CN103137871A - Polymer solar energy cell and preparation method thereof - Google Patents
Polymer solar energy cell and preparation method thereof Download PDFInfo
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- CN103137871A CN103137871A CN2011103873858A CN201110387385A CN103137871A CN 103137871 A CN103137871 A CN 103137871A CN 2011103873858 A CN2011103873858 A CN 2011103873858A CN 201110387385 A CN201110387385 A CN 201110387385A CN 103137871 A CN103137871 A CN 103137871A
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Abstract
The invention discloses a polymer solar energy cell and a preparation method thereof. The polymer solar energy cell comprises an anode, a hole buffer layer, an active layer, an electron buffer layer and a metal cathode. The hole buffer layer is a p type hole buffer layer formed by inorganic metallic oxide and small organic molecule hole transmission materials in a doping mode. Through using of the p type hole buffer layer by the polymer solar energy cell, not only is machining difficulty reduced, but also a hole can be well injected to the anode, hole transmission rate is further improved, collection efficiency for a hole by electrodes is improved, and thus photoelectric conversion efficiency is improved. In addition, the p type hole buffer layer does not corrode an anode film, and thus service life of the polymer solar energy cell can be prolonged.
Description
Technical field
The present invention relates to a kind of polymer solar battery and preparation method thereof, particularly, relate to a kind of polymer solar battery with p-type Hole-injecting Buffer Layer for Improvement and preparation method thereof.
Background technology
Nineteen eighty-two, Weinberger etc. have studied the Photovoltaic Properties of polyacetylene, and have produced first and have truly solar cell, but photoelectric conversion efficiency at that time is extremely low by (10
-3%).And then, Glenis etc. have made the solar cell of various polythiophenes, and the problem that faced at that time is all extremely low open circuit voltage and photoelectric conversion efficiency.Until 1986, C.W.Tang etc. are incorporated into p-type semiconductor and N-shaped semiconductor in double-deck solar cell first, just make photoelectric current obtain the raising of very big degree, from then on, take this work as milestone, organic polymer solar cell is flourish.
1992, Sariciftci etc. find at poly-2-methoxyl group-5-(2'-ethyl-own oxygen base)-1, there is quick Photoinduced Electron transfer phenomena in 4-phenylene vinylidene (MEH-PPV) and C60 compound system, caused people's very big interest, and in nineteen ninety-five, the use MEH-PPV such as Yu mix as active layer with C60 derivative PCBM and have prepared organic polymer bulk heterojunction solar cell.This solar cell is at 20mW/cm
2, 430nm monochromatic light irradiation under energy conversion efficiency be 2.9%.This is first body heterojunction solar cell based on polymeric material and the preparation of PCBM acceptor, and has proposed the concept of inierpeneirating network structure in the composite membrane.So far, the application of body heterojunction structure in polymer solar battery obtained development rapidly.This structure also becomes the organic polymer solar cell structure that present people generally adopt.
The operation principle of polymer solar battery mainly is divided into four parts: the formation of (1) optical excitation and exciton; (2) diffusion of exciton; (3) division of exciton; (4) transmission of electric charge and collection.At first, conjugated polymer absorbs photon under the incident light irradiation, electronics transits to lowest unoccupied molecular orbital (LUMO) from polymer highest occupied molecular orbital (HOMO), thereby formation exciton, exciton is diffused under the effect of internal electric field to body/acceptor and is separated at the interface electronics and the hole that moves freely, then electronics transmits and is collected by negative electrode in mutually at acceptor, and the hole is by being collected by anode to body, thus the generation photoelectric current.This has just formed an effective photoelectric conversion process.
Yet in photoelectric conversion process, the transmission at the interface of photo-generated carrier between organic layer and inorganic electrode, to collect be an extremely important problem.It is difficult to form a good ohmic contact, usually at its interface formation Mo Te-Schottky barrier (Mott-Schottky barrier), causes the reduction of electrode place charge collection efficiency.
