CN104966617B - For the complex light anode and preparation method of quantum dot sensitized solar cell - Google Patents
For the complex light anode and preparation method of quantum dot sensitized solar cell Download PDFInfo
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Abstract
The invention discloses a kind of complex light anode for quantum dot sensitized solar cell, including with TiO2The electro-conductive glass on barrier layer, in TiO2On barrier layer, TiO is accompanied by from the bottom to top2Nanocrystalline/ZnO nano-wire composite bed and TiO2Nano-crystalline layers.The present invention is for the preparation method of complex light anode of quantum dot sensitized solar cell：First prepare TiO2/ ZnO nano crystalline substance mixed slurry；Again with TiO2TiO is coated on the electro-conductive glass on barrier layer2/ ZnO nano crystalline substance mixed slurry, obtains porous TiO2/ ZnO composite Nano epitaxials；Then in porous TiO2Synthesis ZnO nano-wire, obtains TiO in/ZnO composite Nanos epitaxial2Nanocrystalline/ZnO nano-wire composite bed；Complex light anode is prepared finally by deposition CdSe quantum dot.The cell photoelectric conversion performance prepared by complex light anode of the present invention is greatly improved, and preparation method is simple, reproducible.
Description
Technical field
The invention belongs to quantum dot sensitized solar cell preparing technical field, and in particular to one kind is for quantum dot sensitized
The complex light anode of solar cell, further relates to the preparation side of the above-mentioned complex light anode for quantum dot sensitized solar cell
Method.
Background technology
In recent years, as people are continuously increased to the demand of the energy and the lasting reduction of fossil fuel reserves, find a kind of
New abundance, the alternative energy source of environmental protection have turned into one of important topic of current scientific research.Solar energy takes as one kind
Natural energy source not to the utmost be increasingly subject to global concern, especially solar energy is converted into the solar cell of electric energy
Research has turned into the focus of current research.
Quantum dot sensitized solar cell (QDSSC) is the third generation solar cell that the nineties in last century occurs, i.e. profit
The base material of broad stopband is sensitized with the inorganic semiconductor quantum dot (QD) of low energy gap.Quantum dot has very big excellent relative to dyestuff
Gesture, on the one hand, it has quantum confined effect, can by controlling its size and dimension come the band gap width of quantum point,
The scope of absorption spectrum is adjusted with this；On the other hand, semiconductor-quantum-point has exciton multiplier effect (MEG), a high energy
The photon excitation semiconductor-quantum-point of amount, can produce multiple electron-hole pairs (see A.Shabaev, Al.L.Efros,
A.J.Nozik, Nano.Letters 2006,6, the 22856-22863 pages).If by this two big advantage of semiconductor-quantum-point
Be applied in solar cell, the theoretical value of QDSSC efficiency can reach 44% (M.C.Hanna, A.J.Nozik,
Appl.Phys.2006,100,074510), the theoretical value 32.9% than crystal silicon solar energy battery is much higher.Therefore, whether
Still upper in application in cost, the potentiality of the development of QDSSC are huge.
At present, the light anode structure of quantum dot sensitized solar cell mainly has two kinds：The first is porous TiO2Receive
Rice epitaxial, this nanometer crystal film can provide the loading of specific surface high for sensitising agent, but the shortcoming of this structure is in nanometer
There is serious electronics capture and scattering in crystal edge circle, the unordered network structure of the small particle of 10-20nm sizes is to light scattering in addition
Ability；It is for second one-dimensional ZnO (or TiO2) nano-wire array, these one-dimentional structures can be provided continuously light induced electron
Passage, the boundary effect of particle is greatly reduced, and light to injecting has good scattering process, so as to strengthen light
Utilize, in addition, the one-dimentional structure of monocrystalline has hundred times of electron diffusion coefficient with respect to zero-dimension structural.Although 1-dimention nano knot
Structure light anode has many merits, but battery efficiency is still far below nanometer crystal film, and it is main reasons is that nano tube/linear array film
Specific surface area there was only the half of nanometer crystal film, greatly reduce the loading of sensitising agent, be mainly manifested in terms of battery parameter
Low photoelectric current and battery efficiency.For the synthesis of both structure advantage and disadvantage, if its shortcoming can be overcome, both excellent is inherited
Point, combines both, then the efficiency of battery is possible to be largely increased.
The content of the invention
It is an object of the present invention to provide a kind of complex light anode for quantum dot sensitized solar cell, this is combined
Light anode has had TiO concurrently2The advantage of nanometer crystal film and ZnO nano-wire, solve prepared by existing light anode it is quantum dot sensitized too
The low problem of positive energy battery efficiency.
Second object of the present invention is to provide the preparation method of above-mentioned complex light anode.
First technical scheme that the present invention is used is that a kind of complex light for quantum dot sensitized solar cell is positive
Pole, including with TiO2The electro-conductive glass on barrier layer, in TiO2On barrier layer, TiO is accompanied by from the bottom to top2Nanocrystalline/ZnO receives
Rice noodles composite bed and TiO2Nano-crystalline layers.
