CN102760834B - A kind of organic thin film solar cell and preparation method thereof - Google Patents
A kind of organic thin film solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of organic thin film solar cell, formed by multiple battery cell compact arrangement in a plane, it is characterized in that: the shape of battery cell is cone, described cone is positive three face cones, positive four face cones or positive six face cones, the medial surface of cone is sensitive surface, each medial surface all comprises a battery unit, and this battery unit is paved with this medial surface.Organic thin film solar cell shaping structures of the present invention is simple, and manufacturing process is simple, and low cost of manufacture, filling rate reaches 100%, and battery unit is planar device, there is not stress problem, is convenient to be integrated into large solar array, has a good application prospect.
Description
Technical field
The present invention relates to organic solar batteries preparation field.
Background technology
Along with human society modernization development, the mankind rise rapidly for the depletion rate of the energy.And the present social energy mainly comes from the non-renewable energy resources such as coal, oil, natural gas, on the one hand because the reserves of the above-mentioned energy are limited, supply human society that can not be permanent; On the other hand, due to the burning of fossil fuel, cause environmental destruction, the discharge of such as greenhouse gas becomes global problem.
In order to solve energy problem, development of new renewable and clean energy resource is an important and urgent job.Solar energy, as a kind of important regenerative resource, is a kind of inexhaustible clean energy resource for the mankind.In the past few decades, inorganic solar cell technical development is swift and violent and reach its maturity, and can realize extensive generating.But, the cost of inorganic solar cell costliness still hinders it to apply widely, and in order to solve this difficult problem, organic polymer solar cell technology is getting the attention in recent years, its energy conversion efficiency improves year by year, develops into the branch that of solar battery technology is important.
The organic polymer cost comparatively inorganic material that organic polymer solar cell uses, as silicon, germanium, much lower.And the preparation technology of polymer solar battery is simple, and easy large-scale production, therefore production cost is lower.End 2012, polymer solar battery efficiency reaches about 9%, close to marketization application critical value 10%.
Although the battery efficiency of organic solar batteries is progressively improving, compared to inorganic solar cell, energy conversion efficiency or on the low side.Mainly organic material mobility is not high for this, and make active layer thickness only have about 100nm, absorption efficiency is lower.And to inorganic solar cell, as monocrystaline silicon solar cell, active layer thickness is 1 ~ 200um, do not need the photon absorption efficiency adopting special optical structure namely can realize 100%.Therefore, the efficiency how improving organic solar batteries becomes current new energy field hot issue.A kind of important method improving solar battery efficiency is the better solar cell device structure of design, can absorb more incident light, thus obtain higher light utilization efficiency.
Kristofer Tvingstedt in 2007 etc. have invented a kind of organic polymer solar cell (K. Tvingstedt of folding V-structure, V. Andersson, F. L. Zhang, and O. Ingan s. Folded reflective tandem polymer solar cell doubles efficiency [J]. App. Phys. Lett, 91:123514).This structure, by two panels independently plane battery device, is spliced into V-type and is connected.By the mutual reflection between two devices, increase the light path of incident light in V-structure, thus increase the absorptivity of device for light and the external quantum efficiency (EQE) of battery, and then improve the energy conversion efficiency of solar cell device.
Array (the Y. H. Zhou that the solar cell that Yinhua Zhou in 2008 etc. design a kind of V-type foldable structure is formed, F. L. Zhang, K. Tvingstedt, W. J. Tian, and O. Ingan. Multifolded polymer solar cells on flexible substrates [J]. App. Phys. Lett, 93:033302).This kind of structure is the extension of V-structure presented hereinbefore, multiple V-type device is carried out connection in series-parallel composition array, has good reference for organic solar batteries large area panel designs.But V-structure can not ABSORPTION AND SCATTERING light completely, there is leakage problem.
