CN102315389A - Single-layer organic solar cell and making method thereof - Google Patents
Single-layer organic solar cell and making method thereof Download PDFInfo
- Publication number
- CN102315389A CN102315389A CN2010102230847A CN201010223084A CN102315389A CN 102315389 A CN102315389 A CN 102315389A CN 2010102230847 A CN2010102230847 A CN 2010102230847A CN 201010223084 A CN201010223084 A CN 201010223084A CN 102315389 A CN102315389 A CN 102315389A
- Authority
- CN
- China
- Prior art keywords
- layer
- metal nano
- electrode layer
- particle
- organic solar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a single-layer organic solar cell, which comprises a transparent insulating substrate, and a transparent anode electrode layer, a photosensitive layer and a cathode electrode layer which are sequentially formed on the transparent insulating substrate in an overlapped manner; a metal nano-particle layer is formed on at least one surface of the cathode electrode layer in the overlapped manner; and the power function value of metal nano particles in the metal nano-particle layer is less than the power function value of the cathode electrode layer. The metal nano-particle layer is arranged in the single-layer organic solar cell, so a built-in electric field of a single-layer organic solar cell device is enhanced, the separation efficiency of right excitons is improved, and the energy transfer efficiency of the right excitons is finally enhanced; by a making method for the single-layer organic solar cell device, all the layers of the single-layer organic solar cell device are sequentially formed and tightly and firmly connected, so the single-layer organic solar cell device is stable in performance, high in production efficiency and applicable for industrialized production.
Description
Technical field
The invention belongs to the electrooptical device technical field, relate to a kind of individual layer organic solar batteries and preparation method thereof specifically.
Background technology
Solar cell be a kind of be the photovoltaic device of electric energy with transform light energy.Reported that since AT&T Labs in 1954 efficient is 4% inorganic solar cell, since half a century, solar cell has obtained development at full speed, all starts Lai Yichang " green energy resource revolution " in the world.After the nineties in 20th century, GaAs, cadmium telluride or the like photovoltaic device has grown up again in the inorganic solar cell family.But up to today, high cost is the matter of utmost importance of restriction inorganic semiconductor solar cell large-scale promotion application.Yet the cost problem is mainly still brought by inorganic material itself, solves energy problem's effective way so have only really cheaply green energy resource to be only.
The research of organic solar batteries starts from 1958; Keams and Calvin are clipped in magnesium phthalocyanine dye (MgPc) between the electrode of two different work functions; Process " sandwich " structure; Thereby obtained the open circuit voltage of 200mV, but its short circuit current output is then very low, so its energy conversion efficiency is also relatively low.This individual layer organic solar energy cell structure was adopted double-deck heterojunction structure to substitute in 1986 by C.W.Tang, had obtained 1% energy conversion efficiency.The reason that energy conversion efficiency is increased dramatically promptly is to think that double-deck heterojunction structure provides the interface of an exciton fractionation efficiently, that is to say that double-deck heterostructure makes neutral electron-hole pair split into free carrier and becomes more easy.It is obvious that; The introducing of double-deck heterostructure has increased the complexity of organic solar batteries device greatly; And because the quality of heterojunction structure is vital to the output of entire cell, so require comparatively harsh to the control of heterojunction growth.Therefore; If can on the basis of original individual layer " sandwich " structure organic solar batteries, improve; Also can access the performance requirement of heterojunction photovoltaic cell, then will further simplify the production routine of organic solar batteries, and can reduce its technology cost.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art; A kind of individual layer organic solar batteries is provided; This solar cell negative electrode layer at least the one side on be provided with the metal nano-particle layer that is lower than the negative electrode layer work function value; Thereby further strengthened the internal electric field of individual layer organic solar batteries device, split efficient, promoted the energy conversion efficiency of individual layer organic solar batteries thereby improved right exciton.
Another object of the present invention is to provide a kind of preparation method of individual layer organic solar batteries.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
A kind of individual layer organic solar batteries; Comprise the transparent insulation substrate and on the transparent insulation substrate, stack gradually transparent anode electrode layer, photosensitive layer and the negative electrode layer of formation; Said negative electrode layer one side at least is formed with metal nano-particle layer, and the work function value of metal nanoparticle is lower than the work function value of negative electrode layer in the said metal nano-particle layer.
And, a kind of individual layer organic solar batteries preparation method, it comprises the steps:
Preparation transparent insulation substrate;
On the wherein one side of said transparent insulation substrate, form the transparent anode electrode layer;
On the transparent anode electrode layer, deposit light-sensitive material, form photosensitive layer;
Range upon range of metal nano-particle layer and the cathode layer of deposition on photosensitive layer, thus described individual layer organic solar batteries obtained, and wherein, at least one surface layer of said negative electrode layer is folded has metal nano-particle layer;
Wherein, the work function value of metal nanoparticle is lower than the work function value of negative electrode layer in the said metal nano-particle layer.