Preferably, TiO2Nanocrystalline/ZnO nano-wire composite bed and TiO2The thickness sum of nano-crystalline layers is 10~15 μm.
The present invention use second technical scheme be, the above-mentioned complex light anode for quantum dot sensitized solar cell
Preparation method, comprise the following steps：
Step 1, prepares TiO2/ ZnO nano crystalline substance mixed slurry；
ZnO nano crystalline substance is scattered in ethanol first and obtains ZnO nano crystalline substance colloid, then ZnO nano crystalline substance is diluted with ethanol in proper amount
Colloid；Then by TiO2Nano powder is put into mortar, first adds water tentatively to be ground, then the ZnO nano that will be diluted with ethanol
Brilliant colloid adds mortar to continue to grind several times, forms suspension；Under conditions of ultrasound with stirring, add in suspension successively
Enter terpinol and ethyl cellulose ethanol solution, last 70 DEG C of water-baths make ethanolic moiety volatilize, obtain viscosity and be suitable for screen printing
The TiO of brush2/ ZnO nano crystalline substance mixed slurry.
Step 2, prepares porous TiO2/ ZnO composite Nano epitaxials；
Using screen printing technique, specifically implement according to following steps：With TiO2Applied on the electro-conductive glass on barrier layer
Cover TiO2/ ZnO nano crystalline substance mixed slurry, after being coated with TiO after slurry curing2Nanocrystalline slurry, is finally putting into Muffle furnace calcining,
Obtain with porous TiO2The substrate of/ZnO composite Nano epitaxials.
Step 3, prepares TiO2Nanocrystalline/ZnO nano-wire composite bed；
First by Zn (NO3)2The aqueous solution adds six methine four ammonia (HMTA) aqueous solution, then sequentially adds polyethyleneimine
(PEI) aqueous solution and NH4The OH aqueous solution, and adjusted to alkaline 9.2-9.4 pH value of solution with nitric acid, obtain the life of ZnO nano-wire
Solution long；Again by step 2 with porous TiO2In the substrate insertion growth solution of/ZnO composite Nano epitaxials, using hydro-thermal method
Growing ZnO nano-wire, obtains with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane.
Step 4, prepares complex light anode；
Deposition of the CdSe quantum dot in composite membrane is realized using SILAR methods, is obtained for quantum dot sensitized solar-electricity
The complex light anode in pond.
The present invention also has the characteristics that：
Preferably, in step 1, TiO2The mass ratio of nano powder, ZnO nano crystalline substance, terpinol and ethyl cellulose is 1:
(0.05-0.5)：4：0.5.
Preferably, in step 2, TiO2The 2-3 coating of mixed slurry point of/ZnO nano crystalline substance, stands after coating every time, etc.
It is put into after pulp flow balance after solidifying in baking oven and is coated with next time.
Preferably, calcining is specially：450 DEG C, re-annealing 30min are first raised to from room temperature with the speed of 3 DEG C/min.
Preferably, in step 3 growth solution, Zn (NO3)2Concentration is 0.025~0.05mol/L, and HMTA concentration is 0.0125
~0.025mol/L, PEI concentration are 0.005mol/L, NH4OH concentration is 0.35~0.45mol/L.
Preferably, Hydrothermal Growth ZnO nano-wire is to be grown 5~10 hours in 93 DEG C of water-bath.
Step 4SILAR methods are specially：By step 3 with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane is successively
Immersion Se2-Solution, deionized water, Cd2+Solution, another deionized water, repeatedly drying obtains complex light anode afterwards；Wherein,
Se2-Solution and Cd2+Solution concentration is equal, with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane is in Se2-Solution and Cd2+
The time immersed in solution is identical.
Preferably, Se2-Solution and Cd2+Solution concentration is 0.05mol/L；With TiO2Nanocrystalline/ZnO nano-wire is combined
The substrate of film is in Se2-Solution and Cd2+The time immersed in solution is 1min.
Raw material used in the present invention is chemical field ordinary articles, can be prepared by laboratory common method,
Can also be by commercially available acquisition, the present invention does not limit the source of these materials.
Electro-conductive glass used of the invention is the common electro-conductive glass such as FTO glass or ito glass, and the present invention is not limited equally and led
The species of electric glass.
