CN102263203A - Organic solar battery and manufacturing method thereof - Google Patents
Organic solar battery and manufacturing method thereof Download PDFInfo
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- CN102263203A CN102263203A CN2011102330854A CN201110233085A CN102263203A CN 102263203 A CN102263203 A CN 102263203A CN 2011102330854 A CN2011102330854 A CN 2011102330854A CN 201110233085 A CN201110233085 A CN 201110233085A CN 102263203 A CN102263203 A CN 102263203A
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
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Abstract
The invention provides an organic solar energy battery and a manufacturing method thereof; the organic solar energy battery comprises a cathode, an electron collecting layer, an activity layer, a cavity collecting layer and an anode, wherein the cathode is a transparent conductive oxide (TCO) film coating layer which is coated on glass or a plastic substrate; the electron collecting layer is a mixing layer formed by doping Cs2CO3 in organic micromolecule; the activity layer is formed by a polymer donor-receptor mixing layer; and the anode is a metal electrode. The organic solar energy battery based on the structure of the invention has higher conversion efficiency and long service life.
Description
Technical field
The present invention relates to technical field of solar batteries, relate to a kind of organic solar batteries and preparation method thereof in particular.
Background technology
The energy is the global problem of restriction social development, and solar energy then is one of following most promising energy.Therefore, be that the photovoltaic solar cell of electric energy more and more comes into one's own based on photovoltaic effect with solar energy converting.Solar cell is divided into inorganic solar cell (silicon solar cell) and organic solar batteries at present.Wherein, organic solar batteries is meant the solar cell that is made of the core organic material.Solar cell based on organic material is easy to get owing to its raw material, and preparation technology is simple, environmental stability is high and good photovoltaic effect is arranged, and is paid attention to by people day by day.
Existing organic solar batteries comprises material layer: anode, collecting layer, hole, active layer (also claiming exciton to produce layer or charge carrier generation layer), electron collection layer and negative electrode, as, ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al.Generally adopt and on glass or plastic, make transparent conductive oxide coatings (TCO, Transparent Conducting Oxide), can be the tin indium oxide ito thin film as the TCO coatings, with the anode substrate of TCO coatings as organic solar batteries, and adopt PEODT:PSS material (promptly poly-3,4 ethene dioxythiophenes: gather the 4-toluenesulfonic acid) as the collecting layer, hole.Because PEODT:PSS is acidic materials, is easy to corrode the tco layer as the anode substrate, and PEDOT:PSS self stability deficiency, thereby influence the life-span of organic solar batteries.
Summary of the invention
In view of this, the invention provides a kind of organic solar batteries and preparation method thereof, have higher transformation efficiency and increase useful life based on the solar cell of structure of the present invention.
For realizing above purpose, the invention provides a kind of organic solar batteries, the composition structure of this solar cell comprises: negative electrode, electron collection layer, active layer, collecting layer, hole and anode;
Described negative electrode is the transparent conductive oxide coatings TCO that coats on glass or the plastic base;
Described electron collection layer is by organic molecule doping Cs
2CO
3The mixed layer of forming;
Described active layer is made up of polymeric donor-acceptor mixed layer;
Described anode is a metal electrode.
Preferably, organic molecule comprises in the described electron collection layer: Bphen, TPBi, Alq
3And/or BCP.
Preferably, described based on Cs in the organic molecule electron collection layer
2CO
3The doping content ratio less than 50%.
Preferably, the thickness of described electron collection layer is 1～200nm.
Preferably, collecting layer, described hole is made up of transition metal oxide, and described transition metal comprises: molybdenum trioxide MoO
3, tungstic acid WO
3And/or vanadic oxide V
2O
5
Preferably, described transparent conductive oxide comprises: tin indium oxide ITO, azo oxide AZO and/or TFO.
Preferably, the material of described metal electrode comprises: aluminium, magnesium, silver and/or copper.
