CN101807670B - Hybridization photovoltaic battery and preparation method thereof - Google Patents
Hybridization photovoltaic battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an organic-inorganic hybridization photovoltaic battery based on senary butoxy benzophenanthrene as an inserting layer; the battery comprises a transparent electric conducting substrate, a hole-transporting layer, an organic activity layer and a metal electrode; and the key points of the battery is as follows: a senary butoxy benzophenanthrene layer is inserted between the hole-transporting layer and the organic activity layer. The invention also provides a preparation method for the organic-inorganic hybridization photovoltaic battery based on the senary butoxy benzophenanthrene as the inserting layer; the preparation method comprises: (1) cleaning and drying the transparent electric conducting substrate; (2) preparing the hole-transporting layer on the transparent electric conducting substrate; (3) depositing a senary butoxy benzophenanthrene thin film on the hole-transporting layer; (4) coating the organic activity layer on the senary butoxy benzophenanthrene thin film in air or under the protection of inert gases; (5) evaporating the metal electrode on the organic activity layer; and annealing. The invention has low cost, simple technique and is apt to the large area production. Compared with the organic solar battery with the conventional structure, the organic-inorganic hybridization photovoltaic battery generally increases the photoelectricity conversion efficiency.
Description
Technical field
The present invention relates to a kind of is organic inorganic hybridization photovoltaic cell that inserts on layer and preparation method thereof based on six butoxy benzos phenanthrene, has both belonged to thin-film material and devices field, also belongs to the new energy materials field.
Background technology
Solar cell is the device that directly changes into luminous energy electric energy through photoelectric effect or Photochemical effects.At present; The application of solar cell gets into departments such as industry, commerce, agricultural, communication, household electrical appliance and public utility from military field, space industry; Especially can be dispersedly in the outlying district, high mountain, desert, island and rural area use, to save the very expensive transmission line of cost.When non-renewable energy resources such as electric power, coal, oil signal for help repeatedly, when energy problem became the bottleneck of restriction international community economic development day by day, more and more countries came into effect " sunlight program ", and the exploitation solar energy resources is sought the new power of economic development.Solar cell is one of solution to this problem.
Solar cell is according to the difference of material therefor; Solar cell also can be divided into: silicon solar cell, multi-element compounds thin-film solar cells, polymer multi-layer modified electrode type solar cell; Wherein silicon solar cell is that development is the most ripe at present, in application, occupies leading position.Because the silicon cost price is high, reduce very difficulty of its cost significantly.
Multi-element compounds thin-film solar cells material is inorganic salts, and it comprises that mainly GaAs III-V compounds of group, cadmium sulfide, cadmium sulfide and copper plugs with molten metal selenium hull cell etc.But because cadmium has severe toxicity, can cause serious pollution to environment, therefore, be not the optimal substitute products of crystal silicon solar energy battery.
Replacing inorganic material with organic polymer is the research direction that a solar cell just having begun is made.Because the organic material flexibility is good, to make easily, material source is extensive, advantage such as at the bottom of the cost, thus to utilizing solar energy on a large scale, provide cheap electric energy significant.
At present, the researcher thinks that organic polymer is applied to structure comparatively desirable in the solar cell and is both at home and abroad:
ITO electro-conductive glass/hole transmission layer/gather 3-hexyl thiophene: the C60 derivative/(P3HT: PCBM)/aluminium (Al)
Wherein: ITO is an indium oxide of mixing tin, as the anode of battery.The net of being made up of P3HT (gathering the 3-hexyl thiophene) constitutes the electron donor, and the net of being made up of PCBM (C60 derivative) has constituted electron acceptor and electron transfer layer, and the mixed solution that P3HT and PCBM form is as photosensitive layer (organic active layer).Al is a negative electrode.At present, with NiO, MoO
3, PEDOT:PSS (gathering the dioxoethyl thiophene: gather p styrene sulfonic acid) had report as the hole transmission layer organic solar batteries.But, the efficient of the solar cell of this structure is limited to some extent owing to can be with the restriction of problems such as coupling and extinction scope.
