TWI803049B - Nano-structure-modified organic component manufacturing method and structure thereof - Google Patents

Abstract

A manufacturing method of nano-structure-modified organic components includes: pre-processing on a substrate to form a modified surface thereon; processing a first spin-coating and heating procedure with a conductive polymer liquid to form a conductive polymer layer on the modified surface; processing a second spin-coating and heating procedure with an inorganic material liquid to form a hole transport layer on the conductive polymer layer; processing a third spin-coating and heating procedure with an ABX₃ material liquid to form a ABX₃ layer on the hole transport layer; processing a fourth spin-coating and heating procedure with a polymer liquid to form an electron transport layer on the ABX₃ layer; processing a deposition procedure with an electrode material to form a plurality of electrodes on the electron transport layer.

Description

Fabrication method and structure of organic element modified by nanometer structure

The present invention relates to a nano-structure (nano-structure) modified (modified) organic component (organic component) manufacturing method and its structure; in particular to a nano-structure modified perovskite [ABX ₃ ] organic component manufacturing method and its structure; more particularly, a nanostructure-modified organic element manufacturing method and its structure can be used to manufacture sensing elements [sensor], light emitting diode elements [light emitted diode, LED] or perovskite solar cells [ Perovskite solar cell, PSC].

For example, the conventional perovskite solar cell manufacturing method and its structure, such as the Republic of China Patent Publication No. TW-202124282 "Perovskite Precursor Solution, Manufacturing Method of Perovskite Light Absorbing Layer, and Perovskite Solar Cell" An invention patent application discloses a perovskite solar cell, and the perovskite solar cell includes a substrate, an electron transport layer, a perovskite absorption layer, a hole transport layer and an electrode layer.

As mentioned above, the substrate of the aforementioned TW-202124282 has a conductive layer, and the electron transport layer is selectively disposed on the substrate, and the perovskite absorbing layer is selectively disposed on the electron transport layer, and the hole transport A layer is selectively disposed on the perovskite absorbing layer, and the electrode layer is selectively disposed on the hole transport layer.

Continuing from the above, the XRD pattern of the perovskite absorbing layer of the aforementioned TW-202124282 has a diffraction peak intensity ratio between (220) crystal direction and (310) crystal direction between 0.9 and 1.1. In addition, the perovskite absorber layer’s The ratio of the diffraction peak intensities at 2θ angles of 28.2° to 28.8° to those at 31.2° and 31.8° in the XRD pattern is between 0.95 and 1.05.

Another conventional perovskite solar cell manufacturing method and its structure, such as the invention patent of the Republic of China Patent Announcement No. TW-474992 "Perovskite Thin Film and Solar Cell Preparation Method", which discloses a perovskite thin film preparation method . The preparation method of the perovskite film comprises the steps of: spin-coating a first solution on a substrate to form a film; and spin-coating a second solution on the film prepared by the first solution to form a calcium Titanium thin film [its general formula is ABX ₃ ].

As mentioned above, the solute of the first solution of the aforementioned TW-474992 contains at least one of AX or BX ₂ , and the solute of the second solution contains at least one of AX or BX ₂ , wherein A is an alkali metal ion, At least one of methylamine ion, ethylamine ion, NH ₂ CH=NH ₂ ion or alkylamine ion, B is group IV element [germanium Gc, tin Sn or lead Pb], group III element indium or group V At least one of antimony elements, and X is at least one of group VII elements [fluorine F, chlorine Cl, bromine Br or iodine I].

As mentioned above, the solvent of the first solution of the aforementioned TW-474992 can be selected as dimethylformamide [DMF] or isopropanol [isopropanol], and the solvent of the second solution can also be selected as dimethyl formamide or isopropanol.

Another conventional perovskite solar cell manufacturing method and its structure, such as the invention patent of the Republic of China Patent Announcement No. TW-I583011 "Large-area perovskite film and perovskite solar cell module and its manufacturing method", which discloses A method for fabricating a large-area perovskite film. The manufacturing method of the large-area perovskite film includes the steps of: providing an initial solution on a conductive substrate by slit-type extrusion coating, so as to form a film material (its general formula is ABX ₃ ), and the starting solution The solutes of the initial solution include at least A, B and X.

Continuing from the above, the manufacturing method of the large-area perovskite film of the aforementioned TW-I583011 further includes the steps of: soaking the film material in an anti-solvent, In order to form a perovskite film, and the perovskite film has several perovskite crystal grains; and annealing the film material, so that the perovskite crystal grains of the perovskite film become larger.

