CN103466696B - Preparation method and application of high dispersity TiO2 nanocrystalline - Google Patents
Preparation method and application of high dispersity TiO2 nanocrystalline Download PDFInfo
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- CN103466696B CN103466696B CN201310364469.9A CN201310364469A CN103466696B CN 103466696 B CN103466696 B CN 103466696B CN 201310364469 A CN201310364469 A CN 201310364469A CN 103466696 B CN103466696 B CN 103466696B
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Abstract
The invention discloses a preparation method and an application of a high dispersity TiO2 nanocrystalline, and belongs to the field of organic polymer thin film solar cell preparation. The preparation method comprises the following steps: taking cheap tetrabutyl titanate as a raw material, adopting n-butyl alcohol as a stabilizing agent, adopting organic acid and inorganic acid as composite catalysts, and adopting a sol-gel composition method to compound the TiO2 nanocrystalline. The compounded nanocrystalline is high in crystallinity, good in dispersity and centralized in particle size distribution. The application of the high dispersity TiO2 nanocrystalline is that the TiO2 nanocrystalline is used to be taken as a buffer layer to modify a negative pole at the top. The photoelectric conversion efficiency of an organic solar cell device is improved, and the problem that an organic polymer solar cell can quickly decay in air is solved. The method and the application are simple in technology, and practical, and facilitate the industrialized production.
Description
Technical field
The invention discloses a kind of polymolecularity TiO
2nanocrystalline preparation method and application; Be specifically related to a kind of novel synthesis TiO
2application in nanocrystalline method and organic polymer thin film solar cell thereof.Belong to organic polymer thin film solar cell preparation field.
Background technology
Energy problem is the significant problem affecting human survival and Sustainable development.Sun power is ideal substitute energy.How to make full use of sun power, become the research topic of various countries' study emphasis, and achieved impressive progress.Organic polymer solar cell due to low cost, light quality, and can combine with flexible substrate, can by printing, the technique such as blade coating and rotary coating big area film forming and receiving much concern.But organic polymer solar cell efficiency is still in lower level, simultaneously because organic polymer has very strong susceptibility to oxygen in air and moisture content, its efficiency can decay rapidly in atmosphere, makes its preparation condition and working conditions very limited.These two shortcomings are unfavorable for scale operation and the application of organic solar batteries.Many research in recent years shows: buffer layer has following function: 1, to current carrier Selective absorber, improves the selection ability of the corresponding current carrier of electrode pair; 2, stop the phase mutual diffusion between electrode with active coating molecule, reduce leakage current and reduce defect state existence; 3, adopt the middle layer with excellent optical property can also play optics buffer action, incident light can be redistributed, active coating photoabsorption is strengthened; 4, the ohmic contact between electrode and active coating is realized; 5, active coating can be completely cut off to a certain extent to contact with air, improve its air stability.Therefore, electrode modification becomes the effective means improving battery efficiency and air stability.
TiO
xsystem possesses fine optical property and electric property, be referred in organic solar batteries, confirmation is obtained in lifting battery efficiency and stability, such as J.Hegger adopts titanium isopropylate to prepare TiOx, modify top cathode with it and will gather 3-hexyl thiophene phenol: [6,6]-phenyl C61 methyl-butyrate (i.e. P3HT:PC
61bM) bulk heterojunction solar battery efficiency rises to 5%, and device lifetime promotes greatly.But Dong Hwan Wang points out that TiOx has temperature instability, is usually unfavorable for post growth annealing time prepared by device.Such TiO
2nanocrystallinely become optimal selection, but TiO
2no matter nanocrystalline be Anatase or Rutile Type, its synthesis temperature is generally greater than 450 DEG C, be difficult to be applied to organic polymer thin film area of solar cell, secondly as buffer layer, the thickness general requirement of film is within tens nanometers, so the particle diameter of nanoparticle generally needs to control at below 10nm, so little nanometer particle size both needed well-crystallized, and dispersiveness will be got well, and synthesis exists great difficulty.