Said individual layer organic solar batteries device at least simultaneously is formed with metal nano-particle layer at its negative electrode layer; The work function value of metal nano-particle layer is lower than the negative electrode layer work function value; The target electrode layer is modified; Reduce the work function of negative electrode layer, thereby further increased work function difference between negative electrode layer and the transparent anode electrode layer, thereby further strengthened the internal electric field of individual layer organic solar batteries device; Thereby improved the efficient that exciton is split, finally promoted the energy conversion efficiency of individual layer organic solar batteries.Simultaneously, individual layer organic solar batteries preparation of devices method is that this each layer of solar cell device is formed successively, make each layer connection closely, firmly; Thereby make this solar cell device stable performance; Production efficiency is high, has reduced production cost, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the structural representation of individual layer organic solar batteries first execution mode of the embodiment of the invention;
Fig. 2 is the structural representation of individual layer organic solar batteries second execution mode of the embodiment of the invention;
Fig. 3 is the structural representation of the third execution mode of individual layer organic solar batteries of the embodiment of the invention.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention will be solved, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
A kind of individual layer organic solar batteries; Comprise the transparent insulation substrate and on the transparent insulation substrate, stack gradually transparent anode electrode layer, photosensitive layer and the negative electrode layer of formation; Said negative electrode layer one side at least is formed with metal nano-particle layer, and the work function value of metal nanoparticle is lower than the work function value of negative electrode layer in the said metal nano-particle layer.Present embodiment individual layer organic solar batteries has following three kinds of execution modes:
See also Fig. 1, show the structural representation of individual layer organic solar batteries first execution mode of the embodiment of the invention.In this execution mode, this individual layer organic solar batteries comprises transparent insulation substrate 5 and on transparent insulation substrate 5, stacks gradually the transparent anode electrode layer 4 of formation, photosensitive layer 3, metal nano-particle layer 2 and negative electrode layer 1.Because the work function value of metal nanoparticle is lower than the work function value of negative electrode layer 1 in the metal nano-particle layer 2, therefore, negative electrode layer 1 chemical stabilization; Difficult oxidized; And the metal nanoparticle chemical in the metal nano-particle layer is active, and easy oxidized, this execution mode is that metal nano-particle layer 2 is arranged between photosensitive layer 3, the negative electrode layer 1; That is to say metal nano-particle layer 2 range upon range of being formed on the one side of negative electrode layer 1 near photosensitive layer 3; Thereby effectively that metal nano-particle layer 2 and oxygen is isolated, effectively protected metal nano-particle layer 2 not oxidized, make the functional of metal nano-particle layer 2 stablize.
See also Fig. 2, show the structural representation of individual layer organic solar batteries second execution mode of the embodiment of the invention.In this execution mode; This individual layer organic solar batteries comprises transparent insulation substrate 5 and on transparent insulation substrate 5, stacks gradually the transparent anode electrode layer 4 of formation, photosensitive layer 3, metal nano-particle layer 2, negative electrode layer 1 and metal nano-particle layer 2 '; Wherein the material of metal nano-particle layer 2 and metal nano-particle layer 2 ' can be the metal nanoparticle that work function value is lower than the work function value of negative electrode layer for the same or different.This execution mode is all range upon range of metal nano-particle layer that is formed with on the two sides of negative electrode layer 1; Can know by above-mentioned analysis; Because the work function value of metal nanoparticle is lower than the work function value of negative electrode layer 1 in the metal nano-particle layer; Therefore, negative electrode layer 1 chemical stabilization, the metal nanoparticle chemical in the metal nano-particle layer is active; And this execution mode is with range upon range of negative electrode layer 1 two sides that is arranged on of metal nano-particle layer; The metal nano-particle layer 2 near photosensitive layer 3 one sides will completely cut off with oxygen on the negative electrode layer 1 thereby effectively will be layered in, and effectively protect metal nano-particle layer 2 not oxidized, make the functional of metal nano-particle layer 2 stablize; Be layered in surface that is to say on negative electrode layer 1 another side be exposed to the metal nano-particle layer 2 ' in the atmosphere As time goes on; Will be by slowly oxidation, thus make the functional stabilization of metal nano-particle layer 2 ' decrease, but do not influence the individual layer organic solar batteries overall performance in this execution mode.Oxidized in order to prevent metal nano-particle layer 2 ', can be coated with last layer anti-oxidation protection rete at metal nano-particle layer 2 ' outer surface.
See also Fig. 3, show the structural representation of the third execution mode of individual layer organic solar batteries of the embodiment of the invention.In this execution mode; This individual layer organic solar batteries comprises transparent insulation substrate 5 and on transparent insulation substrate 5, stacks gradually the transparent anode electrode layer 4 of formation, photosensitive layer 3, negative electrode layer 1 and metal nano-particle layer 2 ', and wherein the material of the metal nano-particle layer 2 in the material of metal nano-particle layer 2 ' and the above-mentioned two kinds of execution modes is the same.This execution mode is that the one side laminated at the negative electrode layer that deviates from photosensitive layer 31 has metal nano-particle layer 2 '; That is to say the outer surface that metal nano-particle layer 2 ' is layered in negative electrode layer 1; Can know by above-mentioned analysis, because the work function value of metal nano-particle layer 2 ' middle metal nanoparticle is lower than the work function value of negative electrode layer 1, therefore; Negative electrode layer 1 chemical stabilization; Metal nanoparticle chemical in the metal nano-particle layer is active, and is easy oxidized, but this execution mode negative electrode layer 1 can not effectively protect metal nano-particle layer 2 ' not oxidized; Make be exposed in the atmosphere metal nano-particle layer 2 ' As time goes on; Its surperficial metal nanoparticle will be by slowly oxidation, thereby makes the functional stabilization of metal nano-particle layer 2 ' decrease, thereby causes the individual layer organic solar batteries overall performance in this execution mode also to descend to some extent.But the oxidized metal nanoparticle on metal nano-particle layer 2 ' surface will play the effect of protective layer; Metal nano-particle layer 2 ' is played the effect of isolated oxygen near the interior metal nano particle of negative electrode layer 1; Make metal nano-particle layer 2 ' not oxidized, make the functional of metal nano-particle layer 2 ' tend towards stability near the interior metal nano particle of negative electrode layer 1.Thereby make the individual layer organic solar batteries overall performance of this execution mode also tend towards stability.Oxidized in order to prevent metal nano-particle layer 2 ', can be coated with last layer anti-oxidation protection rete at metal nano-particle layer 2 ' outer surface.
