not limited to): Yb, Er, Ho, Tm, Eu or a combination thereof.
In another preference, described metal-oxide includes (but being not limited to): molybdenum oxide, vanadium oxide,
Tungsten oxide, titanium oxide, zinc oxide, nickel oxide or a combination thereof.
In another preference, based on the gross weight of described nano material, the doping of described rare earth element is 0.8
-3.5wt%, preferably 1-3wt%, more preferably 1.2-2.5wt%, most preferably 1.3-1.6wt%, most preferably
Ground 2-2.4wt%.
In another preference, the particle diameter of described nano material is 5-500nm, preferably 8-300nm, more preferably
Ground 10-200nm, most preferably 50-150nm.
In another preference, the particle diameter of described nano material is 5-100nm, preferably 10-60nm, more preferably
15-60nm。
In another preference, described nano material is crystal.
In another preference, described nano material, under near infrared light excites, has i.e. upper turn of anti-Stokes
Change fluorescent emission.
In another preference, described nano material, under ultraviolet excitation, has Stokes fluorescent emission.
Preparation method
Present invention also offers the preparation method of a kind of described nano material, described method comprises the steps:
A-1) provide the first mixed solution, described first mixed solution comprise the first solvent and be dissolved in therein for
Form the salt of the metallic element of metal-oxide, for the salt of rare earth element of the described metal-oxide that adulterates；
A-2) heating abovementioned steps gained mixed solution, obtains presoma precipitate；
A-3) calcine described presoma precipitate, obtain described nano material.
In another preference, in step a-2) further comprise the steps of: before
A-2-00) the second mixed solution, described second mixed solution is provided to comprise the second solvent and are dissolved in therein sinking
Shallow lake agent；
A-2-01) under agitation, mix described first mixed solution and described second mixed solution, obtain
Three mixed solutions.
In another preference, described precipitant is hydroxide.
In another preference, described hydroxide includes (but being not limited to): sodium hydroxide, potassium hydroxide,
Barium hydroxide or a combination thereof.
In another preference, described first solvent and described second solvent may be the same or different, separately
Selected from including the material of group under (but being not limited to): water, alcohols or a combination thereof.
In another preference, described alcohols includes (but being not limited to): methanol, ethanol, propanol, butanol,
Or a combination thereof.
In another preference, described salt includes (but being not limited to): ammonium salt, acetate, halogenated acetic acids salt,
Or a combination thereof.
In another preference, the pH of described first mixed solution is 2-6, preferably 2.5-4.5, preferably 3.
In the present invention, step a-2) treatment temperature of described heat treated is 30-120 DEG C；And/or
Step a-2) process time of described heat treated is 0.5-3 hour；And/or
Step a-3) treatment temperature of described calcination processing is 600-800 DEG C；And/or
Step a-3) process time of described calcination processing is 2-6 hour.
In another preference, step a-2) treatment temperature of described heat treated is 40-80 DEG C.
In another preference, step a-2) process time of described heat treated is 0.8-2 hour.
In another preference, step a-3) treatment temperature of described calcination processing is 650-720 DEG C.
In another preference, step a-3) process time of described calcination processing is 3-5 hour.
In another preference, in step a-3) before the most optionally include step:
A-3-00) centrifugal treating abovementioned steps products therefrom；
A-3-01) abovementioned steps products therefrom is cleaned.
In another preference, cleanout fluid used by described cleaning includes (but being not limited to): water, alcohols or
A combination thereof.
In another preference, described centrifugal treating and described clean cycle are carried out, and cycle-index is 2-5 time,
Preferably 3-4 time.
Application
Present invention also offers a kind of solaode, described solaode includes anode layer, active layer and bears
Pole layer,
I) there is hole transport boundary layer between described anode layer and described active layer, the most described negative electrode layer and
There is electric transmission boundary layer between described active layer, and described hole transport boundary layer is by described nano material system
Become, and the most described electric transmission boundary layer is made up of described nano material；Or
Ii) there is electric transmission boundary layer between described anode layer and described active layer, the most described negative electrode layer and
There is hole transport boundary layer between described active layer, and described electric transmission boundary layer is by described nano material system
Become, and the most described hole transport boundary layer is made up of described nano material.
In another preference, form the material of described anode layer include (but being not limited to): ITO, FTO,
Ag, Au or a combination thereof.
In another preference, form the material of described active layer include (but being not limited to): P3HT, PCE-10,
PCE-11、PC61BM、PC71BM or a combination thereof.
In another preference, the thickness of described active layer is 50-300nm, preferably 100-200nm.
