CN206076057U - A kind of electronics point and dyestuff composite sensitization heterojunction solar battery - Google Patents
A kind of electronics point and dyestuff composite sensitization heterojunction solar battery Download PDFInfo
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- CN206076057U CN206076057U CN201621104571.0U CN201621104571U CN206076057U CN 206076057 U CN206076057 U CN 206076057U CN 201621104571 U CN201621104571 U CN 201621104571U CN 206076057 U CN206076057 U CN 206076057U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
This utility model belongs to technical field of solar batteries, the utility model discloses a kind of electronics point and dyestuff composite sensitization heterojunction solar battery, include from bottom to up successively：Lower end FTO film layers (1), ZnO crystal seed layers (2), to electrode A u layer (7), upper end FTO film layers (1), electrode A u layer (7) and ZnO crystal seed layers (2) are connected by the wire (8) with resistance；To inlaying hetero junction layer between electrode A u layer (7) and ZnO crystal seed layers (2)；This utility model battery low cost, simple structure, battery performance are good.
Description
Technical field
This utility model belongs to technical field of solar batteries, is more particularly to a kind of electronics point and dyestuff composite sensitization is different
Matter connection solar cell.
Background technology
Currently, energy environment issues are increasingly serious, and scientific circles are devoted to studying the resourceful energy in addition to silicon always
Source material.Metal oxide materials have extraordinary optically and electrically performance, and ZnO is the wide band gap semiconducter of important N-shaped
Material, under its room temperature, energy gap is 3.37eV, and exciton bind energy is 60meV, much larger than the hot ionization energy of room temperature (26meV), can
Exciton stimulated radiation is produced under lower threshold, exciton recombination luminescence is capable of achieving at a room temperature and a high temperature, is that one kind prepares shortwave
The ideal material of long luminescent device, Cu2O is a kind of semi-conducting material being found very early, it is rare can be by excited by visible light
Semi-conducting material, its energy gap is about 2.17eV, can be by the excited by visible light that wavelength is 400～800nm, Cu in addition2O without
Poison, rich reserves, preparation cost are low, and theoretical utilization ratio is high, in electrode material, catalytic field, electronic device and gas sensor
Etc. aspect have important application.Research prepares the Cu of low cost2O based solar batteries are realized too to substituting high cost battery
The extensive civil nature of positive energy battery is significant.It is sensitized by interfacial structure, prepares three dimensional structure laminated film heterogeneous
Joint solar cell, can be effectively increased heterojunction boundary area, so can shorten photoproduction while multiple extinction is increased
The collection length of carrier, reduces the recombination probability of photo-generated carrier, is conducive to improving battery efficiency.As solid inorganic is partly led
Body material in the filling process often cannot be in nanostructured table by the restriction of the shadow effect relevant with complex geometry
The conformal covering in face is difficult to realize its densification filling in nanoporous, therefore, one kind is explored in orientation array using electricity
Son point and dye-sensitized semiconductor technology come prepare composite heterogenous junction battery be improve battery technology key.
So a kind of composite heterogenous junction battery of exploitation has great application prospect and economic implications.
Utility model content
The purpose of this utility model is to overcome in prior art complex structure, the shortcoming of photoelectric properties difference in battery, there is provided
A kind of composite heterogenous junction battery.
A kind of electronics point and dyestuff composite sensitization heterojunction solar battery, include from bottom to up successively：Lower end FTO films
Layer, ZnO crystal seed layers, to electrode A u layer, upper end FTO film layers, to electrode A u layer and ZnO crystal seed layers by the wire with resistance
Connection；To inlaying hetero junction layer between electrode A u layer and ZnO crystal seed layers.
The hetero junction layer includes ZnO nano-rod array, and nanoscale CdSe quantum are provided with the ZnO nano-rod array
Point, nanometer grade dye N719 and Cu2O thin film.
2.1 μm of the ZnO nano-rod array rod length, diameter and interrod spacing are respectively less than 1 μm.
This utility model provides a kind of electronics point and dyestuff composite sensitization nano heterojunction solar cell preparation method, described
Electronics point is CdSe electronics point, and the dyestuff is ruthenium N719 dyestuffs；By CdSe and ruthenium N719 dye sensitization ZnO nanorod battle arrays
Row, then with magnetron sputtering technique by Cu2O is deposited on ZnO nanorod surface and forms ZnO/CdSe/N719/Cu2O composite heterogenous junctions are too
The method in positive electricity pond, using battery low cost obtained in this method, prepares simply, and battery performance is good.