Benzophenanthrene is a kind of discotic liquid-crystalline molecules, is the focus that people study in recent years based on the discotic mesogenic of benzophenanthrene, and this type of compound is synthetic simple, and rerum natura is stable, and is wide between the phase change zone.The molecular structure of this compounds is rigid central nuclear with the benzophenanthrene, usually 2,3, has 6 identical or different flexible side-chains on 6,7,10,11 positions.Six butoxy benzos luxuriant and rich with fragrance (preparation method document: the J.Mater.Chem. that sees reference, 2003,13,470-474) C
42H
60O
6(2,3,6,7,10,11-HexAbutoxyTriphenylene) be called for short HAT4, it is a kind of derivative of benzophenanthrene.Owing to the special physical characteristic of discotic mesogenic causes the great interest of people, for example electron transfer of one dimension property and power transfer, electroluminescent effect, characteristics such as ferroelectric property and surperficial self assembly.These character make discotic mesogenic in optical storage, organic semiconductor, and liquid crystal display, there is potential application aspects such as electric transmission.
Summary of the invention
To above-mentioned PEDOT:PSS, NiO, MoO
3, Cr
2O
3As the restriction of hole transmission layer to solar conversion efficiency; It serves as organic inorganic hybridization photovoltaic cell that inserts on layer and preparation method thereof with six butoxy benzos luxuriant and rich with fragrance (HAT4) that problem to be solved by this invention provides a kind of; This method is with low cost, stable performance, be easy to large tracts of land production, and the photovoltaic cell transformation efficiency that obtains is higher.
Technical scheme provided by the invention is: a kind of hybrid photovoltaic cells, comprise electrically conducting transparent substrate, hole transmission layer, organic active layer and metal electrode, and its main points are: between hole transmission layer and organic active layer, be inserted with the luxuriant and rich with fragrance layer of six butoxy benzos.
Said electrically conducting transparent substrate is FTO or ITO electro-conductive glass.
Said hole transmission layer is PEDOT:PSS or NiO or MoO
3Or Cr
2O
3Thin layer.
Said organic active layer is P3HT:PCBM (by gathering mixed solution that 3-hexyl thiophene and C60 derivative form as photosensitive layer).
Metal electrode is the Al electrode.
Said hole transmission layer is method with the magnetron sputtering NiO film or the MoO of deposition respectively on electrically conducting transparent substrate FTO
3Film or Cr
2O
3Film or prepare the film of PEDOT:PSS with the mode of even glue whirl coating.
It serves as the preparation method who inserts the organic inorganic hybridization photovoltaic cell of layer with six butoxy benzo phenanthrene that the present invention also provides above-mentioned, comprising:
(1) cleans electrically conducting transparent substrate and oven dry;
(2) on the electrically conducting transparent substrate, deposit hole transmission layer or prepare hole transmission layer with magnetically controlled sputter method with the method for sparing the glue whirl coating;
(3) on hole transmission layer, deposit the poor film of six butoxy benzos with thermal evaporation deposition process;
(4) in air or under inert gas shielding, on the poor film of six butoxy benzos, get rid of organic active layer with the method for even glue whirl coating;
(5) preparation of electrode: at organic active layer surface evaporation metal electrode, through after annealing under the inert gas shielding (120-150 ℃ is toasted 5-10min down).
The present invention uses the heat deposition method on hole transmission layer, to deposit the poor film condition of six butoxy benzos:
(1) the base vacuum degree 1.5 * 10
-3Pa;
(2) the luxuriant and rich with fragrance quality of evaporation six butoxy benzos is 5～44mg;
(3) evaporation current is 10～40A;
(4) evaporation time is 3-5 minute.
The hole transmission layer of magnetically controlled sputter method deposition according to the invention is Cr
2O
3Or NiO or MoO
3Transparent membrane; Use the hole transmission layer of the method preparation of even glue whirl coating to be PEDOT:PSS.
The present invention is with the method for thermal evaporation deposition HAT4 film; Between different hole transmission layers and organic layer, insert HAT4; Obtaining a kind of is organic inorganic hybridization photovoltaic cell of inserting on layer and preparation method thereof with six butoxy benzo phenanthrene, and it is with low cost, technology is simple, be easy to large tracts of land production.With respect to the organic solar batteries of traditional structure (hole transmission layer/organic active layer), photoelectric conversion efficiency has generally and to improve: with Cr
2O
3In the solar cell for hole transmission layer, insert the HAT4 behind efficiency and improved 22%; Be in the solar cell of hole transmission layer with NiO, inserting the HAT4 behind efficiency and improved 35%; With MoO
3In the solar cell for hole transmission layer, insert the HAT4 behind efficiency and improved 43%; Be in the solar cell of hole transmission layer with PEDOT:PSS, inserting the HAT4 behind efficiency and improved 43%.
