CN108682743A - A kind of preparation method of the titania-doped quantum dot of holmium ytterbium magnesium and its application in perovskite battery - Google Patents
A kind of preparation method of the titania-doped quantum dot of holmium ytterbium magnesium and its application in perovskite battery Download PDFInfo
- Publication number
- CN108682743A CN108682743A CN201810526071.3A CN201810526071A CN108682743A CN 108682743 A CN108682743 A CN 108682743A CN 201810526071 A CN201810526071 A CN 201810526071A CN 108682743 A CN108682743 A CN 108682743A
- Authority
- CN
- China
- Prior art keywords
- layer
- solution
- tio
- quantum dot
- perovskite
- 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
Classifications
-
- 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
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Luminescent Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of preparation methods of the titania-doped quantum dot of holmium ytterbium magnesium, include the following steps：1）The preparation of TiO 2 precursor；2）The preparation of quantum dot：By Ho (NO3)3·5H2O、Yb(NO3)3·5H2O and Mg (NO3)2·6H2O is added in TiO 2 precursor solution, obtains mixed solution C, and mixed solution C is dry, annealing obtains the titania-doped quantum dot of holmium ytterbium magnesium；The titania-doped quantum dot of holmium ytterbium magnesium can be used as electron transport material to be applied to prepare in perovskite battery, and near infrared light can be converted into visible light by the perovskite battery being prepared, and transfer efficiency is higher.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to a kind of Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot
Preparation and its application in perovskite battery.
Background technology
In recent years, perovskite solar cell becomes a research hotspot in solar cell field, because it has efficiency
The advantages that high, at low cost, preparation method is simple.The transfer efficiency of perovskite battery improves quickly, is had reached by 2017
22.1% （Science, 2017, 356:1376）.However, perovskite solar cell can only absorb the sub-fraction of solar spectrum
（280~800 nm）, near infrared light cannot be absorbed, the energy loss of incident light is very big, hinders further carrying for battery efficiency
It is high.An approach for solving the problems, such as this is exactly that near infrared light, which is converted into battery, using up-conversion luminescent material to absorb
Visible light, to improve battery conversion efficiency.Currently, people mainly use rare earth ion doped NaYF4Electronics passes in preparation
Defeated material is applied to solar cell.But NaYF4Electric conductivity it is bad, the transmission of electronics can be hindered（Inorg. Chem.,
2014, 53:8045）.In perovskite solar cell, TiO2It is a kind of common electron transport material, if using rare earth member
Element doping TiO2Electron transport material in preparation, neither influencing the transmission of electronics again can convert the near infrared light in sunlight
It at visible light, is absorbed by perovskite battery, to improve battery efficiency.
Invention content
The object of the present invention is to provide a kind of Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot preparation method, by this method
The Ho of preparation3+-Yb3+-Mg2+Adulterate TiO2Near infrared light can be converted into visible light, and transfer efficiency is higher.This will be used
Ho prepared by kind method3+-Yb3+-Mg2+Adulterate TiO2As electron transport material, perovskite solar cell is prepared, has expanded calcium titanium
Absorption of the mine battery near infrared light, improves the photoelectric conversion efficiency of battery.
The invention discloses a kind of Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot preparation method, include the following steps：
1）TiO2The preparation of presoma：
The positive four fourths fat of metatitanic acid is uniformly mixed with acetylacetone,2,4-pentanedione, isopropanol is then added, obtains solution A, wherein positive four fourth of metatitanic acid
The volume ratio of fat, acetylacetone,2,4-pentanedione and isopropanol is (7 ~ 8): ( 2~3) :100；
Nitric acid and water are added in isopropanol, are uniformly mixed, obtains solution B, wherein nitric acid, water, isopropanol volume ratio be (7
~8) : ( 2~3) :100；
According to solution A and B solution (2 ~ 3):1 volume ratio mixes solution B with solution A, obtains TiO2Precursor solution.
2）The preparation of quantum dot：By Ho (NO3)3·5H2O、Yb(NO3)3·5H2O and Mg (NO3)2·6H2TiO is added in O2Before
It drives in liquid solution, obtains mixed solution C, mixed solution C is dry under the conditions of 90 ~ 110oC, then in 450 ~ 550oC conditions
30 ~ 90 min of lower annealing are to get to Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot；
The molar ratio of Ho and Ti, Yb and Ti, Mg and Ti are respectively 0.5 ~ 1.5 in the mixed solution C:100、1~5:100、1~4:
100。
The step 1）The concrete mode that middle solution B is mixed with solution A is：Solution B is added dropwise in solution A, stirring 6
Hour.