In order to address this problem, usually between anode and organic layer, Hole-injecting Buffer Layer for Improvement is set.For example, in CN101562231A, a kind of organic solar batteries that is provided with Hole-injecting Buffer Layer for Improvement is disclosed.
at present, Hole-injecting Buffer Layer for Improvement material commonly used is poly-3, 4-dioxy ethene thiophene (PEDOT) and polyphenyl sulfonate (PSS) the blend aqueous solution (PEDOT-PSS), but, this solution is due to the existence of PSS, make solution be faintly acid, can certain corrosion be arranged to conductive anode film (as ITO), stability to solar cell exerts an influence, and, the PEDOT price is more expensive, and its preparation process is complicated, the general purity of polymer is not high, there is certain impurity, efficient to solar cell has a great impact, simultaneously, it is more difficult that spin coating proceeding is controlled for the film (below 10nm) of thinner thickness, affect the processing of solar cell, the needs that are difficult to the satisfying the market competition.
Summary of the invention
The object of the invention is to, provide a kind of Hole-injecting Buffer Layer for Improvement can not corrode anode, and improve injection and the transmission in hole, and then improve the collection efficiency in electrode pair hole and improve photoelectric conversion efficiency, the polymer solar battery in the life-span of device improved to a certain extent.
Another object of the present invention is to, the preparation method of above-mentioned polymer solar battery is provided.
The inventor is through research discovery with keen determination, when by inorganic, metal oxide and organic molecule hole mobile material, the Hole-injecting Buffer Layer for Improvement of polymer solar battery being formed the p-type Hole-injecting Buffer Layer for Improvement, Hole-injecting Buffer Layer for Improvement can be accessed and anode can be do not corroded, and improve injection and the transmission in hole, and then improve the collection efficiency in electrode pair hole and improve the polymer solar battery of photoelectric conversion efficiency, thereby completed the present invention.
The invention provides polymer solar battery, comprise anode, Hole-injecting Buffer Layer for Improvement, active layer, electron buffer layer and metallic cathode, wherein, described Hole-injecting Buffer Layer for Improvement is the p-type Hole-injecting Buffer Layer for Improvement that the doping of inorganic, metal oxide and organic molecule hole mobile material is formed.
The present invention also provides the manufacture method of polymer solar battery, and it comprises: the step of preparation anode; The step of evaporation Hole-injecting Buffer Layer for Improvement on anode; The step of spin coating active layer on Hole-injecting Buffer Layer for Improvement; The step of evaporation electron buffer layer on active layer; And, the step of evaporation negative electrode on electron buffer layer, wherein, described on anode the step of evaporation Hole-injecting Buffer Layer for Improvement, be the step of the evaporation p-type Hole-injecting Buffer Layer for Improvement on anode by inorganic, metal oxide and organic molecule hole mobile material.
In p-type Hole-injecting Buffer Layer for Improvement of the present invention, the p doping that is formed by inorganic, metal oxide and organic molecule hole mobile material can further improve injection and the transmission rate in hole, thereby raising photoelectric conversion efficiency, and the not corrosion of this p-type Hole-injecting Buffer Layer for Improvement antianode film, thereby, the life-span that also can improve polymer solar cell device.In addition, p-type Hole-injecting Buffer Layer for Improvement material of the present invention is with respect to polymer, and synthetic simple, purity is higher, and cost is lower.
Description of drawings
Fig. 1 is the structural representation of polymer solar battery of the present invention.
Fig. 2 represents current density and the voltage relationship of the polymer solar battery of the polymer solar battery of embodiment 1 and comparative example 1, wherein, the current density voltage curve of the polymer solar battery of curve 1 expression embodiment 1, the current density voltage curve of the polymer solar battery of curve 2 expression comparative examples 1.
Embodiment
Below, the present invention will be described in detail by reference to the accompanying drawings.
