CN115404444B - AZO transparent conductive film manufacturing method and transparent solar cell device - Google Patents
AZO transparent conductive film manufacturing method and transparent solar cell device Download PDFInfo
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- CN115404444B CN115404444B CN202210885338.4A CN202210885338A CN115404444B CN 115404444 B CN115404444 B CN 115404444B CN 202210885338 A CN202210885338 A CN 202210885338A CN 115404444 B CN115404444 B CN 115404444B
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- 239000002184 metal Substances 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
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- WFFZGYRTVIPBFN-UHFFFAOYSA-N 3h-indene-1,2-dione Chemical group C1=CC=C2C(=O)C(=O)CC2=C1 WFFZGYRTVIPBFN-UHFFFAOYSA-N 0.000 description 1
- BKYWEUVIGUEMFX-UHFFFAOYSA-N 4h-dithieno[3,2-a:2',3'-d]pyrrole Chemical compound S1C=CC2=C1NC1=C2SC=C1 BKYWEUVIGUEMFX-UHFFFAOYSA-N 0.000 description 1
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- 229920001167 Poly(triaryl amine) Polymers 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a method for manufacturing an AZO transparent conductive film and a transparent solar cell device, wherein the method comprises the steps of taking zinc oxide with the metal aluminum content of 1% -5% as a raw material to manufacture an AZO metal oxide target; setting the working pressure of argon plasma in the magnetron sputtering process to be 0.15-0.35 Pa, the film forming power to be 4KW and the film forming temperature to be 200-300 ℃; AZO transparent conductive film with thickness larger than 400nm is manufactured, at the moment, hexagonal crystal beams with obvious crystal lattices are formed on the transparent conductive film, and the surface morphology of the transparent conductive film is three, four, five and six pyramid mixed tip surface shapes; when the film forming pressure is gradually increased from 0.15Pa to 0.35Pa, the crystal face angle formed by the 111 or 112 crystal directions of the polygonal pyramid is also changed obviously due to the width change of the crystal beam. The prepared AZO transparent conductive film can be used as a light-condensing structure or a transparent positive electrode in a solar cell device. The transparent solar cell device comprises the AZO transparent conductive film, fully utilizes incident light and improves photoelectric conversion efficiency.
Description
Technical Field
The invention belongs to the technical field of product design and manufacturing of solar cell devices, and particularly relates to a manufacturing method of an AZO transparent conductive film and a transparent solar cell device.
Technical Field
At present, based on the fact that the dependence of consumers on various wearing electronic devices, portable electronic devices and handheld electronic devices is higher and higher, the electric quantity and power consumption problems of various electronic devices become increasingly prominent, and the schemes of low power consumption of electronic devices, high capacity of batteries, quick charge and the like are also the problems that development and design personnel need to solve in a hollow way. In addition, designers have come to recognize that it is necessary to mount a plug-in device capable of supplying power continuously to electronic devices, including, but not limited to, the development of photovoltaic solar cell devices, thermoelectric power generation devices, and the like, and have become the mainstream of electronic product design. Aiming at a solar photovoltaic power generation battery device, considering that the front surface of the device cannot be perpendicular to the incidence direction of ambient light in the actual application process, most of the incident light is reflected or scattered, the actual photoelectric conversion efficiency of the battery is lower than the design efficiency, and sunlight and indoor ambient light cannot be fully utilized.
Disclosure of Invention
The present invention addresses the above-mentioned shortcomings of the prior art, namely, the technical problem to be solved by the present invention is to effectively improve the utilization rate of incident light.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, the present invention provides a method for manufacturing an AZO transparent conductive film, including:
Zinc oxide with the metal aluminum content of 1% -5% is used as a raw material to manufacture an AZO metal oxide target;
setting the working pressure of argon plasma in the magnetron sputtering process to be 0.15-0.35 Pa, the film forming power to be 4KW and the film forming temperature to be 200-300 ℃;
AZO transparent conductive film with thickness larger than 400nm is manufactured, at the moment, hexagonal crystal beams with obvious crystal lattices are formed on the transparent conductive film, and the surface morphology of the transparent conductive film is three, four, five and six pyramid mixed tip surface shapes; when the film forming pressure is gradually increased from 0.15Pa to 0.35Pa, the crystal face angle formed by the 111 or 112 crystal directions of the polygonal pyramid is also changed obviously due to the width change of the crystal beam.