Use the Ho being prepared3+-Yb3+-Mg2+Adulterate TiO2Quantum dot can be used as electron transport material can answer
For perovskite battery.
A kind of addition Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot perovskite battery preparation method, including with
Lower step：
1）The processing of FTO sheet glass：The FTO sheet glass of etching is cleaned, ultraviolet lighting is used in combination to handle, obtains clean FTO glass
Piece.
2）Prepare compacted zone：0.05 ~ 0.1 ml titanium acetylacetones are added in 0.5 ~ 1.5 ml butanol solutions and are mixed
Compacted zone presoma is obtained, compacted zone precursor solution is dropped in into step 1）On obtained clean FTO sheet glass, spin coating is moved back
Compacted zone/FTO is made in fire.
3）Prepare electron transfer layer：By TiO2With absolute ethyl alcohol in mass ratio 1:6 are mixed to get TiO2Slurry, by TiO2Slurry
Gob is on compacted zone, spin coating, annealing, and electron transfer layer/compacted zone/FTO is made.
4）Prepare decorative layer：On the electron transport layer by mixed solution C drop, Ho is made in spin coating, annealing3+-Yb3+-Mg2+It mixes
Miscellaneous TiO2Decorative layer/electron transfer layer/compacted zone/FTO.
5）Perovskite absorbed layer：By 0.5 ~ 1.5 mmol FAI, 1 ~ 1.5 mmol PbI2, 0.1 ~ 0.5mmol MABr,
0.1~0.5 mmol PbBr2It is dissolved in the mixed solution of 1mL DMF and DMSO, adds the CsI solution of 40-50 μ l, mix
Conjunction uniformly obtains perovskite precursor solution, and perovskite precursor solution is dropped in Ho3+-Yb3+-Mg2+Adulterate TiO2Decorative layer
On, chlorobenzene is added dropwise in spin coating, and heating obtains perovskite absorbed layer/decorative layer/electron transfer layer/compacted zone/FTO.
6）Prepare hole transmission layer：70 ~ 80 mg spiro-oMeTAD are dissolved in 1mL chlorobenzenes, are then added 28.8
Pair of the tertiary yl pyridines of ul 4- and a concentration of 520 mg/ml of 17.5 ul（Fluoroform sulphonyl）The acetonitrile solution of imine lithium, mixing
Uniformly obtain hole transmission layer solution, hole transmission layer/perovskite absorbed layer/decorative layer/electron transfer layer/compacted zone/FTO.
7）Hot evaporation layer of Au electrode obtains Ho on the hole transport layer3+-Yb3+-Mg2+Adulterate TiO2Electron-transport material
The perovskite battery of material, i.e. Au/ hole transmission layers/perovskite absorbed layer/decorative layer/electron transfer layer/compacted zone/FTO.
Step 1）Described in the concrete mode of FTO glass cleanings that etches be：The FTO sheet glass of etching is sequentially placed into and is led
In electric glass cleaning solution, acetone and isopropanol, it is cleaned by ultrasonic each 20 min.
The implementation parameter of the spin coating is：Step 2）When prepared by middle compacted zone, rotating speed is 3500 revs/min；Step 3）In
When prepared by electron transfer layer, rotating speed is 4000 revs/min；Step 4）When prepared by middle decorative layer, rotating speed is 5000 revs/min；Step
Rapid 5）When prepared by middle perovskite absorbed layer, rotating speed is with the condition of 1000 rpm 10s and 6000 rpm 20s；Step 6）It is hollow
When prepared by cave transport layer, speed is 4000 revs/min.
The implementation parameter of the annealing is：Step 2）When prepared by middle compacted zone, annealing temperature 500oC, time are 30 ~ 60
min；Step 3）When prepared by middle electron transfer layer, annealing temperature 450oC, time are 30 ~ 60 min；Step 4）Middle decorative layer system
When standby, annealing temperature 500oC, time are 30 ~ 120 min；Step 5）When prepared by middle perovskite absorbed layer, annealing temperature is
500oC, time are 30 ~ 60 min；Step 6）When prepared by hole-transporting layer, annealing temperature 100oC, time are 60 min.