The material of above-mentioned transparent insulation substrate 5 is preferably clear glasses such as quartz glass, silicate glass, vagcor or soda-lime glass; Perhaps polyvinyl chloride (PVC), Merlon (PC) or polyester transparent insulation plastic cement such as (PET), its thickness is preferably 1.1-1.5mm.
The material of above-mentioned transparent anode electrode layer 4 is preferably tin indium oxide (ITO), zinc oxide aluminum (AZO), zinc-gallium oxide (GZO), indium zinc oxide transparent oxide films such as (IZO); The metallic film of perhaps golden (Au) film, aluminium (A1), silver (Ag) etc.; The perhaps conductive film of CNT, its thickness is preferably the 80-120 nanometer.Because this transparent anode electrode layer 4 adopts transparent conductive material or metallic film to constitute, and thin thickness, therefore can play the effect of electrode, does not influence seeing through of sunlight again.This transparent anode electrode layer 4 that is to say the anode of individual layer organic solar batteries, and can adopt the photoetching corrosion method that it is corroded into stripe, thereby forms the stripe electrode.
The material of above-mentioned photosensitive layer 3 is preferably hole mobile materials such as phthalocyanine dye, pentacene, porphyrin compound, cyanine dyes, and perhaps fullerene is (like C
60, C
70Deng), electron transport materials such as PTCDA, Pe, Pe derivative, again or be CdSe, CdS, CdTe, TiO
2, ZnO, PbS, SnO
2, inorganic nano material such as CNT or Graphene, its thickness is preferably 50-100nm.This photosensitive layer 3 is as the main photosensitive region of absorbing light generation photoelectric current, and its effect is that photosensitive layer 3 absorbs after the photon energies, can produce a spot of free carrier; Situation but more is to produce the electron-hole pair with certain binding force; Exciton just, exciton is electric neutrality, under the internal electric field effect of individual layer organic solar batteries device, is split into free carrier; This free carrier respectively to two drift electrodes, is exported thereby form photoelectric current in photosensitive layer 3.
Metal nanoparticle in above-mentioned metal nano-particle layer 2 and the metal nano-particle layer 2 ' is preferably the metal material that its work function value is lower than negative electrode layer 1 work function value; For example adopt lithium (Li)), at least a in the caesium (Cs), potassium (K), sodium (Na), the thickness of this metal nano-particle layer 2 is preferably 0.5-1nm.Because metal nano-particle layer 2 very thin thickness, thereby its loss to sunlight is very little, can ignore; So most of sunlight still is 3 absorptions of photosensitive layer, when thickness during greater than 1nm, can reflected sunlight; Be unfavorable for absorbing, impact effect, and thickness is during less than 0.5nm; Do not have the purpose that reduces work function, effect is also bad.Certainly metal nano-particle layer 2 ' is owing to be layered on the negative electrode layer 1 that exposes the atmosphere one side; The preferred 0.5-1nm of the thickness of metal nano-particle layer 2 ', but be not limited only to this thickness, also can be greater than 1nm; Because; The thickness of metal nano-particle layer 2 ' can not cause the loss of the sunlight that is absorbed by photosensitive layer 3, and the suitable increase of metal nano-particle layer 2 ' thickness, more helps protecting in the metal nano-particle layer 2 ' the interior metal nano particle near negative electrode layer 1 not oxidized; Make the functional of metal nano-particle layer 2 ' tend towards stability, thus feasible the stable of individual layer organic solar batteries overall performance that guaranteed.
Above-mentioned negative electrode layer 1 is by Ag, Al, and metallic films such as Ca-Al alloy, Mg-Ag alloy perhaps are the high reflectance electrode that metal oxides such as ITO or ZnO constitute, and the thickness of this negative electrode layer 1 is 80-120nm.This negative electrode layer 1 that is to say the negative electrode of individual layer organic solar batteries.
Why efficient is not high for the conventional monolayers organic solar batteries, and its main cause is that the photoproduction exciton in the battery can not effectively be split.This process of exciton fractionation mainly occurs at the interface, the impurity defect place splits under effect of electric field.Yet in the individual layer organic solar batteries, lacked the donor-receiver interface that exciton splits, the fractionation of exciton mainly is under the effect of electric field in the material internal particle trap to be carried out, and also has a spot of exciton fractionation at organic material and electrode interface place simultaneously.But this a part of exciton fractionation efficient is many a little less than comparing with the heterojunction boundary fractionation and wanting, and this also is the lower most important reason of individual layer organic solar batteries efficient.Based on this theory; The embodiment of the invention has or the two sides is all also range upon range of metal nano-particle layer 2 is arranged or/and 2 ' in that negative electrode layer 1 one side is range upon range of; Preferably range upon range of between photosensitive layer 3 and negative electrode layer 1 have a metal nano-particle layer 2, because metal nano-particle layer 2 is or/and 2 ' work function value is lower than the work function value of negative electrode layer 1, target electrode layer 1 is modified; Thereby reduce the work function of negative electrode layer 1, thereby strengthen individual layer organic solar batteries device inside electric field.The metallic particles that the embodiment of the invention is selected the low work function value for use as metal nano-particle layer 2 or/and 2 ' material; This metal nano-particle layer 2 is or/and 2 ' work function value is preferably 4.5-2eV; For example the work function of lithium is at 2.9eV; Work function 4.3eV than aluminium Al is much lower; Like this, the difference of the work function value between transparent anode electrode layer 4 (work function like ITO is 4.6-4.8eV) and the negative electrode layer 1 will further increase, thereby has strengthened the internal electric field of individual layer organic solar batteries device.