As a preferable technical scheme, the working pressure is set to be 0.2 Pa-0.25 Pa, the thickness of the AZO transparent conductive film is 500-1000 nm, the width of the top of the crystal lattice of the hexagonal crystal beam of the AZO transparent conductive film is 200-300 nm, the included angle of the crystal face of the crystal direction 111 or 112 of the polygonal cone is 100-105 degrees, and the refractive index of the AZO transparent conductive film is n=1.75-1.85.
In a second aspect, the present invention provides a transparent solar cell device, including a transparent front substrate, a transparent positive electrode layer, a PV photovoltaic layer, a reflective metal negative electrode layer, and a rear cover, which are stacked; wherein the transparent front substrate comprises the AZO transparent conductive film manufactured by the method of any one of claims 1-2, and the AZO transparent conductive film is arranged on the inner side of the transparent front substrate and used as a light condensing structure.
As a preferable technical scheme, the refractive index of the transparent front substrate body material is smaller than or equal to that of the AZO transparent conductive film, so that light obliquely entering the device surface from the outside of the solar cell device is refracted for multiple times and then enters in a direction which tends to be perpendicular to the device surface.
As an optimal technical scheme, an anti-reflection coating is arranged on the outer surface of the transparent front substrate so as to further improve the utilization rate of incident light.
As a preferable technical scheme, the transparent front substrate is a colorless transparent rigid or flexible substrate; when the transparent front substrate is a flexible base material, one or more water vapor barrier optical film layers are manufactured on the surface of the transparent front substrate.
As the preferable technical scheme, the material of the water vapor barrier optical film layer is one or more of silicon nitride, silicon oxide and organic resin coating, and is arranged on one side or two sides of the transparent front substrate; when the water vapor barrier optical film layer is arranged on one side of the transparent front substrate, the water vapor barrier optical film layer is arranged on the inner side of the transparent front substrate, namely, one side provided with the AZO transparent conductive film.
As the preferable technical scheme, the transparent positive electrode layer is made of PEDOT/PSS material with the conductivity of more than or equal to 800S/cm.
The preferable technical scheme also comprises a frame adhesive, wherein the frame adhesive is made of UV (ultraviolet) curing or thermosetting resin or glass powder material and is used for bonding the rear cover and the transparent front substrate together; the resin is filled with water-oxygen adsorption particles and spacers with uniform particle size, and the particle size of the spacers is 2-100 mu m; when the frame glue material is UV curing type or thermosetting type resin, a drying agent is coated or adhered on the inner surface of the rear cover.
In a third aspect, the present invention further provides a transparent solar cell device, including a transparent front substrate, a transparent positive electrode layer, a PV photovoltaic layer, a reflective metal negative electrode layer, and a rear cover that are stacked; wherein the transparent positive electrode layer is an AZO transparent conductive film produced by the method of any one of claims 1 to 2; and depositing a layer of ITO or IZO transparent conductive film on the surface of the AZO transparent conductive film, wherein the thickness of the ITO or IZO transparent conductive film is less than 500nm.
Compared with the prior art, the invention has the following technical effects: the AZO transparent conductive film with certain thickness is manufactured under specific working pressure, film forming temperature and film forming power by means of a magnetron sputtering process, the surface appearance of the transparent conductive film is three, four, five and six pyramid-shaped mixed tip surface shapes, the included angle of crystal faces of the 111 or 112 crystal directions of the polygonal pyramid is 100-105 degrees, and when the included angle is larger, the light incident from the outside can be more fully utilized.
The AZO transparent conductive film can be used on the inner side of a substrate of a transparent solar cell device, can be used as a light condensing structure, and can also be directly used as a transparent positive electrode layer of the transparent solar cell device.
Further, a layer of transparent conductive film with high work function such as ITO or IZO is deposited on the surface of the AZO transparent conductive film. The work function of the transparent positive electrode can be better matched with the HOMO (highest occupied orbit of occupied electron, expressed by HOMO) energy level of the HTL layer, so that incident light can be better utilized.