In prior art, sol-gel method and hydrothermal synthesis method are the common methods of synthesizing nano-particle, and both particle prepared all possesses that purity is high, the advantage of narrow diameter distribution.Conventional sol gel method forms precursor sol at low temperatures, needs could form crystal through high temperature sintering, but high temperature sintering is bound to cause serious reunion; And hydrothermal method degree of crystallinity is better, but technique is comparatively complicated, and it is comparatively large that synthesis condition controls difficulty, and High Temperature High Pressure must cause the carbonization of reunion and organic solvent.So the degree of crystallinity adopting conventional sol-gel method and hydrothermal synthesis method to be difficult to obtain meeting the requirement of organic polymer thin film area of solar cell and dispersiveness.Some scholars are at improvement collosol and gel and hydrothermal synthesis method synthesis TiO
2nanocrystallinely do a few thing to be applied to organic polymer thin film area of solar cell, propose two kinds and think now effective synthesis way: non-hydrolytic sol-gel and modified version Hydrothermal Synthesis, but effect has not been very desirable always.As John Wang has synthesized the TiO of the pure Anatase of 5nm at the method for employing non-hydrolytic in 2007 utilizes titanium tetrachloride for presoma 90 DEG C
2nanocrystalline (TiO2NPS).From XRD figure spectrum, its degree of crystallinity is general, but needs the unreacted impurity of centrifugal rear removing and solvent in the method preparation process, then needs just can be applied in ultrasonic disperse to solvent.This is also that present Application and preparation is in the TiO of organic polymer thin film solar cell
2nanocrystalline the most frequently used way.The people such as YangY adopt the TiO of the method synthesis for 2009
2be applied in organic polymer thin film solar cell, show that particle is easy to be distributed in spirituous solution in research, but in the film of preparation, it is reunited comparatively serious (agglomerate size particle dia is about 50nm), peak crystallization broadening, the device efficiency of preparation is on the low side.Then, the 4-9nmTiO of the people such as Teddy Salim in 2011 the dispersed good pure Anatase that adopted the method for Hydrothermal Synthesis to prepare
2nanocrystalline dispersion soln, avoid centrifugal step, its degree of crystallinity better and be pure Anatase, dispersiveness is improved, but in the film of preparation, still there is the reunion of 100nm size, device efficiency up to 3.94%, but due to particle aggregation problem device air stability poor, after 3 hours, device efficiency just drops to less than 50% originally.In view of the complexity of hydrothermal process, low temperature sol-gel is adopted to prepare small-particle TiO
2nanocrystalline, and be applied to organic polymer solar cell field and seem and mean a great.
Summary of the invention
In order to overcome prior art at a lower temperature, be difficult to the TiO preparing polymolecularity
2nanocrystalline grade is not enough, the object of this invention is to provide one at a lower temperature, adopts sol-gel method to prepare polymolecularity TiO
2nanocrystalline and this polymolecularity TiO
2nanocrystalline application.
The present invention take tetrabutyl titanate as raw material, and propyl carbinol is stablizer, and strong acid+organic acid is catalyzer synthesis TiO
2nanocrystalline, concrete steps are as follows:
The preparation of step one frozen glue
The pH value of stablizer is adjusted to 0.1-2, in 30-60 DEG C, in stablizer, adds tetrabutyl titanate, after stirring, add water hydrolysis, stirs, make tetrabutyl titanate hydrolysis, obtain frozen glue; Described stablizer is propyl carbinol, and the add-on of tetrabutyl titanate and the volume ratio of stablizer are 1:2-3; The speed that adds of water is 0.12-1.2mL/min;
The preparation of step 2 colloidal sol
At 30-60 DEG C, it is 0.36-0.75mol/L that step one gained frozen glue is diluted to Ti concentration, is stirred to transparent, obtains colloidal sol; Or be stirred to transparent, leave standstill, separating stable agent, obtains colloidal sol;
Step 3 polymolecularity TiO
2nanocrystalline preparation
Step 2 gained colloidal sol is heated to 60 DEG C-100 DEG C, stirring reaction 4-48 hour; Obtain polymolecularity TiO
2nanocrystalline, the speed of stirring is 400-1000rpm.
A kind of polymolecularity TiO of the present invention
2in nanocrystalline preparation method, the pH value of stablizer adopts acid solution regulation and control, described acid solution by strong acid and organic acid by volume 1:1.5-3.5 form.
A kind of polymolecularity TiO of the present invention
2in nanocrystalline preparation method, strong acid is selected from the one in nitric acid, hydrochloric acid, sulfuric acid; Described organic acid is acetic acid or citric acid.