Polymer solar battery Fig. 1 of the present invention is the structural representation of polymer solar battery of the present invention.As shown in Figure 1, polymer solar battery of the present invention, comprise anode, Hole-injecting Buffer Layer for Improvement, active layer, electron buffer layer and metallic cathode, wherein, described Hole-injecting Buffer Layer for Improvement is the p-type Hole-injecting Buffer Layer for Improvement that the doping of inorganic, metal oxide and organic molecule hole mobile material is formed.
As above-mentioned inorganic, metal oxide, be that work function value is that 5.0 ~ 5.5eV scope and visible light transmissivity are the inorganic, metal oxide more than 90%, be preferably molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2O
5).
As above-mentioned organic molecule hole mobile material, so long as its HOMO energy level can mate well with the work function of above-mentioned inorganic oxide, and the hole transport rate is high, can produce in batches organic molecule hole material gets final product, and can enumerate the HOMO energy level is that 5.4eV left and right and hole transport efficient are 10
-3The organic molecule hole mobile material that the order of magnitude is above.Particularly, can enumerate 1,1-, two { 4-[N, N '-two (p-tolyl) amino] phenyl } cyclohexane (TAPC), N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD), 4,4', 4''-three (carbazole-9-yl) triphenylamine (TCTA) or N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB).
In the present invention, doping ratio as above-mentioned inorganic, metal oxide and above-mentioned organic molecule hole mobile material, be expressed as 10 ~ 50 quality % with (inorganic, metal oxide/organic molecule hole mobile material), if above-mentioned doping ratio is less than 10 quality %, the hole injectability is insufficient, if above-mentioned doping ratio is greater than 50 quality %, optical transmission is relatively poor, thereby not preferred.
In the present invention, the thickness of above-mentioned p-type Hole-injecting Buffer Layer for Improvement is 20 ~ 80nm.If the thickness of p-type Hole-injecting Buffer Layer for Improvement less than 20nm, affects film forming, cause rete fracture, discontinuous, can't play the effect of Hole-injecting Buffer Layer for Improvement, if greater than 80nm, there is too much electron trap in the thickness of p-type Hole-injecting Buffer Layer for Improvement, electronics or hole are fallen into into, can not be effectively compound.
Because above-mentioned inorganic, metal oxide has the ability that the hole is injected, therefore, the hole is injected in anode, and, above-mentioned hole mobile material can improve hole transport speed, thereby both doping can form the p doping favourable to hole transport, can further improve thus hole transport speed, improve the collection efficiency in electrode pair hole, thereby improve photoelectric conversion efficiency, and the not corrosion of these material antianode films, therefore, also can extend the life-span of solar cell.In addition, inorganic, metal oxide and little molecular hole transport material are with respect to polymer, and synthetic simple, cost is lower.
Be polymer at the Hole-injecting Buffer Layer for Improvement material of polymer solar battery in the past, be not suitable for adopting evaporation process, normally formed by spin coating proceeding, need to remove the solvent in solution, in this process, the more difficult control of temperature is if temperature is lower, the meeting residual solvent, if excess Temperature, the form of polymer might change, therefore, processing technology is numerous and diverse, and difficulty is high.And, because polymer is to synthesize to complete through multistep, and each step all might introduce new material, form accessory substance, therefore cause the purity of final polymer low.And in the present invention, owing to can high inorganic, metal oxide (more than purity to 99.99%) and the organic small molecule material (more than purity to 95%) of the purity of employing own forming Hole-injecting Buffer Layer for Improvement, therefore, can guarantee that the purity of formed Hole-injecting Buffer Layer for Improvement is also high.And, owing to can adopting evaporation process to form Hole-injecting Buffer Layer for Improvement, do not need the removing step of solvent etc., therefore, reduced difficulty of processing.
In addition, in polymer solar battery of the present invention, as above-mentioned anode, can adopt known anode in polymer solar battery usually, can enumerate indium tin oxide glass (ITO), fluorine doped tin oxide glass (FTO), mix the zinc oxide glass (AZO) of aluminium or mix the zinc oxide glass (IZO) of indium.