By combining the above, the AZO transparent conductive film manufactured by the invention is applied to a transparent solar cell device, has a good light condensation effect, and can improve the photoelectric conversion rate of the device.
Drawings
Fig. 1 is a flowchart of a method for manufacturing an AZO transparent conductive film according to embodiment 1 of the present invention;
Fig. 2 is an electron microscope scanning front view of an AZO transparent conductive film provided in embodiment 1 of the present invention;
fig. 3 is an electron microscope scanning top view of an AZO transparent conductive film provided in embodiment 1 of the present invention;
fig. 4 is a schematic structural diagram of a transparent solar cell device according to embodiment 2 of the present invention;
fig. 5 is a schematic diagram of the working principle of the light focusing structure provided in embodiment 2 of the present invention;
fig. 6 is a schematic diagram of the working principle of the light focusing structure provided in embodiment 2 of the present invention;
fig. 7 is a schematic structural diagram of a transparent solar cell device according to embodiment 3 of the present invention;
reference numerals illustrate: a transparent front substrate 1; AZO transparent conductive film 2; a transparent positive electrode layer 3; HTL41, ACT-L42, ETL43, reflective metal negative electrode layer 5, back cover 6, frame glue 7; a spacer 8; a desiccant 9; an antireflection coating 10; an ITO transparent conductive film 11; the moisture barrier optical film layer 12.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the azimuth or positional relationship indicated by the terms "upper", "lower", "inner", "outer", etc., are based on the azimuth or positional relationship shown in the drawings, or the azimuth or positional relationship conventionally put in place when the product of the present invention is used, or the azimuth or positional relationship conventionally understood by those skilled in the art, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific azimuth, be configured and operated in a specific azimuth, and therefore should not be construed as limiting the present invention.
The invention provides a method for manufacturing AZO transparent conductive film 2, which is characterized in that by means of a magnetron sputtering process, working pressure is set to be 0.15-0.35 Pa, film forming power is set to be 4KW, film forming temperature is set to be 200-300 ℃, transparent conductive film with thickness being more than 400nm is manufactured, and the transparent conductive film is scanned and displayed by an electron microscope, so that hexagonal crystal bundles with obvious crystal lattices are formed on the transparent conductive film, and the surface morphology of the transparent conductive film is three, four, five and six pyramid mixed tip surface shapes; when the film formation pressure is gradually increased from 0.15Pa to 0.35Pa, the angle of the crystal face formed by the 111 or 112 crystal directions of the polygonal pyramid is also significantly changed due to the change in the width of the crystal beam. Preferably, when the working pressure is set to be 0.2 Pa-0.25 Pa, the thickness of the AZO transparent conductive film 2 is 500-1000 nm, the width of the top of the crystal lattice of the hexagonal crystal beam of the AZO transparent conductive film 2 is 200-300 nm, the included angle of the crystal face of the crystal direction 111 or 112 of the polygonal cone is 100-105 degrees, and the refractive index of the AZO transparent conductive film 2 is n=1.75-1.85. The AZO transparent conductive film 2 thus produced can be used as a light condensing structure or a transparent positive electrode in a solar cell device at the same time.
In one aspect, the invention provides a transparent solar cell device, which comprises an AZO transparent conductive film 2 prepared by the method, and the AZO transparent conductive film is used as a light condensing structure and is arranged on the inner side of a transparent front substrate 1, so that light obliquely incident on the surface of the transparent front substrate 1 can be fully absorbed by an active layer material after multiple refraction to the greatest extent, and the photoelectric conversion efficiency of the device is higher.