In another preference, form the material of described negative electrode layer include (but being not limited to): Al, Ag, Au,
Ca or a combination thereof.
In another preference, the thickness of described negative electrode layer is 20-200nm, preferably 60-150nm.
In another preference, form the metallic element bag of the described metal-oxide of described electric transmission boundary layer
Include (but being not limited to): Zn, Ti, Ni or a combination thereof.
In another preference, form the metallic element bag of the described metal-oxide of described hole transport boundary layer
Include (but being not limited to): Mo, V, W or a combination thereof.
Generally, the thickness of described hole transport boundary layer is 5-150nm；And/or
The thickness of described electric transmission boundary layer is 10-100nm.
In another preference, the thickness of described hole transport boundary layer is 10-100nm, preferably 15-50nm,
More preferably 20-40nm.
In another preference, the thickness of described electric transmission boundary layer is 20-80nm, preferably 30-60nm.
In the present invention, the material made compared to the metal-oxide of the identical type with undoped p rare earth element
As electric transmission boundary layer or the solaode of hole transport boundary layer, the opto-electronic conversion of described solaode
Efficiency improves at least 5%, the most at least 20-30%, more preferably at least 40%.
Present invention also offers the purposes of a kind of described nano material, for making the boundary layer of solaode.
In another preference, described solaode includes (but being not limited to): organic, silica-based class,
Thin film class, organic inorganic hybridization class, dye sensitization class or a combination thereof.
Present invention also offers a kind of goods, described goods comprise described nano material or by described nano material system
Become.
In another preference, described goods include (but being not limited to): solaode, light emitting diode,
Transistor.
Present invention also offers a kind of method improving solar cell photoelectric conversion efficiency, in described solar-electricity
Electric transmission boundary layer and/or hole transport boundary layer, described electric transmission is added between electrode and the active layer in pond
Boundary layer and/or described hole transport boundary layer comprise described nano material or are made up of described nano material.
In the present invention, described nano material has transfer characteristic on excellent electrical properties and fluorescence concurrently, with it
Prepare resulting materials to be applied in solaode as boundary layer, gained solaode can be effectively improved
Photoelectric transformation efficiency.Owing to described nano material has transfer characteristic on the fluorescence of excellence so that the gained sun
Can have the potential realizing that near-infrared photon is absorbed by battery.
Should be understood that in solaode of the present invention, using rare earth-doped semiconductor metal-oxide as
Electron transfer layer, has more preferable electrical conductivity, can realize big thickness, more preferable hole barrier effect and more
Stable device performance；Using rare earth-doped semiconductor metal-oxide as hole transmission layer, have higher
Carrier mobility, more preferable electronic blocking effect and preferably device stability.
Should be understood that, in described solaode, in described active layer, donor and acceptor material also can rise respectively
To hole and the transmitting effect of electronics, constitute fully functional diode structure and then form solaode.
But generally construct one layer of electronics and/or hole transmission layer the most again, carrier can be helped to pass
Defeated and collect, thus effectively promote solar cell properties.
Generally, described solaode can be just to put and inverted structure, described is just putting in structure, anode layer and
Hole transmission layer is positioned at the bottom of battery device, and optional electron transfer layer and negative electrode layer are positioned at battery device
Top；In described inverted structure, negative electrode layer and electron transfer layer are positioned at the bottom of battery device, anode layer and
Hole transmission layer is positioned at the top of battery device.
In another preference, prepare gained using described nano material and be incorporated into described solar energy as external layer
The back of battery.In the case, the near-infrared photon through solaode can be absorbed by external layer and on
Conversion, to visible ray, is finally absorbed by solar cell.
Compared with prior art, the present invention has a following major advantage:
(1) described nano material has the regulatable feature of electrical properties, using it as solaode
Interlayer materials can realize the regulation and control to solar cell interface electrical properties, thus improve carrier transport and
Carrier collection efficiency at electrode, and then boost device performance；
(2) described nano material has transfer characteristic in optical frequency, is applied in solaode, can
Realize solaode the low-energy light such as near infrared light are absorbed, thus improve the light of solaode
Photoelectric transformation efficiency；
(3) utilize the synergism of transfer characteristic in the electrical properties of described nano material and optical frequency, can have
Effect improves the opto-electronic conversion performance of solaode；
(4) described nano material is applied in solaode as interlayer materials, can significantly improve
The diode characteristic of gained solaode, and gained solaode excites existence substantially near infrared light
Photocurrent response；
(5) present invention firstly provides rare earth doping fluorescent up-conversion nano material is applied to (organic) too
Sun energy cell interface layer, is incorporated into inside battery device by conversion in optical frequency first, is regulated and controled by interface electricity
With change bifunctional synergism boost device performance in optical frequency, widened rare earth doping metal oxide and existed
Application in photoelectric device.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate
The present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example is logical
Often according to normal condition or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage ratio and number
Calculate by weight.