Continuing from the above, the perovskite crystals of the perovskite film of the aforementioned TW-I583011 can be selected to be continuously and uniformly distributed on a conductive substrate, and the distribution area of the perovskite crystals of the perovskite film can be between between 25cm ² and 1000cm ² , and the area of the conductive substrate can be between 25cm ² and 1000cm ² .

As mentioned above, the anti-solvent of the aforementioned TW-I583011 produces the perovskite crystal in the membrane material, wherein A is an alkali metal ion, methylamine ion [CH ₃ NH ₃ ⁺ ], formamidine ion [NH ₂ At least one of CH=NH ₂ ⁺ ], B is at least one of lead [Pb], tin [Sn], germanium [Ge], X is a group VII element [fluorine F, chlorine Cl, bromine Br, iodine I] , at least one of phosphorus hexafluoride [PF ₆ ], and thiocyanic acid [SCN].

As mentioned above, the solvent of the starting solution of the aforementioned TW-I583011 can be selected from dimethylformamide [DMF], dimethylsulfoxide [DMSO], gamma butyrolactone [GBL] or any mixture thereof solution. In addition, the anti-solvent is thiophene [] thiophene), derivatives of thiophene, iodobenzene [Iodobenzene], ether [ether], chlorobenzene [CB], dichlorobenzene [DCB], toluene [toluene], benzene [Benzene] or any mixture thereof.

Another conventional perovskite solar cell manufacturing method and its structure, such as the invention patent of the Republic of China Patent Publication No. TW-I699370 "Perovskite solar cell and its manufacturing method", which discloses a trans-type perovskite solar cell [ inverted p-i-n PVSCs]. The reverse perovskite solar cell comprises a conductive substrate, a first carrier transfer layer, an active layer, a second carrier transfer layer and an opposite electrode layer.

Continuing from the above, the active layer of the aforementioned TW-I699370 includes a heterostructure, and the heterostructure includes: a mixture of a metal-organic framework (MOFs) and a perovskite material; or a double-layer structure, and the double-layer structure The layer structure is composed of a first layer and a second layer. The first layer includes a first metal organic framework, and the first metal organic framework includes a first perovskite material, and the second layer includes a second metal organic framework, and the second metal organic framework includes a The second perovskite material, and the first metal organic framework and the second metal organic framework are in contact with the second carrier transport layer.

As above, the first carrier transport layer of the aforementioned TW-I699370 is a hole transport layer, and its material is selected from nickel oxide [NiO _x ], 2,2',7,7'-4-[N,N -Bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene [Spiro-OMeTAD], polydioxyethylthiophene: styrenesulfonic acid [PEDOT:PSS], N,N'- Bis(3-methylphenyl)-N,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine [TPD], polytrihexylpolythiophene [P3HT], Vanadium pentoxide [V ₂ O ₅ ], graphene [graphene], molybdenum sulfide [MoS ₂ ], molybdenum selenide [MoSe ₂ ], polyalkyl-thiophene [polyalkyl-thiophene] and molybdenum trioxide [MoO ₃ ] composed of groups.

As mentioned above, the second carrier transfer layer of the aforementioned TW-I699370 is an electron transfer layer, and its material is selected from fullerene, carbon-60 [C ₆₀ ], [6.6]-phenyl-C61-butyric acid methyl Ester [[6,6]-phenyl-C61-butyric acid methyl ester, PCBM], titanium dioxide [TiO ₂ ], zinc oxide [ZnO], tin dioxide [SnO ₂ ] and zinc stannate [Zn ₂ SnO ₄ ] composed of groups.

Based on the above, a hole blocking layer is further included between the second carrier transport layer and the opposite electrode layer of the aforementioned TW-I699370, and the material of the hole blocking layer includes 2,9-dimethyl-4 ,7-diphenyl-1,10-phenanthroline [bathocuproine, BCP], 4,7-diphenyl-1,10-phenanthroline [4,7-diphenyl-1,10-phenanthroline, Bphen] , 1,3,5-tri(4-pyridin-3-ylphenyl)benzene [1,3,5-tri(p-pyrid-3-yl-phenyl)benzene, TpPyPB] or diphenylbis[4 -(pyridin-3-yl)phenyl]silane [diphenyl bis(4-(pyridin-3-yl)phenyl)silane, DPPS].