A kind of polymolecularity TiO of the present invention
2nanocrystalline preparation method, in step 2, frozen glue dilutes thinner used and is selected from water, ethylene glycol monomethyl ether, Virahol, ethanol or methyl alcohol a kind of.
A kind of polymolecularity TiO of the present invention
2nanocrystalline preparation method, in step 2, described leave standstill, separating stable agent be by stir after mixture leave standstill, if there is larger difference (as adopted water as thinner in stablizer and Diluent Polarity, then need to carry out to leave standstill, the operation of separating stable agent), occur not dissolving each other, make colloidal sol major part be present in thinner, there is layering, now need with separating funnel separating stable agent and colloidal sol; Gained stablizer continues to recycle.
A kind of polymolecularity TiO of the present invention
2nanocrystalline preparation method, in step 2, the time of stirring is 4-48 hour, and the speed of stirring is 400-1000rpm.
A kind of polymolecularity TiO of the present invention
2nanocrystalline application is by polymolecularity TiO
2the nanocrystalline cathode buffer layer as organic polymer solar cell device.
A kind of polymolecularity TiO of the present invention
2nanocrystalline application, the thickness of described buffer layer is 10-100nm.
A kind of polymolecularity TiO of the present invention
2nanocrystalline application, described organic polymer solar cell device is eurymeric structure, and described eurymeric structure is respectively anode (1), anode buffer layer (2), organic active layer (3), cathode buffer layer (4), negative electrode (5) from bottom to up.Organic polymer solar cell device of the present invention is except TiO
2outward, other structure is identical with conventional eurymeric polymer solar cell device structure, adds TiO for nanocrystalline buffer layer (4)
2nanocrystalline buffer layer can intrude into active coating and causes the deterioration of active coating performance by the oxygen/water effectively completely cut off in electrode atom and air, reduces interface catagen speed, the air stability of boost device.
A kind of polymolecularity TiO of the present invention
2nanocrystalline application, by described polymolecularity TiO
2nanocrystalline dilution directly uses afterwards, and thinner is selected from the one in methyl alcohol, ethanol, propyl alcohol, ether, chlorobenzene, chloroform; The consumption of thinner is 9-99 times of sol volume.During actually operating, in order to make step 4 polymolecularity TiO
2nanocrystalline through dilution after be directly used in organic polymer solar cell, generally according to the principle that thinner used and active coating soak mutually, choose thinner
A kind of polymolecularity TiO of the present invention
2nanocrystalline application, described anode (1) can be the one in the transparency conductive electrodes such as tin indium oxide (ITO), fluorine-doped tin oxide (FTO), nano silver wire, nanowires of gold.A kind of polymolecularity TiO of the present invention
2nanocrystalline application, described negative electrode (5) is aluminium (Al), gold (Au), silver (Ag), the one in the good conductor metals such as copper (Cu).
A kind of polymolecularity TiO of the present invention
2nanocrystalline application, the material of described anode buffer layer (2) is P type polymer poly (3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (EDOT:PSS) and metal oxide molybdenum (MoOx), Tungsten oxide 99.999 (WO
3), one in nickel oxide (NiOx).
A kind of polymolecularity TiO of the present invention
2nanocrystalline application, the material of described active coating (3) is the blended layer of a kind of donor material and the mixing of a kind of acceptor material, donor material is poly-3-hexyl thiophene phenol (P3HT), poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-1, 4-phenylene ethylene supports] (MEH-PPV), poly-[[9-(1-octyl group nonyl)-9H-carbazole-2, 7-bis-base]-2, 5-thiophene two base-2, 1, 3-diazosulfide-4, 7-bis-base-2, 5-thiophene two base] (PCDTBT), poly-[[4, two (2-ethylhexyl) the oxygen base of 8-] benzo [1, 2-b:4, 5-b '] two thiophenes-2, 6-substituting group] [the fluoro-2-of 3-[(2-ethylhexyl) carbonyl] thieno-[3, 4-b] thiophene two base]] (PTB7).Electron acceptor material is [6,6]-phenyl C61 methyl-butyrate layer (PC
61cM), [6,6]-phenyl C71 methyl-butyrate (PC
70bM), two addition C60 derivative (the soccerballene IC of indenes
60and two addition C70 derivative (the soccerballene IC of indenes BA)
70bA).Active layer thickness is greater than 50nm, is less than 300nm.