Description of drawings
Accompanying drawing 1 is as the organic solar energy cell structure sketch map that inserts layer with HAT4; 1-electrically conducting transparent substrate, 2-hole transmission layer: can be respectively NiO, MoO
3, Cr
2O
3, PEDOT:PSS, 3-HAT4 layer, 4-P3HT:PCBM bulk heterojunction photoactive layer, 5-aluminium electrode;
Accompanying drawing 2 inserts the typical structure organic solar energy cell structure sketch map of layer for no HAT4; 1-electrically conducting transparent substrate, 2-hole transmission layer: can be respectively NiO, MoO
3, Cr
2O
3, PEDOT:PSS, 3-P3HT:PCBM bulk heterojunction photoactive layer, 4-aluminium electrode;
Accompanying drawing 3 is for to be respectively ITO/Cr with structure
2O
3/ HAT4/P3HT:PCBM/Al and ITO/Cr
2O
3The J-V curve of the organic solar batteries of/P3HT:PCBM/Al.
Accompanying drawing 4 is for to be respectively FTO/NiO/HAT4/P3HT:PCBM/Al and FTO/NiO/P3HT:PCBM/Al organic solar batteries J-V curve with structure.
Accompanying drawing 5 is for to be respectively FTO/MoO with structure
3/ HAT4/P3HT:PCBM/Al and FTO/MoO
3/ P3HT:PCBM/Al organic solar batteries J-V curve.
Embodiment
The present invention serves as that the organic inorganic hybridization photovoltaic cell that inserts layer can be taked following step with six butoxy benzo phenanthrene:
1 substrate processing
The substrate that adopts in the test is FTO and ITO electro-conductive glass, before test, should at first clean substrate.At first the electro-conductive glass sheet is cut into required shape; With cleaning agent it is cleaned up; Running water flushing then, deionized water rinsing then places it in and used deionized water, ethanol, each ultrasonic cleaning of acetone in the ultrasonic cleaner successively 20 minutes; Use deionized water rinsing at last, dry up and dry the substrate that can obtain surface cleaning with dry high pure nitrogen.Conductive plastics is cut into required shape, cleans with cleaning agent, deionized water rinsing then, ethanol cleans, and dries up for use with dry high pure nitrogen.
2 hole transmission layer thin-film process
2.1 NiO, MoO
3, Cr
2O
3The preparation of film
(1) target and clean Conducting Glass are put into the relevant position of settling chamber, adjustment specimen holder position makes it to aim at target surface, and keeps suitable distance.
(2) vacuum system is vacuumized.At first open cooling water.Open mechanical pump and take out low vacuum, after the system vacuum degree is lower than 10Pa, open the molecular pump pumping high vacuum, be superior to 3 * 10 until the system vacuum degree
-3Pa.
(3) in the settling chamber, feed an amount of high purity oxygen gas and argon gas, make oxygen and ar pressure reach required deposition pressure.
(4) adopt general radio frequency planar magnetic control sputtering technology.High-purity Ar and O
2Gas is respectively as sputter and reacting gas, and oxygen content changes at 30%--50% in the whole process.The contrast temperature is 30--200 ℃ of variation during sputter, and sputtering pressure is at 1.0Pa, and sputtering power changes at 80--130W, through sedimentation time control film thickness.Sputtering time is 2--6 minute.
(5) after thin film deposition was accomplished, sample was taken out in shutdown.
2.2PEDOT:PSS the preparation of film
(1) glass substrate of cleaning is put into the center of rotary-tray, changeed time and the revolution that changes with the back before adjusting.
(2) get the solution of the PEDOT:PSS of 0.2ml, drop on the substrate.
(3) press the starting switch of photoresist spinner, make it to start working.
(4) after rotation stopped, taking-up glass is placed on the hot platform dried 20 minutes with 90 ℃ in air.
(5) PEDOT:PSS film preparation success behind the natural cooling in air is taken out for use.
3HAT4 thin film deposition processes process
(1) with being coated with NiO, MoO respectively
3, Cr
2O
3Or the glass substrate of PEDOT:PSS film puts into the relevant position of settling chamber, and adjustment specimen holder position makes it to aim at evaporating boat, puts into HAT4 powder (5-44mg) and evaporates boat.