In polymer solar battery of the present invention, above-mentioned active layer material can adopt present polymer solar cell device photoactive layer material used, particularly, can enumerate the system of P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM.Wherein, (Poly (3-hexylthiophene) is a kind of polythiophene to P3HT, PCBM ([6.6]-Phenyl-C61-butyric Acid Methyl Ester) is the derivative of fullerene (C60), MDMO-PPV is poly-[2-methoxyl group, 5-(3 ', 7 ' dimethyl-octyloxy)]-to the penylene ethylene, MEH-PPV is poly-2-methoxyl group-5-(2 '-ethyl-own oxygen base)-Isosorbide-5-Nitrae-phenylene vinylidene.In addition, the solvent of solution is one or both the mixed solvent in toluene, dimethylbenzene, chlorobenzene, chloroform.The concentration of every kind of system is controlled at 8 ~ 30mg/mL.When adopting the P3HT:PCBM system, its mass ratio is controlled at the scope of 1:0.8 ~ 1:1.When adopting MDMO-PPV:PCBM or MEH-PPV:PCBM, its mass ratio is controlled at the scope of 1:1 ~ 1:4.
The thickness of above-mentioned active layer is 80 ~ 300nm.
In the present invention, it is that 1:4, concentration are the MDMO-PPV:PCBM chlorobenzene solution system of 18mg/mL that preferred above-mentioned active layer adopts mass ratio, and at this moment, preferably its thickness is 200nm.
In polymer solar battery of the present invention, above-mentioned electron buffer layer can adopt common electron buffer layer material used in present polymer solar cell device, particularly, can enumerate lithium fluoride (LiF), lithium carbonate (Li
2CO
3) or cesium carbonate (Cs
2CO
3).This electron buffer layer thickness is 0.5 ~ 10nm.Preferred this electron buffer layer is LiF, and thickness is 1nm.
In addition, in polymer solar battery of the present invention, described metallic cathode is aluminium (Al), silver (Ag), gold (Au) or platinum (Pt).The thickness of this metallic cathode is 80 ~ 200nm.And in the present invention, the preferable alloy negative electrode is Al, and thickness is 150nm.
The manufacture method of polymer solar battery of the present invention comprises: the step of preparation anode; The step of evaporation Hole-injecting Buffer Layer for Improvement on anode; The step of spin coated active layer on Hole-injecting Buffer Layer for Improvement; The step of evaporation electron buffer layer on active layer; And, the step of evaporation negative electrode on electron buffer layer, wherein, described on anode the step of evaporation Hole-injecting Buffer Layer for Improvement, be the step of the evaporation p-type Hole-injecting Buffer Layer for Improvement on anode by inorganic, metal oxide and organic molecule hole mobile material.
In the manufacture method of polymer solar battery of the present invention, at first, photoetching treatment is carried out in the anode conducting substrate, and be cut into needed size.Then, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning of isopropyl alcohol 15min after removing the organic pollution on surface, carries out oxygen plasma treatment or UV-ozone treatment to this conductive substrates.When adopting oxygen plasma treatment, the processing time is 5 ~ 15min, and power is 10 ~ 50W.When adopting the UV-ozone treatment, the processing time is 5 ~ 20min.
Then, take the organic molecule hole mobile material as main body, inorganic, metal oxide is object, and with 10 ~ 50% doping ratio (inorganic, metal oxide/organic molecule hole mobile material), evaporation thickness is the p-type Hole-injecting Buffer Layer for Improvement of 20 ~ 80nm on anode.At this moment, described inorganic, metal oxide and organic molecule hole mobile material are identical with record in above-mentioned " polymer solar battery of the present invention ", omit repeated description at this.
Then, spin coating active layer on resulting p-type Hole-injecting Buffer Layer for Improvement.Spin coating is to carry out in being full of the glove box of non-active gas, and the 5 ~ 100min that anneals under 50 ~ 200 ℃ at last perhaps at room temperature places 24 ~ 48h, thus with THICKNESS CONTROL at 80 ~ 300nm.Described non-active gas preferably adopts nitrogen.