Hongyu Zhen in 2012 etc. devise a kind of organic solar batteries (H. Y. Zhen of conical structure, K. L. Z.Y., Huang, Z., Tang, R., Wu et al. Inverted indium-tin-oxide-free cone-shaped polymer solar cells for light trapping [J]. App.Phys.Lett, 100:213901).This structure uses flexible substrate to make fan-shaped plan device, is then rolled into three-dimensional conical, acts on similar light trapping, incident light can be made in conical structure to carry out multiple reflections, and reduce the light reflected away.But when above-mentioned pyramidal structure forms dull and stereotyped plate array, filling rate is lower, this is that the space between adjacent circle can not make full use of, and loses area because conical structure light entrance face is for circular.In addition, organic solar batteries device common electrode material ITO or Al metal not resist bending, easily strip off, and the existence of stress can affect the useful life of device.
Application number is the manufacture method that the Chinese invention patent of 201010611615.X discloses Multi-hole pyramid structure on a kind of based single crystal silicon substrate, belongs to technical field of semiconductors.Described method comprises: first prepare pyramid structure on a monocrystaline silicon substrate with conventional solar cell etching method, recycling plasm immersion ion implantation prepares nanostructure in pyramid structure, thus forms Multi-hole pyramid structure on monocrystalline substrate surface.The present invention prepares Multi-hole pyramid structure on a monocrystaline silicon substrate, only needs two-step process to complete, and manufacture process is simple, and cost is low, has wide industrialization prospect; Meanwhile, the Multi-hole pyramid structure utilizing the inventive method to prepare at monocrystalline silicon surface, reduces the reflectivity of monocrystalline silicon surface.
Application number be 201110252280.1 Chinese invention patent disclose a kind of porous pyramid-type silicon surface light trapping structure preparation method for solar cell, after cleaning silicon chip, alkaline etching is adopted to prepare pyramid structure surface, and then obtain Multi-hole pyramid surface light trapping structure in conjunction with the method for noble metal nano particles catalysis etching, the silicon face porous pyramid-type light trapping structure adopting method of the present invention to prepare, in the spectral region of 300nm to 1000nm, its average reflectance has dropped to the level of 3.3%, for the efficiency improving silicon solar cell provides new technological means.The present invention fully utilizes the process of traditional alkaline etching and noble metal nano particles auxiliary etch, keeps the feature of wet etching, obtains the higher anti-reflective effect of silicon face.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of organic thin film solar cell is provided, which increase the utilization to unit are incident light, improve the energy conversion efficiency of battery.
Technical scheme of the present invention is as follows:
A kind of organic thin film solar cell, formed by multiple battery cell compact arrangement in a plane, it is characterized in that: the shape of battery cell is cone, described cone is positive three face cones, positive four face cones or positive six face cones, the medial surface of cone is sensitive surface, each medial surface all comprises a battery unit, and this battery unit is paved with this medial surface.
Further, the side of cone and the angle of bottom surface are 45 ~ 75 °.This angle is the important feature parameter of described cone, and according to described solar cell body layer absorption characteristic, different angles are different for described solar cell unit are absorptivity impact.Cone structure lateral area is also the important parameter of described structure simultaneously, and lateral area is the real work area of described solar cell.
Further, described battery unit is followed successively by substrate, transparent anode thin layer, solar cell active layer, cathode thin film layer from light incident direction, and solar cell active layer carries out opto-electronic conversion.Also can be inverted battery unit, namely light incidence is successively by transparent anode thin layer, solar cell active layer, cathode thin film layer, substrate.
Further, the opposite side of cathode thin film layer is provided with encapsulated layer.
Further, described substrate can be flexible substrate, requires energy water proof oxygen barrier, has high sunlight transmitance, and have certain mechanical performance.General employing poly terephthalic acid class plastic film (PET), also can use polyimide film (PI) at present.Described substrate also can be rigid substrate, as glass etc.
Further, the solar cell active layer in the battery unit of multiple medial surfaces of battery cell is the complementary activity layer with Different lightwave section absorption characteristic.