(2) vacuum system is vacuumized.At first open cooling water.Open mechanical pump and take out low vacuum, after the system vacuum degree is lower than 10Pa, open the molecular pump pumping high vacuum, be superior to 1.5 * 10 until the system vacuum degree
-3Pa.
(3) open the evaporation power supply, improve evaporation current slowly, electric current rises to 40A gradually from 10A.Evaporation time is 3-5 minute.
(4) after thin film deposition is accomplished, cool off shutdown taking-up sample after 30 minutes in a vacuum.
The preparation of 4 solar cells
(1) organic photosensitive layer formula: claim 50.0 milligrams of P3HT (Rieke Metals) with electronic balance, PCBM (Nano C) 40.0-60.0 milligram.After the mixing, it is dissolved in 2.0 milliliters the chlorobenzene.Be placed on then on the temperature controlled magnetic stirring apparatus, stirred 48 hours less than 50 ℃.Wait upon usefulness.
(2) in the gas tank of inert gas shielding, on the good HAT4 film of deposition, get rid of one deck P3HT:PCBM. with the method for even glue whirl coating.
(3) preparation of electrode: difference evaporated metal aluminium on the P3HT:PCBM surface.Through after annealing under the inert gas shielding (120-150 ℃ is toasted 5-10min down).
5 materials and device performance test
In order to estimate with six butoxy benzo phenanthrene is the photovoltaic property of the organic inorganic hybridization photovoltaic cell of insertion layer, and we utilize Keithley SMU tester to carry out the test of J-V curve with nothing six butoxy benzo phenanthrene for the photovoltaic cell that inserts layer for the photovoltaic cell that inserts layer to six butoxy benzo phenanthrene are arranged.
Below in conjunction with embodiment the present invention is further described, this description is just in order better to explain the present invention rather than to limit it.The present invention is not limited to described particular example and embodiment here.Any those of skill in the art are easy to further improving without departing from the spirit and scope of the present invention and perfect, all fall into protection scope of the present invention.
Embodiment one:
(1) cleans ITO (doping SnO
2In
2O
3) the electro-conductive glass sheet: earlier the electro-conductive glass slide is put into the solution that fills cleaning agent (like upright person who is not a member of any political party's liquid detergent) and soaked 10 minutes, clean the back clear water then repeatedly and rinse; Then carry out polishing with polishing powder; Put into the vessel that deionized water, acetone and alcohol are housed then respectively and distinguish ultrasonic 20 minutes; After putting twice of deionized water rinsing at last into, dry up and put into baking oven 80 degree oven dry to eliminate stress with nitrogen gun.
(2) chromium target and substrate are packed in the magnetron sputtering apparatus, carry out sputter with radio-frequency power supply.Condition of work is: base vacuum: 1 * 10
-4Pa; O
2/ (Ar+O
2)=40%, underlayer temperature: 200 ℃, sputtering pressure: 1.0Pa, sputtering power are at 100W, and sputtering time 6min obtains being coated with Cr
2O
3The ito glass substrate of film.
(3) preparation of HAT4 film: will be coated with Cr
2O
3The glass substrate of film is put into the relevant position of settling chamber, and adjustment specimen holder position makes it to aim at evaporation boiler, and keeps the distance of 12cm, puts into evaporation boiler to the HAT4 powder of 22mg.Vacuum system is vacuumized.At first open cooling water.Open mechanical pump and take out low vacuum, after the system vacuum degree is lower than 10Pa, open the molecular pump pumping high vacuum, until system vacuum degree excellent 1.5 * 10
-3Pa.Open the evaporation power supply, improve evaporation current slowly, electric current rises to 40A gradually from 10A.Evaporation time is 4 minutes.After thin film deposition was accomplished, cooling off in a vacuum shut down after the kind in 30 minutes took out sample.
(4) organic photosensitive layer formula: claim P3HT 50.0 milligrams with electronic balance, 50.0 milligrams of PCBM.After the mixing, it is dissolved in 2.0 milliliters the chlorobenzene.Be placed on then on the temperature controlled magnetic stirring apparatus, 50 ℃ were stirred 48 hours.
