CN104183704B - A kind of preparation method of quantum dot sensitization type perovskite solaode altogether - Google Patents
A kind of preparation method of quantum dot sensitization type perovskite solaode altogether Download PDFInfo
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Abstract
The preparation method of a kind of quantum dot sensitization type perovskite solaode altogether, comprises the following steps: (1) prepares TiO2Light anode；(2) quantum dot sensitized TiO is prepared2Light anode；(3) methylamine lead iodine solution is prepared；(4) TiO of Ca-Ti ore type methylamine lead iodine and quantum dot sensitization altogether2Light anode；(5) hole transmission layer is prepared；(6) assembling of quantum dot sensitization type perovskite solaode altogether.The method of the quantum dot of present invention sensitization type perovskite solaode altogether utilizes the transmutability of quantum dot light absorption range, can strengthen and expand the absorbing ability of perovskite solaode thus improve the electricity conversion of device.
Description
Technical field
The present invention relates to a kind of method preparing perovskite solaode, especially relate to the preparation method of a kind of quantum dot sensitization type perovskite solaode altogether.
Background technology
In recent years, the research of field of photoelectric devices achieves huge progress, is increasingly becoming one of research field of most strategic importance in this century.In this area, owing to low cost, technique are simple and environmental friendliness, nano-crystalline thin film solar cell becomes the study hotspot of field of photoelectric devices.Wherein, inorganic/organic hybrid perovskite solaode is the another novel nano crystal thin-film solar cell with unique photoelectric properties in addition to dye sensitization, quantum dot sensitized solaode, organic solar batteries, and it all demonstrates big advantage at the aspect such as electricity conversion, cost.2006, with Ca-Ti ore type Organic leadP halogenide (ABX3: A=CH3NH3,
B=Pb, X=Cl, I, Br) it is that the perovskite solaode of light absorbent is suggested first.Hereafter, perovskite material rapidly be extensive research at photoelectric field.2012, Science reports electricity conversion and is up to all solid state inorganic/organic hybrid perovskite solaode of 10.9%, allow the research of perovskite solaode enter brand-new epoch.After short 2 years 2014, such solaode transformation efficiency is close to 20%, exceed the electricity conversion that non-crystal silicon solar cell is current, it is chosen as one of ten big science breakthroughs in 2013 by " Science ", show high development and application potentiality, be the Main way of a new generation's nano-crystalline thin film solar cell research.Actively develop the research of perovskite solaode, the field of this great potential is captured prospective main strategy, to national economy persistence from now on and the development of novelty, be significant.The primary approach realizing solaode height transformation efficiency is exactly to improve the utilization rate of sunlight as far as possible, and this is the problem always making us special concern in photovoltaic scientific technological advance.It is obvious that absorb at the light of ultraviolet and infrared light region by further enhancing the perovskite solaode light in visible region and absorbing and expand it, it it is the key point improving device photoelectric performance.
At present, have been developed that quantum dot solar cell and perovskite solaode, but the perovskite solaode of quantum dot and perovskite sensitization altogether have not been reported；The electricity conversion of the quantum dot solar cell of present stage is generally than relatively low and stability is not good enough；Although perovskite solaode has the biggest breakthrough relative to quantum dot solar cell on electricity conversion, but its defect essentially consists in: perovskite solaode extinction wavelength is mainly at visible region 400-800nm, and in ultraviolet 300-400nm, and the absorptance of near infrared region 800-1400nm is less.
Summary of the invention
The technical problem to be solved in the present invention is, overcome the perovskite solaode defect that absorbing ability is weak and electricity conversion is low to ultraviolet and infrared light region sunlight in prior art, further enhance the absorption of perovskite solaode visible region sunlight simultaneously, the preparation method of a kind of quantum dot sensitization type perovskite solaode altogether is provided, using solaode prepared by the method, electricity conversion improves.