The preparation method of a kind of electronics point and dyestuff composite sensitization heterojunction solar battery, detailed process include following step
Suddenly：
Step one, by N-shaped ZnO nano-rod array thin film, is put into Cd (NO3)2In aqueous solution place deposition, then spend from
Sub- water is rinsed；Place into Na2Deposition is placed in Se aqueous solutions, then deionized water is rinsed；In N-shaped ZnO nano-rod array
Electronics point CdSe is deposited in space, the ZnO/CdSe composite nano films that electronics point CdSe was sensitized are defined；Circular treatment 15
～25 times, loop start is from being put into Cd (NO3)2Place deposition procedures to start to being put into Na in aqueous solution2It is heavy to place in Se aqueous solutions
Long-pending, then deionized water is rinsed operation and is terminated；
Step 2, the ZnO/CdSe composite nano films immersion dyestuff ruthenium N719 ethanol solution that electronics point CdSe was sensitized
In, soaking at room temperature 10～24 hours is dried, that is, made the ZnO/CdSe/N719 composite nano films that composite sensitization is crossed；
Step 3, adopts the ZnO/CdSe/N719 composite nano films that composite sensitization is crossed for substrate, is put into three target of fine vacuum
In magnetic control co-sputtering coating system vacuum chamber, 5 × 10 are evacuated down to-4Pa, elemental metals copper target are sputtering target, in argon and oxygen
Mixed atmosphere under sputtered, the purity of argon and oxygen is 99.99%, in ZnO/CdSe/N719 composite nano films
One layer of p-type Cu is deposited on surface2O clads, prepare ZnO/CdSe/N719/Cu2O nano-array hetero-junctions；Then in ZnO/
CdSe/N719/Cu2The Cu of O nano heterojunctions2The surface splash-proofing sputtering metal electrode of O layers as to electrode, with wire with expose
The conducting film connection of conducting oxide electrode, forms electronics point and dyestuff composite sensitization heterojunction solar battery；
Preferably, in the step one：Cd(NO3)2Concentration of aqueous solution is 0.1～0.2M, and pH is 12～13, is by hydrogen
The pH value that potassium oxide is adjusted；Na2Se concentration of aqueous solution be 0.1～0.2M, pH be 12～13 be by potassium hydroxide adjust pH
Value；Cd (the NO3)2And Na2Se depositing temperatures are 15～25 DEG C, and sedimentation time is 5～10min.
Preferably, in the step 2, in dyestuff N719 ethanol solution, dyestuff N719 concentration is 0.3～0.8M；
Preferably, in the step 3 oxygen and argon flow-rate ratio O2/ Ar=20～100, the input power of sputtering target
For 60～100W, sputtering pressure 0.1Pa, thin film deposition time are 20～500min.
In the step one, N-shaped ZnO nano-rod array thin film prepares gained by following preparation method：Using sol-gal process
ZnO seed presomas are prepared, then ZnO seed presomas is applied in substrate, form thin film, it is thermally treated to obtain one layer uniformly
Nanoscale ZnO crystal seed layers；The hanging back-off in face of nanoscale ZnO crystal seed layers is immersed in into ZnO growth solutions in reaction vessel
In, good seal reaction vessel, is placed in electric heating constant temperature tank afterwards, under 20～50 DEG C of water bath conditions, insulation 10min～
12h, takes out, successively deionized water rinsing, and dehydrated alcohol is rinsed, and room temperature in vacuo drying obtains the height-oriented ZnO nano of N-shaped
Rod array film.
The concrete preparation process of the ZnO crystal seed layers is as follows：With Zinc diacetate dihydrate Zn (AcO)2·2H2O is reaction precursor
Body, monoethanolamine NH2CH2CH2OH is stabilizer, ethylene glycol monomethyl ether CH3OCH2CH2OH is solvent, Polyethylene Glycol PEG4000 is table
Face activating agent prepares the ZnO colloidal sols of 0.3M～0.5M；One layer is prepared using the method for spin coating plated film in cleaned substrate
ZnO colloid film；350 DEG C～550 DEG C annealing DEG C 10min～30min in vacuum tube furnace, i.e., form one layer uniformly in substrate surface
Fine and close nanoscale ZnO crystal seed layers, the substrate are ITO or FTO electro-conductive glass.