(5) in the gas tank of inert gas shielding, on the good HAT4 film of deposition, get rid of the thick P3HT:PCBM of the about 100nm of one deck with the method for even glue whirl coating.
(6) preparation of electrode: evaporate the thick metallic aluminium of about 150nm on the P3HT:PCBM surface respectively.Through after annealing under the inert gas shielding (150 ℃ of baking 5min).Obtain the organic photovoltaic battery of structure as shown in Figure 1: transparent conducting glass substrate ITO-1, Cr
2O
3Film-2, HAT4 film-3, P3HT:PCBM bulk heterojunction photoactive layer-4, aluminium electrode-5.
(7) battery performance explanation: open circuit voltage as shown in Figure 3 is: 0.55V; The short circuit current of battery is: 8.9mA/cm
2, fill factor, curve factor is: 57%, and energy conversion efficiency is: 2.8%.
Embodiment two:
(1) cleans ITO electro-conductive glass sheet, with embodiment one
(2) preparation Cr
2O
3Film is with embodiment one.
(3) organic photosensitive layer formula is with embodiment one.
(4) in the gas tank of inert gas shielding, at the good transparent Cr of deposition
2O
3Get rid of the thick P3HT:PCBM of the about 100nm of one deck on the film.
(5) preparation of electrode: evaporate the thick metallic aluminium of about 150nm on the P3HT:PCBM surface respectively.Through after annealing under the inert gas shielding (150 ℃ of baking 5min).Obtain the organic photovoltaic battery of structure as shown in Figure 2: transparent conducting glass substrate-1, Cr
2O
3Film-2, P3HT:PCBM bulk heterojunction photoactive layer-3, aluminium electrode-4.
(6) battery performance explanation: open circuit voltage as shown in Figure 3 is: 0.52V; The short circuit current of battery is: 8.2mA/cm
2, fill factor, curve factor is: 54%, and energy conversion efficiency is: 2.3%.
Embodiment three:
(1) cleans the FTO (SnO of doped with fluorine
2) glass: with embodiment one.
(2) nickel target and substrate are packed in the magnetron sputtering apparatus, carry out sputter with radio-frequency power supply.Condition of work is: base vacuum: 3 * 10
-3Pa, O
2/ (Ar+O
2)=30%, temperature: 30 ℃, sputtering pressure: 1.0Pa, power is respectively, and 80W, sputtering time 6min obtain being coated with the FTO glass substrate of NiO film.
(3) preparation of HAT4 film: the glass substrate that will be coated with the NiO film is put into the relevant position of settling chamber, and adjustment specimen holder position makes it to aim at evaporation boiler, and keeps the distance of 12cm, puts into evaporation boiler to the HAT4 powder of 44mg.Vacuum system is vacuumized.At first open cooling water.Open mechanical pump and take out low vacuum, after the system vacuum degree is lower than 10Pa, open the molecular pump pumping high vacuum, until system vacuum degree excellent 1.5 * 10
-3Pa.Open the evaporation power supply, improve evaporation current slowly, electric current rises to 40A gradually from 10A.Evaporation time is 5 minutes.After thin film deposition is accomplished, cool off shutdown taking-up sample after 30 minutes in a vacuum.
(4) organic photosensitive layer formula: with embodiment one.
(5) on the HAT4 film, get rid of organic membrane: with embodiment one.
(6) preparation of electrode: with embodiment one.Through after annealing under the inert gas shielding (120 ℃ of baking 10min).Obtain the organic photovoltaic battery of structure as shown in Figure 1: transparent conducting glass substrate FTO-1, NiO film-2, HAT4 film-3, P3HT:PCBM bulk heterojunction photoactive layer-4, aluminium electrode-5.
(7) battery performance explanation: open circuit voltage as shown in Figure 4 is: 0.62V, the short circuit current of battery is: 10.1mA/cm
2, fill factor, curve factor is: 56%, and energy conversion efficiency is: 3.5%.
Embodiment four:
(1) cleans the FTO (SnO of doped with fluorine
2) the electro-conductive glass sheet, with embodiment one
(2) preparation NiO film is with embodiment three.
(3) organic photosensitive layer formula is with embodiment one.
(4) in the gas tank of inert gas shielding, on the good transparent NiO film of deposition, get rid of the thick P3HT:PCBM of the about 100nm of one deck.
