CN110854269B - Small-molecule organic solar cell device and preparation method thereof - Google Patents
Small-molecule organic solar cell device and preparation method thereof Download PDFInfo
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- CN110854269B CN110854269B CN201911034900.7A CN201911034900A CN110854269B CN 110854269 B CN110854269 B CN 110854269B CN 201911034900 A CN201911034900 A CN 201911034900A CN 110854269 B CN110854269 B CN 110854269B
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Abstract
The invention discloses a micromolecule organic solar cell device and a preparation method thereof, on the basis of the structure of a traditional organic solar cell body heterojunction, a thermal evaporation method is utilized, the inclination degree of a substrate is changed under the condition of not damaging the vacuum condition, a donor material with a certain thickness is evaporated at a glancing angle between an active layer and an acceptor material, the phase separation morphology is manufactured, the interface roughness is increased, the light absorption is increased, and the generation of current carriers is facilitated; meanwhile, the energy band bending condition of the contact between C60(C70) and AlPcCl is utilized to reduce the series resistance of the device, so that electrons are collected by a cathode. The invention provides a new idea for optimizing the structure of the small-molecule organic battery device.
Description
Technical Field
The invention belongs to the field of small molecule organic solar cell devices, and particularly relates to a small molecule organic solar cell device with an optimized structure and a preparation method thereof.
Background
A solar cell is a device that directly converts sunlight into electrical energy. The organic solar cell material has wide sources, simple synthesis, low cost and flexibility, so that the organic solar cell material has strong competitiveness in large-scale production or preparation of flexible devices.
When light is irradiated on the surface of the solar cell, the material absorbs sunlight to generate excitons with weak binding, the excitons diffuse to the interface of the donor-acceptor material and are separated by a charge separation potential, and then, electrons are along the acceptor material and holes are respectively collected by the cathode and the anode along the donor material (fig. 1).
The device performance is measured by the following measurement indexes:
1. short circuit current density (Jsc): the current density at the time of short-circuiting of the device is affected by the series resistance and the parallel resistance.
2. Open circuit voltage (Voc), the value of the voltage at which the device opens, is generally defined as the difference between the HOMO level of the donor material and the LUMO level of the acceptor material; affected by temperature and the intensity of incident light radiation.
3. Fill Factor (FF): the parameter reflects the quality of the device, the smaller the series resistance is, the larger the parallel resistance is, the larger the filling factor is, the higher the quality of the device is, and the closer the curve is to a rectangle on the I-V characteristic curve. The calculation formula is as follows:
4. energy conversion efficiency (PCE): the indexes for measuring the comprehensive performance of the device have the following calculation formula:
in order to improve the device performance, there are many research ideas, such as manufacturing of a stacked device, selection of a new material, optimization of a device structure, and the like.
Referring to fig. 3, the more common device structure is: ITO/donor material/active layer (donor-acceptor material mixed layer)/acceptor material/buffer layer/Al (ITO/donor/active layer)/acceptor/buffer layer/Al). The bulk heterojunction structure of the device can fully mix the donor material and the acceptor material, increases the interface of the donor and acceptor materials, and is beneficial to the effective separation of excitons, thereby improving the performance of the device and solving the limitation of a planar heterojunction.
At present, in an organic small molecule solar cell device using thermal evaporation and evaporation, further structural optimization is not realized, so that the improvement of the device performance is completed.
Disclosure of Invention
The invention aims to provide a small molecule organic solar cell device with an optimized structure and a preparation method thereof. A schematic of the grazing angle deposition is shown in fig. 5.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a small molecule organic solar cell device with an optimized structure comprises the following steps:
1) pretreating an anode substrate material of the organic solar cell;
2) placing the substrate material in a vacuum system at a vacuum degree of not less than 10-5When pa, the donor material and the active layer are evaporated layer by layer;
3) after the deposition of the active layer is finished, evaporating the donor material at a glancing angle;
4) and (5) evaporating the receptor material, the buffer layer and the cathode material layer by layer, and finishing the manufacture of the device.
Further, in step 1), the anode material on the base material has a work function matched with that of the donor material (the donor material alpcch is 5.3eV), preferably Indium Tin Oxide (ITO), and the work function is 4.8 eV; the substrate material is preferably ITO-coated plexiglass.