Step 5）Described in DMF and DMSO volume ratio be 4:1.
The Ho being prepared3+-Yb3+-Mg2+Adulterate TiO2Quantum dot perovskite battery, including be sequentially overlapped
FTO glass, compacted zone, electron transfer layer, decorative layer, perovskite absorbed layer, hole transmission layer, Au electrodes；The Au electrodes are thick
80 nm。
The present invention has the following advantages：
1）The present invention prepares Ho using this preparation method3+-Yb3+-Mg2+Adulterate TiO2Quantum dot, due to Mg2+Addition, make
Ho3+-Yb3+Adulterate TiO2Up-conversion luminescence performance enhanced.It can be by changing the doping of magnesium nitrate, electronics in change
The luminous intensity of transmission material can obtain the corresponding Mg of most strong luminous intensity2+Optimum doping amount.
2）Ho prepared by the present invention3+-Yb3+-Mg2+Adulterate TiO2Quantum dot as electron transport material, prepare calcium titanium
Mine solar cell.Due to Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot near infrared light can be converted into perovskite is absorbent can
It is light-exposed, the spectral response range of perovskite battery has been expanded, battery conversion efficiency can be improved.
Description of the drawings
Fig. 1 is Ho described in embodiment 13+-Yb3+-Mg2+Adulterate TiO2The energy transmission schematic diagram of quantum dot；
Fig. 2 is Ho described in embodiment 13+-Yb3+-Mg2+Adulterate TiO2Quantum dot X-ray diffractogram（XRD）；
Fig. 3 is Ho described in embodiment 13+-Yb3+-Mg2+Adulterate TiO2Ultraviolet-visible-infrared absorpting light spectra of quantum dot；
Fig. 4 is Ho described in embodiment 1 and comparative example 13+-Yb3+-Mg2+Adulterate TiO2Quantum dot conversion illuminated diagram；
Fig. 5 is Ho described in embodiment 23+-Yb3+-Mg2+Adulterate TiO2The perovskite battery structure schematic diagram of quantum dot；
Fig. 6 is the current -voltage curve figure corresponding with the peak efficiency of perovskite battery described in comparative example 2 of embodiment 2.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but the following example is only used for
The bright present invention, without that should be to limit the scope of the invention.The room temperature is 25 ± 5 DEG C.
The positive four fourths fat of heretofore described metatitanic acid, acetylacetone,2,4-pentanedione, isopropanol, Ho (NO3)3·5H2O、Yb(NO3)3·5H2O、
Mg(NO3)2·6H2O, electro-conductive glass cleaning solution（Shenzhen Rui Geruisi Science and Technology Ltd.s）, acetone, absolute ethyl alcohol, chlorobenzene, iodine
Carbonamidine（FAI）, lead iodide（PbI2）, bromine methylamine（MABr）, lead bromide（PbBr2）, dimethylformamide（DMF）, dimethyl sulfoxide (DMSO)
（DMSO）, CsI solution, spiro-oMeTAD, chlorobenzene, the tertiary yl pyridines of 4-, bis- (fluoroform sulphonyl) imine lithiums, acetonitrile belong to
Commercial product.
Heretofore described TiO2Slurry is the TiO of commercialization2, buy from Dyesol, model 30NR-D.
Embodiment 1：
A kind of Ho3+-Yb3+-Mg2+Adulterate TiO2The preparation method of upper quantum dot comprising following steps：
1）The preparation of TiO2 presomas：
Positive four fourths fat, 0.75 ml of metatitanic acid is mixed into 1h at room temperature with 0.225 ml of acetylacetone,2,4-pentanedione, boil together reaction, then adds
Enter 10 ml isopropanols（iso-propyl）, obtain solution A；
0.045 ml of nitric acid and 0.105 ml of deionized water are added in 5 ml isopropanols, 1h is mixed, obtains solution B；
Solution A is added dropwise in solution B, magnetic agitation 6 hours obtains TiO2Precursor solution.