The ZnO growth solutions prepare gained by following preparation method：With KOH and Zn (NO3)2In molar ratio 1:8 prepare dense
Spend [the Zn (OH) for 0.10～0.25M4]2-Aqueous solution, abundant magnetic agitation obtain settled solution, and as required ZnO growths are molten
Liquid.
In the step 3, metal electrode used is Au or Pt；Conducting oxide electrode used is ITO or FTO.
Positive effect of the present utility model is：This utility model is being sensitized with electronics point CdSe and ruthenium dye N719
ZnO nano-rod array, then with magnetron sputtering technique by Cu2O is deposited on ZnO nanorod surface and forms ZnO/CdSe/N719/Cu2O
Composite heterogenous junction thin film solar cell, using battery low cost obtained in this method, prepares simply, and battery performance is good.
ITO described in this utility model is tin-doped indium oxide；FTO is Fluorin doped tin-oxide.
Because CdSe quantum dot (3) in this utility model；Dyestuff N719 (5) nanoscale, so the shape shown in accompanying drawing 4 is only
It is schematic, does not represent its true form.
Description of the drawings
Fig. 1 is transverse section field emission scanning electron microscope (SEM) photo of the ZnO nano-rod array thin film of hydro-thermal method synthesis.
Fig. 2 is the ZnO/CdSe/N719/Cu that this utility model is implemented to prepare2The transverse section and top of O composite heterogenous junction materials
Scanning electron microscope (SEM) photo in face.
Fig. 3 is the curve chart of the electric current and voltage of the different hetero-junction solar cells after sensitization, including 1) ZnO/CdSe/N719/
Cu2O；2)ZnO/Cu2O；3)ZnO/N719/Cu2O；4)ZnO/CdSe/Cu2Tetra- kinds of hetero-junction solar cells of O.
Fig. 4 is that (code name is abbreviated as ZnO/ for electronics point of the present utility model and dyestuff composite sensitization heterojunction solar battery
CdSe/N719/Cu2O schematic diagram), comprising FTO film layers -1, ZnO crystal seed layers -2, nanoscale CdSe quantum dot -3, ZnO nano
Rod array -4, nanometer grade dye N719-5, Cu2O thin film -6, to electrode A u layer -7 and the wire -8 with resistance.
Specific embodiment
To make the purpose of this utility model, technical scheme and advantage of greater clarity, with reference to specific embodiment,
This utility model is further described.It should be understood that these descriptions are simply exemplary, and it is new to be not intended to limit this practicality
The scope of type.
Embodiment
Accompanying drawing 4 is that (code name is abbreviated as electronics point of the present utility model and dyestuff composite sensitization heterojunction solar battery
ZnO/CdSe/N719/Cu2O representative schematic diagram), a kind of electronics point and dyestuff composite sensitization heterojunction solar battery, under
It is supreme to include successively：Lower end FTO film layers 1, ZnO crystal seed layers 2, to electrode A u layer 7, upper end FTO film layer 1, to 7 He of electrode A u layer
ZnO crystal seed layers 2 are connected by the wire 8 with resistance；To inlaying hetero junction layer between electrode A u layer 7 and ZnO crystal seed layers 2.
The hetero junction layer includes ZnO nano-rod array 4, and nanoscale CdSe amounts are provided with the ZnO nano-rod array 4
Son point 3, nanometer grade dye N7195 and Cu2O thin film 6.
2.1 μm of ZnO nano-rod array (4) the rod length, diameter and interrod spacing are respectively less than 1 μm.