(5) preparation of electrode: with embodiment three.Obtain the organic photovoltaic battery of structure as shown in Figure 2: transparent conducting glass substrate-1, NiO film-2,, P3HT:PCBM bulk heterojunction photoactive layer-3, aluminium electrode-4.
(6) battery performance explanation: open circuit voltage as shown in Figure 4 is: 0.58V; The short circuit current of battery is: 8.8mA/cm
2, fill factor, curve factor is: 52%, and energy conversion efficiency is: 2.6%.
Embodiment five:
(1) cleans FTO glass: with embodiment one.
(2) molybdenum target and substrate are packed in the magnetron sputtering apparatus, carry out sputter with radio-frequency power supply.Condition of work is: base vacuum: 3 * 10
-3Pa, O
2/ (Ar+O
2)=50%, temperature: 100 ℃, sputtering pressure: 1.0Pa, power is respectively, 130W, sputtering time 2min. obtains being coated with MoO
3The FTO glass substrate of film.
(3) preparation of HAT4 film: will be coated with MoO
3The glass substrate of film is put into the relevant position of settling chamber, and adjustment specimen holder position makes it to aim at evaporation boiler, and keeps the distance of 12cm, puts into evaporation boiler to the HAT4 powder of 5mg.Vacuum system is vacuumized.At first open cooling water.Open mechanical pump and take out low vacuum, after the system vacuum degree is lower than 10Pa, open the molecular pump pumping high vacuum, until system vacuum degree excellent 1.5 * 10
-3Pa.Open the evaporation power supply, improve evaporation current slowly, electric current rises to 40A gradually from 10A.Evaporation time is 3 minutes.After thin film deposition is accomplished, cool off shutdown taking-up sample after 30 minutes in a vacuum.
(4) organic photosensitive layer formula: with embodiment one.
(5) on the HAT4 film, get rid of organic membrane: with embodiment one.
(6) preparation of electrode:, obtain the organic photovoltaic battery of structure as shown in Figure 1: transparent conducting glass substrate FTO-1, MoO with embodiment one
3Film-2, HAT4 film-3, P3HT:PCBM bulk heterojunction photoactive layer-4, aluminium electrode-5.
(7) battery performance explanation: open circuit voltage as shown in Figure 5 is: 0.58V, the short circuit current of battery is: 9.8mA/cm
2, fill factor, curve factor is: 53%, and energy conversion efficiency is: 3.0%.
Embodiment six:
(1) cleans the FTO (SnO of doped with fluorine
2) the electro-conductive glass sheet, with embodiment one
(2) preparation MoO
3Film is with embodiment five.
(3) organic photosensitive layer formula is with embodiment one.
(4) in the gas tank of inert gas shielding, on the good transparent NiO film of deposition, get rid of the thick P3HT:PCBM of the about 100nm of one deck.
(5) preparation of electrode: with embodiment one.Obtain the organic photovoltaic battery of structure as shown in Figure 2: transparent conducting glass substrate-1, MoO
3Film-2, P3HT:PCBM bulk heterojunction photoactive layer-3, aluminium electrode-4.
(6) battery performance explanation: open circuit voltage as shown in Figure 5 is: 0.58V; The short circuit current of battery is: 7.9mA/cm
2, fill factor, curve factor is: 47%, and energy conversion efficiency is: 2.1%.
Embodiment seven:
(1) cleans FTO glass: with embodiment one.
(2) the glass substrate FTO of cleaning is put into the center of rotary-tray, transfers 700 revolutions per seconds before adjusting to, the time be 12 seconds with after transfer 2000/ second to, the time is 30 seconds.Get PEDOT:PSS (Clevios P) solution of 0.2ml, drop on the substrate.Press the starting switch of photoresist spinner, make it to start working.After rotation stopped, taking-up glass is placed on the hot platform dried 20 minutes with 90 ℃ in air.Natural cooling film forming in air then.
(3) preparation of HAT4 film: the glass substrate that will be coated with the PEDOT:PSS film is put into the relevant position of settling chamber, and adjustment specimen holder position makes it to aim at evaporation boiler, and keeps the distance of 12cm, puts into evaporation boiler to the HAT4 powder of 11mg.Vacuum system is vacuumized.At first open cooling water.Open mechanical pump and take out low vacuum, after the system vacuum degree is lower than 10Pa, open the molecular pump pumping high vacuum, until system vacuum degree excellent 1.5 * 10
-3Pa.Open the evaporation power supply, improve evaporation current slowly, electric current rises to 40A gradually from 10A.Evaporation time is 4 minutes.After thin film deposition is accomplished, cool off shutdown taking-up sample after 30 minutes in a vacuum.