2）The preparation of quantum dot：By Ho (NO3)3·5H2O、Yb(NO3)3·5H2O and Mg (NO3)2·6H2TiO is added in O2
In precursor solution, mixed solution C is obtained, the molar ratio of Ho and Ti, Yb and Ti, Mg and Ti are respectively in the mixed solution C
0.5~1.5:100、1~5:100、1~4:100；
Mixed solution C is 12 hours dry under the conditions of 100 DEG C（Remove solvent）, the then annealing 30 ~ 90 under the conditions of 500 DEG C
Min is to get to Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot, be denoted as Ho3+-Yb3+-Mg2+：TiO2。
Comparative example 1
Difference lies in Mg (NO are omitted with embodiment 1 for this comparative example3)2·6H2The addition of O, quanta point material are denoted as Ho3+-
Yb3+：TiO2。
The optical property of quantum dot described in embodiment 1 and comparative example 1 is detected：
One, Ho described in the present embodiment3+-Yb3+-Mg2+Adulterate TiO2Quantum dot energy transmission schematic diagram as shown in Figure 1, TiO2Make
For host material, Ho3+It is activator, as the centre of luminescence, Yb3+It is sensitizer, energy can be absorbed and transferred energy to sharp
Agent Ho living3+。
Two, the Ho being prepared is detected3+-Yb3+-Mg2+Adulterate TiO2Quantum dot X diffraction, as shown in Fig. 2, being located at
The characteristic peak of 25.9o, 38.7o, 48.6o and 62.9o are respectively belonging to TiO2Anatase TiO2's（101）、（004）、（200）
With（204）Crystal face, the characteristic peak positioned at 54.9o correspond to TiO2Rutile Type（211）Crystal face, this illustrates that the present invention prepares
TiO2It is the mixed phase of anatase and Rutile Type.
Three, Ho described in the present embodiment is detected3+-Yb3+-Mg2+Adulterate TiO2Quantum dot ultraviolet-visible-infrared Absorption
Situation, as shown in figure 3, due to Yb3+Ion2F7/2→2F5/2Energy level transition and Ho3+'s5I7→5F5Energy level transition, Ho3+-
Yb3+-Mg2+Adulterate TiO2Quantum dot can absorb near infrared light.
Four, the Ho described in detection the present embodiment in the case where excitation light source is the excitation of 980 nm lasers3+-Yb3+-Mg2+Doping
TiO2The conversion of quantum dot shine situation, as shown in figure 4, belonging to respectively positioned at the up-conversion luminescence peak of 547 nm and 663 nm
In Ho3+'s5F4,5S2→5I8With5F5→5I8Energy level transition.It can be seen from the figure that due to Mg2+Addition, described in embodiment 1
Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot compared to Ho described in comparative example 13+-Yb3+Adulterate TiO2Quantum dot on, conversion hair
Luminous intensity is enhanced.
Embodiment 2
In the present embodiment, the mixed solution C being prepared in Application Example 1 participates in the preparation of the present embodiment perovskite battery,
Specific preparation method is as follows：
1）The processing of FTO sheet glass：FTO sheet glass is cleaned, ultraviolet lighting is used in combination to handle 20 min, obtains clean FTO glass
Piece；The concrete mode of FTO glass cleanings is：It will etching（Zn powder and dilute hydrochloric acid FTO sheet glass are used according to experiment conventional means
Perform etching processing）FTO sheet glass be sequentially placed into electro-conductive glass cleaning solution, acetone and isopropanol, be cleaned by ultrasonic each 20
min。
2）Prepare compacted zone：0.072 ml titanium acetylacetones are added in 1 ml n-butanols and are uniformly mixed, densification is obtained
Layer presoma, step 1 is dropped in by compacted zone precursor solution）On obtained clean FTO sheet glass, with 3500 revs/min
30 s of rotating speed spin coating, then anneal under the conditions of 500oC 30 ~ 60 min, and compacted zone/FTO is made；
3）Prepare electron transfer layer：By TiO2With absolute ethyl alcohol in mass ratio 1:6 are mixed to get TiO2Slurry, by TiO2Slurry drips
On compacted zone, with 4000 revs/min of 30 s of rotating speed spin coating, then anneal under the conditions of 450oC 30 ~ 60 min, and electricity is made
Sub- transport layer/compacted zone/FTO；
4）Prepare decorative layer：On the electron transport layer by the mixed solution C obtained in embodiment 1 drop, with 5000 revs/min