In another aspect, the present invention provides a transparent solar cell device, including the AZO transparent conductive film 2 manufactured by the above method, where the transparent positive electrode layer 3 used as the device may be directly manufactured on the surface of the AZO transparent conductive film 2 to form the first HTL41 layer of the PV photovoltaic layer, so that, in order to better match the work function of the transparent positive electrode with the HOMO (the highest occupied orbit of the occupied electron is called the highest occupied orbit, and expressed by HOMO) energy level of the HTL41 layer, a layer of ITO transparent conductive film 11 or IZO transparent conductive film with a high work function is deposited on the surface of the AZO transparent conductive film 2, where the refractive index of the ITO transparent conductive film 11 or IZO transparent conductive film is similar to that of the AZO transparent conductive film 2, and the thickness is less than 500nm, so that the appearance of the surface of the AZO transparent conductive film 2 is still in a convex multi-pyramid state, and the radial propagation of incident light is facilitated.
Example 1
As shown in fig. 1, a flowchart of a method for manufacturing an AZO transparent conductive film 2 is provided, and the manufacturing method is completed by means of a magnetron sputtering process, specifically includes:
s10: zinc oxide with the metal aluminum content of 1% -5% is used as a raw material to manufacture an AZO metal oxide target;
s20: setting the working pressure of argon plasma in the magnetron sputtering process to be 0.15-0.35 Pa, the film forming power to be 4KW and the film forming temperature to be 200-300 ℃;
s30: AZO transparent conductive film 2 with thickness larger than 400nm is manufactured, and hexagonal crystal bundles with obvious crystal lattice are formed on the transparent conductive film.
As shown in fig. 2-3, an electron microscope scan of an AZO transparent conductive film 2 is provided, the surface morphology of which is three, four, five, six pyramid-shaped mixed tip surface shape; when the film forming pressure is gradually increased from 0.15Pa to 0.35Pa, the crystal face angle formed by the 111 or 112 crystal directions of the polygonal pyramid is also changed obviously due to the width change of the crystal beam.
Preferably, when the working pressure is set to be 0.2 Pa-0.25 Pa, the thickness of the AZO transparent conductive film 2 is 500-1000 nm, the width of the top of the crystal lattice of the hexagonal crystal beam of the AZO transparent conductive film 2 is 200-300 nm, the included angle of the crystal face of the crystal direction 111 or 112 of the polygonal cone is 100-105 degrees, and the refractive index of the AZO transparent conductive film 2 is n=1.75-1.85. The refractive index (n is approximately equal to 1.4-1.5) of the front substrate is far greater than that of the front substrate, and the transparent conductive film can furthest enable light obliquely incident on the surface of the front substrate to be fully absorbed by the active layer material after being refracted for multiple times when being used as a light condensing structure, so that the photoelectric conversion efficiency of the device is higher.
Example 2
As shown in fig. 4, a schematic structural diagram of a transparent solar cell device is provided, the device comprising: a transparent front substrate 1, a transparent positive electrode layer 3, a PV photovoltaic layer, a reflective metal negative electrode layer 5 and a rear cover 6 which are stacked; the transparent front substrate 1 includes an AZO transparent conductive film 2 manufactured as in example 1, and the AZO transparent conductive film 2 is disposed inside the transparent front substrate 1 as a light condensing structure.
Preferably, the refractive index of the bulk material of the transparent front substrate 1 is less than or equal to the refractive index of the AZO transparent conductive film 2, so that light obliquely incident on the device surface from the outside of the solar cell device is incident in a direction which tends to be perpendicular to the device surface after multiple times of refraction. Sequentially enters the transparent positive electrode layer 3, the HTL41 and the photovoltaic active layer (ACT-L42), is absorbed in the photovoltaic active layer ACT-L42 to generate excitons, and is separated at an acceptor interface to form electrons and holes, and then a loop is formed through the positive electrode and the negative electrode.
As shown in fig. 5-6, a schematic diagram of the working principle of the light focusing structure is given. The working principle is as follows:
let the incident angle alpha, the reflection angle beta, and the refraction angle theta. The light-condensing structure (AZO transparent conductive film 2) is a light-tight medium, the refraction is n3, the transparent front substrate 1 is also a light-tight medium relative to air (n 1), and the refractive index is n2; and n3 is greater than or equal to n2 and greater than n1.
When light is incident from air into the transparent front substrate 1, according to the refraction law n1=n2=nθ, since n1 < n2, the incident angle is pushed out to be larger than the refraction angle (i.e., α > θ).