Certainly; Present embodiment can directly be a negative electrode layer 1 with above-mentioned low workfunction metal nano particle directly also; But this execution mode is prone to produce the adverse effect of two aspects: on the one hand, low workfunction metal generally all compares vivaciously, and is oxidized easily in atmosphere; Thereby influence the carrier collection efficient of electrode, protect so will be aided with comparatively stable metallic cathode in its outside; On the other hand; Boundary reflection rate after low workfunction metal (for example lithium) is oxidized reduces greatly; Make the sunlight of incident organic solar batteries partially absorbed afterwards in cathode electrode 1 place loss by photosensitive layer 3; And experience the secondary absorption of photosensitive layer 3 after can't passing through 1 reflection of high reflectance cathode electrode, thereby reduced the light utilization ratio.So, adopt the nano-particle modified cathode electrode 1 of low workfunction metal can avoid its loss to sunlight, can reach the enhance device internal electric field simultaneously again and improve the effect that the interface exciton splits efficient.Thereby finally promote individual layer organic solar batteries energy conversion efficiency.When the low workfunction metal nano particle directly is negative electrode layer 1; For fear of the appearance of above-mentioned two unfavorable factors, can take to be coated with last layer anti-oxidation protection rete like above-mentioned negative electrode layer 1 outer surface of doing material at the low workfunction metal nano particle.
Because individual layer organic solar batteries device of the present invention has or the two sides is all range upon range of that metal nano-particle layer arranged in that the wherein one side of its negative electrode layer is range upon range of; The work function value of metal nano-particle layer is lower than the negative electrode layer work function value; Target electrode layer 1 is modified, and has reduced the work function of negative electrode layer 1, thereby has further increased work function difference between negative electrode layer 1 and the transparent anode electrode layer 4; Thereby further strengthened the internal electric field of individual layer organic solar batteries device; Thereby improved the efficient that exciton is split, finally promoted the energy conversion efficiency of individual layer organic solar batteries, the energy conversion efficiency of present embodiment individual layer organic solar batteries is up to about in the of 0.1; And for the individual layer organic solar batteries; Split the interface owing to lack effective exciton, thereby its efficient is generally all very low, like the energy conversion efficiency of existing individual layer organic solar batteries when low-function function decorative layer not being set modifying negative electrode below 0.05%; Existing relatively individual layer organic solar batteries, the energy conversion efficiency of present embodiment individual layer organic solar batteries improves significantly.
Present embodiment also provides individual layer organic solar batteries preparation of devices method, comprises the steps:
1) preparation transparent insulation substrate 5;
2) on the wherein one side of said transparent insulation substrate 5, form transparent anode electrode layer 4;
3) on transparent anode electrode layer 4, deposit light-sensitive material, form photosensitive layer 3;
4) range upon range of metal nano-particle layer and the cathode layer of deposition on photosensitive layer, thus described individual layer organic solar batteries obtained, and wherein, at least one surface layer of said negative electrode layer is folded has metal nano-particle layer;
Wherein, the work function value of metal nanoparticle is lower than the work function value of negative electrode layer 1 in the said metal nano-particle layer.
In above-mentioned steps 1) in; The thickness of transparent insulation substrate 5 is preferably 1.1-1.5mm, transparent, insulation material that its material is preferred above-mentioned, and the big I of the area of this transparent insulation substrate 5 is done flexible adjustment according to actual needs; As can be little to several square millimeters, greatly to tens square centimeters.
In above-mentioned steps 2) in; The preferred version of preparation transparent anode electrode layer 4 is: with transparent insulation substrate 5 after cleaning; Adopt the method for sputter; On the wherein one side of said transparent insulation substrate 5, plate the layer of conductive film layer, and adopt photoetching corrosion to become the stripe electrode conductive membrane layer, form transparent anode electrode layer 4.Wherein, The in advance cleaning of said transparent insulation substrate 5 before sputter is preferred to place deionized water with the transparent insulation substrate earlier; Use ultrasonic waves for cleaning 2-3 hour again; But be not limited only to ultrasonic waves for cleaning, also can adopt present technique field other cleaning ways commonly used to clean, as long as finally reach the purpose that makes that transparent insulation substrate 5 cleans.The material of the transparent anode electrode layer 4 of this step preparation is preferably above-mentioned transparent oxide, metallic film or carbon nanotube conductive thin film; Its thickness is 80-120nm, and the splash-proofing sputtering process parameter of sputtering method can adopt present technique field technological parameter commonly used in this step.
In above-mentioned steps 3) in, the preferred version of preparation photosensitive layer 3 is: the transparent insulation substrate 5 that will be coated with transparent anode electrode layer 4 on transparent anode electrode layer 4, adopts the method deposition growing light-sensitive material of vacuum evaporation after cleaning, form photosensitive layer 3.Wherein, The said cleaning in advance that is coated with the transparent insulation substrate 5 of transparent anode electrode layer 4 is preferably the organic solvent that utilizes absolute methanol, acetone earlier the transparent insulation substrate 5 that will be coated with transparent anode electrode layer 4 is cleaned; After combining ultrasonic waves for cleaning 1-2 hour again; Place 120-150 ℃ down baking can certainly adopt present technique field other modes commonly used to dry its oven dry in 10-15 minute, as infrared etc.; The material of photosensitive layer 3 is preferably hole mobile material, electron transport material or inorganic nano material, concrete material as stated, its thickness is preferably 50-100nm; Described in this step in the method for vacuum evaporation vacuum degree be higher than 10
-5Pa; The growth rate of deposition growing light-sensitive material is 0.01-0.05nm/s on the said transparent anode electrode layer 4.