30 s of rotating speed spin coating, then anneal under the conditions of 500oC 30 ~ 120 min, and Ho is made3+-Yb3+-Mg2+Adulterate TiO2Quantum dot
Decorative layer/electron transfer layer/compacted zone/FTO；
5）Prepare perovskite absorbed layer：By 1 mmol iodine carbonamidines（FAI）, 1.1 mmol lead iodides（PbI2）, 0.2 mmol bromine first
Amine（MABr）, 0.2 mmol lead bromides（PbBr2）It is dissolved in 1mL dimethylformamides（DMF）And dimethyl sulfoxide (DMSO)（DMSO）'s
Mixed solution（DMF:DMSO=4:1, volume ratio）In, add the CsI solution of 1.5 M of 42 μ l（Solvent is DMSO）, mixing
It is uniformly mixing to obtain perovskite precursor solution, perovskite precursor solution is dropped in into Ho3+-Yb3+-Mg2+Adulterate TiO2Modification
On layer, with spin coating under conditions of 1000 rpm 10s and 6000 rpm 20s, and 100 ul chlorine are added dropwise in 10s before rotation terminates
Then sample is placed in 100oC heating dish and heats 60 min by benzene, obtain perovskite absorbed layer/decorative layer/electron transfer layer/
Compacted zone/FTO；
6）Prepare hole transmission layer：72.3 mg spiro-oMeTAD are dissolved in 1mL chlorobenzenes, 28.8 ul 4- are then added
The acetonitrile solution of bis- (fluoroform sulphonyl) imine lithiums of tertiary yl pyridines and a concentration of 520 mg/ml of 17.5 ul is uniformly mixed
Hole transmission layer solution is obtained, hole transmission layer is dropped on perovskite absorbed layer, with 4000 revs/min of speed spin coating 30s,
Obtain hole transmission layer/perovskite absorbed layer/decorative layer/electron transfer layer/compacted zone/FTO；
7）Prepare electrode：Vacuum thermal evaporation layer of Au electrode obtains Ho on the hole transport layer3+-Yb3+-Mg2+Adulterate TiO2Electricity
The perovskite battery of sub- transmission material, i.e. Au/ hole transmission layers/perovskite absorbed layer/decorative layer/electron transfer layer/compacted zone/
FTO；The Au thickness of electrode is 80 nm.
The structural schematic diagram of the perovskite battery, as shown in figure 5,1-FTO, 2- compacted zone, 3- electron transfer layers, 4-
Ho3+-Yb3+-Mg2+Adulterate TiO2The decorative layer of quantum dot, 5- perovskite absorbed layers, 6- hole transmission layers, 7-Au electrodes.
Comparative example 2
Difference from Example 2 is：This comparative example prepares the preparation for omitting decorative layer described in embodiment 2, i.e., directly in electricity
Perovskite absorbed layer is prepared in sub- transport layer, obtained battery is denoted as Au/ hole transmission layers/perovskite absorbed layer/electron-transport
Layer/compacted zone/FTO.
The cell photoelectric performance of embodiment 2 and comparative example 2 is detected：
One, the photovoltaic property parameter of perovskite battery described in embodiment 2 and comparative example 2 is detected, testing result such as 1 institute of table
Show.
The photovoltaic property parameter of perovskite battery described in 1 embodiment 2 of table and comparative example 2
Compared with perovskite battery described in comparative example 2, based on there is Ho3+-Yb3+-Mg2+Adulterate TiO2The short circuit current of battery by
21.2 mA/cm2It is increased to 22.6 mA/cm2, electricity conversion（PCE）It is increased to 16.3% by 15.2%.
Two, the current density for detecting the perovskite solar cell described in embodiment 2 and comparative example 2, is depicted as electric current-electricity
It buckles line, as shown in Figure 6.Fig. 6 is that embodiment 2 is corresponding with the peak efficiency of perovskite solar cell described in comparative example 2
Current -voltage curve.Current -voltage curve is in AM1.5 standard solar simulators（Illumination is 100 mW/cm2）Under irradiation
Test.The peak efficiency of the perovskite battery of comparative example 2 is 15.7%, and the peak efficiency of the battery of embodiment 2 reaches 16.8%.
Although to illustrate and describe the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope, it is, therefore, intended that in the claim
All changes and modification including the scope of the invention belong to the scope of the present invention.
