CN100530744C - Structure of organic solar cell and organic solar cell produced with the same structure - Google Patents
Structure of organic solar cell and organic solar cell produced with the same structure Download PDFInfo
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- CN100530744C CN100530744C CN 200610043110 CN200610043110A CN100530744C CN 100530744 C CN100530744 C CN 100530744C CN 200610043110 CN200610043110 CN 200610043110 CN 200610043110 A CN200610043110 A CN 200610043110A CN 100530744 C CN100530744 C CN 100530744C
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Abstract
This invention discloses an organic solar energy cell structure and the cell prepared by said structure, in which, the structure includes at least a positive, a negative and a photovoltaic character organic material layer prepared on the base plate, a cavity transmission layer composed of directional carbon nano-tube array is set between the positive and photovoltaic organic material layer. This invention applies a directional carbon nano-tube to be deposited on the positive of the cell and forms a very good ohm contact with the positive, the directional carbon diode array is parallel to the base plate and the tubes are parallel to each other.
Description
Technical field
The present invention relates to a kind of solar cell, a kind of structure of organic photovoltaic cell and adopt the organic photovoltaic cell of this structure preparation particularly, the structure of this organic photovoltaic cell utilizes directional carbon nanotube array as hole transmission layer, improve the hole and be transported to anodal probability, shorten hole transport to anodal transmission path, thereby improve the efficient of solar cell.
Background technology
Huge change will take place in world energy sources 21 century, will progressively change the variation of the regenerative resource unlimited based on resource, that cleaning is clean, compound energy resource structure into based on the energy resource structure of resource-constrained, with serious pollution fossil energy.Solar energy is one of perfect energy sources replacement scheme in the people mind as a kind of inexhaustible, nexhaustible clean energy resource always.The photovoltaic generation that solar energy directly is converted to electric energy be various solar energy utilize in the mode the most flexibly, be of universal significance most a kind of.Solar cell is the core parts of photovoltaic generating system, and the solar cell development of technology has great significance for the popularization of solar energy utilization, is the criterion of present solar cell technical development and raise the efficiency and reduce cost.
The silicon materials solar cell has developed for many years, but the price of solar level silicon materials that is used to make battery is very expensive, add that battery manufacturing process complexity, equipment investment are big, material consumption and with factors such as TV universities, cause the price of osmanthus solar cell higher, thereby limited its more massive promotion and application.Organic substance solar cell based on dye molecule or polymer comes into one's own just day by day.Its sharpest edges are that manufacture craft is simple, cost is low.The subject matter of organic photovoltaic cell is that its photoelectric conversion efficiency is low at present, and the efficient that improves organic photovoltaic cell becomes the key that it is applied.
Cause the lower reason of organic photovoltaic cell efficient to be carrier transport in the organic substance material.HOMO in the organic semiconducting materials and lumo energy do not form conduction band and valence band, and the transmission of charge carrier is to finish by the jump between the local energy state, and its mobility will be significantly less than inorganic semiconductor material.Charge carrier in the material is difficult to arrive electrode, thereby has limited photoelectric conversion efficiency.In addition, the electron hole pair that organic substance produces under optical excitation fetters more intense mutually, often forms exciton.And exciton need just can dissociate under the effect of electric field of interface usually, and this interface electric field is usually located at organic substance and metal electrode at the interface.Yet the contact-making surface of organic substance and metal electrode is very limited, have only apart from the interface be no more than exciton diffusion length the zone in exciton could effectively arrive the exciton dissociation interface.So increase the effective exciton place of dissociating, and provide the passage that transports in effective electronics and hole to become the key that improves the organic photovoltaic cell photoelectric conversion efficiency.