The beneficial effects of the invention are as follows：(1) the complex light anode tool for quantum dot sensitized solar cell of the invention
There is composite construction, be effectively combined with each other nanocrystalline with nano wire, nano wire is introduced in nanometer crystal film can improve nanometer
Scattering process of the epitaxial to injection light, while monocrystal nanowire can provide the express passway of electric transmission.(2) preparation side of the invention
The key point of method is TiO2The preparation of/ZnO nano crystalline substance composite mortar and the control of ZnO nano-wire hydrothermal growth.It is introduced directly into
The seed of nanowire growth, by a step growth in situ obtain nano wire and nanocrystalline composite membrane, advantage be process is simple, into
This is cheap, can large area prepare, it is reproducible.(3) light anode prepared using the present invention is inhaled using nanocrystalline big specific surface
Attached more quantum dots, improve light capture, are acted on using one-dimensional nano line light scattering high, reduce light anode to the reflection of light with
Transmission loss, strengthens light absorbs, and unimpeded electron propagation ducts are provided using mono-crystalline structures electron diffusion coefficient high, and the above is excellent
The set of point causes that the opto-electronic conversion performance of battery is greatly improved.
Brief description of the drawings
Fig. 1 is the preparation flow figure of complex light anode of the invention；
Fig. 2 is the structural representation of complex light anode of the invention；
Fig. 3-a are the low resolution figures of complex light anode of the invention；
Fig. 3-b are the High-Resolution Maps of the ZnO nano-wire growth 5 hours of complex light anode of the invention；
Fig. 3-c are the High-Resolution Maps of the ZnO nano-wire growth 10 hours of complex light anode of the invention；
Fig. 4-a are TiO2：ZnO nano crystalline substance mass ratio is 1:0.05 complex light anode section SEM figures；
Fig. 4-b are TiO2：ZnO nano crystalline substance mass ratio is 1:0.15 complex light anode section SEM figures；
Fig. 4-c are TiO2：ZnO nano crystalline substance mass ratio is 1:0.25 complex light anode section SEM figures；
Fig. 5 is TiO of the present invention2Nanocrystalline/ZnO nano-wire composite membrane and pure TiO2The diffusing reflection spectrum of nanometer crystal film；
Fig. 6 is TiO of the present invention2Nanocrystalline/ZnO nano-wire composite membrane and pure TiO2The transmitted spectrum of nanometer crystal film；
Fig. 7 is complex light anode of the invention and pure TiO2The absorption spectrum of nanocrystalline light anode；
Fig. 8 is battery and pure TiO prepared by complex light anode of the invention2The J-V of battery prepared by nanocrystalline light anode
Curve.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
The invention provides a kind of complex light anode for quantum dot sensitized solar cell, including with TiO2Stop
The electro-conductive glass of layer, in TiO2On barrier layer, TiO is accompanied by from the bottom to top2Nanocrystalline/ZnO nano-wire composite bed and TiO2Nanometer
Crystal layer.Structural representation is shown in Fig. 2.
Wherein, TiO2Nanocrystalline/ZnO nano-wire composite bed and TiO2The thickness sum of nano-crystalline layers is 10~15 μm.
Present invention also offers the preparation method of the above-mentioned complex light anode for quantum dot sensitized solar cell, reference
Fig. 1, comprises the following steps：
Step 1, prepares TiO2/ ZnO nano crystalline substance mixed slurry.
ZnO nano crystalline substance is scattered in ethanol first and obtains ZnO nano crystalline substance colloid, then ZnO nano crystalline substance is diluted with ethanol in proper amount
Colloid；Then by TiO2Nano powder is put into mortar, first adds water tentatively to be ground, then the ZnO nano crystalline substance glue that ethanol is diluted
Body adds mortar to continue to grind several times, forms suspension；It is loose to being added in suspension successively under conditions of ultrasound with stirring
Oleyl alcohol and ethyl cellulose ethanol solution, last 70 DEG C of water-baths make ethanolic moiety volatilize, and obtain viscosity and are suitable for silk-screen printing
TiO2/ ZnO nano crystalline substance mixed slurry.
Preferably, TiO2The mass ratio of nano powder, ZnO nano crystalline substance, terpinol and ethyl cellulose is 1:(0.05-0.5)：
4：0.5.
ZnO nano crystalline substance of the invention can be prepared by laboratory common method, it is also possible to by commercially available acquisition.
Step 2, with TiO2Porous TiO is prepared on the electro-conductive glass on barrier layer2/ ZnO composite Nano epitaxials.
With screen printing technique with TiO2TiO is coated successively on the electro-conductive glass on barrier layer2/ ZnO nano crystalline substance mixing slurry
Material and TiO2Nanocrystalline slurry, TiO2The 2-3 coating of mixed slurry point of/ZnO nano crystalline substance, stands, etc. stream of slurry after coating every time
It is put into after dynamic balancing after solidifying in baking oven and is coated with next time.TiO2After nanocrystalline slurry coating terminates, Muffle furnace calcining is put into,
Obtain with porous TiO2The substrate of/ZnO composite Nano epitaxials.
Preferably, calcining is specially：450 DEG C, re-annealing 30min are first raised to from room temperature with the speed of 3 DEG C/min.
Step 3, in porous TiO2Synthesis ZnO nano-wire, obtains TiO in/ZnO composite Nanos epitaxial2Nanocrystalline/ZnO nano
Line composite bed.