When light continues to enter the light-condensing structure from the transparent front substrate 1, according to the refraction law n2 x Sin α '=n3 x Sin θ', since n2 is less than or equal to n3, the incident angle is greater than or equal to the refraction angle (i.e., α '. Gtoreq.θ').
When light continues to enter the transparent positive electrode layer 3 from the light-condensing structure, since n3≡n4, it can be assumed that light continues to enter the transparent positive electrode layer 3 in the original direction, and according to the refraction law n4×sin α "=n5×sin θ", the propagation directions of refracted light rays when n4 is greater than and less than n5 can be respectively assumed, and it can be determined that when the included angle of crystal faces of the AZO transparent conductive film 2 is greater, light rays incident from the outside can be more fully utilized. Therefore, the included angle of the crystal face of the AZO transparent conductive film 2 prepared in the embodiment 1 is 100-105 degrees, and the light incident from the outside can be more fully utilized, so that the photoelectric conversion efficiency of the device is improved.
Preferably, the outer surface of the transparent front substrate 1 is provided with an anti-reflection coating 10 in order to further enhance the utilization of the incident light.
Preferably, the transparent front substrate 1 is a colorless transparent rigid or flexible substrate. The rigid substrate can be made of glass or thick (t is more than or equal to 0.3 mm) PC board, PET board and other materials, the flexible substrate can be made of CPI, PET, PC, COP, COC, PMMA and other colorless transparent films (t is less than or equal to 0.15 mm) as the substrate, and the flexible substrate is generally required to be peeled off from the surface of the rigid substrate after the whole manufacturing process is completed by using the rigid substrate as the substrate in the manufacturing process.
Preferably, when the transparent front substrate 1 is a flexible substrate, one or more water vapor barrier optical film layers 12 are fabricated on the surface of the transparent front substrate 1. So as to ensure the electrical property and reliability of the device.
Preferably, the material of the water vapor barrier optical film layer 12 includes, but is not limited to, silicon nitride, silicon oxide, silicon oxynitride, organic resin coating, or a combination of the above, and is disposed on one side or both sides of the transparent front substrate 1; when the water vapor barrier optical film layer 12 is disposed on only one side of the transparent front substrate 1, it is disposed on the inner side of the transparent front substrate 1, i.e., on the side where the AZO transparent conductive film 2 is disposed.
Preferably, the transparent positive electrode layer 3 can be made of TCO (transparent conductive oxide), nano silver, carbon nano tube, graphene, ultrathin metal layer (such as magnesium silver alloy layer), or PEDOT: PSS material with conductivity more than or equal to 800S/cm.
A PV photovoltaic layer comprising a three layer basic structure of HTL41 (hole transport layer), ACT-L42 (photovoltaic active layer) and ETL43 (electron transport layer).
The HTL41 of the OPV solar cell is generally made of P 3 HT, PTAA, spiro-OMeTAD, PEDOT: PSS and the like, the film thickness ranges from 40nm to 80nm, and the film thickness is preferably 50nm. The HTL41 of the perovskite solar cell may include the organic HT material, or may be an inorganic or inorganic complex compound such as Cu 2 O, cuI, cuSCN, niO.
The active layer (ACT-L42) of OPV solar cells is composed of a polymer donor material (P 3 HT, PM6, PTZDI, etc.) and a polymer or macromolecular acceptor material (PCBM, Y6, DTY6, etc.). The OPV may be an active layer formed by blending a small molecule donor material based on oligothiophene, benzodithiophene, BDT, DTS, porphyrin, IDT/idttt, dithienopyrrole, and the like, with a small molecule acceptor based on fullerene, perylene diimide, dithienopyrrolopyrrole dione, rhodamine end group, indandione end group, and the like. The active layer of the perovskite solar cell may be a simple inorganic perovskite (ABX 3 type, a 2BBX6 type, etc.), or an organic-inorganic hybrid perovskite cell.
The ETL43 of the OPV cell may be made of a small molecular material or a polymer material, and the small molecular compound is generally manufactured by vapor deposition, including an aromatic amine compound, an alkali metal compound, and the like; polymers are typically made using solution processes, including but not limited to fullerenes and their derivatives (PC 60BM、PC61BM、PC71 BM, etc.), PCBA, ICBA, PFN, bis-C 60, etc. The ETL43 of the perovskite solar cell comprises the organic ETL43 material, inorganic TiO2, znO and the like.