Typical organic photovoltaic cell is the sandwich structure that is made of positive electrode (anode), photovoltaic organic matter layer and three parts of negative electrode (cathode).Positive electrode material is high work function (high work-function) material of similar p type-Metal Contact, for example ITO transparent conductive oxide.Negative electrode material is similar n type-Metal Contact low work function (low work-function) material, for example metallic aluminium etc.On the basis of this typical structure, in order to improve energy conversion efficiency, people further propose to add electron transfer layer and hole transmission layer (as Fig. 1) between organic matter layer and electrode.Transport layer should have such characteristic: can provide the effective exciton place of dissociating at the interface at them and photovoltaic organic matter layer, and electron transfer layer obtains the electronics of excitation state easily and has the good electron transport capability, and hole transmission layer obtains the hole easily and has good hole transport capability.Studies show that the introducing of transport layer often can become the conversion efficiency of the raising organic photovoltaic cell of the order of magnitude.It is one of transport layer material that extensively adopts at present that good fortune is reined in alkene.Carbon nano-tube is a kind of as fullerene, is a kind of transport layer material that has potentiality.Simultaneously as the one dimension lead can be very fast with carrier transport to electrode, thereby effectively separate exciton, improve the photoelectric conversion efficiency of battery.
The separative efficiency of exciton is relevant with the transmission path in the separating interface of exciton and electronics and hole.In order to increase the separating interface of exciton, people have proposed the notion of build heterojunction (bulk heterojunction), and promptly electron transfer layer and hole transmission layer interpenetrate, and increase contact interface.But along with the increase of infiltration, the transmission path in electronics and hole is elongated gradually, thereby recombination probability increases, and causes exciton dissociation efficient to reduce.If as transport layer, existing way is that carbon nano-tube is mixed with the photovoltaic organic substance with carbon nano-tube.Though this method can provide enough exciton dissociation interfaces, carbon nano-tube but is far from being fully used as the function of good carrier transport passage.Because the many carbon nano-tube that are scattered in the organic substance do not contact with electrode, the charge carrier that these carbon nano-tube obtain must could arrive electrode by the tunnel effect between the carbon nano-tube.Simultaneously thisly be scattered in the carbon nano-tube in the organic substance because the orientation that not have to determine, cause the transport path of the charge carrier complications that become.
Summary of the invention
The objective of the invention is to, the organic photovoltaic cell that a kind of structure of organic photovoltaic cell is provided and adopts this structure to prepare, in the structure of this organic photovoltaic cell, utilize directional carbon nanotube array as hole transmission layer, can improve the hole and be transported to anodal probability, shorten the hole through transmission path, thereby improve the efficient of solar cell to positive pole.
In order to realize above-mentioned task, the present invention adopts following technical solution:
A kind of structure of organic photovoltaic cell is included in the organic matter layer of the positive pole, negative pole and the photovoltaic property that prepare on the substrate at least, it is characterized in that the hole transmission layer that has directional carbon nanotube array to constitute between the organic matter layer of positive pole and photovoltaic property.
Adopt the organic photovoltaic cell of the structure preparation of above-mentioned organic photovoltaic cell, comprise a substrate, it is characterized in that, the battery cathode that has one deck to constitute on the substrate by continuous low-work-function material, be manufactured with comb finger-like bar shaped insulating barrier on the negative pole, the carbon nano-tube that is parallel to substrate is set on the insulating barrier, carbon nano-tube is suspended between the comb finger-like insulation strip, the bus of being made by high work function material is arranged on the insulation strip, carbon nano-tube on bus and the insulating barrier forms good Ohmic contact, bus is derived and the positive pole of formation battery via the bus electrode of substrate one end, the organic matter layer of photovoltaic property is filled on the negative terminal surface between the carbon nano-tube, unsettled carbon nano-tube is wrapped up fully, and form excellent contact with negative pole on the substrate.
Hole transmission layer of the present invention is the parallel carbon nano-tube that is arranged between the comb finger electrode, and exciton is in carbon nano-tube and the effectively ionization of photovoltaic organic substance near interface.Carbon nano-tube all directly is connected with strip electrode simultaneously, and the hole that is generated after the exciton dissociation can arrive electrode smoothly, thereby has improved the photoelectric conversion efficiency of solar cell.
Description of drawings
Fig. 1 is the typical structure with organic photovoltaic cell of electron transfer layer and hole transmission layer.
Fig. 2 is the perspective view that adopts the solar cell of parallel substrate carbon nanotubes arranged array.
Fig. 3 is the cross-sectional view that adopts the solar cell of parallel substrate carbon nanotubes arranged array.
Fig. 4 adopts parallel substrate carbon nanotubes arranged battle array to have the perspective view of the solar cell of hole transmission layer.