Further, battery cell is fixed on bracing frame.
A preparation method for organic thin film solar cell, is characterized in that comprising the following steps:
(1) battery cell is made, that 3,4 or 6 triangle battery units are produced on same a slice substrate, by half dark line, battery unit is converted into cone, the medial surface of cone is sensitive surface, described cone is positive three face cones, positive four face cones or positive six face cones, and junction uses press mold or bonding mode to fix;
(2) battery cell compact arrangement in a plane is formed organic thin film solar cell.
Making battery cell also can alternatively, and first prepare some triangle batteries that are onesize and shape first, then be spliced into cone structure, fixing means can with boning or press mold mode.
Transparent anode thin layer described in the present invention can be single layer of conductive material composition, also can be the sandwich construction of multiple electric conducting material composition, sandwich construction comprises anode layer and anode modification layer, and which kind of structure all needs to have high light transmittance in the scope of solar spectrum.Described single layer structure generally selects indium tin oxide (ITO), described sandwich construction is generally made up of indium tin oxide (ITO) layer and anode modification layer, anode modification layer material generally selects 4-ethylenedioxy thiophene: polystyrolsulfon acid (PEDOT:PSS), and conventional is 4083, or MoO
3.
Cathode thin film layer of the present invention can be single layer of conductive material composition, and also can be the sandwich construction of multiple electric conducting material composition, sandwich construction comprises cathode layer and cathodic modification layer.Described single layer structure generally selects Al, and in described sandwich construction, cathode layer generally selects high conductivity, the metal of high reflectance, as: Al, Ag, Au etc., described cathodic modification layer selects LiF, ZnO or TiO
2deng.
Described solar cell active layer can be the blended bulk heterojunction functional layer of donor material and acceptor material, also can be to the duplex heterojunction functional layer of body and acceptor film forming respectively.Described donor material is generally conjugated polymer and organic molecule, as poly-(3-hexyl thiophene) (P3HT), poly-[1-methoxyl group-4-(2 '-ethyl-own oxygen base)-2, 5-styrene] (MEH-PPV), poly-[2, 3-pair-(the pungent alkoxyl phenyl of 3-) quinoxaline-5, 8-bis-base-alternately-thiophene-2, 5-bis-base] (TQ1), CuPc (CuPc) etc., described acceptor material is generally the derivative of fullerene, as 6, 6-phenyl-C61-methyl butyrate (PCBM-C60), 6, 6-phenyl-C71-methyl butyrate (PCBM-C70), C60, C70 etc.
The battery unit of described battery cell can select same active layer material, also can select two or more different activities layer material, and the relative battery unit of such as four face cones can select the different activities layer material with complementary absorption wave band.
Organic thin film solar cell of the present invention, supporting construction can be used to be fixed it and guarantee device towards, simultaneously supporting construction can draw device electrode, facilitates battery pack connection in series-parallel.
Battery cell of the present invention, when forming extensive flat plate array, can use transparent glass to carry out entirety encapsulating, ensureing device lifetime and stability simultaneously, be convenient to the maintenance to device products and cleaning.
Organic thin film solar cell of the present invention, can change absorptivity to sunlight by the adjustment pyramid side gradient.On the one hand, cone structure can play the diluting effect of light, effectively can extend the life-span of solar cell; On the other hand, due to light multiple reflections, scattering and absorption in cone, the organic thin film solar cell unit are absorbing incident light of cone structure is strengthened.
Organic thin film solar cell of the present invention, battery cell adopts cone structure, and be different from planar structure of the prior art completely, its flat plate array can realize the filling rate of 100%, has a good application prospect.This construction geometry morphology Control is convenient, is absorbed again, effectively increase light-receiving area by multiple reflections in structure and scattering.And the battery unit forming battery cell in the present invention can facilitate series and parallel, increase delivery efficiency.