Unless otherwise defined, all specialties used in literary composition are familiar with one skilled in the art with scientific words
Same meaning.Additionally, any method similar or impartial to described content and material all can be applicable to the present invention
In method.Preferable implementation described in literary composition only presents a demonstration with material and is used.
Method of testing
Up-conversion fluorescence is launched
Excitation source is 100mW, 975nm near infrared light, uses resolution 0.3nm monochromator to carry out light splitting,
Use locked mode photomultiplier tube for photon counting.
Battery j-V curve is tested
Current-voltage j-V curve uses BoTest to measure testing equipment, and solar source uses OrielSol
The 1A analog light source of company, intensity is 0.1W/cm2。
Embodiment 1
Synthesis MoO3: Yb, Er nano material 1
1) 250mg ammonium molybdate four hydrate (AHM, (NH are taken4)6·Mo7O24·4H2O)、150mg
Trifluoroacetic acid ytterbium (Yb-TFA) and 15mg trifluoroacetic acid erbium (Er-TFA) join 20mL deionized water
Reaction bulb in, stirring to the reactant that added all is dissolved, and forms transparent homogeneous solution；
2) trifluoroacetic acid (TFA) regulation pH value of solution is added to 3；
3) by oil bath heated solution to 60 DEG C, keep 60min, separate out white precipitate；
4) after question response certain time, centrifugal segregation supernatant also collects precipitation, adds deionized water/ethanol
Mixed solution washing precipitation, repeats pelleting centrifugation 3 times；
5) by above-mentioned steps 4) in finally obtain be deposited under 700 DEG C of high temperature annealing sintering 4h, i.e. obtain
Particle diameter be 10-200nm, Yb doping be 1.3wt%, Er doping be the MoO of 0.13wt%3:Yb,Er
Nano material 1.
Prepare organic solar batteries 1
1) ITO substrate is cleaned successively by acetone, isopropanol, dry for standby；
2) in washed ITO substrate, deposit (blade coating, spin coating or spraying) MoO3: Yb, Er nano material 1
Alcohol dispersion liquid (MoO3: the concentration of Yb, Er nano material 1 is 2mg/mL), 140 DEG C of annealing 10min,
Obtain MoO3: Yb, Er nano material 1, gained MoO3: the thickness that Yb, Er nano material is 1 layer is 30nm；
3)O2Plasma treatment step 2) in sample 3min, power 200W, vacuum 0.2mbar；
4) P3HT:PC of the 2wt% dissolved in advance is then deposited61BM chlorobenzene solution, prepared thickness about 150
The active layer of nm；
5) on active layer, 100nm metal aluminium electrode it is deposited with as battery cathode；
6) whole device is carried out 10 minutes, the thermal annealing of 120 DEG C in the glove box of atmosphere of inert gases
Process, obtain organic solar batteries 1.
Comparative example 1
Prepare organic solar batteries C1
With embodiment 1, difference is: in step 2) the unadulterated MoO of middle employing3Replace MoO3:Yb,Er
In nano material 1, i.e. gained organic solar batteries C1, cavitation layer is MoO3Cavitation layer.
Comparative example 2
Prepare organic solar batteries C2
With embodiment 1, difference is: omit step 2) and step 3), i.e. gained organic solar batteries
Without hole transmission layer in C2.
Result
To embodiment 1 gained MoO3: Yb, Er nano material 1 carries out XRD, SEM, up-conversion fluorescence transmitting
Deng test.
Fig. 1 is embodiment 1 gained MoO3: the XRD test result of Yb, Er nano material 1.
As can be seen from Figure 1: gained MoO3: Yb, Er nano material 1 mainly shows α-MoO3Characteristic peak,
And with a small amount of Yb2Mo4O15Crystal formation.
Fig. 2 is embodiment 1 gained MoO3: the SEM test result of Yb, Er nano material 1.
As can be seen from Figure 2: gained sample is that nano-scale particle, uniform particle diameter, and particle diameter are about 50-200nm.
Fig. 3 is embodiment 1 gained MoO3: the up-conversion fluorescence of Yb, Er nano material 1 launches spectrogram, and
The absorption spectra of the organic active layer material P3HT used in embodiment 1.