In above-mentioned steps 4) in, range upon range of metal nano-particle layer and the cathode layer of deposition has following three kinds of optimal ways on photosensitive layer:
First kind of optimal way: elder generation's plated metal nano particle on photosensitive layer 3; Form metal nano-particle layer 2; Plated metal or metal-oxide film on metal nano-particle layer 2 form negative electrode layer 1, thereby obtain described individual layer organic solar batteries again; The further scheme of this optimal way is: on photosensitive layer 3, adopt the method deposition growing low workfunction metal nano particle of vacuum evaporation, form metal nano-particle layer 2; Adopt the method for vacuum evaporation again; And being aided with the electrode mask plate, deposition growing metal or metal-oxide film on metal nano-particle layer 2 form negative electrode layer 1; Thereby obtain described individual layer organic molecule solar cell, like above-mentioned first kind of execution mode or as shown in Figure 1;
Second kind of optimal way: elder generation plated metal or metal-oxide film on photosensitive layer 3; Form negative electrode layer 1; Plated metal nano particle on negative electrode layer 1 forms metal nano-particle layer 2 ', thereby obtains described individual layer organic solar batteries again; The further scheme of this optimal way is: adopt the method for vacuum evaporation, and be aided with the electrode mask plate, deposition growing metal or metal-oxide film on photosensitive layer 3; Form negative electrode layer 1; Adopt the method for vacuum evaporation again, the long-pending metal nanoparticle of deposition growing forms metal nano-particle layer 2 ' on negative electrode layer 1; Thereby obtain described individual layer organic molecule solar cell, like above-mentioned second kind of execution mode or as shown in Figure 2;
The third optimal way: elder generation's plated metal nano particle on photosensitive layer 3; Form metal nano-particle layer 2; Plated metal or metal-oxide film on metal nano-particle layer 2 form negative electrode layer 1, plated metal nano particle on negative electrode layer 1 then again; Form another metal nano-particle layer 2 ', thereby obtain described individual layer organic solar batteries; The further scheme of this optimal way is: on photosensitive layer 3, adopt the method deposition growing low workfunction metal nano particle of vacuum evaporation, form metal nano-particle layer 2; Adopt the method for vacuum evaporation again, and be aided with the electrode mask plate, deposition growing metal or metal-oxide film on metal nano-particle layer 2; Form negative electrode layer 1; Adopt the method for vacuum evaporation then, deposition growing low workfunction metal nano particle on negative electrode layer 1 forms metal nano-particle layer 2 '; Thereby obtain described individual layer organic molecule solar cell, like above-mentioned the third execution mode or as shown in Figure 3.
Above-mentioned steps 4) in; In the preparation process of metal nano-particle layer 2 and 2 ', metal nano-particle layer 2,2 ' material are preferably the metal nanoparticle of above-mentioned low work function, wherein; Metal nano-particle layer 2 thickness are preferably 0.5-1nm; The thickness of metal nano-particle layer 2 ' is preferably more than 0.5nm, and the growth rate of metal nanoparticle is preferably 0.01-0.02nm/s, and the evaporation process parameter of vacuum deposition method can adopt present technique field technological parameter commonly used in this step; Can be according to the difference of vapor deposition material and do suitable adjustment according to the attribute of this material, vacuum degree should be higher than 10
-4Pa, certainly, vacuum degree is high more good more; In the preparation process of negative electrode layer 1; Negative electrode layer 1 preferably is made up of metallic film or metal-oxide film; Concrete material as stated, its thickness is preferably 80-120nm, the evaporation process parameter of vacuum deposition method can adopt present technique field technological parameter commonly used in this step; Can be according to the difference of vapor deposition material and do suitable adjustment according to the attribute of this material, vacuum degree should be higher than 10
-4Pa, certainly, vacuum degree is high more good more, and the growth rate of metal or metal-oxide film is 0.1-0.2nm/s.
Above-mentioned individual layer organic solar batteries preparation of devices method is that this each layer of solar cell device is formed successively; Make each layer connection closely, firmly, thereby make this solar cell device stable performance, production efficiency is high; Reduce production cost, be suitable for suitability for industrialized production.
The operation principle of present embodiment individual layer organic solar batteries is following:
Shown in Fig. 1 or 2,,, transparent insulation substrate 5 constitutes and metal nano-particle layer 2 very thin thickness because being conductive material or the metallic film transparent, that 4 employings of transparent anode electrode layer are transparent when sunlight is mapped to behind transparent insulation substrate 5; Thereby its loss to sunlight is very little; Can ignore, and thin thickness, therefore; Overwhelming majority sunlight sees through transparent insulation substrate 5, transparent anode electrode layer 4 is mapped on the photosensitive layer 3; And absorbed by photosensitive layer 3, photosensitive layer 3 absorbs after the sunlight photon energies, produces free carrier or/and to produce the electron-hole pair with certain binding force be exciton.Owing to have work function difference between transparent anode electrode layer 4 and the negative electrode layer 1; Thereby the inside at individual layer organic solar batteries device produces internal electric field; Again owing to be provided with metal nano-particle layer 2 or/and 2 ' at negative electrode layer 1 one or both sides; Target electrode layer 1 is modified, and reduces the work function of negative electrode layer 1, thereby has further increased work function difference between negative electrode layer 1 and the transparent anode electrode layer 4; Thereby further strengthened the internal electric field of individual layer organic solar batteries device; Be equivalent between photosensitive layer 3 and cathode electrode 1, form a direction of an electric field for pointed to the eelctric dipole layer of photosensitive layer 3 by cathode electrode 1, under the inconsistent effect of this eelctric dipole layer, the exciton at interface is split into free carrier more easily; Under the effect of exciton that produces on the photosensitive layer 3, be split into the free carrier of two kinds of polarity at this internal electric field; This free carrier respectively to transparent anode electrode layer 4 and negative electrode layer 1 drift, is exported thereby form photoelectric current in photosensitive layer 3 under above-mentioned internal electric field effect.Simultaneously because negative electrode layer 1 is high reflecting electrode; The sunlight that is not absorbed by photosensitive layer 3 is mapped to be reflected onto by photosensitive layer 3 behind the negative electrode layer 1 and is absorbed once more; Excite photosensitive layer 3 to produce free carriers or/and exciton, thereby strengthened the conversion ratio to sunlight of present embodiment individual layer organic solar batteries.