The present invention solves described technical problem and be the technical scheme is that the preparation method of a kind of quantum dot sensitization type perovskite solaode altogether, comprises the following steps:
(1) spin coating method is used, by TiO2Slip is deposited on conductive glass surface, is allowed to film forming, forms TiO after 450-500 DEG C processes 30-60 minute2Light anode；
Described spin coating rotating speed controls at 2000-4000rpm, and rotational time controls at 30-60s, TiO2The solvent of slip is dehydrated alcohol or terpineol, TiO2Solid-to-liquid ratio (the i.e. TiO of slip2Mass ratio with solvent)=1:2-4；
(2) use SILAR method (SILAR) at TiO2Deposit quanta point material on light anode, form quantum dot sensitized TiO2Light anode；
Described quanta point material is preferably CdS, CdSe, PbSe or PbTe quanta point material；
During described SILAR method prepares quantum dot, the cation of quanta point material such as CdS, CdSe, PbSe or PbTe is (such as Cd2+, Pb2+) and anion (such as S2-, Se2-,
Te2-) ion concentration in the solution is the preferred 0.04-0.2mol/L of 0.02-0.5mol/L(, more preferably 0.04mol/L)；
Described anions in solution and ion molar concentration rate=1 1 of anion；
The solvent that described quantum dot solution is used is methanol, ethanol or water；
In described SILAR method, the number of times of deposition is 1-5 time；
(3) raw material of following mass percent is prepared: dimethylformamide 60-80%, methylamine iodine 10-40%, lead iodide 5-10%；In organic solvent dimethylformamide, adding methylamine iodine and lead iodide, stirring 12-18 hour under 60-80 DEG C of constant temperature sand-bath, until forming homogeneous methylamine lead iodine solution；
(4) by the dropping of step (3) gained methylamine lead iodine solution in the quantum dot sensitized TiO of step (2) gained2On light anode, first make methylamine lead iodine solution at quantum dot sensitized TiO2Stand on photo-anode film and stop 30-60s, place in spin coater, rotary speed is set to 2500-4000rpm, rotational time 30-60s so that methylamine lead iodine solution is at quantum dot sensitized TiO2Form uniform methylamine lead iodine film on light anode, then this deposition is had the quantum dot sensitized TiO of methylamine lead iodine2Light anode toasts 10-30 minute at 80-110 DEG C, makes the TiO of Ca-Ti ore type methylamine lead iodine and quantum dot sensitization altogether2Light anode；
(5) raw material of following mass percent is prepared: chlorobenzene 90-99.5%, poly-3-hexyl thiophene 0.1-0.5%, two (fluoroform sulphonyl) imine lithium 0.1-0.4%, 4-tert .-butylpyridine 0.02-0.1%；In organic solvent chlorobenzene, adding poly-3-hexyl thiophene, two (fluoroform sulphonyl) imine lithium and 4-tert .-butylpyridine, stirring 12-18 hour under 60-80 DEG C of sand-bath, until forming henna homogeneous poly-3-hexyl thiophene hole mobile material solution；
Described hole mobile material poly-3-hexyl thiophene can use Spiro-OMeTAD { chemical name is 2,2,7,7-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9-spiral shell two fluorenes } to replace；
(6) the poly-3-hexyl thiophene hole mobile material solution obtained by step (5) is added drop-wise to the TiO of the Ca-Ti ore type methylamine lead iodine prepared by step (4) and quantum dot sensitization altogether2On light anode, at room temperature stand 10-30 minute, until hole mobile material solution becomes thickness, add platinum to electrode, toast 10-30 minute at 60-80 DEG C, make quantum dot sensitization type perovskite solaode altogether.