Principle and advantage
Principle of the present invention: the present invention is through repeatedly testing, adopt simple collosol and gel route, successfully avoid in non-hydrolytic sol-gel method the additional reunion of particle that steps such as needing centrifugal-dispersion causes, it also avoid the micelle reunion that High Temperature High Pressure in Hydrothermal Synthesis causes.Utilize tetrabutyl titanate for precursor, propyl carbinol is stablizer, strong acid+organic acid is composite catalyst, tetrabutyl titanate hydrolysis is made to obtain frozen glue, form a series of nucleus and cross-linked network, again by stirring the cross-linking system interrupting frozen glue, again form stable sol, through the effect of relatively-high temperature (60 DEG C-100 DEG C) and synthetic system environment, especially the effect of thinner, catalyzer, under Ostwald slaking machining function, nucleus selectivity is grown up, for growing up to pure anatase octahedrite, and the TiO that grain-size is homogeneous
2nanocrystallinely provide guarantee, avoiding problems conventional sol gel method and prepare TiO
2time nanocrystalline, must calcine and just can obtain TiO
2nanocrystalline.Seldom partial cross-linked its formation colloidal sol network that allows simultaneously existed in system, increases dispersion of particles characteristic.Adopt the TiO of the method synthesis
2nanocrystalline colloidal sol is directly used in film forming on active coating, the organic solvent diluting of dissimilar polarity can be selected according to the polarity of active coating film, colloidal sol after dilution can be directly used in film, thus avoids other technological processs such as centrifugal removal of impurities, can not introduce additional reunion factor and impurity.After film forming, its dispersiveness there will not be larger difference.Do not need high temperature sintering and water-heat process, dispersiveness so as well provides guarantee.Adopt the TiO of the method synthesis
2nanocrystalline, crystal type is excellent, good dispersity.According to active coating surface properties, select organic solvent diluting TiO wetting very easily with it
2nanoparticle sol, simultaneously colloidal sol is compared general solution and is had better film-forming properties, adds that good dispersiveness itself can prepare homogeneous film on active coating.After film forming, nanoparticle uniform spreading is on active coating, and anneal strengthens the sticking power between nanoparticle and active coating, has sloughed the hydroxyl that may cause nanocrystalline reunion, so subsequent handling can not cause TiO simultaneously
2secondary agglomeration, the effective like this roughness improving active coating film, also improves the contact between organic layer and negative electrode simultaneously, can effective reduced series resistance.In addition TiO
2be a kind of N-type semiconductor material of broad stopband, effectively can extract the electronics that in active coating, exciton dissociation produces, blocking hole, plays the function of effective selective extraction electronics.TiO
2nano-crystalline layers also has good optical effect, can strengthen the reallocation of incident light in active coating, improves efficiency of light absorption, promotes the opto-electronic conversion performance of battery.The present invention adopts polymer solar battery eurymeric structure, by this TiO
2nano-crystal film is placed between top cathode and active coating and can intrudes into active coating and cause the deterioration of active coating performance by the oxygen/water effectively completely cut off in electrode atom and air, reduces interface catagen speed, the air stability of the fine boost device of energy.
The beneficial effect that the present invention obtains:
The TiO that patent system of the present invention is standby
2nanocrystalline is pure Anatase, and it is of a size of 5nm-10nm.Possess good dispersiveness, centralized particle diameter, maximum reunion size of particles is at about 20nm.Compared with the eurymeric organic polymer solar cell not having top cathode buffer layer, there is TiO
2the device of nanocrystalline buffer layer, its photoelectric transformation efficiency can promote more than 30%, device efficiency half life promote more than 200 hours.