Then, evaporation electron buffer layer and negative electrode successively on active layer, thus obtain polymer solar battery of the present invention.
In addition, in the manufacture method of polymer solar battery of the present invention, spin coating condition and evaporation condition can adopt normal condition well known in the art to get final product, and do not have special restriction, and those skilled in the art can select suitable spin coating condition and evaporation condition according to the material that adopts.
Below, by embodiment and comparative example, the present invention is described in further detail.
Embodiment 1: make solar cell of the present invention according to following step.
A, at first carries out photoetching treatment to ITO, after forming needed light-emitting area pattern, is cut into the size of 2 * 2mm.Then, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning of isopropyl alcohol 15min after removing the organic pollution on surface, carries out oxygen plasma treatment to this anode substrate, and the processing time is 5min, and power is 35W.
B, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), take TCTA as main body, MoO
3Be object, and with the doping ratio (MoO of 40 quality %
3/ TCTA), evaporation thickness is the p-type Hole-injecting Buffer Layer for Improvement of 60nm on above-mentioned anode.
C, employing mass ratio are that 1:4, concentration are the MDMO-PPV:PCBM chlorobenzene solution of 18mg/mL, in being full of the glove box of nitrogen, carry out spin coating on above-mentioned p-type Hole-injecting Buffer Layer for Improvement, then, the 5min that anneals under 200 ℃, obtaining thickness is the 200nm active layer.
D, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), evaporation thickness is that the lithium fluoride (LiF) of 1nm is with as electron buffer layer on above-mentioned active layer.
E, on above-mentioned lithium fluoride electron buffer layer, evaporation thickness be the Al of 150nm with as metallic cathode, obtain thus the polymer solar battery of embodiment 1.
Employing current-voltage tester (U.S. Keithly company, 2602), be the white light source of simulated solar irradiation with the filter set cooperation of 500W xenon lamp (Osram) and AM 1.5 model:, at room temperature measure current-voltage, energy conversion efficiency and the fill factor, curve factor of the solar cell that embodiment 1 obtains.Measurement result is shown in Table 1.
Embodiment 2:a, at first carries out photoetching treatment to IZO, after forming needed light-emitting area pattern, is cut into the size of 2 * 2mm.Then, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning of isopropyl alcohol 15min after removing the organic pollution on surface, carries out oxygen plasma treatment to this anode substrate, and the processing time is 15min, and power is 10W.
B, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), take NPB as main body, MoO
3Be object, and with the doping ratio (MoO of 10 quality %
3/ NPB), evaporation thickness is the p-type Hole-injecting Buffer Layer for Improvement of 80nm on above-mentioned anode.
C, employing mass ratio are that 1:0.8, concentration are the P3HT:PCBM chloroformic solution of 18mg/mL, in being full of the glove box of nitrogen, carry out spin coating on above-mentioned p-type Hole-injecting Buffer Layer for Improvement, then, the 15min that anneals under 150 ℃, obtaining thickness is the 160nm active layer.
D, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), evaporation thickness is that the lithium fluoride (LiF) of 0.5nm is with as electron buffer layer on above-mentioned active layer.
E, on above-mentioned lithium fluoride electron buffer layer, evaporation thickness be the Ag of 80nm with as metallic cathode, obtain thus the polymer solar battery of embodiment 2.
According to the method for measurement identical with embodiment 1, current-voltage, energy conversion efficiency (η) and the fill factor, curve factor of the solar cell that measurement embodiment 2 obtains.Measurement result is shown in Table 1.
Embodiment 3:a, at first carries out photoetching treatment to FTO, after forming needed light-emitting area pattern, is cut into the size of 2 * 2mm.Then, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning of isopropyl alcohol 15min after removing the organic pollution on surface, carries out oxygen plasma treatment to this anode substrate, and the processing time is 10min, and power is 20W.
B, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), take TCTA as main body, WO
3Be object, and with the doping ratio (WO of 50 quality %
3/ TCTA), evaporation thickness is the p-type Hole-injecting Buffer Layer for Improvement of 20nm on above-mentioned anode.
C, employing mass ratio are that 1:3, concentration are the MEH-PPV:PCBM xylene solution of 16mg/mL, in being full of the glove box of nitrogen, carry out spin coating on above-mentioned p-type Hole-injecting Buffer Layer for Improvement, then, the 100min that anneals under 100 ℃, obtaining thickness is the 200nm active layer.
D, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), evaporation thickness is the lithium carbonate (Li of 5nm on above-mentioned active layer
2CO
3) with as electron buffer layer.
E, on above-mentioned lithium carbonate electron buffer layer, evaporation thickness be the Au of 180nm with as negative electrode, obtain thus the polymer solar battery of embodiment 3.
According to the method for measurement identical with embodiment 1, current-voltage, energy conversion efficiency and the fill factor, curve factor of the solar cell that measurement embodiment 3 obtains.Measurement result is shown in Table 1.
Embodiment 4:a, at first carries out photoetching treatment to ITO, after forming needed light-emitting area pattern, is cut into the size of 2 * 2mm.Then, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning of isopropyl alcohol 15min after removing the organic pollution on surface, carries out oxygen plasma treatment to this anode substrate, and the processing time is 7min, and power is 25W.
B, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), take TPD as main body, MoO
3Be object, and with the doping ratio (MoO of 30 quality %
3/ TPD), evaporation thickness is the p-type Hole-injecting Buffer Layer for Improvement of 50nm on above-mentioned anode.
C, employing mass ratio are that 1:2, concentration are the MDMO-PPV:PCBM toluene solution of 8mg/mL, in being full of the glove box of nitrogen, carry out spin coating on above-mentioned p-type Hole-injecting Buffer Layer for Improvement, then, the 100min that anneals under 70 ℃, obtaining thickness is the 300nm active layer.
D, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), evaporation thickness is the cesium carbonate (Cs of 10nm on above-mentioned active layer
2CO
3) with as electron buffer layer.
E, on above-mentioned cesium carbonate electron buffer layer, evaporation thickness be the Al of 200nm with as negative electrode, obtain thus the polymer solar battery of embodiment 4.
According to the method for measurement identical with embodiment 1, current-voltage, energy conversion efficiency and the fill factor, curve factor of the solar cell that measurement embodiment 4 obtains.Measurement result is shown in Table 1.
Embodiment 5:a, at first carries out photoetching treatment to AZO, after forming needed light-emitting area pattern, is cut into the size of 2 * 2mm.Then, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning of isopropyl alcohol 15min after removing the organic pollution on surface, carries out oxygen plasma treatment to this anode substrate, and the processing time is 12min, and power is 30W.
B, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), take TAPC as main body, V
2O
5Be object, and with the doping ratio (V of 30 quality %
2O
5/ TAPC), evaporation thickness is the p-type Hole-injecting Buffer Layer for Improvement of 30nm on above-mentioned anode.
C, employing mass ratio are that 1:1, concentration are the P3HT:PCBM toluene solution of 30mg/mL, in being full of the glove box of nitrogen, carry out spin coating on above-mentioned p-type Hole-injecting Buffer Layer for Improvement, then, at room temperature place 24 hours, and obtaining thickness is the 80nm active layer.
D, (scientific instrument development center, Shenyang Co., Ltd makes, pressure＜1 * 10 to adopt high vacuum coating equipment
-3Pa), evaporation thickness is the lithium fluoride (Cs of 0.7nm on above-mentioned active layer
2CO
3) with as electron buffer layer.
E, on above-mentioned cesium carbonate electron buffer layer, evaporation thickness be the Pt of 100nm with as negative electrode, obtain thus the polymer solar battery of embodiment 5.
According to the method for measurement identical with embodiment 1, current-voltage, energy conversion efficiency and the fill factor, curve factor of the solar cell that measurement embodiment 5 obtains.Measurement result is shown in Table 1.