Multiple quanta point material involved in the present invention, all can use solution chemical method: SILAR method is simply prepared, the kind of quanta point material can be changed by the kind changing cation and anion solutions, by changing frequency of depositing, the particle diameter of quantum dot can control that (frequency of depositing is the most, particle diameter is the biggest, and light absorption range also can move to long wave direction accordingly)；Thus reach to control the purpose of its light absorption range and performance.CdS or CdSe quantum dot have obvious light to absorb in ultraviolet-visible light interval；PbSe or PbTe quantum dot has stronger light to absorb at near-infrared；Can effectively expand perovskite solaode by compound above quanta point material to absorb and photoelectric conversion at ultraviolet-visible and near infrared light, thus improve the electricity conversion of device.
The present invention using quantum dot as ultraviolet-visible (such as CdSe or CdS), infrared light (such as PbSe, PbTe) absorbent is combined with the Perovskite Phase with visible light absorption, reaches extension or strengthens the purpose of perovskite light absorption range, simultaneously raising perovskite solar cell photoelectric transformation efficiency.
The present invention uses the quantum dot (CdS or CdSe) with UV-Visible absorption characteristic and narrow band gap quantum dot (PbSe or PbTe) and the Ca-Ti ore type Organic leadP halogenation (CH with infrared extinction characteristic3NH3PbX3,X=Cl,
I, Br) it is combined and prepares quantum dot/perovskite altogether sensitization type perovskite solaode, the visible of perovskite solaode and infrared absorbing ability can be strengthened, be finally reached the purpose preparing higher electricity conversion perovskite solaode.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Reference examples
This reference examples comprises the following steps:
(1) spin coating method (rotating speed 2000rpm, rotational time 30s) is used, by TiO2Slip (solid-to-liquid ratio=1:4) is deposited on conductive glass surface, is allowed to film forming, forms TiO after 450 DEG C process 30 minutes2Light anode；TiO2The solvent of slip is ethanol；
(2) raw material of following mass percent is prepared: dimethylformamide 60%, methylamine iodine 30%, lead iodide 10%；In organic solvent dimethylformamide, adding methylamine iodine and lead iodide, stirring 16 hours under 80 DEG C of constant temperature sand-baths, until forming homogeneous methylamine lead iodine solution；
(3) step (2) gained methylamine lead iodine solution is dripped in step (1) gained TiO2On light anode, first make methylamine lead iodine solution at quantum dot sensitized TiO2Stand on photo-anode film and stop 30s, place in spin coater, rotary speed is set to 3000rpm, rotational time 45s so that methylamine lead iodine solution is at TiO2Form uniform methylamine lead iodine film on light anode, then this deposition is had the TiO of methylamine lead iodine2Light anode toasts 15 minutes at 100 DEG C, makes the TiO of Ca-Ti ore type methylamine lead iodine sensitization2Light anode；
(4) raw material of following mass percent is prepared: chlorobenzene 99.2%, poly-3-hexyl thiophene 0.3%, two (fluoroform sulphonyl) imine lithium 0.4%, 4-tert .-butylpyridine 0.1%；In organic solvent chlorobenzene, adding poly-3-hexyl thiophene, two (fluoroform sulphonyl) imine lithium and 4-tert .-butylpyridine, stirring 12 hours under 60 DEG C of sand-baths, until forming henna homogeneous poly-3-hexyl thiophene hole mobile material solution；
(5) the poly-3-hexyl thiophene hole mobile material solution obtained by step (4) is added drop-wise to the TiO of the sensitization altogether of the Ca-Ti ore type methylamine lead iodine prepared by step (3)2On light anode, at room temperature stand 10 minutes, until hole mobile material solution becomes thickness, add platinum to electrode, toast 15 minutes at 80 DEG C, make the perovskite solaode not having quantum dot sensitization altogether of solid-state.
The battery performance test of this reference examples, encapsulates in atmosphere and does not carries out in glove box, simultaneously in order to reduce the preparation cost of battery, selects P3HT to replace the Spiro-OMeTAD of costliness, replaces the disposable Au of evaporation to electrode with the Pt sheet of reusable edible.Following example are same.