Claims (9)
1. a kind of Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot preparation method, which is characterized in that include the following steps：
1）TiO2The preparation of presoma：
The positive four fourths fat of metatitanic acid is uniformly mixed with acetylacetone,2,4-pentanedione, isopropanol is then added, obtains solution A, wherein positive four fourth of metatitanic acid
The volume ratio of fat, acetylacetone,2,4-pentanedione and isopropanol is (7 ~ 8): ( 2~3) :100,
Nitric acid and water are added in isopropanol, are uniformly mixed, obtains solution B, wherein nitric acid, water, isopropanol volume ratio be (7
~8) : ( 2~3) :100,
According to solution A and B solution (2 ~ 3):1 volume ratio mixes solution B with solution A, obtains TiO2Precursor solution；
2）The preparation of quantum dot：By Ho (NO3)3·5H2O、Yb(NO3)3·5H2O and Mg (NO3)2·6H2TiO is added in O2Presoma
In solution, mixed solution C is obtained, mixed solution C is dry under the conditions of 90 ~ 110oC, then moved back under the conditions of 450 ~ 550oC
30 ~ 90 min of fire are to get to Ho3+-Yb3+-Mg2+Adulterate TiO2Quantum dot；
The molar ratio of Ho and Ti, Yb and Ti, Mg and Ti are respectively 0.5 ~ 1.5 in the mixed solution C:100、1~5:100、1~4:
100。
2. Ho as described in claim 13+-Yb3+-Mg2+Adulterate TiO2Quantum dot preparation method, which is characterized in that step 1）
The concrete mode that middle solution B is mixed with solution A is：Solution B is added dropwise in solution A, is stirred 6 hours.
3. using the Ho that preparation method is prepared described in claim 1 or claim 2 claim 23+-Yb3+-Mg2+Adulterate TiO2Quantum
Point.
4. adding Ho described in claim 33+-Yb3+-Mg2+Adulterate TiO2Quantum dot perovskite battery preparation method, it is special
Sign is, includes the following steps：
1）The processing of FTO sheet glass：The FTO sheet glass of etching is cleaned, ultraviolet lighting is used in combination to handle, obtains clean FTO glass
Piece；
2）Prepare compacted zone：0.05 ~ 0.1 ml titanium acetylacetones are added in 0.5 ~ 1.5 ml butanol solutions and are mixed to get
Compacted zone precursor solution is dropped in step 1 by compacted zone presoma）On obtained clean FTO sheet glass, spin coating, annealing, system
Obtain compacted zone/FTO；
3）Prepare electron transfer layer：By TiO2With absolute ethyl alcohol in mass ratio 1:6 are mixed to get TiO2Slurry, by TiO2Slurry drips
On compacted zone, electron transfer layer/compacted zone/FTO is made in spin coating, annealing；
4）Prepare decorative layer：On the electron transport layer by mixed solution C drop, Ho is made in spin coating, annealing3+-Yb3+-Mg2+Doping
TiO2Decorative layer/electron transfer layer/compacted zone/FTO；
5）Perovskite absorbed layer：By 0.5 ~ 1.5 mmol FAI, 1 ~ 1.5 mmol PbI2, 0.1 ~ 0.5mmol MABr, 0.1 ~ 0.5
mmol PbBr2It is dissolved in the mixed solution of 1mL DMF and DMSO, adds the CsI solution of 40-50 μ l, be uniformly mixed
To perovskite precursor solution, perovskite precursor solution is dropped in into Ho3+-Yb3+-Mg2+Adulterate TiO2Decorative layer on, spin coating,
Chlorobenzene is added dropwise, heating obtains perovskite absorbed layer/decorative layer/electron transfer layer/compacted zone/FTO；
6）Prepare hole transmission layer：70 ~ 80 mg spiro-oMeTAD are dissolved in 1mL chlorobenzenes, 28.8 ul are then added
Pair of the tertiary yl pyridines of 4- and a concentration of 520 mg/ml of 17.5 ul（Fluoroform sulphonyl）The acetonitrile solution of imine lithium, mixing are equal
It is even to obtain hole transmission layer solution, hole transmission layer/perovskite absorbed layer/decorative layer/electron transfer layer/compacted zone/FTO；
7）Hot evaporation layer of Au electrode obtains the electron transport material of Ho3+-Yb3+-Mg2+ doping TiO2 on the hole transport layer
Perovskite battery, i.e. Au/ hole transmission layers/perovskite absorbed layer/decorative layer/electron transfer layer/compacted zone/FTO.