Combine instantiation at present, the present invention is further elaborated.
The structure of individual layer organic solar batteries is as shown in Figure 1; High reflectance negative electrode layer 1 adopts the aluminium membrane electrode; Metal nanoparticle 2 is lithium (Li) nano particle, and photosensitive layer 3 adopts the CuPc phthalocyanine copper film, and transparency electrode 4 adopts the ITO stripe electrode; Its square resistance is 15 ohm/, transparent insulating layer 5 adopting quartz glass.
Its concrete preparation method is following:
(1) the polishing quartz glass of selecting 1.1mm thickness for use adopts hyperacoustic method that quartz glass was cleaned 2-3 hour as transparent insulation substrate 5;
(2) method that adopts sputter is at quartz glass one superficial growth one deck ITO conductive film, and ito thin film thickness is 120nm;
(3) the ITO conductive photolithographic film is lost into needed stripe electrode pattern as transparent anode electrode layer 4, that is to say the anode of battery;
(4) entire I TO glass substrate passes through the scouring of absolute methanol, acetone, and cleans 1-1.5 hour in deionized water for ultrasonic, afterwards ito glass substrate is toasted 15 minutes in 130 degrees centigrade high temperature furnace;
(5) sample is taken out from high temperature furnace, send in the growth chamber of vacuum evaporation system, its vacuum degree is 10-8Torr, adopts the mode of vacuum evaporation to grow the CuPc phthalocyanine copper film as photosensitive layer 3, and its thickness is 50nm, and growth rate is 0.01nm/s;
(6) adopt the mode of vacuum evaporation to grow lithium (Li) nano particle as low workfunction metal nano particle 2 on photosensitive layer 3 surfaces, its thickness is 0.5nm, and growth rate is 0.01nm/s;
(7) on metal nanoparticle 2 surfaces; Be aided with striped mask plate vacuum evaporation 120nm thickness A l aluminum strip line electrode as high reflectance cathode electrode 1; Growth rate is 0.15nm/s; Treat that negative electrode layer 1 stops vacuum evaporation when growing into 120nm thickness, thereby obtain the individual layer organic solar batteries of present embodiment that the individual layer organic solar batteries energy conversion efficiency of present embodiment preparation is 0.094%.
As shown in Figure 2, high reflectance electrode 1 adopts Ag silver membrane electrode, and metal nanoparticle 2 adopts lithium Li nano particle; Photosensitive layer 3 adopts pentacene thin film; Transparency electrode 4 adopts the ITO stripe electrode, and its square resistance is 15 ohm/, transparent insulating layer 5 adopting quartz glass.
Its concrete preparation method is following:
(1) the polishing quartz glass of selecting 1.5mm thickness for use adopts hyperacoustic method that quartz glass was cleaned 2-2.5 hour as transparent insulation substrate 5;
(2) method that adopts sputter is at quartz glass one superficial growth one deck ITO conductive film, and ito thin film thickness is 80nm;
(3) the ITO conductive photolithographic film is lost into the anode of needed stripe electrode pattern as solar cell; As transparent anode electrode layer 4, that is to say the anode of battery;
(4) entire I TO glass substrate passes through the scouring of absolute methanol, acetone, and cleans 1.5-2 hour in deionized water for ultrasonic, afterwards ito glass substrate is toasted 12-15 minute in 150 degrees centigrade high temperature furnace;
(5) sample is taken out from high temperature furnace, send in the growth chamber of vacuum evaporation system, its vacuum degree is 10
-7Torr adopts the mode of vacuum evaporation to grow pentacene thin film as photosensitive layer 3, and its thickness is 80nm, and growth rate is 0.04nm/s;
(6) adopt the mode of vacuum evaporation to grow sodium (Na) metal nanoparticle as low workfunction metal nano-particle layer 2 on photosensitive layer 3 surfaces, its thickness is 0.8nm, and growth rate is 0.02nm/s;
(7) on metal nanoparticle 2 surfaces; Be aided with striped mask plate vacuum evaporation 80nm thickness silver bar line electrode that is to say solar cell as high reflectance negative electrode layer 1 negative electrode; Growth rate is 0.1nm/s, treats that negative electrode layer 1 stops vacuum evaporation when growing into 80nm thickness;
(8) adopt the mode of vacuum evaporation to grow caesium (Cs) metal nanoparticle on negative electrode layer 1 surface as low workfunction metal nano-particle layer 2 '; Its thickness is 1.5nm; Growth rate is 0.02nm/s; Treat that metal nano-particle layer 2 ' stops vacuum evaporation when growing into 80nm thickness, thereby obtain the individual layer organic solar batteries of present embodiment that the individual layer organic solar batteries energy conversion efficiency of present embodiment preparation is 0.11%.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. individual layer organic solar batteries; It is characterized in that: comprise the transparent insulation substrate, on the transparent insulation substrate, stack gradually transparent anode electrode layer, photosensitive layer and the negative electrode layer of formation; Said negative electrode layer one side at least is formed with metal nano-particle layer, and the work function value of metal nanoparticle is lower than the work function value of negative electrode layer in the said metal nano-particle layer.
2. individual layer organic solar batteries according to claim 1 is characterized in that: metal nanoparticle is at least a metal nanoparticle in lithium, caesium, potassium, the sodium in the said metal nano-particle layer.