Accompanying drawing explanation
Accompanying drawing 1 is prepared TiO in embodiment 1
2nanocrystalline X-ray diffractogram
Accompanying drawing 2 is prepared TiO in embodiment 1
2nanocrystalline TEM figure
Accompanying drawing 3 is prepared TiO in embodiment 1
2nanocrystalline particle diameter distribution profile
Accompanying drawing 4 organic polymer solar cell device architecture schematic diagram
Accompanying drawing 5(a) be P3HT:PC prepared in embodiment 1
61the AFM figure of BM; Accompanying drawing 5(b) be P3HT:PC prepared in embodiment 1
61bM/TiO
2nanocrystalline AFM figure
Under accompanying drawing 6 illumination, ITO/PEDOT:PSS/P3HT:PC prepared by embodiment 1
61bM/TiO
2the I-V curve of nanocrystalline/Al device and Comparative Examples I TO/PEDOT:PSS/P3HT:PC
61the I-V curve of BM/Al device;
The ITO/PEDOT:PSS/P3HT:PC of accompanying drawing 7 prepared by embodiment 1
61bM/TiO
2the air stability detection curve of nanocrystalline/Al device and the ITO/PEDOT:PSS/P3HT:PC prepared by comparative example
61the air stability detection curve of BM/Al device.
As can be seen from Figure 1 the nanoparticle synthesized is pure Anatase, well-crystallized.
As can be seen from Figure 2 synthesized nanocrystalline grain size is 5nm-10nm, better dispersed.
The distribution of this nano particle diameter is concentrated as can be seen from Figure 3, good dispersity.
As shown in Figure 4, eurymeric organic polymer solar cell structure each several part name is called: 1 anode, 2 anode buffer layers, 3 organic active layers, 4TiO
2nanocrystalline buffer layer, 5 negative electrodes.
Fig. 5 (a) is P3HT:PC
61bM active coating surface topography, Fig. 5 (b) is at P3HT:PC
61bM surface coverage one deck TiO
2aFM pattern after nanocrystalline, AFM figure can learn, spin coating TiO
2nanocrystalline rear film surfaceness is slightly improved.Film formed by nanoparticle is even, does not have serious agglomeration particle.
Fig. 6 is at 100mW/cm
2xenon light shining under the I-V curve that records, digital sourcemeter is KEITHLEY2400.Curve 1 is not for having TiO
2the device I-V curve of nanocrystalline buffer layer, the ITO/PEDOT:PSS/P3HT:PC namely prepared by comparative example
61the I-V curve of BM/Al device; , curve 2 is for the addition of TiO
2the I-V curve of the device of nanocrystalline buffer layer, the ITO/PEDOT:PSS/P3HT:PC namely prepared by embodiment 1
61bM/TiO
2the I-V curve of nanocrystalline/Al device.Add TiO as can be seen from Fig.
2the nanocrystalline short-circuit current significantly improving device, promotes ratio and reaches 30%.
The buffer layer device of Fig. 7 prepared by embodiment 1 and the buffer layer device prepared by comparative example have carried out the test curve figure of the life test of 200 hours in atmosphere.Curve 1 is not for having TiO
2the efficiency extinction curve of the efficiency extinction curve of nanocrystalline buffer layer device and the buffer layer device prepared by comparative example, curve 2 is for the addition of TiO
2the efficiency extinction curve of the efficiency extinction curve of the device of nanocrystalline buffer layer and the buffer layer device prepared by embodiment 1, correlation curve 1,2 can be found out, adopts TiO
2layer device place 200 hours in atmosphere after, its photoelectric transformation efficiency still remains on about 75% of originally efficiency, and comparative example device efficiency only just for one day in atmosphere, its efficiency have dropped half, after 200 hours, its efficiency has only had about 15 % of original efficiency.
Embodiment
Comparative example
In order to the TiO that patent of the present invention is synthesized is described
2nano application is to the advantage of organic polymer thin film area of solar cell, and prepare its parametric device according to traditional organic polymer thin film solar cell device preparation technology, concrete implementation step is as follows:
1) ITO business bought successively at acetone, liquid detergent, deionized water, ultrasonic cleaning in Virahol, dries up with nitrogen after cleaning, puts into culture dish for subsequent use after ozonize 10-30min;
2) PEDOT:PSS is adopted spin coating process film forming on ITO, thickness is about 30-40nm, and in thermal station, 120-150 DEG C of anneal, proceeds to (N in glove box
2under atmosphere);
3) by the P3HT:PC of 27mg/mL
61bM(1:0.8-1:1) mixing solutions is spun on PEDOT:PSS rete with the speed of 1Krpm, adopts 50-80 DEG C to toast 10min after spin coating;
4) device prepared is moved in vacuum evaporation instrument, vacuum is evacuated to 1 × 10
-4~ 8 × 10
-4below Pa, adopts the mask plate of strip with good conducting metals such as thick bar shaped Al or Ag of the speed evaporation 100nm of 0.1-0.6nm/S.Cell area is 0.12cm
2.