As can be seen from Figure 3: embodiment 1 gained MoO3: the up-conversion fluorescence of Yb, Er nano material 1 is launched
Compose the absorption spectra with P3HT to match.
Fig. 4 is the structural representation of organic solar batteries of the present invention, and wherein figure a is for just putting structure, schemes b
For inverted structure, but its structure is not limited to shown in Fig. 4.
Respectively to embodiment 1 gained organic solar batteries 1 (MoO3: Yb, Er nano material 1 hole transport
Layer), comparative example 1 gained organic solar batteries C1 (MoO3Cavitation layer) and the organic sun of comparative example 2 gained
The test of battery j-V curve can be carried out by battery C2 (without hole transmission layer).
Fig. 5 is embodiment 1 gained organic solar batteries 1, comparative example 1 gained organic solar batteries C1
Battery j-V curve test result with comparative example 2 gained organic solar batteries C2.
As can be seen from Figure 5: compared to comparative example 1 gained organic solar batteries C1 and comparative example 2 institute
Obtaining organic solar batteries C2, embodiment 1 gained organic solar batteries 1 has more preferable diode characteristic,
(photoelectric transformation efficiency of battery C1 is 1.5%, electricity to show more preferable device performance and photoelectric transformation efficiency
The photoelectric transformation efficiency of pond C2 is 0.17%, and the photoelectric transformation efficiency of battery 1 is 2.12%, about improves 41
%).
Fig. 6 is that embodiment 1 gained organic solar batteries device 1 excites lower observation at 975nm near infrared light
The up-conversion fluorescence figure arrived.
As can be seen from Figure 6: under near infrared light shines, MoO3: the upper conversion function of Yb, Er boundary layer can be
Part near-infrared photon is converted to the photon of short wavelength, and then is used by solaode.
Embodiment 2
Preparation PCE-10:PC71BM organic solar batteries 2
With embodiment 1, difference is: active layer material uses PCE-10:PC71BM replaces P3HT:PC61BM。
Embodiment 3
Synthesis ZnO:Yb, Er nano material 3
1) 1.1g bis-water and zinc acetate (Alfa 99.9%), appropriate rare earth ion predecessor such as acetic acid ytterbium are taken
(about 56mg) and acetic acid erbium (about 5.6mg), be dissolved in 48mL methanol and obtain solution, and oil bath is heated to 65
DEG C, it is stirred vigorously 20min；
2) take 0.49mg KOH (Aldrich 99.99%) and 24mL methanol (Aldrich 99.9%) is joined
Put mixed solution；
3) by step 2) gained mixed solution is slowly dropped to step 1) in solution (65 DEG C, be stirred vigorously),
Drip off rear solution muddy, white precipitate occurs；
4) centrifugal collecting precipitate, under the conditions of being placed in 750 DEG C calcine 2 hours, obtain particle diameter be 20-50nm,
Yb doping is 2%, Er doping is the ZnO:Yb of 0.2%, Er nano material 3.
PCE-10:PC is inverted in preparation71BM organic solar batteries 3
1) ITO substrate is cleaned 10min, dry for standby successively by acetone, isopropanol；
2) in washed ITO substrate, deposit (blade coating, spin coating or spraying) ZnO:Yb, Er nano material 3
Alcohol dispersion liquid (concentration of ZnO:Yb, Er nano material 3 is 2mg/mL), 120 DEG C annealing 10min,
The thickness of gained ZnO:Yb, Er nano material 3 layers is 50nm；
3) PCE-10:PC of the 2wt% dissolved in advance is then deposited71BM chlorobenzene solution, prepared thickness is about
The active layer of 150nm；
4) evaporation thickness is the MoO of 8nm3As hole transmission layer；
5) evaporation thickness is that the metal aluminium electrode of 100nm is as anode.
The all documents mentioned in the present invention are incorporated as reference the most in this application, just as each document
It is individually recited as with reference to like that.In addition, it is to be understood that after the above-mentioned teachings having read the present invention,
The present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within this Shen equally
Please appended claims limited range.
Claims (10)
1. a rare earth doping metal oxide-based nanomaterial, it is characterised in that described nano material comprises metal
Oxide and the rare earth element being doped in described metal-oxide, and described metal-oxide is semi-conducting material,
And based on the gross weight of described nano material, the doping of described rare earth element is 0.5-5wt%.
2. nano material as claimed in claim 1, it is characterised in that form the metal unit of described metal-oxide
Element is selected from lower group: Mo, V, W, Ti, Zn, Ni or a combination thereof；And/or
Described rare earth element is selected from lower group: Yb, Er, Ho, Tm, Eu or a combination thereof.