Preferably, the composition material of polymeric donor-acceptor mixed layer comprises: P3HT and PCBM.
Preferably, the composition structure of described solar cell also comprises: resilient coating, and described resilient coating is made of transition metal oxide or fluoride materials;
Described resilient coating is close to described negative electrode or described anode.
The present invention also provides a kind of manufacture method of organic solar batteries, comprising:
Coating transparent conductive oxide TCO on glass or plastic base, with the TCO coatings that forms as negative electrode;
Deposition organic molecule and Cs on described TCO coatings
2CO
3, obtain one deck doping Cs
2CO
3Organic molecule electron collection layer, described organic molecule comprises: Bphen, TPBi, Alq
3And/or BCP;
The glass and/or the plastic base that will be formed with the electron collection layer are put into glove box, and the mixed solution of spin on polymers donor-receiver obtains active layer on described electron collection layer, and polymeric donor-acceptor mixed solution comprises: P3HT:PCBM;
On described active layer, make hole transmission layer;
At the metal material of hole transmission layer deposition predetermined thickness, generate the anode of this organic solar batteries.
Via above-mentioned technical scheme as can be known, compared with prior art, the present invention openly provides a kind of organic solar batteries and preparation method thereof, the device architecture of organic solar batteries of the present invention adopts inverted structure, tco layer is modified to the negative electrode of organic solar batteries, and the metal electrode utmost point is set to anode, has avoided material in the collecting layer, hole to the corrosion of tco layer, thereby has prolonged the useful life of solar cell.
Simultaneously, be provided with in the organic solar batteries among the present invention by organic molecule film doping Cs
2CO
3The electron collection layer of forming is because Cs
2CO
3Be doped to the organic molecule film and can modulate between tco layer and the active layer and form ohmic contact, improve open circuit voltage, and Cs
2CO
3Being doped in the organic molecule to increase free charge, improves the conductivity of electron collection layer, has improved the transmission of electronics, and then has improved the efficient of organic solar batteries.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is embodiments of the invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to the accompanying drawing that provides.
Fig. 1 is the structural representation of an embodiment of a kind of organic solar batteries provided by the present invention;
Fig. 2 is the schematic flow sheet of an embodiment of the manufacture method of a kind of organic solar batteries provided by the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that is obtained under the creative work prerequisite.
Lower in order to solve in the prior art organic solar batteries efficient, the problem that useful life is short, the invention provides a kind of organic solar batteries, the composition structure of this solar cell comprises: negative electrode, electron collection layer, active layer, collecting layer, hole and anode; Wherein, negative electrode is the transparent conductive oxide coatings TCO that coats on glass or the plastic base; The electron collection layer is by organic molecule doping Cs
2CO
3The mixed layer of forming, organic molecule can comprise Bphen, TPBi, Alq
3And/or BCP, certainly other organic molecules can also be arranged; Active layer is made by polymeric donor-acceptor mixed solution spin coating, and polymer mixed solution includes but not limited to P
3HT and PCBM form; Anode is a metal electrode.
Wherein, organic solar energy cell structure of the present invention is an inverted structure, be about to be coated on the negative electrode that including transparent conducting oxide layer TCO on glass and/or the plastic is modified to organic solar batteries, top metal electrode is set to the anode of organic solar batteries owing to the structure sheaf adjacent with the negative electrode tco layer of organic solar batteries among the present invention is neutral substance, thereby can avoid corrosion, and then prolong the useful life of organic solar batteries tco layer.
Simultaneously, be provided with in the organic solar batteries among the present invention by organic molecule doping Cs
2CO
3The electron collection layer of forming is because Cs
2CO
3Be doped to organic molecule and can modulate the work function of tco layer, make it and active layer between form ohmic contact, improve open circuit voltage and Cs
2CO
3Being doped to increase the free charge of electron collection layer density in the organic molecule, improve conductivity, and then improved the electric transmission efficient of organic solar batteries and the power conversion efficiency of battery.