Test the perovskite solaode not having quantum dot sensitization altogether of this reference examples gained solid-state: at room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 60mW/cm2(light intensity: under the conditions of using silicon photoelectric diode to demarcate), records the perovskite solaode not having quantum dot sensitization altogether, and effective illuminating area is 0.1cm2Photoelectric transformation efficiency be 3%.
Embodiment 1
The present embodiment comprises the following steps:
(1) use spin coating method (rotating speed 2200rpm, rotational time 45s) by TiO2Slip (solid-to-liquid ratio=1:3) is deposited on conductive glass surface, is allowed to film forming, forms TiO after 480 DEG C process 40 minutes2Light anode；TiO2The solvent of slip is terpineol；
(2) use SILAR method (SILAR) at TiO2Deposit CdS quantum dot material on light anode, form the TiO of CdS quantum dot sensitization2Light anode；
During described SILAR method prepares quantum dot, the cationic solution (Cd (NO of quanta point material CdS3)2) and anion solutions (Na2S) ion concentration is ion molar concentration rate=1 1 of 0.2 mol/L, cation and anion solutions；The solvent used is ethanol；The cycle-index of deposition is 3 times；
(3) raw material of following mass percent is prepared: dimethylformamide 64%, methylamine iodine 27%, lead iodide 9%；In organic solvent dimethylformamide, adding methylamine iodine and lead iodide, stirring 12 hours under 70 DEG C of constant temperature sand-baths, until forming homogeneous methylamine lead iodine solution；
(4) by the dropping of step (3) gained methylamine lead iodine solution in the quantum dot sensitized TiO of step (2) gained2On light anode, first make methylamine lead iodine solution at the TiO of CdS quantum dot sensitization2Stand on photo-anode film and stop 36 s, place in spin coater, rotary speed is set to 3500rpm, rotational time 30s so that methylamine lead iodine solution is at quantum dot sensitized TiO2Form uniform methylamine lead iodine film on light anode, then this deposition is had the quantum dot sensitized TiO of methylamine lead iodine2Light anode toasts 10 minutes at 80 DEG C, makes the TiO of Ca-Ti ore type methylamine lead iodine and quantum dot sensitization altogether2Light anode；
(5) raw material of following mass percent is prepared: chlorobenzene 99.4%, poly-3-hexyl thiophene 0.25%, two (fluoroform sulphonyl) imine lithium 0.3%, 4-tert .-butylpyridine 0.05%；In organic solvent chlorobenzene, adding poly-3-hexyl thiophene, two (fluoroform sulphonyl) imine lithium and 4-tert .-butylpyridine, stirring 15 hours under 70 DEG C of sand-baths, until forming henna homogeneous poly-3-hexyl thiophene hole mobile material solution；
(6) the poly-3-hexyl thiophene hole mobile material solution obtained by step (5) is added drop-wise to the TiO of the Ca-Ti ore type methylamine lead iodine prepared by step (4) and quantum dot sensitization altogether2On light anode, at room temperature stand 15 minutes, until hole mobile material solution becomes thickness, add platinum to electrode, toast 10 minutes at 75 DEG C, make solid-state CdS quantum dot sensitization type perovskite solaode altogether.
The performance of test the present embodiment gained solid-state CdS quantum dot sensitization type perovskite solaode altogether: at room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 60mW/cm2(light intensity: under the conditions of using silicon photoelectric diode to demarcate), effective illuminating area is 0.1 cm2Photoelectric transformation efficiency be 4%.