Fig. 5 adopts parallel substrate carbon nanotubes arranged array to have the cross-sectional view of the solar cell of hole transmission layer.
Label among the above-mentioned figure is represented respectively: 1, substrate, 2, negative pole, 3, insulating barrier, 4, catalyst layer, 5, comb finger-like positive pole, 6, anodal bus electrode, 7, the horizontal orientation carbon nano-tube, 8, the organic photovoltaic layer, 9, electron transfer layer.
In order to further specify content of the present invention, the present invention is described in further detail below in conjunction with specific embodiment that accompanying drawing and inventor provide.
Embodiment
The structure of a kind of organic photovoltaic cell provided by the present invention is included in the organic matter layer of the positive pole, negative pole and the photovoltaic property that prepare on the substrate at least, the hole transmission layer that has directional carbon nanotube array to constitute between the organic matter layer of positive pole and photovoltaic property.
Above-mentioned directional carbon nanotube array is for being deposited on the carbon nano-tube that aligns on the positive pole in a large number, and form ohmic contact with positive pole, the carbon nano-tube carbon nano-tube is the Single Walled Carbon Nanotube that is parallel to substrate, or multi-walled carbon nano-tubes, or the mixing of Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.
On the basis of said structure, between negative pole and photovoltaic organic material, can also add one deck electron transfer layer.
The high work function material of described positive pole can be ITO, platinum;
The low-work-function material of described negative pole can be aluminium, calcium, magnesium, magnesium/indium;
Described photovoltaic organic material comprises: polymer one class has: P3OT, P3HT, poly vinylcarbozole (PVK, polyvinylcarbazole amine), poly sulphur nitride (poly-nitrogen sulfide), polyacetylene (polyacetylene), polythiophene (polythiophene), PPV, MEH-PPV, cyano-PPV; Dye molecule one class has: anthrancene (anthracene), porphyrin (porphyrin), phthalocyanine (phthalocyanine).
Described photovoltaic organic material is not limited to a kind of of above-mentioned material, also comprises the combination between them.
Described baseplate material comprises: ceramic substrate, silicon chip, quartz substrate or glass substrate;
Solar cell implementation method provided by the present invention is as follows:
1) on substrate, deposits the negative pole of the continuous low work function electric conducting material of one deck earlier as solar cell;
2) on this negative pole, deposit a layer insulating by conventional thin-film technique;
3) on insulating barrier, deposit one deck appropriate carbon nanotube growth catalysts by conventional thin-film technique;
4) pass through conventional thin-film technique deposits one deck high work function on catalyst layer electric conducting material;
5), successively high work function conductive layer, catalyst layer and insulating barrier are corroded three layers of stacking provisions of insulating barrier, catalyst layer and the high work function conductive layer of producing elongated comb finger-like by conventional photoetching process;
6) by chemical vapour deposition technique (CVD), between referring to, adjacent comb grows the carbon nano-tube that is parallel to substrate;
7) by modes such as dipping, spin coating or vacuum sputterings the organic photovoltaic material is filled on the negative terminal surface, and the carbon nano-tube between fully the parcel comb refers to;
Perhaps:
1) on substrate, deposits the negative pole of the continuous low work function electric conducting material of one deck as solar cell;
2) on this positive pole, deposit a layer insulating by conventional thin-film technique;
3) by self-assembly process, deposition one deck is parallel to the substrate orientation carbon nanotubes arranged on insulating barrier;
4) electric conducting material of deposition one deck high work function on carbon nanotube layer;
5) etch the bonding jumper of combing finger-like by photoetching process, bonding jumper is vertical with the carbon nano-tube orientation;
6) under the bonding jumper of comb finger-like, further etch the insulating barrier bar of comb finger-like by photoetching process, expose comb between referring to unsettled carbon nano-tube and the negative pole on the substrate;
7) by modes such as dipping, spin coating or vacuum sputterings the photovoltaic organic material is filled on the negative terminal surface, and unsettled carbon nano-tube between fully the parcel comb refers to;
When if solar cell provided by the present invention comprises electron transfer layer, in above-mentioned implementation method, should add the electron transfer layer making step.