Need to prove, satisfying under the photoelectric prerequisite of organic solar batteries, among the present invention in the composition structure of organic solar batteries each layer distribution sequence can change, referring to Fig. 1, be the schematic diagram of a kind of each layer of organic solar batteries of the present invention distributed architecture, this organic solar batteries comprises: negative electrode, electron collection layer, active layer, collecting layer, hole and the anode with total reflection character.
The negative electrode of the organic solar batteries among the present invention is made of the transparent conductive oxide TCO coatings of coating on glass or the plastic base; With this negative electrode neighbour and on negative electrode the material structure layer be the electron collection layer, coating organic molecule electron transport material obtains the electron collection layer on the tco layer of negative electrode, and the organic molecule electron transport material in this electron collection layer comprises organic molecule and cesium carbonate Cs
2CO
3Dopant material.Concrete, this organic molecule comprises Bphen (that is, 4,7-diphenyl-1,10-phenanthroline), TPBi, Alq
3And/or BCP etc.Can be for by Bphen doping cesium carbonate Cs as, this electron collection layer
2CO
3The mixed layer of forming.
Above the electron collection layer is active layer at this, and this active layer is to constitute by spin on polymers donor-receiver mixed layer on the electron collection layer.This polymeric donor-acceptor mixed layer includes but not limited to the mixed solution of poly-3-hexyl thiophene P3HT and PCBM (derivative of fullerene), can also obtain active layer by the mixed solution of spin coating other polymeric donor-acceptors of the prior art on the electron collection layer certainly.
Be the collecting layer, hole on active layer, the composition material of this collecting layer, hole can comprise transition metal oxide, and transition metal oxide can comprise: molybdenum trioxide MoO
3Deng.Certainly the collecting layer, hole also can be made of the PEODT:PSS material; At this is the anode that is made of metal electrode above collecting layer, hole.The metal electrode that constitutes anode can have multiple, can be in aluminium, magnesium, silver, the copper any, or appoint several combinations, can be for almag as the metal electrode of anode etc.
Wherein, the transparent conductive oxide TCO film that forms negative electrode is selected as required.This concrete TCO film can include but not limited to: tin indium oxide ITO, azo oxide AZO and/or TFO.
Cs in the electron collection layer
2CO
3The doping content ratio less than 50%.That is to say, adopting organic small molecule material and Cs
2CO
3When deposition forms the electron collection layer, organic small molecule material and Cs
2CO
3The ratio of concentration be greater than 50%.The thickness of the electron collection layer that deposition forms can be set as required, and concrete can be arranged on the thickness of this electron collection layer between 1～200nm.
In order clearly to describe the structure of organic solar batteries of the present invention, the preparation process of the organic solar batteries of structure shown in Fig. 1 is described.Referring to Fig. 2, be the schematic flow sheet of the manufacture method of a kind of organic solar batteries of the present invention, the manufacture method of present embodiment comprises:
Step 201: coating transparent conductive oxide TCO on glass or plastic base, with the TCO coatings that forms as negative electrode.
Unlike the prior art, the present invention will be coated on TCO coatings on glass substrate (glass substrate) or the plastic base as the negative electrode of organic solar batteries.
When finishing after the step of coating TCO on the glass substrate, the glass and/or the substrate that are coated with TCO can be put into ultrasonic water bath, and utilize respectively acetone, absolute ethyl alcohol and deionized water as solvent to each ultrasonic cleaning fixed time of described TCO film, as can setting-up time being 20min, dry afterwards.
Step 202: deposition organic small molecule material and Cs on the TCO coatings
2CO
3, obtain one deck doping Cs
2CO
3Organic molecule electron collection layer.