3. individual layer organic solar batteries according to claim 1 is characterized in that: the work function value of metal nanoparticle is 4.3-2eV in the said metal nano-particle layer, and the thickness of said metal nano-particle layer is 0.5-1nm.
4. individual layer organic solar batteries according to claim 1 is characterized in that: the material of said transparent insulation substrate is quartz glass, silicate glass, vagcor, soda-lime glass, polyvinyl chloride, Merlon or polyester;
Said transparent anode electrode layer is that material is the conductive film of tin indium oxide, zinc oxide aluminum, zinc-gallium oxide, indium zinc oxide, gold, aluminium, silver or CNT;
The material of said photosensitive layer is phthalocyanine dye, pentacene, porphyrin compound, cyanine dyes, fullerene, PTCDA, Pe, Pe derivative, CdSe, CdS, CdTe, TiO
2, ZnO, PbS, SnO
2, CNT or Graphene;
The thickness of said transparent insulation substrate is 1.1-1.5mm;
The thickness of said transparent anode electrode layer is 80-120nm;
The thickness of said photosensitive layer is 50-100nm.
5. individual layer organic solar batteries according to claim 1 is characterized in that: the material of said negative electrode layer is silver, aluminium, calloy, magnesium silver alloy, tin indium oxide or zinc oxide;
The thickness of said negative electrode layer is 80-120nm.
6. individual layer organic solar batteries preparation method, it comprises the steps:
Preparation transparent insulation substrate;
On the wherein one side of said transparent insulation substrate, form the transparent anode electrode layer;
On the transparent anode electrode layer, deposit light-sensitive material, form photosensitive layer;
Range upon range of metal nano-particle layer and the cathode layer of deposition on photosensitive layer, thus described individual layer organic solar batteries obtained, and wherein, at least one surface layer of said negative electrode layer is folded has metal nano-particle layer;
Wherein, the work function value of metal nanoparticle is lower than the work function value of negative electrode layer in the said metal nano-particle layer.
7. individual layer organic solar batteries preparation method according to claim 6 is characterized in that: said on photosensitive layer the range upon range of metal nano-particle layer of deposition and cathode layer through any one realization in following three kinds of formation steps:
Plated metal nano particle on photosensitive layer forms metal nano-particle layer earlier, on metal nano-particle layer, forms negative electrode layer again, thereby obtains described individual layer organic solar batteries;
Perhaps, plated metal or metal-oxide film on photosensitive layer form negative electrode layer earlier, and plated metal nano particle on negative electrode layer forms metal nano-particle layer, thereby obtains described individual layer organic solar batteries again;
Perhaps; Plated metal nano particle on photosensitive layer forms metal nano-particle layer, plated metal or metal-oxide film on metal nano-particle layer more earlier; Form negative electrode layer; Plated metal nano particle on negative electrode layer forms another metal nano-particle layer then, thereby obtains described individual layer organic solar batteries.
8. individual layer organic solar batteries preparation method according to claim 7 is characterized in that:
It is that the method that adopts sputter is wherein plated conductive film on the one side at the transparent insulation substrate that said transparent anode electrode layer forms step;
It is to adopt the method for the vacuum evaporation light-sensitive material of on the transparent anode electrode layer, growing that said photosensitive layer forms step;
It is to adopt method growing metal nano particle on photosensitive layer of vacuum evaporation that said metal nano-particle layer forms step;
It is to adopt method growing metal or metal-oxide film on metal nano-particle layer of vacuum evaporation that said negative electrode layer forms step.
9. individual layer organic solar batteries preparation method according to claim 8 is characterized in that:
In the said metal nano-particle layer preparation process, the vacuum degree of said vacuum evaporation is higher than 10
-4Pa, the metal nanoparticle growth rate on photosensitive layer is 0.01-0.02nm/s;
In the said photosensitive layer preparation process, the vacuum degree of said vacuum evaporation is higher than 10
-5Pa, the growth rate of light-sensitive material on the transparent anode electrode layer is 0.01-0.05nm/s;
In the said negative electrode layer preparation process, the vacuum degree of said vacuum evaporation is higher than 10
-4Pa, metal or the metal-oxide film growth rate on metal nano-particle layer is 0.1-0.2nm/s.