First by Zn (NO under conditions of stirring3)2The aqueous solution slowly pours into six methine four ammonia (HMTA) aqueous solution, then
Sequentially add polyethyleneimine (PEI) aqueous solution and NH4The OH aqueous solution, and adjusted to alkaline 9.2-9.4 pH value of solution with nitric acid,
Obtain the solution of ZnO nano-wire growth；Again by step 2 with porous TiO2The substrate insertion growth of/ZnO composite Nano epitaxials
In solution, using Hydrothermal Growth ZnO nano-wire, obtain with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane.
In growth solution, Zn (NO3)2Concentration is 0.025~0.05mol/L, and HMTA concentration is 0.0125~0.025mol/
L, PEI concentration are 0.005mol/L, NH4OH concentration is 0.35~0.45mol/L.
Preferably, Hydrothermal Growth ZnO nano-wire is to be grown 5~10 hours in 93 DEG C of water-bath.
Step 4, complex light anode is prepared by depositing CdSe quantum dot.
Deposition of the CdSe quantum dot in composite membrane is realized using SILAR methods, is obtained for quantum dot sensitized solar-electricity
The complex light anode in pond.Specially：By step 3 with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane immerses dense successively
Spend the Se for 0.05mol/L2-Solution, deionized water, concentration are the Cd of 0.05mol/L2+Solution, another deionized water, have
TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane is in Se2-Solution and Cd2+Immersed in solution the time is identical, repeatedly after
Drying obtains complex light anode.
Preferably, Se2-Solution and Cd2+Solution concentration is 0.05mol/L；With TiO2Nanocrystalline/ZnO nano-wire is combined
The substrate of film is in Se2-Solution and Cd2+The time immersed in solution is 1min.
Embodiment 1
A kind of complex light anode for quantum dot sensitized solar cell is prepared, specific method is as follows.
The brilliant preparation of ZnO nano：First respectively by 0.82g Zn (Ac)2·2H2O and 0.49g KOH are dissolved in 42mL and 23mL
Methyl alcohol, be sufficiently stirred for rear Zn (Ac)2Precursor liquid is transferred to there-necked flask, and heating stirring fully dissolves in 60 DEG C of water-baths；Then
KOH precursor liquids are added dropwise over tiny disposable needle tubing, transparent light blue reaction solution is obtained, will be anti-after being refluxed 2 hours
The ZnO nano crystalline substance that should be obtained utilizes methyl alcohol eccentric cleaning 3-4 times, and the quantity of methyl alcohol of cleaning halves every time；Finally the ZnO of cleaning is received
Using ultrasonic disperse in ethanol, it is the ZnO nano crystalline substance colloid of 50mg/mL to obtain concentration to meter Jing.
Prepare TiO2/ ZnO nano crystalline substance mixed slurry：ZnO nano crystalline substance colloid (50mg/mL) of 1mL is measured first in 20mL
Ethanol in ultrasound dilution；Then the titanium dioxide P of 1g is weighed25Powder is put into mortar, adds the deionized water of 0.2mL to grind 1 point
Clock, is repeated 5 times, and the ZnO nano crystalline substance colloid 0.2mL for sequentially adding dilution grinds 1 minute, is repeated 15 times, and adds 0.5mL grindings
1 minute, it is repeated 5 times；Then it is transferred into the glass container of 40mL using remaining ZnO nano crystalline substance colloid, the magnetic of interruption
Power stirs with ultrasonic disperse 1 hour the terpinol for adding 4g afterwards, continues to stir and ultrasound 1 hour；Finally it is dissolved in 5.4g
0.5g ethyl cellulose mixtures in ethanol are added thereto, repeat stirring, ultrasound 1 hour, then through 24 hours stir after,
Stirred in water bath by mixture at 70 DEG C evaporates part ethanol, obtains the TiO that viscosity is applied to silk-screen printing2/ ZnO nano
Brilliant mixed slurry.
Porous TiO2The preparation of/ZnO composite Nano epitaxials：Use first and be screen printed onto with TiO2The FTO glass on barrier layer
TiO is coated on glass2/ ZnO nano crystalline substance mixed slurry once, and is placed 10 minutes in atmosphere, waits pulp flow to be put into after balancing
Heated 5 minutes in 80 DEG C of drying baker；Then the film substrate that will be cooled down uses three coating mixed slurries of the above method again,
Third time coats pure TiO using identical technique2Nanocrystalline slurry, this layer can prevent the growth of upper surface ZnO nano-wire；Finally
The substrate that three layers of wet film will be coated is put into Muffle furnace, and 450 DEG C are raised to from room temperature with 3 DEG C/min of speed, re-annealing 30min,
Obtain the porous TiO for ZnO nano-wire growth2/ ZnO composite Nano epitaxials.