Deposition organic molecule and Cs are arranged in preparation on the glass or plastic base of TCO coatings
2CO
3, obtain by organic small molecule material and Cs
2CO
3The mixed material layer that constitutes, this mixed material layer is the electron collection layer.Deposition organic molecule and Cs
2CO
3Process is carried out in vacuum chamber, and the pressure of vacuum chamber can be arranged on 5*10
-7～9*10
-7Between the torr.In the process of deposition electron collection layer, organic molecule and Cs
2CO
3Deposition velocity can set according to actual needs, the deposition velocity of this concrete organic molecule can be 0.2-10nm/sec, and Cs
2CO
3Deposition velocity then can change accordingly along with the variation of doping content.
Deposition organic molecule and Cs
2CO
3The thickness of the electron collection layer that obtains also can be set according to actual needs, as, the thickness of this electron collection layer can be arranged between 1～200nm.
Wherein, said herein organic molecule can comprise Bphen (that is, 4,7-diphenyl-1,10-phenanthroline), TPBi, Alq
3And/or BCP etc.Can be for by Bphen doping cesium carbonate Cs as, this electron collection layer
2CO
3The mixed layer of forming.
Step 203: the glass or the plastic base that will be formed with the electron collection layer are put into glove box, spin on polymers donor-receiver mixed solution on described electron collection layer, obtain active layer, the polymeric donor of active layer-acceptor mixed solution includes but not limited to poly-3-hexyl thiophene P
3HT and PCBM (derivative of fullerene).
The glass and/or the plastic base that deposit the electron collection layer are put into the glove box that is full of nitrogen, on the electron collection layer spin on polymers donor-receiver mixed solution as, should be on the electron collection layer the poly-3-hexyl thiophene P of spin coating
3The mixed solution of HT and PCBM (derivative of fullerene).Concrete rotary speed and the spin coating time when carrying out spin coating can be set as required, and rotary speed can be 2000r/min during as spin coating, and the spin coating time is 60s.And after spin coating is finished in glove box to substrate be heated to assigned temperature (as, can be 120 degree), and keep this assigned temperature certain hour, until more stable by the active layer that polymeric donor-the acceptor mixed solution forms.
Step 204: on described active layer, make hole transmission layer.
On the active layer that forms, can make hole transmission layer, make hole transmission layer and can adopt and existing identical materials, promptly adopt PEODT:PSS to prepare hole transmission layer.
Certainly, the present invention can also adopt and deposit transition metal oxide on active layer, generates the filtering metal that hole transmission layer deposits and can comprise molybdenum trioxide MoO on active layer
3, tungstic acid WO
3And/or vanadic oxide V
2O
5Deng.Process at deposition transition metal oxide on the active layer is also carried out under vacuum environment, as finishing in vacuum chamber.
Step 205:, generate the anode of organic solar batteries at the metal material of hole transmission layer deposition predetermined thickness.
On hole transmission layer, deposit the metal material of appointed thickness, obtain the anode of organic solar batteries.Metal material in the hole transmission layer deposition can be aluminium, magnesium, copper, silver or metal alloy etc., and the speed during deposit metallic material can be 0.5nm/sec, can certainly set as required.
In the organic solar batteries of producing by organic solar manufacture method of the present invention with the above structure, adjacent with the negative electrode tco layer is the electron collection layer, the mixed layer that organic molecule in the electron collection layer and Cs2CO3 constitute is a neutral substance, can avoid the corrosion of anticathode TCO, and this electron transfer layer can at room temperature form, do not need heating or handling return, go for flexible base, boards such as plastics.
In the electron collection layer Cs
2CO
3Be doped to organic small molecule material and can modulate the work function of tco layer, make it and active layer between form ohmic contact, improve open circuit voltage and doping Cs
2CO
3After, increased the free charge density of electron collection layer, realize the raising of conductivity, thereby improved the efficient of electric transmission.