Below be the embodiment that the inventor provides.
Embodiment 1:
Present embodiment adopts and is parallel to the carbon nano pipe array of substrate as hole transmission layer.Make according to structure shown in Figure 2.Adopt Al
2O
3Potsherd is as substrate 1.Utilizing magnetron sputtering deposit one layer thickness on substrate 1 is 0.3 micron to 1 micron aluminium (Al) conduction negative pole 2.Then with the SiO of magnetron sputtering deposition one layer thickness 10 nanometers to 10 micron on conduction negative pole 2
2Insulating barrier 3.On insulating barrier 3, apply one deck appropriate carbon nanotube growth catalysts 4 then.And then the photoetching process of deposition one deck ITO (tin indium oxide) and employing routine becomes comb finger-like anodal 5 and anodal bus electrode 6 with metal ITO (tin indium oxide) layer photoetching.The finger beam of comb finger-like positive pole 5 is 100 nanometers to 10 micron, refers to that spacing is 100 nanometers to 1 millimeter, refers to that length is 1 micron to 1 centimetre, and anodal bus electrode 6 electrode widths are 1 micron to 1 millimeter.Be mask further, catalyst layer 4 and insulating barrier 3 are carried out etching respectively with comb finger electrode 5 and anodal bus electrode 6.Adopt chemical vapour deposition technique, go out unsettled carbon nano-tube 7 in the lateral growth of catalyst layer.In the carbon nano tube growth process, between adjacent comb finger electrode 5, apply certain voltage, keep comb and refer to that the electric field of 0.1v/ μ m to 1v/ μ m is to guide carbon nano-tube oriented growth.Chloroform soln with P3OT is spin-coated on sample surfaces then, treats to obtain after chloroform soln evaporates the organic matter layer 9 of P3OT photovoltaic property.For P3OT fully being filled between unsettled carbon nano-tube 7 and the negative pole 2 and good coated unsettled carbon nano-tube 7, sample can be immersed in a period of time in the chloroform soln of P3OT, obtain uniform P3OT packed layer by spin coating proceeding then.Negative pole 2 and anodal bus electrode 6 are finally drawn positive pole and the negative pole that forms solar cell by the both sides of substrate.P3OT photovoltaic organic substance 9 upper press cover glass are packaged into complete solar cell as cover plate.
Embodiment 2:
Present embodiment adopts and is parallel to the carbon nano pipe array of substrate as hole transmission layer.Make according to structure shown in Figure 4.Adopt glass as substrate 1.Utilizing magnetron sputtering deposit one layer thickness on substrate 1 is 0.3 micron to 1 micron aluminium (Al) conduction negative pole 2.Then with the SiO of magnetron sputtering or chemical vapour deposition technique (CVD) deposition one layer thickness 10 nanometers to 10 micron on conduction negative pole 2
2Insulating barrier 4.Adopt conventional photoetching process insulating barrier to be etched into and to comb the corresponding figure of finger electrode and bus electrode.On the aluminium electrode, deposit one deck PPV with technique for vacuum coating again.Adopt mask lithography technology, remove the PPV that covers on the comb finger-like insulation strip, expose comb finger-like insulating barrier 3, and guarantee that the insulation strip height is not less than the PPV surface.The air-flow of Li Yonging blows the solution that the method for being coated with will be dispersed with carbon nano-tube and is coated to the sample P PV surface of having exposed comb finger-like insulating barrier then, and airflow direction is vertically combed finger-like insulating barrier 3.Treat both to have obtained vertically to comb the horizontal orientation carbon nano-tube 7 that the finger-like insulation strip is arranged behind the solution evaporate to dryness.And then deposition one deck ITO (tin indium oxide) adopts conventional photoetching process that ITO (tin indium oxide) layer photoetching is become comb finger-like anodal 5 and anodal bus electrode 6 as the negative pole of solar cell; Comb finger-like positive pole 5 forms good Ohmic contact on insulating barrier 3 surfaces with carbon nano-tube, and anodal bus electrode 6 is covered on the insulating barrier 3.Comb finger-like anodal 6 is close with the planar graph parameter of comb finger-like insulating barrier 3, and in typical case, both graphic parameters are identical.The finger beam of comb finger-like positive pole 5 is 100 nanometers to 10 micron, refers to that spacing is 100 nanometers to 1 millimeter, refers to that length is 1 micron to 1 centimetre; Anodal bus electrode 6 electrode widths are 1 micron to 1 millimeter.Making by lithography after the conduction positive pole promptly combs finger-like anodal 5 and anodal bus electrode 6, the zone that distributes in comb finger-like anodal 5 is the photo-absorption region of solar cell, again with technique for vacuum coating deposition one deck PPV, the PPV that itself and previous step deposit fully wraps up carbon nano-tube 7 jointly, forms the organic photovoltaic layer 8 that the light absorption exciton produces layer.Negative pole 2 and anodal bus electrode 6 are finally drawn positive pole and the negative pole that forms solar cell by the both sides of substrate.Organic photovoltaic layer 8 upper press cover glass are packaged into complete solar cell as cover plate.