5) device is moved in glove box again, keep oxygen water-content all at below 1ppm, device is placed in thermal station at 150 DEG C of annealing 10min.
Embodiment 1
TiO of the present invention
2the specific examples of NPS synthesis and raising OPV device efficiency and stability, its concrete steps are as follows:
1) 50mL propyl carbinol and 1.6mL nitric acid are mixed in wide mouthed Erlenmeyer bottle, fully stir 10min, add 5mL acetic acid simultaneously, evenly to be mixed, now the pH value of system is 0.2, and this system is heated to 40 DEG C;
2) in above-mentioned solution, slowly drip 24mL tetrabutyl titanate, and stir 40min at 40 DEG C of temperature;
3) drip deionized water 8mL with 0.02mL/S speed to solution in B, after its hydrolysis forms frozen glue, after add 100mL deionized water, continue stirrings 24 hours at 40 DEG C, obtain vitreosol;
4) colloidal sol is heated to 80 DEG C of violent stirring 7 hours, obtains polymolecularity TiO
2nanocrystalline;
5) by above-mentioned polymolecularity TiO
2the nanocrystalline colloidal sol alcohol of 50 times of sol volume dilutes, stand-by.
6) ITO business bought successively at acetone, liquid detergent, deionized water, ultrasonic cleaning in Virahol, dries up with nitrogen after cleaning, puts into culture dish for subsequent use after ozonize 20min;
7) PEDOT:PSS is adopted spin coating process film forming on ITO, thickness is about 30-40nm, and in thermal station, 140 DEG C of anneal, proceed to (N in glove box
2under atmosphere);
8) by the P3HT:PC of 27mg/mL
61bM(1:0.8) mixing solutions is spun on PEDOT:PSS rete with the speed of 1Krpm, adopts 70 DEG C of baking 10min after spin coating;
9) TiO after alcohol being diluted
2nanocrystalline colloidal sol is spun on P3HT:PC with 1-5Krpm speed
61on BM active coating.
10) device prepared is moved in vacuum evaporation instrument, vacuum is evacuated to 6 × 10
-4below Pa, adopts the mask plate of strip with good conducting metals such as thick bar shaped Al or Ag of the speed evaporation 100nm of 0.4nm/S.Cell area is 0.12cm
2.
11) device is moved in glove box again, keep oxygen water-content all at below 1ppm, device is placed in thermal station at 150 DEG C of annealing 10min.
TiO prepared by the present embodiment
2the parameter such as nanocrystalline structure, performance is embodied respectively in accompanying drawing 1-7, describes in detail below in conjunction with accompanying drawing:
Fig. 1 is synthesized TiO
2nanocrystalline X-ray diffractogram.The nanoparticle synthesized as can be seen from Fig. is pure Anatase, well-crystallized.
Fig. 2 is synthesized TiO
2nanocrystalline TEM figure.Nanocrystalline grain size is 5nm-10nm, better dispersed.
Fig. 3 is TiO
2nanocrystalline diameter of nano particles distribution plan, the TiO of present method synthesis as can be seen from Fig.
2nPS size distribution is placed in the middle, does not have serious reunion to occur.Be applicable to the ultra-thin TiO of preparation
2thin film layer.
Fig. 4 is organic polymer solar cell device architecture schematic diagram, and 1 is ITO transparency conducting layer, and 2 is PEDOT:PSS thin film layer, and 3 is P3HT:PC
61the blended active coating of BM, 4TiO
2nanocrystalline buffer layer, 5 is bar shaped aluminium electrode
Fig. 5 is (a) P3HT:PC
61bM and (b) P3HT:PC
61bM/TiO
2nanocrystalline AFM figure, nano particle covers P3HT:PC uniformly as can be seen from Fig.
61bM film top layer, reduces the roughness on active coating surface slightly.RMS9.1 is reduced to from RMS9.81.