Further, in step 1), the pretreatment comprises: firstly, cleaning oil stains on the surface of a substrate material by using a neutral cleaning agent; subsequently, ultrasonically cleaning the substrate material by using ethanol and deionized water for 20min respectively; then, washing the substrate material with deionized water; and finally, placing the dried substrate material in an ultraviolet-ozone environment for treatment for 5-10min, and improving the work function of the substrate material to enable the work functions of the ITO and the AlpcCl to be closer.
Further, in step 2), the organic material evaporated on the substrate is selected from small organic molecular substances such as AlPcCl, C60, and C70.
Further, in the step 2), AlPcCl is selected as a donor material for evaporation, and 10-12nm is selected for evaporation; and simultaneously evaporating the active layer with AlPcCl: c60 (or AlPcCl: C70), the thickness is controlled between 30 and 40 nm; the speed should not be controlled too high in the evaporation process, and the organic material should be controlled in
Further, in step 3), after the deposition of the active layer is finished, the acceptor material is not directly evaporated, at this time, the base support in the vacuum chamber is rotated, the substrate is rotated to be close to a vertical state from an original horizontal state, a layer of donor material is continuously evaporated in a glancing angle state, and the rotating angle of the base is kept approximately between 70 and 80 degrees, so that the range is selected, because the material on the tungsten boat cannot be evaporated and deposited on the substrate due to an overlarge angle, and a continuous film is easily formed when the material on the tungsten boat is evaporated and deposited due to an undersize angle, a reverse plane heterojunction is formed, and the carrier transportation is hindered. Maintaining 70-80 deg. allows for the formation of discontinuous alpcch, which does not interfere with carrier extraction while subsequently increasing interface roughness.
The thickness of alpcch should not be too thick and should be controlled to 15-20nm (the crystal plate index shows that the actual thickness is less than 20nm, for example 75 °, approximately 20sin15 ° -5 nm), and if the thickness is too large, there is still a risk of forming a continuous thin film.
Further, in the step 4), the acceptor material C60 (or C70) is horizontally evaporated for 10-15nm at a speed controlled in
The buffer material is BCP, and the speed is very slow
6-8nm of evaporation plating; according to the matching of work function, Al is preferably used as cathode material, so that
And evaporating at 80-100nm speed.
It should be noted that the vacuum condition is not destroyed during the device manufacturing process, which would otherwise affect the device performance. In order to take account of the light absorption degree and the resistance of the device, the thickness of the device is controlled within 150nm, and in the range, the light absorption of the device can be increased as much as possible, and meanwhile, excessive series resistance cannot be formed.
Another aspect of the present invention provides a small molecule organic solar cell device with an optimized structure, which comprises: the anode comprises an anode substrate material, a donor material, an active layer, an acceptor material, a buffer layer and a cathode material, wherein the donor material with the sweep angle of 15-20nm is evaporated between the active layer and the acceptor material, the sweep angle is 70-80 degrees, and the thickness of the device is less than 150 nm.
The invention has the following beneficial effects:
in the device preparation process introduced by the invention, after grazing angle evaporation is added, phase separation morphology is generated, interface roughness is increased, light absorption is increased, and generation of current carriers is facilitated; the series resistance of the device is reduced by utilizing the energy band bending condition of the contact between C60(C70) and AlPcCl, so that electrons are conveniently collected by a cathode, and a new idea is provided for optimizing the structure of the small-molecule organic battery device.
Drawings
FIG. 1: working principle diagram of solar cell.
FIG. 2: the invention discloses a schematic diagram of a vacuum coating device used for preparing a device, wherein:
1-vacuum coating cavity; 2-a diffusion pump; 3-a mechanical pump; 4-cooling water; 5-main valve; 6-rough vacuum valve; 7-high vacuum valve; 8-a vacuum gauge; 9-air relief valve.
FIG. 3: conventional bulk heterojunction solar cell structures.
FIG. 4: a glancing angle phase separation body heterojunction solar cell structure.
FIG. 5: schematic view of grazing angle deposition.
FIG. 6: and the appearance of the device is schematic.
FIG. 7: I-V curves for a glancing-angle phase-separated device versus a conventional bulk heterojunction device were prepared using AlPcCl and C60.
FIG. 8: I-V curves for a glancing-angle phase-separated device versus a conventional bulk heterojunction device were prepared using AlPcCl and C70.
FIG. 9: grazing angle phase separation device light absorption diagram.
Detailed Description
The invention is described in further detail below with reference to the figures and the detailed description.