However, the aforementioned ROC Patent Publication No. TW-202124282, ROC Patent Publication No. TW-474992, TW-I583011 and TW-I699370 disclose various manufacturing methods and structures of perovskite solar cells , but it still has the need to improve various technical problems, so it must have the need for further technical improvement.

In short, the aforementioned ROC Patent Application Publication No. TW-202124282, ROC Patent Publication No. TW-474992, TW-I583011 and TW-I699370 are only references and descriptions of the technical background of the present invention. It is merely a state of technology development and is not intended to limit the scope of the present invention.

In view of this, in order to meet the above-mentioned technical problems and demands, the present invention provides a nanostructure-modified organic element manufacturing method and its structure, which performs a pre-treatment operation on a substrate in order to obtain a treated surface, and Using a conductive polymer solution to perform a first coating and heating operation on the treated surface so as to form a conductive polymer film, and using an inorganic material solution to perform a second coating and heating on the conductive polymer film Heating operation to form a hole transport layer, and using a perovskite material solution to perform a third coating and heating operation on the hole transport layer to form a perovskite layer, and using a polymer material solution A fourth coating and heating operation is performed on the perovskite layer to form an electron transport layer, so that compared with the conventional perovskite solar cell manufacturing method and its structure, the device stability, hole transport efficiency and power can be improved The purpose of conversion efficiency.

The main purpose of the present invention is to provide a nanostructure modified organic element manufacturing method and its structure, which performs a pre-treatment operation on a substrate, in order to obtain a treated surface, and utilizes a conductive polymer solution on the processed surface A first coating and heating operation is carried out on the treated surface so that forming a conductive polymer film, and using an inorganic material solution to perform a second coating and heating operation on the conductive polymer film to form a hole transport layer, and using a perovskite material solution to coat the hole performing a third coating and heating operation on the transport layer to form a perovskite layer, and performing a fourth coating and heating operation on the perovskite layer using a polymer material solution to form an electron transport layer, In order to achieve the effects of improving device stability, hole transmission efficiency and power conversion efficiency.

In order to achieve the above-mentioned purpose, the nanostructure-modified organic element manufacturing method of the preferred embodiment of the present invention includes:

performing a pretreatment on a substrate in order to obtain a treated surface;

performing a first coating and heating operation on the treated surface with a conductive polymer solution, so as to form a conductive polymer film;

Using an inorganic material solution to perform a second coating and heating operation on the conductive polymer film, so as to form a hole transport layer;

performing a third coating and heating operation on the hole transport layer by using a perovskite material solution to form a perovskite layer;

performing a fourth coating and heating operation on the perovskite layer with a polymer material solution to form an electron transport layer; and

An electrode material is subjected to an evaporation operation on the electron transport layer, so as to form several electrodes.

The substrate in a preferred embodiment of the present invention is selected from a conductive substrate or an indium tin oxide substrate.

The conductive polymer solution in a preferred embodiment of the present invention is selected from a styrene sulfonic acid solution or a solution containing styrene sulfonic acid.

The inorganic material solution in a preferred embodiment of the present invention is selected from a nanoscale inorganic material solution, a nanoscale nickel monoxide solution, a solution containing nanoscale nickel monoxide or other solutions containing nanoscale nickel oxide .

The perovskite material solution of the preferred embodiment of the present invention is optional An antisolvent is optionally added, and the antisolvent is selected from a toluene solvent or a toluene-containing solvent.

The polymer material solution in a preferred embodiment of the present invention is selected from a solution of a fullerene derivative or a solution containing a fullerene derivative.

In order to achieve the above-mentioned purpose, the nanostructure-modified organic element structure of the preferred embodiment of the present invention includes:

A substrate on which a pretreatment operation is performed to obtain a processed surface;

A conductive polymer film, which uses a conductive polymer solution to perform a first coating and heating operation on the treated surface to form the conductive polymer film;

A hole transport layer, which uses an inorganic material solution to perform a second coating and heating operation on the conductive polymer film to form the hole transport layer;

A perovskite layer, which uses a perovskite material solution to perform a third coating and heating operation on the hole transport layer to form the perovskite layer;

An electron transport layer, which uses a polymer material solution to perform a fourth coating and heating operation on the perovskite layer to form the electron transport layer; and

at least one electrode, which forms the electrode by performing an evaporation operation on the electron transport layer with an electrode material;

The inorganic material of the inorganic material solution is used to replace the organic polymer of the conductive polymer solution.

The substrate in a preferred embodiment of the present invention is selected from a conductive substrate or an indium tin oxide substrate.