First, follow the steps below and prepare electronics point and dyestuff composite sensitization heterojunction solar battery, code name is write a Chinese character in simplified form
For ZnO/CdSe/N719/Cu2O)：
Step one, by N-shaped ZnO nano-rod array thin film, is put into concentration for 0.2M, pH value for 13 Cd (NO3)2Solution
It is middle to place deposition, 25 DEG C of depositing temperature, sedimentation time 10min, then deionized water rinse, place into 0.2M, pH value for
13 Na2Deposition, 25 DEG C of depositing temperature, sedimentation time 10min, then deionized water flushing are placed in Se solution；Circulation Cd
(NO3)2And Na2Deposition in Se operations and washing step 15～25 times, deposit electronics in the space of N-shaped ZnO nano-rod array
Point CdSe, defines the ZnO/CdSe composite nano films that electronics point CdSe was sensitized；
Step 2, the ZnO/CdSe composite nano films that electronics point CdSe was sensitized immerse the dyestuff ruthenium N719 second of 0.8M
In alcoholic solution, soaking at room temperature 10～24 hours is dried, that is, made the ZnO/CdSe/N719 composite Nanos that composite sensitization crosses thin
Film；
Step 3, adopts the ZnO/CdSe/N719 nano thin-films that composite sensitization is crossed for substrate, is put into three target magnetic control of fine vacuum
In cosputtering coating system vacuum chamber, 5 × 10 are evacuated down to-4Pa, elemental metals copper target are sputtering target, in the mixed of argon and oxygen
Close and sputtered under atmosphere, the purity of argon and oxygen is 99.99%, the flow-rate ratio (O of oxygen and argon2/ Ar) for 20～
100, the input power of sputtering target is 60～100W, and sputtering pressure 0.1Pa, thin film deposition time are 20～50min, in ZnO half
One layer of p-type Cu is deposited on conductor nano-array surface2O clads, prepare ZnO/CdSe/N719/Cu2O nano-arrays are heterogeneous
Knot.Then in the Cu of hetero-junctions2The surface splash-proofing sputtering metal Au or Pt of O layers as to electrode, with wire and the ITO for exposing or
The conducting film connection of FTO glass, forms simple heterojunction solar battery device.
ZnO crystal seed layers, concrete preparation process are as follows：With Zinc diacetate dihydrate Zn (AcO)2·2H2O is precursors, list
Ethanolamine NH2CH2CH2OH is stabilizer, ethylene glycol monomethyl ether CH3OCH2CH2OH is solvent, Macrogol 4000 (PEG4000) is
Surfactant prepares the ZnO colloidal sols of 0.3M～0.5M；One is prepared using the method for spin coating plated film in cleaned substrate
Layer ZnO colloid film；350 DEG C～550 DEG C annealing DEG C 10min～30min in vacuum tube furnace, i.e., form one layer in substrate surface
Even fine and close nanoscale ZnO crystal seed layers, the substrate are ITO or FTO electro-conductive glass.By taking the ZnO colloidal sols of 0.5M as an example, specifically match somebody with somebody
Process processed is as follows：5.488g Zinc diacetate dihydrates are weighed, is put in beaker, and be added thereto to the ethylene glycol monomethyl ether of 25ml, magnetic
Power stirs 15min；Measure 1.5ml ethanolamine to be added in the ethylene glycol monomethyl ether of 15ml, mechanical agitation ultrasonic disperse 5min；Will
The ethylene glycol monomethyl ether solution of ethanolamine being added drop-wise in the ethylene glycol monomethyl ether solution of the zinc acetate that magnetic agitation dropwise, then Deca
The deionized water of 0.9ml, then adds proper amount of glycol methyl ether adjustment liquor capacity to reach 50ml, sealed beaker, and in 60 DEG C of water
Bath vigorous magnetic stirring 2h, still aging 24h.It is eventually adding 0.25g Macrogol 4000s (PEG4000), 60 DEG C of stirring in water bath
30min, obtains faint yellow ZnO precursor sol.
ZnO growth solutions, concrete preparation process are as follows：With KOH and Zn (NO3) 2 in molar ratio 1:8 compound concentrations are 0.10
[the Zn (OH) of～0.25M4]2-Aqueous solution, abundant magnetic agitation obtain settled solution, as required ZnO growth solutions.
N-shaped ZnO nano-rod array thin film, concrete preparation process are as follows：ZnO seed forerunners are prepared using sol-gal process
Body, then applies ZnO seed presomas in substrate, forms thin film, thermally treated to obtain one layer of uniform nanoscale ZnO crystal seed
Layer；The hanging back-off in face of nanoscale ZnO crystal seed layers is immersed in ZnO growth solutions in reaction vessel, good seal is anti-afterwards
Container is answered, is placed in electric heating constant temperature tank, under 20～50 DEG C of water bath conditions, be incubated 10min～12h, take out, use successively
Deionized water is rinsed, and dehydrated alcohol is rinsed, and room temperature in vacuo drying obtains the height-oriented ZnO nano-rod array thin film of N-shaped.