The synthesis of ZnO nano-wire：Prepare 15mL Zn (NO respectively under magnetic stirring first3)2Solution and six methines four
Ammonia (HMTA) aqueous solution；Then by the Zn (NO for stirring3)2Solution lentamente pours into HMTA solution, persistently stirs 1 hour；So
Afterwards by 0.08mL polyethyleneimines (PEI) and 0.72mL NH4OH is added dropwise over mixed liquor successively, it is ensured that in growth solution, Zn
(NO3)2Concentration is 0.025mol/L, and HMTA concentration is 0.0125mol/L, and PEI concentration is 0.005mol/L, NH4OH concentration is
0.35mol/L.The PH of solution is adjusted to 9.3 using the nitric acid of 0.23mL；Last porous TiO2/ ZnO composite Nanos epitaxial is inserted
In entering the growth solution of obturator, and grown 5 hours in 93 DEG C of hydro-thermal, the TiO of acquisition2Nanocrystalline and ZnO nano-wire
Composite membrane, dries in 100 DEG C of Muffle furnaces, obtains with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane.
CdSe quantum dot is deposited：With KBH4It is reducing agent, SeO is reduced in 40mL deionized waters2Se is obtained2-Concentration is
Solution (the logical Ar or N of 0.05mol/L2Gas shielded), and by Cd (NO3)2Be dissolved in deionized water to prepare 40mL concentration is 0.05mol/
The Cd of L2+Solution, will be with TiO using SILAR methods (successive ionic layer adsorption and reaction)2Nanocrystalline/ZnO nano-wire composite membrane
Substrate immerse Se successively2-Solution 1 minute, deionized water, Cd2+Solution 1 minute, another deionized water, this process repeat 15
It is secondary；Complex light anode is obtained after drying.
Complex light anode manufactured in the present embodiment, has TiO successively from the bottom to top on electro-conductive glass2Barrier layer, TiO2Receive
Meter Jing/ZnO nano-wire composite bed and TiO2Nano-crystalline layers.Wherein, TiO2Nanocrystalline/ZnO nano-wire composite bed and TiO2It is nanocrystalline
The thickness of layer is 10 μm.
Embodiment 2
A kind of complex light anode for quantum dot sensitized solar cell is prepared, specific method is as follows.
The brilliant preparation of ZnO nano：Zinc acetate Solid solution decomposition is obtained using the method for thermal decomposition, first by Zn
(CH3COO)2·2H2O dissolvings obtain concentration and are less than 0.3Kg/L clear solutions in deionized water, and then homogeneous solution is at 100 DEG C
Moisture is evaporated, the powder that will finally obtain is annealed 1-3 hours at 270~500 DEG C, collect tiny ZnO nano crystalline flour end.Most
The brilliant ZnO nano crystalline substance colloid for utilizing ultrasonic disperse in ethanol, obtaining that concentration is 50mg/mL of ZnO nano that will be cleaned afterwards.
Prepare TiO2/ ZnO nano crystalline substance mixed slurry：ZnO nano crystalline substance colloid (50mg/mL) of 3mL is measured first in 20mL
Ethanol in ultrasound dilution；Then the titanium dioxide P of 1g is weighed25Powder is put into mortar, adds the deionized water of 0.2mL to grind 1 point
Clock, is repeated 5 times, and the ZnO nano crystalline substance colloid 0.2mL for sequentially adding dilution grinds 1 minute, is repeated 15 times, and adds 0.5mL grindings
1 minute, it is repeated 5 times；Then it is transferred into the glass container of 40mL using remaining ZnO nano crystalline substance colloid, the magnetic of interruption
Power stirs with ultrasonic disperse 1 hour the terpinol for adding 4g afterwards, continues to stir and ultrasound 1 hour；Finally it is dissolved in 5.4g
0.5g ethyl cellulose mixtures in ethanol are added thereto, repeat stirring, ultrasound 1 hour, then through 24 hours stir after,
Stirred in water bath by mixture at 70 DEG C evaporates ethanol, obtains the TiO that viscosity is applied to silk-screen printing2/ ZnO nano is brilliant mixed
Close slurry.
Porous TiO2The preparation of/ZnO composite Nano epitaxials：Use first and be screen printed onto with TiO2The FTO glass on barrier layer
TiO is coated on glass2/ ZnO nano crystalline substance mixed slurry once, and is placed 10 minutes in atmosphere, waits pulp flow to be put into after balancing
Heated 5 minutes in 80 DEG C of drying baker；Then the film substrate that will be cooled down uses the secondary coating mixed slurry of the above method again,
Third time coats pure TiO using identical technique2Nanocrystalline slurry, this layer can prevent the growth of upper surface ZnO nano-wire；Finally
The substrate that three layers of wet film will be coated is put into Muffle furnace, and 450 DEG C are raised to from room temperature with 3 DEG C/min of speed, re-annealing 30min,
Obtain the porous TiO for ZnO nano-wire growth2/ ZnO composite Nano epitaxials.