Compared with prior art, organic thin film solar cell of the present invention has following advantage:
(1) V-structure organic solar batteries only has 2 symmetrical device side, comparatively large to the dependence of the incident angle of sunlight, reflects or the light that scatters to V-structure both sides blank face directly goes out to penetrate structure and can not again utilize.The battery cell of organic thin film solar cell of the present invention is cone, each medial surface is solar cell unit, less to the dependence of the incident angle of sunlight, and light can only from the outgoing of structure upper shed face, so light trapping effect more effectively can be realized, increase light utilization efficiency.
(2) conical structure solar cell light entrance face is circular cone bottom surface, it is circular entrance face, when conical structure solar cell forms solar energy in large area cell plate array side by side, can there is white space between the plane of incidence of adjacent conical structure, solar battery array actual device area only accounts for about 79% of whole array area.Cone of the present invention is positive three face cones, positive four face cones or positive six face cones, and the organic thin film solar cell of composition, can be seamless spliced between adjacent cell monomer, there is not space, can realize the face filling rate of 100%, the effective efficiency improving battery.Conical structure solar cell needs first to make fan-shaped plan device in flexible substrate, then is bent by planar device, and be made into circular cone stereochemical structure by bonding or press mold mode, the effective efficiency district of its solar cell works under curved surface state.Become in the process of curved surface at device from plane, suffered by each function film layer that may cause forming device, stress becomes large, and the change of stress directly may cause greatly the tearing of film, come off, and make thin film damage, performance and the life-span of device are affected.Battery unit of the present invention is plane, and each functional film layer does not exist bending and stress increase problem, thus has better performance and longer life-span.In addition, device substrate of the present invention is both flexible, may also be rigidity.
Accompanying drawing explanation
Fig. 1 is the structural representation of the battery unit of organic thin film solar cell of the present invention;
Fig. 2 is the schematic diagram of the battery cell of positive four sides taper of the present invention;
Fig. 3 is that embodiment 1 is connected and to be tiled the voltage-to-current Data Comparison figure connected with device;
Fig. 4 is the embodiment 1 voltage-to-current Data Comparison figure tiling in parallel with device in parallel;
Fig. 5 is that embodiment 1 connection in series-parallel and device tile series-parallel voltage-to-current Data Comparison figure;
Fig. 6 is that embodiment 2 is connected and to be tiled the voltage-to-current Data Comparison figure connected with device;
Fig. 7 is the embodiment 2 voltage-to-current Data Comparison figure tiling in parallel with device in parallel;
Fig. 8 is that embodiment 2 connection in series-parallel and device tile series-parallel voltage-to-current Data Comparison figure;
Fig. 9 is that embodiment 3 is connected and to be tiled the voltage-to-current Data Comparison figure connected with device;
Figure 10 is the embodiment 3 voltage-to-current Data Comparison figure tiling in parallel with device in parallel;
Figure 11 is that embodiment 3 connection in series-parallel and device tile series-parallel voltage-to-current Data Comparison figure;
Figure 12 is that embodiment 4 is connected and to be tiled the voltage-to-current Data Comparison figure connected with device;
Figure 13 is the embodiment 4 voltage-to-current Data Comparison figure tiling in parallel with device in parallel;
Figure 14 is that embodiment 4 connection in series-parallel and device tile series-parallel voltage-to-current Data Comparison figure.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described, but the present invention is not limited to this.
As shown in Figure 1, the battery unit of organic thin film solar cell of the present invention, comprises 4 layers, is followed successively by flexible substrate layer 104 along incident light direction, transparent anode thin layer 103, solar cell active layer 102, cathode thin film layer 101.In following examples, flexible substrate layer 104 is poly terephthalic acid plastics (PET); Transparent anode thin layer 103 is sandwich construction, the ITO(tin indium oxide by high conductivity and light transmittance) film and anode modification film form, and anode modification thin layer is a kind of 4-ethylenedioxy thiophene of high conductivity: polystyrolsulfon acid (PEDOT:PSS); Solar cell active layer 102 is donor material poly-[2,3-pair-(the pungent alkoxyl phenyl of 3-) quinoxaline-5,8-bis-base-alternately-thiophene-2,5-bis-base] the bulk heterojunction functional layer of (TQ1) and acceptor material (6,6)-phenyl-C61-methyl butyrate (PCBM) blended composition; Cathode thin film layer 101 is single layer structure Al.