5. Ho as claimed in claim 43+-Yb3+-Mg2+Adulterate TiO2Quantum dot perovskite battery preparation method, it is special
Sign is, step 1）Described in the concrete mode of FTO glass cleanings that etches be：The FTO sheet glass of etching is sequentially placed into and is led
In electric glass cleaning solution, acetone and isopropanol, it is cleaned by ultrasonic each 20 min.
6. Ho as claimed in claim 43+-Yb3+-Mg2+Adulterate TiO2Quantum dot perovskite battery preparation method, it is special
Sign is that the implementation parameter of the spin coating is：Step 2）When prepared by middle compacted zone, rotating speed is 3500 revs/min；Step 3）Middle electricity
When prepared by sub- transport layer, rotating speed is 4000 revs/min；Step 4）When prepared by middle decorative layer, rotating speed is 5000 revs/min；Step
5）When prepared by middle perovskite absorbed layer, rotating speed is with the condition of 1000 rpm 10s and 6000 rpm 20s；Step 6）Middle hole
When prepared by transport layer, speed is 4000 revs/min.
7. Ho as claimed in claim 43+-Yb3+-Mg2+Adulterate TiO2Quantum dot perovskite battery preparation method, feature
It is,
The implementation parameter of the annealing is：Step 2）When prepared by middle compacted zone, annealing temperature 500oC, time are 30 ~ 60
min；Step 3）When prepared by middle electron transfer layer, annealing temperature 450oC, time are 30 ~ 60 min；Step 4）Middle decorative layer system
When standby, annealing temperature 500oC, time are 30 ~ 120 min；Step 5）When prepared by middle perovskite absorbed layer, annealing temperature is
500oC, time are 30 ~ 60 min；Step 6）When prepared by hole-transporting layer, annealing temperature 100oC, time are 60 min.
8. Ho as claimed in claim 43+-Yb3+-Mg2+Adulterate TiO2Quantum dot perovskite battery preparation method, feature
It is, step 5）Described in DMF and DMSO volume ratio be 4:1.
9. the Ho being prepared using any preparation methods of claim 4-83+-Yb3+-Mg2+Adulterate TiO2Quantum dot
Perovskite battery, which is characterized in that FTO glass, compacted zone, electron transfer layer, decorative layer, perovskite including being sequentially overlapped are inhaled
Receive layer, hole transmission layer, Au electrodes；80 nm of the Au electrodes thickness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810526071.3A CN108682743B (en) | 2018-05-29 | 2018-05-29 | Preparation method of holmium-ytterbium-magnesium-doped titanium dioxide quantum dots and application of holmium-ytterbium-magnesium-doped titanium dioxide quantum dots in perovskite battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810526071.3A CN108682743B (en) | 2018-05-29 | 2018-05-29 | Preparation method of holmium-ytterbium-magnesium-doped titanium dioxide quantum dots and application of holmium-ytterbium-magnesium-doped titanium dioxide quantum dots in perovskite battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108682743A true CN108682743A (en) | 2018-10-19 |
| CN108682743B CN108682743B (en) | 2020-05-05 |
Family
ID=63807038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810526071.3A Active CN108682743B (en) | 2018-05-29 | 2018-05-29 | Preparation method of holmium-ytterbium-magnesium-doped titanium dioxide quantum dots and application of holmium-ytterbium-magnesium-doped titanium dioxide quantum dots in perovskite battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108682743B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651197A (en) * | 2019-01-07 | 2019-04-19 | 南方科技大学 | A kind of neighbour's benzene dicyan derivative and preparation method thereof, a kind of metal phthalocyanine derivative and its preparation method and application |
| CN113193127A (en) * | 2021-05-07 | 2021-07-30 | 河南大学 | Ytterbium and erbium co-doped perovskite film and application thereof in photoelectric detector |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694888A (en) * | 2016-02-29 | 2016-06-22 | 武汉理工大学 | Mg2+ doped NaREF4 upconversion fluorescence material and preparation method thereof |
| CN107267145A (en) * | 2017-05-19 | 2017-10-20 | 河南大学 | A kind of holmium ytterbium lithium codoping titanium dioxide nano material, its preparation method and perovskite solar cell |
-
2018