Comparative example 1: except with conventional spin-coating method, adopt the PEDOT:PSS aqueous solution to form common Hole-injecting Buffer Layer for Improvement, to replace the MoO of embodiment 1
3: beyond the p-type Hole-injecting Buffer Layer for Improvement of TCTA, other and embodiment 1 operate in the same manner, obtain the polymer solar battery of comparative example 1.
And, according to the method for measurement identical with embodiment 1, current-voltage, energy conversion efficiency (η) and the fill factor, curve factor of the solar cell that measurement comparative example 1 obtains.Measurement result is shown in Table 1.
| ? | Current density (mAcm -2） | Voltage (V) | η（%） | Fill factor, curve factor |
| Embodiment 1 | 8.39 | 0.73 | 2.13 | 0.34 |
| |
8.31 | 0.73 | 1.94 | 0.32 |
| Embodiment 3 | 7.15 | 0.73 | 1.70 | 0.33 |
| Embodiment 4 | 7.82 | 0.75 | 1.92 | 0.33 |
| Embodiment 5 | 8.05 | 0.72 | 2.00 | 0.35 |
| Comparative example 1 | 7.15 | 0.72 | 1.67 | 0.34 |
Table 1: as can be known from Table 1, the solar cell with embodiment 1 ~ 5 of p-type Hole-injecting Buffer Layer for Improvement of the present invention is compared with the solar cell of the comparative example 1 with conventional Hole-injecting Buffer Layer for Improvement, and its current density and energy conversion efficiency all are improved.
In addition, Fig. 2 represents polymer solar battery (curve 1, the structure: ITO/MoO of embodiment 1
3: TCTA/MDMO-PPV:PCBM/LiF/Al) with polymer solar battery (curve 2, the structure: current density ITO/PEDOT:PSS/MDMO-PPV:PCBM/LiF/Al) and voltage relationship of comparative example 1.
As seen from Figure 2, the current density of the solar cell of comparative example 1 is 7.15mA/cm
2, and add the current density of the solar cell of the present invention of p-type Hole-injecting Buffer Layer for Improvement to bring up to 8.39mA/cm
2, this explanation forms the p doping and can improve injection and the transmission rate in hole, thereby improved photoelectric conversion efficiency, and the energy conversion efficiency of comparative example 1 is 1.67%, and the energy conversion efficiency of structure of the present invention is 2.13%.
Above; describe polymer solar battery of the present invention and preparation method thereof in detail by embodiment; yet; the present invention is not limited to above-mentioned disclosed exemplary embodiment; those skilled in the art are to be understood that; do not break away from interior any modification of doing of aim of the present invention, be equal to replacement and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. polymer solar battery, comprise anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, electron buffer layer and metallic cathode, it is characterized in that, described Hole-injecting Buffer Layer for Improvement is the p-type Hole-injecting Buffer Layer for Improvement that the doping of inorganic, metal oxide and organic molecule hole mobile material is formed.
2. polymer solar battery as claimed in claim 2, wherein, described inorganic, metal oxide is that work function value is that 5.0 ~ 5.5eV and visible light transmissivity are the inorganic, metal oxide more than 90%.
3. polymer solar battery as claimed in claim 3, wherein, described inorganic, metal oxide is to be molybdenum trioxide, tungstic acid or vanadic oxide.
4. polymer solar battery as claimed in claim 1, wherein, described organic molecule hole mobile material is 1,1-two { 4-[N, N '-two (p-tolyl) amino] phenyl } cyclohexane (TAPC), N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD), 4,4', 4''-three (carbazole-9-yl) triphenylamine (TCTA) or N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB).
5. polymer solar battery as claimed in claim 2, wherein, the doping ratio of described inorganic, metal oxide and described organic molecule hole mobile material is 10 ~ 50 % by mass percentage.