Be illustrated in figure 2 the structural representation of the battery cell of following examples, 4 leg-of-mutton battery units 1 are placed on bracing frame 5, form the battery cell of positive four sides taper.After 4 battery units 1 complete, extraction electrode on bracing frame 5 can be fixed on, carry out connecting and/or parallel connection, composition battery cell.Carry out again between battery cell connecting and/or parallel connection, composition organic thin film solar cell.
embodiment 1
In the present embodiment, the positive side of wimble structure, four sides and the angle β of bottom surface are 75 °, and lateral area is 4cm
2, floor space is 4 cm
2* sin(15 °)=1.04cm
2.
The preparation flow of the present embodiment is as follows:
The cutting of PET substrate ito film obtains the isosceles triangle substrate of 4 formed objects and shape, and on substrate, then prepare isosceles triangle battery unit and extraction electrode, isosceles triangle bottom side length is 1.02cm, and height is 1.97cm.Anode modification layer PEDOT:PSS is obtained by spin coating in ito film, and solar cell active layer is that the spin coating on PEDOT:PSS film of TQ1:PCBM solution obtains, and plates one deck Al as negative electrode finally by vacuum vapour deposition on active layer.After 4 battery units complete, be fixed on pyramid bracing frame extraction electrode.
Use the solar simulator through calibration to test the battery cell that the present embodiment obtains, the performance parameter of acquisition is as shown in table 1, and I-V characteristic curve is as shown in Fig. 3, Fig. 4 and Fig. 5.Wherein devices in series refers to the series connection of 4 battery units together, parallel connection refers to that 4 battery units are in parallel, the battery unit that device connection in series-parallel is connected with other 2 after referring to the series connection of 2 battery units is again in parallel, and tiling instigates 4 battery units to be fixed on flat support frame to make it perpendicular to incident light.
Table 1 embodiment 1 test result
As can be seen from table 1, Fig. 3, Fig. 4 and Fig. 5, the battery cell of the present embodiment, the battery tuple open circuit voltage comparing tiling is substantially identical with fill factor, curve factor, but the battery cell due to the present embodiment improves the absorption for light, short circuit current is improved, and therefore energy conversion efficiency obtains more than 3 times and improves.
embodiment 2
The difference of the present embodiment and embodiment 1 is, the positive side of wimble structure, four sides and the angle β of bottom surface are 67.5 °, and lateral area is 4cm
2, floor space is 1.53cm
2.
Method of testing is identical with embodiment 1, and the performance parameter of acquisition is as shown in table 2, and I-V characteristic curve is as shown in Fig. 6, Fig. 7 and Fig. 8.
Table 2 embodiment 2 test result
As can be seen from table 2, Fig. 6, Fig. 7 and Fig. 8, the battery cell of the present embodiment, the battery tuple open circuit voltage comparing tiling is substantially identical, but improves the absorption for light due to the battery cell of the present embodiment, short circuit current is improved, and therefore energy conversion efficiency obtains more than 2 times and improves.
embodiment 3
The difference of the present embodiment and embodiment 1 is, the positive side of wimble structure, four sides and the angle β of bottom surface are 60 °, and lateral area is 4cm
2, floor space is 2cm
2.
Method of testing is also identical with embodiment 1, and performance parameter is as shown in table 3, and I-V characteristic curve is as shown in Fig. 9, Figure 10 and Figure 11.