Organic solar batteries of the present invention can make short circuit current, open circuit voltage, fill factor, curve factor and the conversion efficiency of solar cell device all be improved.In order to show clearly that organic solar batteries of the present invention has above advantage, referring to as following table 1:
Table 1
Wherein, be numbered 1 organic solar batteries corresponding parameters information of the present invention, be numbered 2 representative electron collection layer and adopt lithium fluoride LiF material to make organic solar batteries, the material of other structure sheafs of the organic solar batteries of numbering 2 and preparation technology can be identical with other structure sheafs of organic solar batteries among the present invention; The electron collection layer that is numbered 3 organic solar batteries is made for adopting the organic molecule electron transport material (the electronic isolation layer only comprises the Bphen material) that undopes, and other structure sheaf can be identical with other structure sheafs of the present invention.
By table as can be seen, compare with other two kinds of organic solar batteries, the open circuit voltage of organic solar batteries provided by the invention (promptly being numbered the organic solar batteries of 1 correspondence), short-circuit current density, fill factor, curve factor, conversion efficiency are all higher relatively.
As seen, in the electron collection layer Cs
2CO
3Be doped to the organic molecule electron transport material and can modulate the work function of tco layer, make it and active layer between form ohmic contact, improve open circuit voltage; When Cs
2CO
3Being doped in the organic molecule electron transport material to have increased free charge, realizes the raising of conductivity.
In actual applications, so long as adopt organic solar batteries to adopt inverted structure of the present invention, with tco layer as negative electrode, the structure sheaf adjacent with this TCO is the neutral material material, and with metal material as anode, satisfying under the photoelectric prerequisite of organic solar batteries, corresponding variation can take place in the distribution sequence between the structure sheaf of organic solar batteries, as the distributed architecture of organic solar batteries among the above embodiment is: negative electrode/electron collection layer/active layer/hole collecting layer/anode.And the distributed architecture of organic solar batteries of the present invention is not limited to this, can also be negative electrode/electron collection layer/active layer/anode, in other words, the negative electrode of organic solar batteries is a tco layer, on this tco layer is being the anode that constitutes for metal material on electron collection layer, the electron collection layer.Preparation technology between each structure sheaf is identical with preparation technology among the above embodiment, only is each layer distribution sequence difference.
Certainly, organic solar batteries can also have other structure distribution, so long as can satisfy photoelectric effect, and the preparation material of each layer and preparation technology and identical getting final product described in the present invention, do not enumerate one by one at this.
In addition, organic solar batteries can also comprise resilient coating, this resilient coating can have the oxide preparation of some inorganic material, as being transition metal oxide or fluoride etc.This resilient coating can be close to negative electrode or anode.The composition structure distribution order that is organic solar batteries can be negative electrode/electron collection layer/active layer/hole collecting layer/anode; Negative electrode/resilient coating/active layer/electron collection layer/hole collecting layer/anode; Or, negative electrode/active layer/electron collection layer/hole collecting layer/resilient coating/anode; Or negative electrode/resilient coating/active layer/collecting layer, hole/electron collection layer/anode; Or, negative electrode/active layer/collecting layer, hole/electron collection layer/resilient coating/structures such as anode.
Each embodiment adopts the mode of going forward one by one to describe in this specification, and what each embodiment stressed all is and the difference of other embodiment that identical similar part is mutually referring to getting final product between each embodiment.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined herein General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. an organic solar batteries is characterized in that, the composition structure of this solar cell comprises: negative electrode, electron collection layer, active layer, collecting layer, hole and anode;
Described negative electrode is the transparent conductive oxide coatings TCO that coats on glass or the plastic base;
Described electron collection layer is by organic molecule doping Cs
2CO
3The mixed layer of forming;
Described active layer is made up of polymeric donor-acceptor mixed layer;
Described anode is a metal electrode.
2. solar cell according to claim 1 is characterized in that, organic molecule comprises in the described electron collection layer: Bphen, TPBi, Alq
3And/or BCP.
3. solar cell according to claim 1 is characterized in that, and is described based on Cs in the organic molecule electron collection layer
2CO
3The doping content ratio less than 50%.
4. solar cell according to claim 1 is characterized in that, the thickness of described electron collection layer is 1～200nm.