6. polymer solar battery as claimed in claim 1, wherein, the thickness of described p-type Hole-injecting Buffer Layer for Improvement is 20 ~ 80nm.
7. the manufacture method of a polymer solar battery, it comprises: the step of preparation anode; The step of evaporation Hole-injecting Buffer Layer for Improvement on anode; The step of spin coated active layer on Hole-injecting Buffer Layer for Improvement; The step of evaporation electron buffer layer on active layer; And, the step of evaporation negative electrode on electron buffer layer,
Wherein, described on anode the step of evaporation Hole-injecting Buffer Layer for Improvement, be the step of the evaporation p-type Hole-injecting Buffer Layer for Improvement on anode by inorganic, metal oxide and organic molecule hole mobile material.
8. the manufacture method of polymer solar battery as claimed in claim 7, wherein, described inorganic, metal oxide is that work function value is that 5.0 ~ 5.5eV and visible light transmissivity are the inorganic, metal oxide more than 90%.
9. the manufacture method of polymer solar battery as claimed in claim 8, wherein, described inorganic, metal oxide is to be molybdenum trioxide, tungstic acid or vanadic oxide.
10. the manufacture method of polymer solar battery as claimed in claim 7, wherein, described organic molecule hole mobile material is 1,1-two { 4-[N, N '-two (p-tolyl) amino] phenyl } cyclohexane (TAPC), N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD), 4,4', 4''-three (carbazole-9-yl) triphenylamine (TCTA) or N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715355A (en) * | 2013-12-06 | 2014-04-09 | 常州大学 | Organic solar cell hole transport layer and preparation method thereof |
| CN106784332A (en) * | 2017-02-04 | 2017-05-31 | 河南师范大学 | A kind of PEDOT:PSS‑MoO3The preparation method of/silicon nanowire array organic inorganic hybridization solar cell |
| CN113838983A (en) * | 2021-08-26 | 2021-12-24 | 电子科技大学 | Based on NPB/V2O5Organic photoelectric sensor of buffer layer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101383400A (en) * | 2008-10-07 | 2009-03-11 | 中国科学院长春应用化学研究所 | Organic light emitting device using high conductive hole transport material as hole transport layer |
| CN101562231A (en) * | 2009-05-08 | 2009-10-21 | 北京大学 | Strong correlation electron system-based organic solar cell and preparation method thereof |
| WO2011056778A2 (en) * | 2009-11-03 | 2011-05-12 | University Of Florida Research Foundation, Inc. | Interlayer for organic solar cells |
-
2011
- 2011-11-29 CN CN2011103873858A patent/CN103137871A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101383400A (en) * | 2008-10-07 | 2009-03-11 | 中国科学院长春应用化学研究所 | Organic light emitting device using high conductive hole transport material as hole transport layer |
| CN101562231A (en) * | 2009-05-08 | 2009-10-21 | 北京大学 | Strong correlation electron system-based organic solar cell and preparation method thereof |
| WO2011056778A2 (en) * | 2009-11-03 | 2011-05-12 | University Of Florida Research Foundation, Inc. | Interlayer for organic solar cells |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715355A (en) * | 2013-12-06 | 2014-04-09 | 常州大学 | Organic solar cell hole transport layer and preparation method thereof |
| CN103715355B (en) * | 2013-12-06 | 2015-12-02 | 常州大学 | A kind of organic solar batteries hole transmission layer and preparation method thereof |
| CN106784332A (en) * | 2017-02-04 | 2017-05-31 | 河南师范大学 | A kind of PEDOT:PSS‑MoO3The preparation method of/silicon nanowire array organic inorganic hybridization solar cell |
| CN113838983A (en) * | 2021-08-26 | 2021-12-24 | 电子科技大学 | Based on NPB/V2O5Organic photoelectric sensor of buffer layer and preparation method thereof |
| CN113838983B (en) * | 2021-08-26 | 2024-03-26 | 电子科技大学 | NPB/V-based 2 O 5 Organic photoelectric sensor of buffer layer and preparation method thereof |
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