Embodiment 2
The present embodiment comprises the following steps:
(1) use spin coating method (rotating speed 3200rpm, rotational time 50s) by TiO2Slip (solid-to-liquid ratio=1:2.5) is deposited on conductive glass surface, is allowed to film forming, forms TiO after 460 DEG C process 45 minutes2Light anode；TiO2The solvent of slip is ethanol；
(2) use SILAR method (SILAR) at TiO2Deposit CdSe quantum dot material on light anode, form the TiO of CdSe quantum dot sensitization2Light anode；
During described SILAR method prepares quantum dot, the cationic solution (Cd (NO of quanta point material CdSe3)2) and anion solutions (Na2Se) ion concentration of solution is ion molar concentration rate=1 1 of 0.1mol/L, cation and anion solutions；The solvent used is ethanol；The cycle-index of deposition is 2 times；
(3) raw material of following mass percent is prepared: dimethylformamide 68%, methylamine iodine 24%, lead iodide 8%；In organic solvent dimethylformamide, adding methylamine iodine and lead iodide, stirring 14 hours under 75 DEG C of constant temperature sand-baths, until forming homogeneous methylamine lead iodine solution；
(4) by the dropping of step (3) gained methylamine lead iodine solution in the quantum dot sensitized TiO of step (2) gained2On light anode, first make methylamine lead iodine solution at quantum dot sensitized TiO2Stand on photo-anode film and stop 42s, place in spin coater, rotary speed is set to 4000rpm, rotational time 45s so that methylamine lead iodine solution is at the TiO of CdSe quantum dot sensitization2Form uniform methylamine lead iodine film on light anode, then this deposition is had the quantum dot sensitized TiO of methylamine lead iodine2Light anode toasts 20 minutes at 90 DEG C, makes the TiO of Ca-Ti ore type methylamine lead iodine and quantum dot sensitization altogether2Light anode；
(5) raw material of following mass percent is prepared: chlorobenzene 99.5%, poly-3-hexyl thiophene 0.33%, two (fluoroform sulphonyl) imine lithium 0.14%, 4-tert .-butylpyridine 0.03%；In organic solvent chlorobenzene, adding poly-3-hexyl thiophene, two (fluoroform sulphonyl) imine lithium and 4-tert .-butylpyridine, stirring 17 hours under 75 DEG C of sand-baths, until forming henna homogeneous poly-3-hexyl thiophene hole mobile material solution；
(6) the poly-3-hexyl thiophene hole mobile material solution obtained by step (5) is added drop-wise to the TiO of the Ca-Ti ore type methylamine lead iodine prepared by step (4) and quantum dot sensitization altogether2On light anode, at room temperature stand 25 minutes, until hole mobile material solution becomes thickness, add platinum to electrode, toast 12 minutes at 80 DEG C, make solid-state CdSe quantum dot sensitization type perovskite solaode altogether.
The performance of test the present embodiment gained solid-state CdSe quantum dot sensitization type perovskite solaode altogether: at room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 60mW/cm2(light intensity: under the conditions of using silicon photoelectric diode to demarcate), effective illuminating area is 0.1cm2Photoelectric transformation efficiency be 4.2%.
Embodiment 3
The present embodiment comprises the following steps:
(1) use spin coating method (rotating speed 4000rpm, rotational time 30s) by TiO2Slip (solid-to-liquid ratio=1:3.5) is deposited on conductive glass surface, is allowed to film forming, forms TiO after 470 DEG C process 35 minutes2Light anode；TiO2The solvent of slip is ethanol；
(2) use SILAR method (SILAR) at TiO2Deposit PbSe quanta point material on light anode, form the quantum dot sensitized TiO of PbSe2Light anode；
During described SILAR method prepares quantum dot, the cationic solution (Pb (NO of quanta point material PbSe3)2) and anion solutions (Na2Se) ion concentration of solution is ion molar concentration rate=1 1 of 0.03mol/L, cation and anion solutions；The solvent used is methanol；The cycle-index of deposition is 4 times；
(3) raw material of following mass percent is prepared: dimethylformamide 76%, methylamine iodine 18%, lead iodide 6%；In organic solvent dimethylformamide, adding methylamine iodine and lead iodide, stirring 15 hours under 78 DEG C of constant temperature sand-baths, until forming homogeneous methylamine lead iodine solution；