Firstly, a laboratory instrument:
HYT98LA electronic moisture-proof cabinet, KQ2200DE type numerical control ultrasonic cleaner, UV-O3 ultraviolet-ozone treatment equipment, KYKY-LS water chiller, vacuum coating device (shown in figure 2), Chenhua CHI660C electrochemical workstation, Agilencay 5000 ultraviolet visible near infrared spectrophotometer
II, experimental materials:
ITO、AlPcCl、C60、C70、BCP、Al
thirdly, an experimental process:
the first step is as follows: ITO cleaning and pretreatment
Cleaning oil stains on the surface of the ITO with a neutral cleaning agent; then, placing the ITO in a clean beaker, and ultrasonically cleaning the ITO for 20min by using ethanol and deionized water respectively; after cleaning, using clean tweezers to clamp the ITO, washing with a large amount of deionized water, and drying the residual deionized water by using a blower; and finally, placing the ITO into ultraviolet-ozone equipment for treatment for 5-10min, and improving the work function of the ITO.
The second step is that: deposition Material Placement and obtaining of high vacuum
Turning on a power supply of the water cooler (4) and a vacuum coating machine, turning on the mechanical pump (3) to obtain rough vacuum of a pipeline, and turning on the diffusion pump (2) for preheating; taking BCP, AlPcCl, C60(C70) and Al out of the moisture-proof cabinet, respectively placing the BCP, AlPcCl, C60(C70) and Al into a tungsten boat of a vacuum coating chamber (1), placing the ITO substrate pretreated in the first step on a bracket, and placing a glass bell jar of a vacuum chamber at a correct position;
opening a rough vacuum valve (6), closing the rough vacuum valve (6) after the vacuum degree is reduced, opening a high vacuum valve (7), slowly opening a main valve (5), and waiting for 3-4 hours until the vacuum degree reaches 10-5pa。
The third step: vapor deposition of organic material and electrode material
Evaporating AlPcCl with the thickness of 10nm at the position I; subsequently, 30-40nm of an AlPcCl: C60 active layer was evaporated.
Rotating the bracket to the position II, and evaporating 20nm AlPcCl at a glancing angle;
the scaffold was rotated back to position i and deposition of 10nm C60 continued; then 8nm BCP and 80nm cathode material Al are evaporated.
The fourth step: coating machine shut down and device removal
After the evaporation is finished, closing the main valve (5) and the diffusion pump (3), opening the gas release valve (9) for gas release treatment, taking off the bell jar, and taking out the sample; and (3) after the diffusion pump (3) is closed for 30min, closing the mechanical pump (3) and the power supply of the film coating machine, and finally closing the water cooling machine (4).
The fifth step: recording device performance parameters
Using electrochemistryWorkstation test Battery Performance (AM 1.5, 100mW/CM2)。
TABLE 1 conventional and optimized device Performance parameters prepared using AlPcCl, C60
To further demonstrate the universality of the glancing angle deposition structure optimization, two types of devices were also prepared by replacing C60 with C70, and the device structure and appearance schematic diagrams are shown in fig. 4 and 6:
TABLE 2 conventional and optimized device Performance parameters prepared using AlPcCl, C70
It can be seen from the above table that the device efficiency after adding the glancing angle deposition is significantly higher than that of the unswept device, and the performance optimization is realized.
And a sixth step: J-V, AFM and light absorption testing
Fig. 7 and 8 are I-V curves of a swept-angle phase separation device prepared using AlPcCl and C60 or AlPcCl and C70, respectively, and a conventional bulk heterojunction device. In the curve, the device added with the grazing angle has an I-V diagram closer to an ideal rectangle, and the diode characteristic is more obvious.
AFM topography of ITO/horizontal deposition Alpc (10nm20nm)/Alpc: C70(40nm)/C70(10nm) and ITO/Alpc (10nm)/Alpc: C70(30 nm)/grazing angle deposition Alpc (20nm) grazing angle/C70 (10nm) shows that the device after the grazing angle has larger roughness (the traditional device Ra is 1.80; the grazing angle device Ra is 2.18).
FIG. 9 is a graph of light absorption measurements of ITO/Alpc (10nm)/Alpc: C70(40nm)/C70(10nm) and a grazing angle phase separation device ITO/Alpc (10nm)/Alpc: C70(30nm)/Alpc (20nm) grazing angle/C70 (10nm) showing that the absorption band of the donor material AlPcCl (700-900nm) is significantly increased after deposition with the addition of a grazing angle, resulting in the generation of more excitons.