Table 3 embodiment 3 test result
As can be seen from table 3, Fig. 9, Figure 10 and Figure 11, the battery cell of the present embodiment, the battery tuple open circuit voltage comparing tiling is substantially identical, but the battery cell due to the present embodiment improves the absorption for light, short circuit current is obtained improve, therefore energy conversion efficiency obtains more than 1 times and improves.
embodiment 4
The difference of the present embodiment and embodiment 1 is, the positive side of wimble structure, four sides and the angle β of bottom surface are 45 °, and lateral area is 4cm
2, floor space is 2.83cm
2.
Method of testing is also identical with embodiment 1, and performance parameter is as shown in table 4, and I-V characteristic curve is as shown in Figure 12, Figure 13 and Figure 14.
Table 4 embodiment 4 test result
As can be seen from table 4, Figure 12, Figure 13 and Figure 14, the battery cell of the present embodiment, the battery tuple open circuit voltage comparing tiling is substantially identical, but the battery cell due to the present embodiment improves the absorption for light, short circuit current is obtained improve, therefore energy conversion efficiency can obtain at most more than 40% raising.
Claims (2)
1. an organic thin film solar cell, formed by multiple battery cell compact arrangement in a plane, it is characterized in that: the shape of battery cell is cone, described cone is positive four face cones, the medial surface of cone is sensitive surface, each medial surface all comprises a battery unit, this battery unit is paved with this medial surface, the side of cone and the angle of bottom surface are 45 ~ 75 °, battery unit is followed successively by substrate from light incident direction, transparent anode thin layer, solar cell active layer, cathode thin film layer, the opposite side of cathode thin film layer is provided with encapsulated layer, substrate is rigid substrate or flexible substrate, solar cell active layer in the battery unit of multiple medial surfaces of battery cell is the complementary activity layer with Different lightwave section absorption characteristic, battery cell is fixed on bracing frame, during battery cell filling flat plate array, filling rate is 100%, the four maximum short circuit current density of battery unit in situation in parallel forming positive four face cones are 13.36mA/cm
2, the maximum open circuit voltage in series connection situation is 3.25V.
2. a preparation method for organic thin film solar cell, is characterized in that comprising the following steps:
(1) making battery cell, is be produced on same a slice substrate by four triangle battery units, and by half dark line, battery unit is converted into cone, and the medial surface of cone is sensitive surface, and described cone is positive four face cones, and junction uses press mold or bonding mode to fix;
(2) battery cell compact arrangement in a plane is formed organic thin film solar cell;
The four maximum short circuit current density of battery unit in situation in parallel forming positive four face cones are 13.36mA/cm
2, the maximum open circuit voltage in series connection situation is 3.25V, under the condition that fill factor, curve factor remains unchanged, effectively improves short circuit current, improves energy conversion efficiency.
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| CN102208473A (en) * | 2011-05-30 | 2011-10-05 | 武汉凹伟能源科技有限公司 | Low-power concentrating power generation module of solar power generation |
| CN102299207A (en) * | 2011-08-30 | 2011-12-28 | 华北电力大学 | Method for manufacturing porous pyramid-type silicon surface light trapping structure for solar cell |
| CN202678419U (en) * | 2012-07-24 | 2013-01-16 | 暨南大学 | Organic solar thin-film battery |
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| CN102208473A (en) * | 2011-05-30 | 2011-10-05 | 武汉凹伟能源科技有限公司 | Low-power concentrating power generation module of solar power generation |
| CN102299207A (en) * | 2011-08-30 | 2011-12-28 | 华北电力大学 | Method for manufacturing porous pyramid-type silicon surface light trapping structure for solar cell |
| CN202678419U (en) * | 2012-07-24 | 2013-01-16 | 暨南大学 | Organic solar thin-film battery |
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| Title |
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| Inverted indium-tin-oxide-free cone-shaped polymer solar cells for light trapping;Hongyu Zhen et al;《Applied Physics Letters》;20120521;第100卷(第21期);第213901-1-213901-4页 * |
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