The conductive polymer solution in a preferred embodiment of the present invention is selected from a styrene sulfonic acid solution or a solution containing styrene sulfonic acid.

The inorganic material solution in a preferred embodiment of the present invention is selected from a Nanoscale inorganic material solution, a nanoscale nickel monoxide solution, a solution containing nanoscale nickel monoxide or other solutions containing nanoscale nickel oxide.

An anti-solvent may optionally be added to the perovskite material solution in a preferred embodiment of the present invention, and the anti-solvent is selected from a toluene solvent or a toluene-containing solvent.

The polymer material solution in a preferred embodiment of the present invention is selected from a solution of a fullerene derivative or a solution containing a fullerene derivative.

1: Perovskite element

10: Substrate

11: Hole transport layer

12: Perovskite layer

13: Electron transport layer

14: electrode

Figure 1: A schematic side view of the nanostructure-modified organic device structure of a preferred embodiment of the present invention.

Fig. 2: A schematic block diagram of the process flow of the nanostructure-modified organic device manufacturing method according to the preferred embodiment of the present invention.

Figures 3A to 3C: SEM images of the surfaces of three nanoscale nickel monoxide materials used in the method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention.

Figures 4A to 4C: SEM images of the perovskite surface after using three nano-scale nickel monoxide materials in the method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention.

Figures 5A to 5C: SEM images and binarized images of the perovskite surface after the nanostructure-modified organic device manufacturing method of the preferred embodiment of the present invention uses three nano-scale nickel monoxide materials.

Fig. 6: A schematic diagram of the current density vs. voltage curve of the nanostructure-modified organic element structure of the preferred embodiment of the present invention using three nano-scale nickel monoxide materials.

In order to fully understand the present invention, preferred embodiments will be described below in detail together with the accompanying drawings, which are not intended to limit the present invention.

The nano-structure modified organic element manufacturing method and its structure of the preferred embodiment of the present invention are suitable for various sensing elements, various light-emitting diode elements, and various perovskite solar cell elements [transverse structure perovskite solar cells Component] or its related products, but it is not intended to limit the scope of application of the present invention.

Fig. 1 shows a schematic side view of a nanostructure-modified organic device structure according to a preferred embodiment of the present invention. Please refer to Figure 1, for example, the structure of the organic element modified by the nanometer structure of the preferred embodiment of the present invention mainly includes a substrate 10, a hole transport layer 11, a perovskite layer 12, and an electron transport layer 13 and several electrodes 14, and the substrate 10, the hole transport layer 11, the perovskite layer 12, the electron transport layer 13 and the electrodes 14 are sequentially stacked to form a perovskite element 1, and the perovskite element 1 can be selected It is a perovskite sensing element, an inverse perovskite solar cell element or a perovskite photoelectric element.

FIG. 2 discloses a schematic block diagram of a method for manufacturing a nanostructure-modified organic device according to a preferred embodiment of the present invention, which corresponds to the structure of the nanostructure-modified organic device in FIG. 1 . Please refer to Figures 1 and 2, the method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention includes step S1: For example, firstly, at least one pre-preparation process is performed on the substrate 10 by appropriate technical means. Treatment operations in order to obtain a treated surface [not marked].

Please refer to Figures 1 and 2 again. For example, the substrate 10 can be selected from a glass substrate or a substrate of similar material, and the substrate 10 can be selected from a conductive substrate or an indium tin oxide (ITO) substrate. , and the pre-treatment operation chooses to use ultraviolet rays to irradiate at least one surface of the substrate 10 for a predetermined time (for example: 15 minutes or other treatment time), so that the treated surface is hydrophilic, so that the treated surface is suitable for use in Subsequent spin coating job.

Please refer to Fig. 1 and Fig. 2 again, the preferred embodiment of the present invention The nanostructure modified organic device manufacturing method includes step S2: for example, then, using a conductive polymer solution to perform a first coating and heating operation on the treated surface by appropriate technical means, so as to form a conductive polymer film. The conductive polymer solution of the preferred embodiment of the present invention is selected from a styrene sulfonic acid [PEDOT:PSS] solution, a solution containing styrene sulfonic acid or an organic material solution [for example: PATT material, Spiro-OMeTAD material or P3HT materials, etc.].

Please refer to Figures 1 and 2 again. For example, the first coating and heating operation adopts a spin-coating (spin-coating) method at 3000 rpm or other speeds, and lasts for 30 seconds or other spin-coating times, and The first coating and heating operation uses a heating plate to heat at an appropriate heating temperature (for example: 120° C. or other temperature) for a predetermined time (for example: 10 minutes or other heat treatment time).