(4) step (3) gained methylamine lead iodine solution is dripped in TiO quantum dot sensitized for step (2) gained PbSe2On light anode, first make methylamine lead iodine solution at TiO quantum dot sensitized for PbSe2Stand on photo-anode film and stop 55 s, place in spin coater, rotary speed is set to 3200rpm, rotational time 38s so that methylamine lead iodine solution is at TiO quantum dot sensitized for PbSe2Form uniform methylamine lead iodine film on light anode, then this deposition is had the quantum dot sensitized TiO of methylamine lead iodine2Light anode toasts 16 minutes at 105 DEG C, makes the TiO of Ca-Ti ore type methylamine lead iodine and quantum dot sensitization altogether2Light anode；
(5) raw material of following mass percent is prepared: chlorobenzene 99.3%, poly-3-hexyl thiophene 0.34%, two (fluoroform sulphonyl) imine lithium 0.34%, 4-tert .-butylpyridine 0.02%；In organic solvent chlorobenzene, adding poly-3-hexyl thiophene, two (fluoroform sulphonyl) imine lithium and 4-tert .-butylpyridine, stirring 13 hours under 69 DEG C of sand-baths, until forming henna homogeneous poly-3-hexyl thiophene hole mobile material solution；
(6) the poly-3-hexyl thiophene hole mobile material solution obtained by step (5) is added drop-wise to the TiO of the Ca-Ti ore type methylamine lead iodine prepared by step (4) and quantum dot sensitization altogether2On light anode, at room temperature stand 19 minutes, until hole mobile material solution becomes thickness, add platinum to electrode, toast 17 minutes at 78 DEG C, make solid-state PbSe quantum dot sensitization type perovskite solaode altogether.
The performance of test the present embodiment gained solid-state PbSe quantum dot sensitization type perovskite solaode altogether: at room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 60mW/cm2(light intensity: under the conditions of using silicon photoelectric diode to demarcate), effective illuminating area is 0.1cm2Photoelectric transformation efficiency be 4.9%.
Embodiment 4
The present embodiment comprises the following steps:
(1) use spin coating method (rotating speed 2200rpm, rotational time 60s) by TiO2Slip (solid-to-liquid ratio=1:2.8) is deposited on conductive glass surface, is allowed to film forming, forms TiO after 500 DEG C process 60 minutes2Light anode；TiO2The solvent of slip is ethanol；
(2) use SILAR method (SILAR) at TiO2Deposit PbTe quanta point material on light anode, form the quantum dot sensitized TiO of PbTe2Light anode；
During described SILAR method prepares quantum dot, the cationic solution (Pb (NO of quanta point material PbTe3)2) and anion solutions (Na2Te) ion concentration of solution is ion concentration=1 1 of 0.04mol/L, cation and anion solutions；The solvent used is methanol；The cycle-index of deposition is 2 times；
(3) raw material of following mass percent is prepared: dimethylformamide 72%, methylamine iodine 21%, lead iodide 7%；In organic solvent dimethylformamide, adding methylamine iodine and lead iodide, stirring 18 hours under 80 DEG C of constant temperature sand-baths, until forming homogeneous methylamine lead iodine solution；
(4) step (3) gained methylamine lead iodine solution is dripped in TiO quantum dot sensitized for step (2) gained PbTe2On light anode, first make methylamine lead iodine solution at TiO quantum dot sensitized for PbTe2Stand on photo-anode film and stop 41s, place in spin coater, rotary speed is set to 3600rpm, rotational time 42s so that methylamine lead iodine solution is at TiO quantum dot sensitized for PbSe2Form uniform methylamine lead iodine film on light anode, then this deposition is had the quantum dot sensitized TiO of methylamine lead iodine2Light anode toasts 13 minutes at 89 DEG C, makes the TiO of Ca-Ti ore type methylamine lead iodine and quantum dot sensitization altogether2Light anode；
(5) raw material of following mass percent is prepared: chlorobenzene 99.25%, poly-3-hexyl thiophene 0.39%, two (fluoroform sulphonyl) imine lithium 0.32%, 4-tert .-butylpyridine 0.04%；In organic solvent chlorobenzene, adding poly-3-hexyl thiophene, two (fluoroform sulphonyl) imine lithium and 4-tert .-butylpyridine, stirring 18 hours under 79 DEG C of sand-baths, until forming henna homogeneous poly-3-hexyl thiophene hole mobile material solution；
(6) the poly-3-hexyl thiophene hole mobile material solution obtained by step (5) is added drop-wise to the TiO of the Ca-Ti ore type methylamine lead iodine prepared by step (4) and quantum dot sensitization altogether2On light anode, at room temperature stand 11 minutes, until hole mobile material solution becomes thickness, add platinum to electrode, toast 30 minutes at 62 DEG C, make solid-state PbTe quantum dot sensitization type perovskite solaode altogether.