3. the preparation method of nano material described in a claim 1, it is characterised in that described method include as
Lower step:
A-1) provide the first mixed solution, described first mixed solution comprise the first solvent and be dissolved in therein for
Form the salt of the metallic element of metal-oxide, for the salt of rare earth element of the described metal-oxide that adulterates；
A-2) heating abovementioned steps gained mixed solution, obtains presoma precipitate；
A-3) calcine described presoma precipitate, obtain nano material described in claim 1.
4. as claimed in claim 3 method, it is characterised in that step a-2) treatment temperature of described heat treated
For 30-120 DEG C；And/or
Step a-2) process time of described heat treated is 0.5-3 hour；And/or
Step a-3) treatment temperature of described calcination processing is 600-800 DEG C；And/or
Step a-3) process time of described calcination processing is 2-6 hour.
5. a solaode, described solaode includes anode layer, active layer and negative electrode layer, its feature
It is,
I) there is hole transport boundary layer between described anode layer and described active layer, the most described negative electrode layer and
There is electric transmission boundary layer between described active layer, and described hole transport boundary layer is received by described in claim 1
Rice material is made, and the most described electric transmission boundary layer is made up of nano material described in claim 1；Or
Person
Ii) there is electric transmission boundary layer between described anode layer and described active layer, the most described negative electrode layer and
There is hole transport boundary layer between described active layer, and described electric transmission boundary layer is received by described in claim 1
Rice material is made, and the most described hole transport boundary layer is made up of nano material described in claim 1.
6. solaode as claimed in claim 5, it is characterised in that the thickness of described hole transport boundary layer
For 5-150nm；And/or
The thickness of described electric transmission boundary layer is 10-100nm.
7. solaode as claimed in claim 5, it is characterised in that compared to undoped p rare earth element
The material that the metal-oxide of identical type is made is as electric transmission boundary layer or the sun of hole transport boundary layer
Energy battery, the photoelectric transformation efficiency of described solaode improves at least 5%, the most at least 20-30%, more
Goodly at least 40%.
8. the purposes of nano material described in a claim 1, it is characterised in that be used for making solaode
Boundary layer.
9. goods, it is characterised in that described goods comprise nano material described in claim 1 or by right
Require that nano material described in 1 is made.
10. the method improving solar cell photoelectric conversion efficiency, it is characterised in that at described solar energy
Adding electric transmission boundary layer and/or hole transport boundary layer between electrode and the active layer of battery, described electronics passes
Defeated boundary layer and/or described hole transport boundary layer comprise nano material described in claim 1 or by claim 1
Described nano material is made.
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| CN110098269A (en) * | 2019-04-29 | 2019-08-06 | 北京铂阳顶荣光伏科技有限公司 | Thin-film solar cells and preparation method thereof |
| CN110473968A (en) * | 2019-07-31 | 2019-11-19 | 青岛大学 | Flexible structure polymer solar battery and preparation method thereof based on europium rare-earth complex doping zinc-oxide electron-transport layer building |
| CN110681376A (en) * | 2019-09-12 | 2020-01-14 | 天津大学 | Morphology-adjustable rare earth ion co-doped tungsten oxide nanoparticle and synthesis method thereof |
| CN113044875A (en) * | 2019-12-27 | 2021-06-29 | Tcl集团股份有限公司 | Nano material and preparation method thereof, quantum dot light-emitting diode and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110098269A (en) * | 2019-04-29 | 2019-08-06 | 北京铂阳顶荣光伏科技有限公司 | Thin-film solar cells and preparation method thereof |
| CN110473968A (en) * | 2019-07-31 | 2019-11-19 | 青岛大学 | Flexible structure polymer solar battery and preparation method thereof based on europium rare-earth complex doping zinc-oxide electron-transport layer building |
| CN110681376A (en) * | 2019-09-12 | 2020-01-14 | 天津大学 | Morphology-adjustable rare earth ion co-doped tungsten oxide nanoparticle and synthesis method thereof |
| CN113044875A (en) * | 2019-12-27 | 2021-06-29 | Tcl集团股份有限公司 | Nano material and preparation method thereof, quantum dot light-emitting diode and preparation method thereof |
| WO2021129706A1 (en) * | 2019-12-27 | 2021-07-01 | Tcl科技集团股份有限公司 | Nanomaterial and preparation method therefor, quantum dot light-emitting diode and preparation method therefor |
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