Preferably, the reflective metal negative electrode layer 5 is made of a metal simple substance or alloy with low resistance and high reflectivity (more than or equal to 70%) such as silver, aluminum, molybdenum, gold, zinc and the like which can be formed by adopting an evaporation method. The purpose of using a metal with high reflectivity is to enable light which is not fully absorbed by the active layer when passing through the active layer to reach the reflective metal negative electrode layer 5 through the ETL43, and then to be reflected back to be absorbed and utilized by the ACT-L42 layer again, thereby further improving the photoelectric conversion efficiency.
Preferably, the material of the sealing material of the rear cover 6 includes, but is not limited to, a rigid (such as glass, quartz, etc.) or flexible (such as CPI, PET, PC, COP, COC, PMMA, etc.) film (t.ltoreq.0.15 mm). When the rear cover 6 is a flexible substrate, in order to improve the reliability of the device, preferably, the device can be packaged by adopting a TFE mode, a water vapor barrier layer can be manufactured on the inner surface of the flexible substrate, and the water vapor barrier layer is directly attached to the surface of the negative electrode through an OCA adhesive tape containing a water vapor adsorbent to form a rear cover 6 protection structure, so that the water vapor barrier effect is achieved, and the reliability of the device is ensured.
Preferably, the packaging structure further comprises a frame adhesive 7, wherein the frame adhesive 7 is a UV (ultraviolet) curing type or thermosetting type resin, and can be a resin combining two types of resins, and the frame adhesive 7 is used for bonding the rear cover 6 with the transparent front substrate 1 for packaging; the frame glue 7 is filled with water-oxygen adsorption particles and spacers 8 with uniform particle sizes, and the particle size of the spacers 8 is 2-100 mu m; furthermore, the drying agent 9 is coated or adhered on the inner surface of the rear cover 6, so that the storage and service life of the product can be more effectively improved.
Further, the frame glue 7 may be made of glass frit, and the substrate and the rear cover 6 may be bonded by laser sintering, and in this way, it is generally not necessary to additionally provide a desiccant 9 inside the device.
Example 3
As shown in fig. 5, there is provided a schematic structural view of another transparent solar cell device, which includes: a transparent front substrate 1, a transparent positive electrode layer 3, a PV photovoltaic layer, a reflective metal negative electrode layer 5 and a rear cover 6 which are laminated. Wherein the transparent positive electrode layer 3 was AZO transparent conductive film 2 produced as in example 1.
Preferably, because the work function of the AZO transparent conductive film 2 is slightly lower than that of the conventional transparent positive electrode layer material, such as TCO material such as ITO or IZO, in order to better match the work function of the transparent positive electrode layer with the HOMO (the highest occupied orbit of the occupied electrons is called the highest occupied orbit, and is denoted by HOMO) energy level of the HTL41 layer, a layer of transparent conductive film with high work function such as ITO or IZO may be further deposited on the surface of the AZO transparent conductive film 2, where the refractive index of the transparent conductive film with high work function is similar to that of the AZO transparent conductive film 2, and the thickness is less than 500nm, so that the morphology of the transparent positive electrode layer on the surface of the AZO transparent conductive film 2 is still in a convex polygonal cone state, which is beneficial to radial propagation of incident light.