2nd, the pattern and its performance characterization of product
SEM is taken to implement the ZnO/CdSe/N719/Cu for preparing to ZnO nano-rod array thin film and this utility model2O is multiple
The transverse section and top surface detection for closing heterojunction material characterizes：
Fig. 1 is transverse section field emission scanning electron microscope (SEM) photo of the ZnO nano-rod array thin film of hydro-thermal method synthesis, from
It can be seen that highly regular nanometer stick array closely stands on the surface of the substrate in figure, 2.1 μm of nanometer rods length, between diameter and rod
Away from less than 1 μm.
Fig. 2 is the ZnO/CdSe/N719/Cu that this utility model is implemented to prepare2The transverse section and top of O composite heterogenous junction materials
Scanning electron microscope (SEM) photo in face, ZnO/CdSe/N719/Cu2The surface topography side view of O heterojunction arrays.Can be with from the figure
Find out, as seen from the figure, almost no space between ZnO nanorod illustrates Cu2O granules be substantially filled to ZnO nanorod it
Between gap, and hetero-junctions is tightly combined.ZnO nanorod top is all about the Cu of 100-300nm by diameter2O granules are tight
Cover, define ZnO/CdSe/N719/Cu2O heterojunction structure arrays.
The electric current of the different hetero-junction solar cells after to sensitization and the curve chart of voltage
Fig. 3 is the curve chart of the electric current with voltage of the different hetero-junction solar cells after sensitization, as seen from Figure 3, when not being sensitized
ZnO/Cu2The open-circuit voltage (Voc) of O heterojunction solar batteries, short-circuit current density (Jsc), fill factor, curve factor (FF) and photoelectricity
Conversion effect (η), respectively 0.28V, 3.45mAcm-2, 43% and 0.43%.After dye sensitization, open-circuit voltage also increase,
Maximum reaches 0.40V.During due to the nanocrystalline sensitizations of CdSe, the degree of roughness of nanorod surfaces is increased, and then is increased
The addition of ability CdSe of surface trapping xenogenesis electric charge result in ZnO conduction bands and Cu2The increase of the energy level difference between O valence band, it is multiple
When closing sensitization, short-circuit current density Jsc reaches maximum 7.18mAcm-2, η reaches 1.57% (being 3.65 times when not depositing).
Although embodiment of the present utility model is described in detail, it should be understood that, without departing from this reality
In the case of with new spirit and scope, various changes can be made to embodiment of the present utility model, replace and change.
Claims (3)
1. a kind of electronics point and dyestuff composite sensitization heterojunction solar battery, it is characterised in that：Include successively from bottom to up：Under
End FTO film layers (1), ZnO crystal seed layers (2), to electrode A u layer (7), upper end FTO film layers (1), to electrode A u layer (7) and ZnO crystal seeds
Layer (2) is connected by the wire (8) with resistance；To inlaying hetero junction layer between electrode A u layer (7) and ZnO crystal seed layers (2).
2. a kind of electronics point according to claim 1 and dyestuff composite sensitization heterojunction solar battery, it is characterised in that：
The hetero junction layer includes ZnO nano-rod array (4), is provided with nanoscale CdSe quantum dot on the ZnO nano-rod array (4)
(3), nanometer grade dye N719 (5) and Cu2O thin film (6).
3. a kind of electronics point according to claim 2 and dyestuff composite sensitization heterojunction solar battery, it is characterised in that：
2.1 μm of ZnO nano-rod array (4) the rod length, diameter and interrod spacing are respectively less than 1 μm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252088A (en) * | 2016-10-08 | 2016-12-21 | 常州大学怀德学院 | A kind of electronics point and dye sensitization composite heterogenous junction solaode and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252088A (en) * | 2016-10-08 | 2016-12-21 | 常州大学怀德学院 | A kind of electronics point and dye sensitization composite heterogenous junction solaode and preparation method thereof |
| CN106252088B (en) * | 2016-10-08 | 2018-08-10 | 常州大学怀德学院 | A kind of electronics point and dye sensitization composite heterogenous junction solar cell and preparation method thereof |
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