Please refer to Figures 1 and 2 again, the method for manufacturing organic elements with nanostructure modification in a preferred embodiment of the present invention includes step S3: for example, then, using an inorganic material solution in the conductive high A second coating and heating operation is performed on the molecular film to form the hole transport layer 11 .

Please refer to Figures 1 and 2 again. For example, the inorganic material of the inorganic material solution [for example: CuSCN, Cu ₂ O, CuS, CuO, CuI, CoO _x , Cu ₂ BaSnS ₄ or NiO _x , etc. or other Inorganic materials or transition metal materials] are used to replace the organic polymers of the conductive polymer solution [for example: PEDOT:PSS or other organic polymers].

Please refer to Figures 1 and 2 again. For example, the inorganic material solution can be selected from a nanoscale inorganic material solution, a nanoscale nickel monoxide [nano-NiO] solution, a nanoscale-containing Nickel oxide solution or other solutions containing nano-scale nickel oxide.

Please refer to Figures 1 and 2 again. For example, the inorganic material solution has a nickel oxide material with a nanostructure, and the nanostructure The nickel oxide material of structure 1 can choose the hydrothermal method to properly synthesize its nanostructure, and the pore characteristics of the nanostructure can be used to increase the contact area with the perovskite layer 12 .

Please refer to Figures 1 and 2 again. For example, the second coating and heating operation adopts a spin coating method at 3000 rpm or other speeds, and lasts for 30 seconds or other spin coating times, and the second coating And the heating operation uses a heating plate to heat for a predetermined time (for example: 15 minutes or other heating treatment time) at an appropriate heating temperature (for example: 80° C. or other temperature).

Please refer to Figures 1 and 2 again, the method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention includes step S4: for example, then, using a perovskite [ _ABX3 ] The material solution is subjected to a third coating and heating operation on the hole transport layer 11 to form the perovskite layer 12 .

Please refer to Figures 1 and 2 again. For example, the third coating and heating operation adopts a two-stage spin coating operation, and the two-stage spin coating operation includes the first stage of spin coating at 1000rpm or other speeds and continuous 10 seconds or other spin coating time and 3500rpm or other rotation speed of the second stage spin coating method and last 20 seconds or other spin coating time, and the third coating and heating operation adopts a heating plate to an appropriate heating temperature [for example: 100° C. or other temperature] for a predetermined time [for example: 5 minutes or other heat treatment time], at this time the perovskite layer 12 can be properly transformed into a bright black film.

Please refer to Figures 1 and 2 again. For example, another preferred embodiment of the present invention selects the perovskite during the second stage of spin coating to a predetermined time (for example: 10 seconds or other addition time). An anti-solvent may optionally be added to the mineral material solution, and the anti-solvent is selected from a toluene solvent or a solvent containing toluene, so that the anti-solvent can properly accelerate the crystallization of the perovskite (eg, increase the grain size specification).

Please refer to Figures 1 and 2 again, the method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention includes step S5: for example, then, using a polymer material solution in the calcium A fourth coating and heating operation is performed on the titanium ore layer 12 to form the electron transport layer 13 .

Please refer to Figures 1 and 2 again. For example, the fourth coating and heating operation adopts a spin coating method at 1500 rpm or other speeds, and lasts for 60 seconds or other spin coating times, and the fourth coating And the heating operation uses a heating plate to heat at an appropriate heating temperature (for example: 100° C. or other temperature) for a predetermined time (for example: 1 minute or other heating treatment time).

Please refer to Figures 1 and 2 again. For example, the polymer material solution can be selected from a fullerene derivative [PCBM] solution or a solution containing a fullerene derivative material, but it is not used for Limit the scope of application of the present invention.

Please refer to Figures 1 and 2 again. The method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention includes step S6: 13 to perform a vapor deposition (deposition) operation, so as to form several of the electrodes 14 (for example: electrode array).

Please refer to Figures 1 and 2 again. For example, the electrode material can be heated by a tungsten boat to melt the silver ingot (or select other conductive materials) to perform the evaporation operation, and the electrode 14 has an appropriate area. [For example: 0.09cm ² or other dimensions].