Fig. 6 is simulated solar light source is AM1.5, and light intensity is 100mW/cm2, and under illumination, structure is ITO/PEDOT:PSS/P3HT:PC
61bM/Al device and structure are ITO/PEDOT:PSS/P3HT:PC
61bM/TiO
2the J-V curve of nanocrystalline/Al, its specific performance parameter is as shown in table 1 below.
Table 1 comparative device and TiO
2nanocrystalline buffer layer battery performance parameter
Fig. 7 is ITO/PEDOT:PSS/P3HT:PC
61bM/Al and device and structure are ITO/PEDOT:PSS/P3HT:PC
61bM/TiO
2nanocrystalline/Al is placed on the beta stability line in air ambient, when having TiO after 200h
2the device efficiency of nano-crystalline layers also remains on about 75% of original efficiency, but does not have TiO
2the device efficiency of NPS layer drops to original 15% through 200h.So TiO
2nano-crystalline layers largely improves the air stability of device.
Embodiment 2
1) 20mL propyl carbinol and 0.1mL nitric acid are mixed in wide mouthed Erlenmeyer bottle, fully stir 10min, add 2mL acetic acid simultaneously, evenly to be mixed, now the pH value of system is 1, and this system is heated to 30 DEG C;
2) in above-mentioned solution, slowly drip 10mL tetrabutyl titanate, and stir 30min at 30 DEG C of temperature;
3) drip deionized water 3mL with 0.002mL/S speed to solution in B, after its hydrolysis forms frozen glue, add 100mL Virahol, continue stirring 4 hours at 40 DEG C, obtain vitreosol;
4) colloidal sol is heated to 80 DEG C of violent stirring 3 hours; Obtain polymolecularity TiO
2nanocrystalline colloidal sol;
5) by above-mentioned polymolecularity TiO
2the nanocrystalline colloidal sol alcohol of 10 times of sol volume dilutes, stand-by.
6) ITO business bought successively at acetone, liquid detergent, deionized water, ultrasonic cleaning in Virahol, dries up with nitrogen after cleaning, puts into culture dish for subsequent use after ozonize 10min;
7) PEDOT:PSS is adopted spin coating process film forming on ITO, thickness is about 30-40nm, and in thermal station, 120 DEG C of anneal, proceed to (N in glove box
2under atmosphere);
8) by the PTB7:PC of 25mg/mL
71bM (1:1.5) mixing solutions is spun on PEDOT:PSS rete with the speed of 1Krpm, adopts 50 DEG C of baking 10min after spin coating;
9) TiO after alcohol being diluted
2nanocrystalline colloidal sol is spun on PTB7:PC71BM active coating with 1Krpm speed.
10) device prepared is moved in vacuum evaporation instrument, vacuum is evacuated to 1 × 10
-4below Pa, adopts the mask plate of strip with good conducting metals such as thick bar shaped Al or Ag of the speed evaporation 100nm of 0.1nm/S.Cell area is 0.12cm
2.
Embodiment 3
1) 60mL propyl carbinol and 1mL nitric acid are mixed in wide mouthed Erlenmeyer bottle, fully stir 10min, add 6mL citric acid simultaneously, evenly to be mixed, now the pH value of system is 0.4, and this system is heated to 60 DEG C;
2) in above-mentioned solution, slowly drip 24mL tetrabutyl titanate, and stir 60min at 60 DEG C of temperature;
3) drip deionized water 10mL with 0.02mL/S speed to solution in B, after its hydrolysis forms frozen glue, add 100mL ethanol, continue stirring 48 hours at 40 DEG C, obtain vitreosol; ;
4) colloidal sol is heated to 100 DEG C of violent stirring 8 hours, obtains polymolecularity TiO
2nanocrystalline colloidal sol;
5) by above-mentioned polymolecularity TiO
2the nanocrystalline colloidal sol alcohol of 98 times of sol volume dilutes, stand-by.
6) ITO business bought successively at acetone, liquid detergent, deionized water, ultrasonic cleaning in Virahol, dries up with nitrogen after cleaning, puts into culture dish for subsequent use after ozonize 30min;
7) PEDOT:PSS is adopted spin coating process film forming on ITO, thickness is about 30-40nm, and in thermal station, 150 DEG C of anneal, proceed to (N in glove box
2under atmosphere);
8) by the PCDTBT:PC of 25mg/mL
71bM (1:4) mixing solutions is spun on PEDOT:PSS rete with the speed of 1Krpm, adopts 80 DEG C of baking 10min after spin coating;
9) TiO after alcohol being diluted
2nanocrystalline colloidal sol is spun on PTB7:PC with 5Krpm speed
71on BM active coating.