Claims (8)
1. The method for manufacturing the AZO transparent conductive film is characterized by comprising the following steps of:
Zinc oxide with the metal aluminum content of 1% -5% is used as a raw material to manufacture an AZO metal oxide target;
Setting the film forming power to be 4KW and the film forming temperature to be 200-300 ℃ in the magnetron sputtering process;
AZO transparent conductive film with thickness larger than 400nm is manufactured, at the moment, the transparent conductive film forms hexagonal crystal beams with obvious crystal lattices, and the surface morphology of the transparent conductive film is three, four, five and six pyramid mixed tip surface shapes; when the film forming pressure is gradually increased from 0.15Pa to 0.35Pa, the crystal face angle formed by the 111 or 112 crystal directions of the polygonal pyramid is also obviously changed due to the width change of the crystal beam;
Setting the working pressure of argon plasma in the magnetron sputtering process to be 0.2 Pa-0.25 Pa, and preparing the AZO transparent conductive film with the thickness of 500-1000 nm, wherein the width of the top of a crystal lattice of a hexagonal crystal beam of the AZO transparent conductive film is 200-300 nm, the included angle of a crystal face in the 111 or 112 crystal directions of a polygonal cone is 100-105 degrees, and the refractive index of the AZO transparent conductive film is n=1.75-1.85.
2. The transparent solar cell device is characterized by comprising a transparent front substrate, a transparent positive electrode layer, a PV photovoltaic layer, a reflective metal negative electrode layer and a rear cover which are stacked; wherein the transparent front substrate comprises an AZO transparent conductive film manufactured by the manufacturing method of claim 1, and the AZO transparent conductive film is arranged on the inner side of the transparent front substrate and used as a light condensing structure;
The refractive index of the transparent front substrate body material is smaller than or equal to that of the AZO transparent conductive film, so that light obliquely entering the device surface from the outside of the transparent solar cell device is refracted for multiple times and then enters in a direction which tends to be perpendicular to the device surface.
3. The transparent solar cell device according to claim 2, wherein the outer surface of the transparent front substrate is provided with an anti-reflection coating layer so as to further improve the utilization ratio of the incident light.
4. A transparent solar cell device according to claim 3, wherein the transparent front substrate is a colorless transparent rigid or flexible substrate; when the transparent front substrate is a flexible base material, one or more water vapor barrier optical film layers are manufactured on the surface of the transparent front substrate.
5. The transparent solar cell device according to claim 4, wherein the material of the water vapor barrier optical film layer is one or more of silicon nitride, silicon oxide, and organic resin coating, and is disposed on one side or both sides of the transparent front substrate; when the water vapor blocking optical film layer is arranged on one side of the transparent front substrate, the water vapor blocking optical film layer is arranged on the inner side of the transparent front substrate, namely, on the side provided with the AZO transparent conductive film.
6. The transparent solar cell device according to claim 2, wherein the transparent positive electrode layer is made of a PEDOT/PSS material with conductivity of 800S/cm or more.
7. The transparent solar cell device according to claim 2, further comprising a frame glue, wherein the frame glue is a UV-curable or thermosetting resin or a glass frit material, and the frame glue is used for bonding the rear cover and the transparent front substrate together; the resin is filled with water-oxygen adsorption particles and spacers with uniform particle sizes, and the particle size of the spacers is 2-100 mu m; when the frame glue material is UV curing type or thermosetting type resin, a drying agent is coated or attached on the inner surface of the rear cover.
8. The transparent solar cell device is characterized by comprising a transparent front substrate, a transparent positive electrode layer, a PV photovoltaic layer, a reflective metal negative electrode layer and a rear cover which are stacked; wherein the transparent positive electrode layer is an AZO transparent conductive film manufactured by the manufacturing method of claim 1; and depositing a layer of ITO or IZO transparent conductive film on the surface of the AZO transparent conductive film, wherein the thickness of the ITO or IZO transparent conductive film is less than 500nm.
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| CN101985735A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Alumina target material and transparent conductive film prepared thereby |
| CN103474576A (en) * | 2013-09-30 | 2013-12-25 | 苏州大学张家港工业技术研究院 | Organic solar cell and manufacturing method thereof |
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| US20180351012A1 (en) * | 2010-06-18 | 2018-12-06 | University Of Florida Research Foundation, Inc. | Thin Film Photovoltaic Devices With Microlens Arrays |
| KR101181225B1 (en) * | 2011-01-06 | 2012-09-10 | 성균관대학교산학협력단 | Fabricating method of solar cell |
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| CN101985735A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Alumina target material and transparent conductive film prepared thereby |
| CN103474576A (en) * | 2013-09-30 | 2013-12-25 | 苏州大学张家港工业技术研究院 | Organic solar cell and manufacturing method thereof |
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