The performance of test the present embodiment gained solid-state PbTe quantum dot sensitization type perovskite solaode altogether: at room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 60mW/cm2(light intensity: under the conditions of using silicon photoelectric diode to demarcate), effective illuminating area is 0.1cm2Photoelectric transformation efficiency be 5.5%.
From embodiment 1-4, it is 4% through the electricity conversion of the CdS quantum dot material of the present invention perovskite solaode of sensitization altogether, improves about 33.3% than without the perovskite solaode 3% of quanta point material sensitization altogether；It is 4.2% through the electricity conversion of the perovskite solaode of CdSe quantum dot material altogether sensitization, improves about 40% than without the perovskite solaode 3% of quanta point material sensitization altogether；It is 4.9% through the electricity conversion of the perovskite solaode of PbSe quanta point material altogether sensitization, improves about 63.3% than without the perovskite solaode 3% of quanta point material sensitization altogether；It is 5.5% through the electricity conversion of the perovskite solaode of PbTe quanta point material altogether sensitization, improves about 83.3% than without the perovskite solaode 3% of quanta point material sensitization altogether；
The preparation method of the quantum dot of present invention sensitization type perovskite solaode altogether is simple, the quantum dot sensitization type perovskite solaode altogether using this method to prepare absorbs raising at the light of ultraviolet-visible and near infrared region, finally improves the electricity conversion of perovskite solaode.
Claims (9)
1. the preparation method of a quantum dot sensitization type perovskite solaode altogether, it is characterised in that comprise the following steps:
(1) spin coating method is used, by TiO2Slip is deposited on conductive glass surface, is allowed to film forming, forms TiO after 450-500 DEG C processes 30-60 minute2Light anode；
(2) use SILAR method at TiO2Deposit quanta point material on light anode, form quantum dot sensitized TiO2Light anode；
(3) raw material of following mass percent is prepared: dimethylformamide 60-80%, methylamine iodine 10-40%, lead iodide 5-10%；In organic solvent dimethylformamide, adding methylamine iodine and lead iodide, stirring 12-18 hour under 60-80 DEG C of constant temperature sand-bath, until forming homogeneous methylamine lead iodine solution；
(4) by the dropping of step (3) gained methylamine lead iodine solution in the quantum dot sensitized TiO of step (2) gained2On light anode, first make methylamine lead iodine solution at quantum dot sensitized TiO2Stand on photo-anode film and stop 30-60s, place in spin coater, rotary speed is set to 2500-4000rpm, rotational time 30-60s so that methylamine lead iodine solution is at quantum dot sensitized TiO2Form uniform methylamine lead iodine film on light anode, then this deposition is had the quantum dot sensitized TiO of methylamine lead iodine2Light anode toasts 10-30 minute at 80-110 DEG C, makes the TiO of Ca-Ti ore type methylamine lead iodine and quantum dot sensitization altogether2Light anode；
(5) raw material of following mass percent is prepared: chlorobenzene 90-99.5%, poly-3-hexyl thiophene 0.1-0.5%, two (fluoroform sulphonyl) imine lithium 0.1-0.4%, 4-tert .-butylpyridine 0.02-0.1%；In organic solvent chlorobenzene, adding poly-3-hexyl thiophene, two (fluoroform sulphonyl) imine lithium and 4-tert .-butylpyridine, stirring 12-18 hour under 60-80 DEG C of sand-bath, until forming henna homogeneous poly-3-hexyl thiophene hole mobile material solution；
(6) the poly-3-hexyl thiophene hole mobile material solution obtained by step (5) is added drop-wise to the TiO of the Ca-Ti ore type methylamine lead iodine prepared by step (4) and quantum dot sensitization altogether2On light anode, at room temperature stand 10-30 minute, until hole mobile material solution becomes thickness, add platinum to electrode, toast 10-30 minute at 60-80 DEG C, make quantum dot sensitization type perovskite solaode altogether.