- 2018-05-29 CN CN201810526071.3A patent/CN108682743B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694888A (en) * | 2016-02-29 | 2016-06-22 | 武汉理工大学 | Mg2+ doped NaREF4 upconversion fluorescence material and preparation method thereof |
| CN107267145A (en) * | 2017-05-19 | 2017-10-20 | 河南大学 | A kind of holmium ytterbium lithium codoping titanium dioxide nano material, its preparation method and perovskite solar cell |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651197A (en) * | 2019-01-07 | 2019-04-19 | 南方科技大学 | A kind of neighbour's benzene dicyan derivative and preparation method thereof, a kind of metal phthalocyanine derivative and its preparation method and application |
| CN109651197B (en) * | 2019-01-07 | 2021-11-02 | 南方科技大学 | Phthalocyanin derivative, preparation method thereof, metal phthalocyanine derivative, preparation method and application thereof |
| CN113193127A (en) * | 2021-05-07 | 2021-07-30 | 河南大学 | Ytterbium and erbium co-doped perovskite film and application thereof in photoelectric detector |
| CN113193127B (en) * | 2021-05-07 | 2022-06-10 | 河南大学 | Ytterbium and erbium co-doped perovskite film and application thereof in photoelectric detector |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108682743B (en) | 2020-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Near-infrared and ultraviolet to visible photon conversion for full spectrum response perovskite solar cells | |
| CN105489773B (en) | The preparation method of organic inorganic hybridization perovskite thin film and solar cell | |
| Hou et al. | High-performance perovskite solar cells by incorporating a ZnGa2O4: Eu3+ nanophosphor in the mesoporous TiO2 layer | |
| Roh et al. | Dual-functional CeO2: Eu3+ nanocrystals for performance-enhanced dye-sensitized solar cells | |
| Yao et al. | Enhanced light harvesting of dye-sensitized solar cells with up/down conversion materials | |
| CN104332560B (en) | Preparation method of chlorine-bromine-iodine-mixing perovskite light absorption layer material | |
| CN106025067B (en) | A kind of solwution method generates film build method and its device application of perovskite thin film | |
| CN108878554A (en) | Based on La rear earth ion doped CsPbBr3Full-inorganic perovskite solar battery and its preparation method and application | |
| CN105810442B (en) | A kind of manufacture method of the enhanced solar cells of g C3N4 | |
| Karunakaran et al. | Research progress on the application of lanthanide-ion-doped phosphor materials in perovskite solar cells | |
| Xu et al. | Lattice-tailored low-temperature processed electron transporting materials boost the open-circuit voltage of planar CsPbBr 3 perovskite solar cells up to 1.654 V | |
| Shi et al. | Interface modification by up-conversion material of Ho3+-Yb3+-Li+ tri-doped TiO2 to improve the performance of perovskite solar cells | |
| CN107267145B (en) | Holmium-ytterbium-lithium co-doped titanium dioxide nano material, preparation method thereof and perovskite solar cell | |
| Deng et al. | Highly bright Li (Gd, Y) F4: Yb, Er upconverting nanocrystals incorporated hole transport layer for efficient perovskite solar cells | |
| CN108336230A (en) | A kind of purely inorganic cubic phase perovskite solar cell of efficient stable and preparation method thereof | |
| CN109216555A (en) | Perovskite-type compounds layer and battery and preparation method thereof | |
| TW201101508A (en) | Dye-sensitized solar cells and manufacturing method for thereof | |
| CN107093669A (en) | A kind of perovskite solar cell light absorption layer | |
| CN106098950B (en) | Precursor solution, ASnX3The preparation method of perovskite material and the preparation method of solar cell | |
| CN109065727A (en) | A kind of preparation method of perovskite solar battery | |
| CN101462768A (en) | Titania mesoporous ball, preparation and use in solar cell | |
| JP6415223B2 (en) | Organic inorganic composite thin film solar cell | |
| CN108682743A (en) | A kind of preparation method of the titania-doped quantum dot of holmium ytterbium magnesium and its application in perovskite battery | |
| CN106328813B (en) | A kind of high stability mixes caesium Ca-Ti ore type solar cell and preparation method thereof | |
| CN106450007A (en) | Solar cell based on cuprous iodide/calcium titanium ore bulk heterojunction and preparation method 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 |