10) device prepared is moved in vacuum evaporation instrument, vacuum is evacuated to 8 × 10
-4below Pa, adopts the mask plate of strip with good conducting metals such as thick bar shaped Al or Ag of the speed evaporation 100nm of 0.6nm/S.Cell area is 0.12cm
2.
Claims (4)
1. a polymolecularity TiO
2nanocrystalline preparation method, is characterized in that comprising the steps:
The preparation of step one frozen glue
The pH value of stablizer is adjusted to 0.1-2, in 30-60 DEG C, in stablizer, adds tetrabutyl titanate, stir
Mix evenly, add water and stir, making tetrabutyl titanate hydrolysis, obtaining frozen glue; Described stablizer is propyl carbinol, and the add-on of tetrabutyl titanate and the volume ratio of stablizer are 1:2-3; The speed that adds of water is 0.12-1.2mL/min; The pH value of stablizer adopts acid solution regulation and control, described acid solution by strong acid and organic acid by volume 1:1.5-3.5 form;
The preparation of step 2 colloidal sol
It is 0.36-0.75mol/L that step one gained frozen glue is diluted to Ti concentration, at 30-60 DEG C, is stirred to transparent, obtains colloidal sol; Or be stirred to transparent, leave standstill, separating stable agent, obtains colloidal sol;
Step 3 polymolecularity TiO
2the preparation of nanocrystalline colloidal sol
Step 2 gained colloidal sol is heated to 60 DEG C-100 DEG C, stirs 4-48 hour with 400-1000 rpm speed, be obtained by reacting polymolecularity TiO
2nanocrystalline colloidal sol.
2. a kind of polymolecularity TiO according to claim 1
2nanocrystalline preparation method, is characterized in that: described strong acid is selected from the one in nitric acid, hydrochloric acid, sulfuric acid; Described organic acid is acetic acid or citric acid.
3. a kind of polymolecularity TiO according to claim 1
2nanocrystalline preparation method, is characterized in that: in step 2, and frozen glue dilution selects the one in water, ethylene glycol monomethyl ether, Virahol, ethanol, methyl alcohol to dilute as thinner.
4. a kind of polymolecularity TiO according to claim 3
2nanocrystalline preparation method, is characterized in that: in step 2, and stirring velocity is 400-1000 rpm, and churning time is 4-48 hour.
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| CN103818953B (en) * | 2014-01-28 | 2015-07-08 | 国家纳米科学中心 | Method for preparing micro-nano-TiO2 spherical particles |
| CN104103761B (en) * | 2014-06-27 | 2016-08-24 | 中南大学 | The TiO that a kind of non-annealing processes2the preparation method and application of cushion |
| CN105280818B (en) * | 2015-03-20 | 2017-10-17 | 中南大学 | A kind of planar heterojunction perovskite solar cell of stabilization and preparation method thereof |
| TWI629810B (en) * | 2015-10-20 | 2018-07-11 | 行政院原子能委員會核能研究所 | Method for improving mass-production yield of large-area organic solar cells |
| CN109133164A (en) * | 2018-11-15 | 2019-01-04 | 湖北天瓷电子材料有限公司 | A kind of high dispersiveness spherical titanium dioxide process |
| CN109456178B (en) * | 2018-11-21 | 2021-03-23 | 常州大学 | Synthesis of high-content fatty acid monoglyceride and co-production of nano SiO2Method (2) |
| CN109502637A (en) * | 2018-11-26 | 2019-03-22 | 湖北天瓷电子材料有限公司 | A kind of method that Hydrolyze method prepares high-purity nm grade titanium dioxide |
| CN110090571A (en) * | 2019-04-01 | 2019-08-06 | 江苏奥净嘉环保科技有限公司 | A kind of preparation method of nano titanium oxide dispersion |
| CN113213533A (en) * | 2021-06-11 | 2021-08-06 | 辽宁石油化工大学 | TiO with polyhedral structure2Preparation method of nano material |
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