The preparation method of quantum dot the most according to claim 1 sensitization type perovskite solaode altogether, it is characterised in that in step (1), described spin coating rotating speed controls at 2000-4000rpm, and rotational time controls at 30-60s, TiO2The solvent of slip is dehydrated alcohol or terpineol, TiO2Solid-to-liquid ratio=the 1:2-4 of slip.
The preparation method of quantum dot the most according to claim 1 and 2 sensitization type perovskite solaode altogether, it is characterised in that in step (2), described quanta point material is CdS, CdSe, PbSe or PbTe.
The preparation method of quantum dot the most according to claim 1 and 2 sensitization type perovskite solaode altogether, it is characterized in that, in step (2), during described SILAR method prepares quantum dot, the cation of quanta point material and anion ion concentration in the solution is 0.02-0.5 mol/L.
The preparation method of quantum dot the most according to claim 4 sensitization type perovskite solaode altogether, it is characterized in that, during described SILAR method prepares quantum dot, the cation of quanta point material and anion ion concentration in the solution is 0.04-0.2 mol/L.
The preparation method of quantum dot the most according to claim 4 sensitization type perovskite solaode altogether, it is characterised in that in step (2), described anions in solution and ion molar concentration rate=1 1 of anion.
The preparation method of quantum dot the most according to claim 4 sensitization type perovskite solaode altogether, it is characterised in that in step (2), the solvent that quantum dot solution is used is methanol, ethanol or water.
The preparation method of quantum dot the most according to claim 1 and 2 sensitization type perovskite solaode altogether, it is characterised in that in step (2), in described SILAR method, the number of times of deposition is 1-5 time.
The preparation method of quantum dot the most according to claim 1 and 2 sensitization type perovskite solaode altogether, it is characterised in that in step (5), described hole mobile material poly-3-hexyl thiophene uses Spiro-OMeTAD to replace.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102364648A (en) * | 2011-10-18 | 2012-02-29 | 西安交通大学 | Method for manufacturing sulfydryl bridge molecular bonded quantum dot and TiO2 nano compound light anode |
| CN103247444A (en) * | 2013-05-07 | 2013-08-14 | 常州大学 | Quantum dot and dye co-sensitization solar battery and preparation method thereof |
| CN103390503A (en) * | 2013-07-04 | 2013-11-13 | 华侨大学 | Preparing method of solid electrolyte for sensitized solar cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102364648A (en) * | 2011-10-18 | 2012-02-29 | 西安交通大学 | Method for manufacturing sulfydryl bridge molecular bonded quantum dot and TiO2 nano compound light anode |
| CN103247444A (en) * | 2013-05-07 | 2013-08-14 | 常州大学 | Quantum dot and dye co-sensitization solar battery and preparation method thereof |
| CN103390503A (en) * | 2013-07-04 | 2013-11-13 | 华侨大学 | Preparing method of solid electrolyte for sensitized solar cells |
Non-Patent Citations (1)
| Title |
|---|
| Gabseok Seo等."Enhancing the Performance of Sensitized Solar Cells with PbS/CH3NH3PbI3 Core/Shell Quantum Dots".《J. Phys. Chem. Lett.》.2014,第5卷(第11期), * |
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