10. individual layer organic solar batteries preparation method according to claim 6; It is characterized in that: in the said transparent anode electrode layer preparation process; Said transparent insulation substrate comprises clean in advance; Said clean is in advance carried out as follows: the transparent insulation substrate is placed deionized water, use ultrasonic waves for cleaning 2-3 hour again;
In the said photosensitive layer preparation process; The said transparent insulation substrate that is coated with the transparent anode electrode layer comprises clean in advance; Said clean is in advance carried out as follows: utilize absolute methanol or/and acetone is cleaned the transparent insulation substrate that will be coated with the transparent anode electrode layer; After combining ultrasonic waves for cleaning 1-2 hour again, place 120-150 ℃ of oven dry down.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102230847A CN102315389A (en) | 2010-07-08 | 2010-07-08 | Single-layer organic solar cell and making method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102230847A CN102315389A (en) | 2010-07-08 | 2010-07-08 | Single-layer organic solar cell and making method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102315389A true CN102315389A (en) | 2012-01-11 |
Family
ID=45428340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102230847A Pending CN102315389A (en) | 2010-07-08 | 2010-07-08 | Single-layer organic solar cell and making method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102315389A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760779A (en) * | 2012-07-17 | 2012-10-31 | 清华大学 | Carbon-based transparent electrode/bismuth ferric photovoltaic device and preparation method thereof |
| CN103872247A (en) * | 2014-03-19 | 2014-06-18 | 太原理工大学 | Organic small-molecule photovoltaic device based on three-terminal electrode structure |
| CN103887073A (en) * | 2014-03-31 | 2014-06-25 | 北京大学 | Solar cell based on surface plasma reinforcing principle and preparing method thereof |
| CN104465867A (en) * | 2014-11-21 | 2015-03-25 | 广西智通节能环保科技有限公司 | Novel method for manufacturing solar cells |
| CN104465869A (en) * | 2014-11-21 | 2015-03-25 | 广西智通节能环保科技有限公司 | Method for manufacturing silicon solar cell |
| CN104465990A (en) * | 2014-11-21 | 2015-03-25 | 广西智通节能环保科技有限公司 | Organic solar cell and manufacturing method thereof |
| CN104485422A (en) * | 2014-11-21 | 2015-04-01 | 广西智通节能环保科技有限公司 | Single-layer solar battery and preparing method of single-layer solar battery |
| CN112490368A (en) * | 2020-12-15 | 2021-03-12 | 华能新能源股份有限公司 | Electrode and battery with optimized charge collection capacity and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1868075A (en) * | 2003-08-14 | 2006-11-22 | 索尼德国有限责任公司 | Carbon nanotubes based solar cells |
| JP4192236B2 (en) * | 2003-05-02 | 2008-12-10 | 独立行政法人産業技術総合研究所 | Solar cell |
| JP2010147276A (en) * | 2008-12-19 | 2010-07-01 | Konica Minolta Holdings Inc | Organic photoelectric conversion element |
-
2010
- 2010-07-08 CN CN2010102230847A patent/CN102315389A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4192236B2 (en) * | 2003-05-02 | 2008-12-10 | 独立行政法人産業技術総合研究所 | Solar cell |
| CN1868075A (en) * | 2003-08-14 | 2006-11-22 | 索尼德国有限责任公司 | Carbon nanotubes based solar cells |
| JP2010147276A (en) * | 2008-12-19 | 2010-07-01 | Konica Minolta Holdings Inc | Organic photoelectric conversion element |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760779A (en) * | 2012-07-17 | 2012-10-31 | 清华大学 | Carbon-based transparent electrode/bismuth ferric photovoltaic device and preparation method thereof |
| CN103872247A (en) * | 2014-03-19 | 2014-06-18 | 太原理工大学 | Organic small-molecule photovoltaic device based on three-terminal electrode structure |
| CN103887073A (en) * | 2014-03-31 | 2014-06-25 | 北京大学 | Solar cell based on surface plasma reinforcing principle and preparing method thereof |
| CN103887073B (en) * | 2014-03-31 | 2016-07-13 | 北京大学 | A kind of solaode strengthening principle based on surface plasma and preparation method thereof |
| CN104465867A (en) * | 2014-11-21 | 2015-03-25 | 广西智通节能环保科技有限公司 | Novel method for manufacturing solar cells |
| CN104465869A (en) * | 2014-11-21 | 2015-03-25 | 广西智通节能环保科技有限公司 | Method for manufacturing silicon solar cell |
| CN104465990A (en) * | 2014-11-21 | 2015-03-25 | 广西智通节能环保科技有限公司 | Organic solar cell and manufacturing method thereof |
| CN104485422A (en) * | 2014-11-21 | 2015-04-01 | 广西智通节能环保科技有限公司 | Single-layer solar battery and preparing method of single-layer solar battery |
| CN112490368A (en) * | 2020-12-15 | 2021-03-12 | 华能新能源股份有限公司 | Electrode and battery with optimized charge collection capacity and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102290529B (en) | Individual layer organic solar batteries and preparation method thereof | |
| Chen et al. | Progress in tandem solar cells based on hybrid organic–inorganic perovskites | |
| CN102315389A (en) | Single-layer organic solar cell and making method thereof | |
| CN101414663B (en) | Stacking polymer thin-film solar cell with parallel connection structure | |
| CN112736200B (en) | Laminated battery and preparation method and application thereof | |
| Shen | Recently-explored top electrode materials for transparent organic solar cells | |
| CN103904224B (en) | A kind of organic photovoltaic battery based on inorganic-quantum-dot and preparation method | |
| CN102280589B (en) | Organic solar cell and preparation method thereof | |
| CN112289933A (en) | Perovskite two-end laminated solar cell and preparation method thereof | |
| KR102372238B1 (en) | Integrated tandem solar cell and manufacturing method thereof | |
| CN102522506A (en) | Organic solar cell of suede light trapping electrode and manufacturing method thereof | |
| CN201156545Y (en) | Solar cell of aluminum antimonide transparent film | |
| CN202308074U (en) | Organic solar battery | |
| CN209963073U (en) | Novel high-efficiency double-sided incident light CdTe perovskite laminated photovoltaic cell | |
| CN114551729A (en) | Preparation method of silicon-based heterojunction perovskite laminated solar cell | |
| CN102386332B (en) | Solar cell and preparation method thereof | |
| CN104485422A (en) | Single-layer solar battery and preparing method of single-layer solar battery | |
| CN104241532A (en) | Organic photovoltaic battery and manufacturing method thereof | |
| CN108172645A (en) | A kind of CIGS/CdTe lamination solar cells and preparation method thereof | |
| CN102931248B (en) | CdSe/CIS laminated film solar battery | |
| CN213366612U (en) | Two-end perovskite heterogeneous crystalline silicon laminated solar cell with high light conversion efficiency | |
| CN104465990A (en) | Organic solar cell and manufacturing method thereof | |
| CN102201288A (en) | Solar battery | |
| CN114914365A (en) | Perovskite/perovskite tandem solar cell with inverted structure | |
| CN220274181U (en) | MIS-perovskite tandem solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120111 |