(4) organic photosensitive layer formula: with embodiment one.
(5) on the HAT4 film, get rid of organic membrane: with embodiment one.
(6) preparation of electrode: with embodiment one.Obtain the organic photovoltaic battery of structure as shown in Figure 1: transparent conducting glass substrate 1, PEDOT:PSS film 2, HAT4 film 3, P3HT:PCBM bulk heterojunction photoactive layer 4, aluminium electrode 5.
(7) battery performance explanation: open circuit voltage as shown in Figure 6 is: 0.57V, the short circuit current of battery is: 8.8mA/cm
2, fill factor, curve factor is: 57%, and energy conversion efficiency is: 3.0%.
Embodiment eight:
(1) cleans the FTO (SnO of doped with fluorine
2) the electro-conductive glass sheet, with embodiment one
(2) preparation PEDOT:PSS film is with embodiment seven.
(3) organic photosensitive layer formula is with embodiment one.
(4) in the gas tank of inert gas shielding, on the PEDOT:PSS film, get rid of the thick P3HT:PCBM of the about 100nm of one deck.
(5) preparation of electrode: with embodiment one.Obtain the organic photovoltaic battery of structure as shown in Figure 2: transparent conducting glass substrate 1, PEDOT:PSS film 2,, P3HT:PCBM bulk heterojunction photoactive layer 3, aluminium electrode 4.
(6) battery performance explanation: open circuit voltage as shown in Figure 6 is: 0.55V; The short circuit current of battery is: 8.1mA/cm
2, fill factor, curve factor is: 47%, and energy conversion efficiency is: 2.1%.
The data declaration that above embodiment obtains is with Cr
2O
3Or NiO or MoO
3Or PEDOT:PSS is in the solar cell of hole transmission layer, insert the poor layer of six butoxy benzos after, the short circuit current of its battery, fill factor, curve factor and energy conversion efficiency all increase significantly.
Claims (7)
1. a hybrid photovoltaic cells comprises electrically conducting transparent substrate, hole transmission layer, organic active layer and metal electrode, it is characterized in that: between hole transmission layer and organic active layer, be inserted with the luxuriant and rich with fragrance layer of six butoxy benzos; Said organic active layer is P3HT:PCBM.
2. organic photovoltaic battery according to claim 1 is characterized in that: said electrically conducting transparent substrate is FTO or ITO electro-conductive glass.
3. organic photovoltaic battery according to claim 1 and 2 is characterized in that: said hole transmission layer is PEDOT:PSS or NiO or MoO
3Or Cr
2O
3Thin layer.
4. organic photovoltaic battery according to claim 1 and 2 is characterized in that: metal electrode is the Al electrode.
5. the preparation method of the said hybrid photovoltaic cells of claim 1 comprises:
(1) cleans electrically conducting transparent substrate and oven dry;
(2) on the electrically conducting transparent substrate, deposit hole transmission layer or prepare hole transmission layer with magnetically controlled sputter method with the method for sparing the glue whirl coating;
(3) on hole transmission layer, deposit the poor film of six butoxy benzos with thermal evaporation deposition process;
(4) in air or under inert gas shielding, on the poor film of six butoxy benzos, get rid of organic active layer with the method for even glue whirl coating;
(5) preparation of electrode: at organic active layer surface evaporation metal electrode, through after annealing under the inert gas shielding.
6. preparation method according to claim 5 is characterized in that: use heat deposition method deposits the poor film condition of six butoxy benzos and is on hole transmission layer:
(1) the base vacuum degree 1.5 * 10
-3Pa;
(2) the luxuriant and rich with fragrance quality of evaporation six butoxy benzos is 5～44mg;
(3) evaporation current is 10～40A;
(4) evaporation time is 3-5 minute.
7. according to claim 5 or 6 described preparation methods, it is characterized in that: the hole transmission layer of said magnetically controlled sputter method deposition is Cr
2O
3Or NiO or MoO
3Transparent membrane; Use the hole transmission layer of the method preparation of even glue whirl coating to be PEDOT:PSS.
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