The experimental results show that the improvement of the device performance is due to: 1. increasing the grazing angle deposition introduces phase separation, increasing light absorption; 2. the interface between the carbon nanotube and the rear layer of C60 or C70 is rougher after the glancing angle is introduced, so that the separation of excitons is facilitated; 3. the grazing angle device also reduces the resistance of the device and is beneficial to the collection of current carriers.
In summary, in the thermal evaporation and evaporation of small molecule organic solar cells, it is effective to increase the grazing angle deposition and introduce phase separation to improve the device efficiency.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (9)
1. A preparation method of a small-molecule organic solar cell device comprises the following steps:
1) cleaning an organic solar cell anode substrate material, drying, and then treating in an ultraviolet-ozone environment;
2) placing the substrate material in a vacuum system at a vacuum degree of not less than 10-5When pa, the donor material and the active layer are evaporated layer by layer;
3) after the deposition of the active layer is finished, evaporating the donor material at a glancing angle, wherein the glancing angle evaporation angle is 70-80 degrees, and the evaporation thickness is 15-20 nm;
4) and (5) evaporating the receptor material, the buffer layer and the cathode material layer by layer, and completing the preparation of the device.
2. The method according to claim 1, wherein the anode substrate material is ITO-coated organic glass.
3. The method for preparing a small molecule organic solar cell device according to claim 1, wherein the cleaning method comprises: firstly, cleaning oil stains on the surface of a substrate material by using a neutral cleaning agent; then ultrasonic cleaning the substrate material with ethanol and deionized water for 20min respectively; finally, the substrate material was rinsed with deionized water.
4. The method of claim 1, wherein the substrate material is treated in the UV-ozone environment for 5-10 min.
5. The method for preparing a small molecule organic solar cell device according to claim 1, wherein in the step 2), the donor material is AlPcCl, and the evaporation thickness is 10-12 nm; and simultaneously evaporating the active layer with AlPcCl: c60 or AlPcCl: c70, evaporating to form a film with the thickness of 30-40 nm; the evaporation speed is
6. The method for preparing the small molecule organic solar cell device as claimed in claim 1, wherein in the step 4), the acceptor material is C60 or C70, the horizontal evaporation thickness is 10-15nm, and the evaporation speed is 10-15nm
The buffer material is BCP, the evaporation thickness is 6-8nm, and the evaporation speed is
The cathode material is Al, the evaporation thickness is 80-100nm, and the evaporation speed is
7. The method for preparing a small molecule organic solar cell device according to claim 1, wherein the thickness of the device prepared in the step 4) is less than 150 nm.
8. A small molecule organic solar cell device, the structure of which comprises: the anode substrate material/donor material/active layer/acceptor material/buffer layer/cathode material is characterized by further comprising a glancing angle evaporation donor material between the active layer and the acceptor material, wherein the glancing angle evaporation thickness is 15-20nm, and the glancing angle evaporation angle is 70-80 degrees.
9. The small molecule organic solar cell device according to claim 8, wherein the device thickness is less than 150 nm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009081275A (en) * | 2007-09-26 | 2009-04-16 | Seiko Epson Corp | Manufacturing method of device |
| CN101548407A (en) * | 2006-07-11 | 2009-09-30 | 普林斯顿大学理事会 | Controlled growth of larger heterojunction interface area for organic photosensitive devices |
| CN102460761A (en) * | 2009-06-05 | 2012-05-16 | 赫里亚泰克有限责任公司 | Photoactive component comprising an inverted layer sequence, and method for the production of said component |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101548407A (en) * | 2006-07-11 | 2009-09-30 | 普林斯顿大学理事会 | Controlled growth of larger heterojunction interface area for organic photosensitive devices |
| JP2009081275A (en) * | 2007-09-26 | 2009-04-16 | Seiko Epson Corp | Manufacturing method of device |
| CN102460761A (en) * | 2009-06-05 | 2012-05-16 | 赫里亚泰克有限责任公司 | Photoactive component comprising an inverted layer sequence, and method for the production of said component |
Non-Patent Citations (1)
| Title |
|---|
| Bulk heterojunction organic solar cells fabricated by oblique angle deposition;zhulin et al.;《Physical chemistry chemical physics》;20151121;第17卷(第43期);第3页实验部分和第4页、第5页、第7页 * |
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