The synthesis of ZnO nano-wire：Prepare 15mL Zn (NO respectively under magnetic stirring first3)2Solution and six methines four
Ammonia (HMTA) aqueous solution；Then by the Zn (NO for stirring3)2Solution lentamente pours into HMTA solution, persistently stirs 1 hour；So
Afterwards by 0.08mL polyethyleneimines (PEI) and 0.72mL NH4OH is added dropwise over mixed liquor successively, it is ensured that in growth solution, Zn
(NO3)2Concentration is 0.038mol/L, and HMTA concentration is 0.0185mol/L, and PEI concentration is 0.055mol/L, NH4OH concentration is
0.4mol/L.The PH of solution is adjusted to 9.3 using nitric acid；Last porous TiO2/ ZnO composite Nanos epitaxial inserts obturator
Growth solution in, and in 93 DEG C of hydro-thermal grow 10 hours, obtain TiO2Nanocrystalline and ZnO nano-wire composite membrane, 100
DEG C Muffle furnace drying, obtain with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane.
CdSe quantum dot is deposited：With KBH4It is reducing agent, SeO is reduced in 40mL deionized waters2Se is obtained2-Concentration is
Solution (the logical Ar or N of 0.05mol/L2Gas shielded), and by Cd (NO3)2Be dissolved in deionized water to prepare 40mL concentration is 0.05mol/
The Cd of L2+Solution, will be with TiO using SILAR methods (successive ionic layer adsorption and reaction)2Nanocrystalline/ZnO nano-wire composite membrane
Substrate immerse Se successively2-Solution 1 minute, deionized water, Cd2+Solution 1 minute, another deionized water, this process repeat 15
It is secondary；Complex light anode is obtained after drying.
Complex light anode manufactured in the present embodiment, has TiO successively from the bottom to top on electro-conductive glass2Barrier layer, TiO2Receive
Meter Jing/ZnO nano-wire composite bed and TiO2Nano-crystalline layers.Wherein, TiO2Nanocrystalline/ZnO nano-wire composite bed and TiO2It is nanocrystalline
The thickness of layer is 12 μm.
Embodiment 3
A kind of complex light anode for quantum dot sensitized solar cell is prepared, specific method is as follows.
The brilliant preparation of ZnO nano：First respectively by 0.82g Zn (Ac)2·2H2O and 0.49g KOH are dissolved in 42mL and 23mL
Methyl alcohol, be sufficiently stirred for rear Zn (Ac)2Precursor liquid is transferred to there-necked flask, and heating stirring fully dissolves in 60 DEG C of water-baths；Then
KOH precursor liquids are added dropwise over tiny disposable needle tubing, transparent light blue reaction solution is obtained, will be anti-after being refluxed 2 hours
The ZnO nano crystalline substance that should be obtained utilizes methyl alcohol eccentric cleaning 3-4 times, and the quantity of methyl alcohol of cleaning halves every time；Finally the ZnO of cleaning is received
Using ultrasonic disperse in ethanol, it is the ZnO nano crystalline substance colloid of 50mg/mL to obtain concentration to meter Jing.
Prepare TiO2/ ZnO nano crystalline substance mixed slurry：ZnO nano crystalline substance colloid (50mg/mL) of 10mL is measured first in 20mL
Ethanol in ultrasound dilution；Then the titanium dioxide P of 1g is weighed25Powder is put into mortar, adds the deionized water of 0.2mL to grind 1 point
Clock, is repeated 5 times, and the ZnO nano crystalline substance colloid 0.2mL for sequentially adding dilution grinds 1 minute, is repeated 15 times, and adds 0.5mL grindings
1 minute, it is repeated 5 times；Then it is transferred into the glass container of 40mL using remaining ZnO nano crystalline substance colloid, the magnetic of interruption
Power stirs with ultrasonic disperse 1 hour the terpinol for adding 4g afterwards, continues to stir and ultrasound 1 hour；Finally it is dissolved in 5.4g
0.5g ethyl cellulose mixtures in ethanol are added thereto, repeat stirring, ultrasound 1 hour, then through 24 hours stir after,
Stirred in water bath by mixture at 70 DEG C evaporates ethanol, obtains the TiO that viscosity is applied to silk-screen printing2/ ZnO nano is brilliant mixed
Close slurry.
Porous TiO2The preparation of/ZnO composite Nano epitaxials：Use first and be screen printed onto with TiO2The FTO glass on barrier layer
TiO is coated on glass2/ ZnO nano crystalline substance mixed slurry once, and is placed 10 minutes in atmosphere, waits pulp flow to be put into after balancing
Heated 5 minutes in 80 DEG C of drying baker；Then the film substrate that will be cooled down uses the secondary coating mixed slurry of the above method again,
Third time coats pure TiO using identical technique2Nanocrystalline slurry, this layer can prevent the growth of upper surface ZnO nano-wire；Finally
The substrate that three layers of wet film will be coated is put into Muffle furnace, and 450 DEG C are raised to from room temperature with 3 DEG C/min of speed, re-annealing 30min,
Obtain the porous TiO for ZnO nano-wire growth2/ ZnO composite Nano epitaxials.