Embodiment 3:
The difference of present embodiment and embodiment 2 is, after making the insulating barrier figure by lithography, deposits one deck PCBM as electron transfer layer 9 with technique for vacuum coating on conduction negative pole 2, and then deposition PPV layer.In addition, before deposition of carbon nanotubes, also need to remove the PCBM that covers on the comb finger-like insulation strip.
As mentioned above, hole transmission layer of the present invention is the parallel carbon nano-tube that is arranged between the comb finger electrode.Exciton is in carbon nano-tube and the effectively ionization of photovoltaic organic substance near interface.Carbon nano-tube all directly is connected with strip electrode simultaneously, and the hole that is generated after the exciton dissociation can arrive electrode smoothly, thereby has improved the photoelectric conversion efficiency of solar cell.
Claims (8)
1. organic photovoltaic cell, be included in the positive pole for preparing on the substrate, the organic matter layer of negative pole and photovoltaic property, the hole transmission layer that has directional carbon nanotube array to constitute between the organic matter layer of described positive pole and photovoltaic property, it is characterized in that, the battery cathode that has one deck to constitute on the substrate by continuous low-work-function material, be manufactured with comb finger-like bar shaped insulating barrier on the negative pole, the carbon nano-tube that is parallel to substrate is set on the insulating barrier, carbon nano-tube is suspended between the comb finger-like insulation strip, the bus of being made by high work function material is arranged on the insulation strip, carbon nano-tube on bus and the insulating barrier forms good Ohmic contact, bus is derived and the positive pole of formation battery via the bus electrode of substrate one end, the organic matter layer of photovoltaic property is filled on the negative terminal surface between the carbon nano-tube, unsettled carbon nano-tube is wrapped up fully, and form excellent contact with negative pole on the substrate.
2. organic photovoltaic cell as claimed in claim 1, it is characterized in that, described directional carbon nanotube array is for being deposited on the carbon nano-tube that aligns on the positive pole in a large number, and form ohmic contact with positive pole, carbon nano-tube is the Single Walled Carbon Nanotube that is parallel to substrate, or multi-walled carbon nano-tubes, or the mixing of Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.
3. organic photovoltaic cell as claimed in claim 1 is characterized in that, described negative material comprises at least a or mixture of aluminium, calcium, magnesium or magnesium/indium.
4. organic photovoltaic cell as claimed in claim 1 is characterized in that, the material selective oxidation indium tin of described positive pole.
5. organic photovoltaic cell as claimed in claim 1 is characterized in that the organic matter layer of described photovoltaic property contacts with positive pole.
6. organic photovoltaic cell as claimed in claim 1 is characterized in that, also accompanies one deck electron transfer layer between the organic matter layer of described photovoltaic property and the negative pole.
7. organic photovoltaic cell as claimed in claim 1 is characterized in that, the organic matter layer of described photovoltaic property is dye molecule or the polymer with photovoltaic property.
8. organic photovoltaic cell as claimed in claim 7 is characterized in that described dye molecule is anthracene, porphyrin or phthalocyanine, or two or more the combination in them; Described polymer with photovoltaic property is: wherein one or both or multiple combination of pvk, poly-nitrogen sulfide, polyacetylene, polythiophene, PPV, MEH-PPV, cyano-PPV.
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