5. solar cell according to claim 1 is characterized in that, collecting layer, described hole is made up of transition metal oxide, and described transition metal comprises: molybdenum trioxide MoO
3, tungstic acid WO
3And/or vanadic oxide V
2O
5
6. solar cell according to claim 1 is characterized in that, described transparent conductive oxide comprises: tin indium oxide ITO, azo oxide AZO and/or TFO.
7. solar cell according to claim 1 is characterized in that, the material of described metal electrode comprises: aluminium, magnesium, silver and/or copper.
8. solar cell according to claim 1 is characterized in that, the composition material of polymeric donor-acceptor mixed layer comprises: P3HT and PCBM.
9. according to claim 1, it is characterized in that the composition structure of described solar cell also comprises: resilient coating, described resilient coating is made of transition metal oxide or fluoride materials;
Described resilient coating is close to described negative electrode or described anode.
10. the manufacture method of an organic solar batteries is characterized in that, comprising:
Coating transparent conductive oxide TCO on glass or plastic base, with the TCO coatings that forms as negative electrode;
Deposition organic molecule and Cs on described TCO coatings
2CO
3, obtain one deck doping Cs
2CO
3Organic molecule electron collection layer, described organic molecule comprises: Bphen, TPBi, Alq
3And/or BCP;
The glass and/or the plastic base that will be formed with the electron collection layer are put into glove box, and the mixed solution of spin on polymers donor-receiver obtains active layer on described electron collection layer, and polymeric donor-acceptor mixed solution comprises: P3HT:PCBM;
On described active layer, make hole transmission layer;
At the metal material of hole transmission layer deposition predetermined thickness, generate the anode of this organic solar batteries.
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| CN103247760A (en) * | 2012-02-10 | 2013-08-14 | 吉林师范大学 | Organic solar cell using fluorescent electronic transfer material Zn (BTZ) 2 as cathode buffer layer |
| CN103258962A (en) * | 2013-04-25 | 2013-08-21 | 南昌大学 | Method for inducing organic solar cell active layer to be crystallized with interface crystalline buffer layer utilized |
| CN105140404A (en) * | 2015-07-21 | 2015-12-09 | 南京邮电大学 | Bulk heterojunction organic thin-film solar cell and preparation method thereof |
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| CN102810575A (en) * | 2011-06-03 | 2012-12-05 | 海洋王照明科技股份有限公司 | Solar energy battery device and preparation method thereof |
| CN102394271A (en) * | 2011-12-01 | 2012-03-28 | 苏州大学 | Organic solar cell and preparation method thereof |
| CN103247760A (en) * | 2012-02-10 | 2013-08-14 | 吉林师范大学 | Organic solar cell using fluorescent electronic transfer material Zn (BTZ) 2 as cathode buffer layer |
| CN102751439A (en) * | 2012-07-05 | 2012-10-24 | 苏州大学 | Organic solar cell |
| CN103258962A (en) * | 2013-04-25 | 2013-08-21 | 南昌大学 | Method for inducing organic solar cell active layer to be crystallized with interface crystalline buffer layer utilized |
| CN103258962B (en) * | 2013-04-25 | 2016-06-15 | 南昌大学 | A kind of method utilizing the induction organic solar batteries active layer crystallization of interfacial crystallization cushion |
| CN105140404A (en) * | 2015-07-21 | 2015-12-09 | 南京邮电大学 | Bulk heterojunction organic thin-film solar cell and preparation method thereof |
| CN105552233A (en) * | 2016-03-04 | 2016-05-04 | 吉林大学 | Bulk heterojunction organic solar cell with dual-anode buffer layer and preparation method of bulk heterojunction organic solar cell |
| CN106898698A (en) * | 2017-03-09 | 2017-06-27 | 南京邮电大学 | It is a kind of using aluminium and sodium chloride as inverse organic solar cell of cathode buffer layer and preparation method thereof |
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