The synthesis of ZnO nano-wire：Prepare Zn (NO respectively under magnetic stirring first3)2Solution and the ammonia of six methine four
(HMTA) aqueous solution；Then by the Zn (NO for stirring3)2Solution lentamente pours into HMTA solution, persistently stirs 1 hour；Then
By polyethyleneimine (PEI) and NH4OH is added dropwise over mixed liquor successively, it is ensured that in growth solution, Zn (NO3)2Concentration is
0.05mol/L, HMTA concentration are 0.025mol/L, and PEI concentration is 0.055mol/L, NH4OH concentration is 0.45mol/L.Utilize
The PH of solution is adjusted to 9.4 by nitric acid；Last porous TiO2In the growth solution of/ZnO composite Nanos epitaxial insertion obturator,
And grown 10 hours in 93 DEG C of hydro-thermal, obtain TiO2Nanocrystalline and ZnO nano-wire composite membrane, in 100 DEG C of Muffle baking oven
It is dry, obtain with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane.
CdSe quantum dot is deposited：With KBH4It is reducing agent, SeO is reduced in 40mL deionized waters2Se is obtained2-Concentration is
Solution (the logical Ar or N of 0.05mol/L2Gas shielded), and by Cd (NO3)2Be dissolved in deionized water to prepare 40mL concentration is 0.05mol/
The Cd of L2+Solution, will be with TiO using SILAR methods (successive ionic layer adsorption and reaction)2Nanocrystalline/ZnO nano-wire composite membrane
Substrate immerse Se successively2-Solution 1 minute, deionized water, Cd2+Solution 1 minute, another deionized water, this process repeat 15
It is secondary；Complex light anode is obtained after drying.
Complex light anode manufactured in the present embodiment, has TiO successively from the bottom to top on electro-conductive glass2Barrier layer, TiO2Receive
Meter Jing/ZnO nano-wire composite bed and TiO2Nano-crystalline layers.Wherein, TiO2Nanocrystalline/ZnO nano-wire composite bed and TiO2It is nanocrystalline
The thickness of layer is 15 μm.
Structure and performance detection have been carried out to complex light anode of the invention, it is as a result as follows.
Can be seen that preparation technology of the invention can be completely achieved proposed composite membrane by Fig. 3-a, black line in figure
Above is TiO2It is nanocrystalline, the following is TiO2Nanocrystalline/ZnO nano-wire composite membrane, its result is consistent with Fig. 2.Fig. 3-b, 3-c
It is section SEM that nano wire hydrothermal growth was respectively 5 hours and obtained for 10 hours composite membrane, when be can be seen that in figure with growth
Between increase, length and the diameter of ZnO nano-wire increase therewith.
Be can be seen that by Fig. 4-a, 4-b, 4-c, on the whole with the increase of ZnO nano crystalline substance ratio, the original of ZnO nano-wire growth
Position increases, so as to the density for causing the ZnO nano-wire in composite membrane significantly increases；Work as TiO2：ZnO is 1：When 0.05, nanometer
The density of line be than relatively low, it is simply fragmentary to be distributed in film；Work as TiO2：ZnO is 1：When 0.25, nano wire is close each other
Weave on the spot.
The light anode of complex light anode of the invention and control group is carried out into Performance comparision, control group light anode is in this hair
The light anode that the synthesis of the ZnO nano-wire that bright complex light anode reduces step 3 on the basis of preparing is obtained, note control group is TiO2
Nanometer crystal film, experimental group is TiO2Nanocrystalline/ZnO nano-wire composite membrane.Be can be seen that in Fig. 5, when ZnO nano-wire introduces TiO2Receive
After rice epitaxial, the scattering process due to nano wire to light intensity so that composite membrane has significantly to the diffusing reflection rate of injection light
Improve, injection light is limited in film, enhances the light path in film, it is possible to decrease the light transmission loss of film, the transmitted spectrum of Fig. 6
After confirming that this result, ZnO nano-wire are introduced, the transmissivity of light reduces 10% or so.
Due to the enhancing that the ZnO nano-wire introduced in composite membrane is acted on light scattering so that light light path in light anode increases
Plus, making full use of for injection light is improved by absorption repeatedly, be can be seen that in Fig. 7, the optical absorption edge of two kinds of light anodes all exists
700nm, illustrates that two kinds of films are similar to size to CdSe quantum dot adsorbance, the scattering process due to composite membrane to light intensity, its
The absorption intensity of visible-range is greatly improved.Enhanced light absorbs are produced by exciting light absorbent in the battery
More light induced electrons, its current density for showing battery has and significantly improves, result as shown in Figure 8, current density from
7.79mA/cm2Increase to 12.53mA/cm2, improve 60.8%.Open-circuit voltage is not changed significantly, and fill factor, curve factor is small size
Reduce, possible cause is nanowire growth long so that some of photo-anode film change loosely (find to work as nanowire growth in experiment
At 15 hours, the upper strata of composite membrane is susceptible to come off when CdSe quantum dot is deposited), increased the transmission resistance of electronics.Always
For body, due to being significantly increased for current density so that the efficiency of battery increased 42.1%.
Above description of the present invention is part case study on implementation, but the invention is not limited in above-mentioned specific embodiment party
Formula.Above-mentioned specific embodiment is schematical, is not restricted.It is every to use material of the invention and method,
Do not depart from the case of present inventive concept and scope of the claimed protection, all specific expansions belong to protection scope of the present invention
Within.
Claims (8)
1. a kind of preparation method of complex light anode for quantum dot sensitized solar cell, the complex light anode includes attached
There is TiO2The electro-conductive glass on barrier layer, in TiO2On barrier layer, TiO is accompanied by from the bottom to top2Nanocrystalline/ZnO nano-wire composite bed
And TiO2Nano-crystalline layers；It is characterised in that it includes following steps：
Step 1, prepares TiO2/ ZnO nano crystalline substance mixed slurry；
ZnO nano crystalline substance is scattered in ethanol first and obtains ZnO nano crystalline substance colloid, then ZnO nano crystalline substance colloid is diluted with ethanol in proper amount；
Then by TiO2Nano powder is put into mortar, first adds water tentatively to be ground, then the ZnO nano crystalline substance colloid point that ethanol was diluted
Repeatedly add mortar to continue to grind, form suspension；Under conditions of ultrasound with stirring, successively to adding terpinol in suspension
With ethyl cellulose ethanol solution, last 70 DEG C of water-baths make ethanolic moiety volatilize, and obtain the TiO that viscosity is adapted to silk-screen printing2/
ZnO nano crystalline substance mixed slurry；
Step 2, prepares porous TiO2/ ZnO composite Nano epitaxials；
Prepared using screen printing technique, specifically implemented according to following steps：With TiO2Coated on the electro-conductive glass on barrier layer
TiO2/ ZnO nano crystalline substance mixed slurry, after being coated with TiO after slurry curing2Nanocrystalline slurry, is finally putting into Muffle furnace calcining, obtains
To with porous TiO2The substrate of/ZnO composite Nano epitaxials；
Step 3, prepares TiO2Nanocrystalline/ZnO nano-wire composite bed；
First by Zn (NO3)2The aqueous solution add the ammonia spirit of six methine four, then sequentially add aq. polyethyleneimine and
NH4The OH aqueous solution, and adjusted to 9.2-9.4 pH value of solution with nitric acid, obtain ZnO nano-wire growth solution；Again by the attached of step 2
There is porous TiO2In the electro-conductive glass insertion growth solution of/ZnO composite Nano epitaxials, using Hydrothermal Growth ZnO nano-wire, obtain
To with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane；
Step 4, prepares complex light anode；
Deposition of the CdSe quantum dot in composite membrane is realized using SILAR methods, is obtained for quantum dot sensitized solar cell
Complex light anode.
2. the preparation method of complex light anode according to claim 1, it is characterised in that TiO described in step 12Nano powder,
The mass ratio of ZnO nano crystalline substance, terpinol and ethyl cellulose is 1:(0.05-0.5)：4：0.5.
3. the preparation method of complex light anode according to claim 1, it is characterised in that TiO described in step 22/ ZnO nano
Point of 2-3 time coating of brilliant mixed slurry, stands after coating every time, waits pulp flow to be put into after balancing in baking oven and is coated with after solidification
Next time.
4. the preparation method of complex light anode according to claim 1, it is characterised in that calcining described in step 2 is specially：
450 DEG C, re-annealing 30min are first raised to from room temperature with the speed of 3 DEG C/min.
5. the preparation method of complex light anode according to claim 1, it is characterised in that in growth solution described in step 3,
Zn(NO3)2Concentration is 0.025~0.05mol/L, and the ammonia density of six methine four is 0.0125~0.025mol/L, polyethyleneimine
Concentration is 0.005mol/L, NH4OH concentration is 0.35~0.45mol/L.
6. the preparation method of complex light anode according to claim 1, it is characterised in that Hydrothermal Growth described in step 3
ZnO nano-wire is specially：Grown 5~10 hours in 93 DEG C of water-bath.
7. the preparation method of complex light anode according to claim 1, it is characterised in that SILAR methods are specific described in step 4
For：By step 3 with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane immerses Se successively2-Solution, deionized water, Cd2+
Solution, another deionized water, repeatedly drying obtains complex light anode afterwards；Wherein, Se2-Solution and Cd2+Solution concentration phase
Deng with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane is in Se2-Solution and Cd2+The time immersed in solution is identical.
8. the preparation method of complex light anode according to claim 7, it is characterised in that the Se2-Solution and Cd2+Solution
Concentration is 0.05mol/L；It is described with TiO2The substrate of nanocrystalline/ZnO nano-wire composite membrane is in the Se2-Solution and Cd2+
The time immersed in solution is 1min.
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