Figures 3A to 3C disclose the schematic diagrams of scanning electron microscope (SEM, Scanning Electron Microscope) images of the surface of three nano-scale nickel monoxide materials used in the method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention. Please refer to Figures 3A to 3C, for example, the nanostructure modified organic device of the preferred embodiment of the present invention The manufacturing method adopts three kinds of nano-scale nickel monoxide materials, which include nano-NiO140, nano-NiO160 and nano-NiO180.

Please refer to Figure 3A, for example, the nanostructured nickel oxide on the film surface of NiO140 nanometer nickel oxide is relatively loose; please refer to Figure 3B and 3C, for example, NiO160 and NiO180 nanometer oxide The nanostructured nickel oxide on the surface of the nickel film is relatively uniformly dispersed, that is, isopropanol causes its uniform dispersion.

Figures 4A to 4C disclose the schematic diagrams of scanning electron microscope images of the perovskite surface after using three nano-scale nickel monoxide materials in the method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention, which are compared with those in Figures 3A to 4C. Figure 3C. Please refer to Figures 4A to 4C, for example, the organic device manufacturing method of nanostructure modification of the preferred embodiment of the present invention uses three kinds of nano-scale nickel monoxide materials [nano-NiO140, nano-NiO160 and nano-NiO160 and nano- After NiO180], its perovskite surface shows that it has a nanostructure.

Figures 5A to 5C show the scanning electron microscope images and their binarized images of the perovskite surface after the nanostructure-modified organic device manufacturing method of the preferred embodiment of the present invention uses three nano-scale nickel monoxide materials. Please refer to Figures 5A to 5C, for example, the organic device manufacturing method of nanostructure modification of the preferred embodiment of the present invention uses three nano-scale nickel monoxide materials [nano-NiO140, nano-NiO160 and nano-NiO160 and nano- After NiO180], the perovskite surface shows black as the part covered by the perovskite light-absorbing layer grains, and white as the pore defects not covered by the perovskite light-absorbing layer grains or grain boundaries.

For example, the method for manufacturing organic devices with nanostructure modification in the preferred embodiment of the present invention aims at the influence of nickel oxide films synthesized at different temperatures on the surface coverage of perovskite crystal grains by depositing perovskite layers: when selectively deposited on On NiO140 film, its surface coverage is about 78%; if it is selectively deposited on NiO160 film, its surface coverage increases to about It is 83.9%; if it is selectively deposited on the NiO180 film, its surface coverage drops to about 82.1%. In short, the increase of its coverage can improve the performance of the battery.

For example, the method for manufacturing organic devices with nanostructure modification in a preferred embodiment of the present invention is aimed at the influence of nickel oxide films synthesized at different temperatures on the average grain size of the perovskite surface: when the perovskite layer is deposited on On NiO140 film, its surface grain size is about 975.255nm ² ; if it is selectively deposited on NiO160 film, its surface grain size increases to about 1441.667nm ² ; if it is selectively deposited on NiO18O film, its The surface grain size then shrinks to about 771.569nm ² . In short, the larger the light-receiving area of the perovskite surface grains, the more electron-hole pairs will be generated. Therefore, the larger the surface grains, the better the performance of the battery.

Fig. 6 shows a schematic diagram of the current density vs. voltage curves of the nanostructure-modified organic device structure of the preferred embodiment of the present invention using three kinds of nano-scale nickel monoxide materials. Please refer to Figure 6, for example, the organic device structure of the nanostructure modification of the preferred embodiment of the present invention uses three nano-scale nickel monoxide materials [nano-NiO140, nano-NiO160 and nano-NiO180], And obtain different characteristics, as shown in Table 1.

Table 1: Properties of Nanostructure Modified Organic Components

Please refer to Figure 6 again. For example, the organic device structure modified by the nanostructure of the preferred embodiment of the present invention is aimed at the hole transport layer with a planar structure of PEDOT:PSS or a nanostructured nickel oxide against the trans The influence of the J-V characteristic curve of perovskite solar cells: it shows that the nanostructured nickel oxide can improve the open circuit voltage and short circuit current.

For example, the nanostructure modification of the preferred embodiment of the present invention The influence of different nanostructured nickel oxides as the hole transport layer on the J-V characteristic curve of the reverse perovskite solar cell: the microspherical nickel oxide synthesized at 160°C has a higher open circuit voltage 0.93V and a short-circuit current of 16.3mA, the main factor is the porous characteristics generated between the microspheres, which effectively increases the efficiency of hole transmission, making the power conversion efficiency reach 9.63%, which is higher than that of PEDOT:PSS planar structure. About 1.32 times.

The above-mentioned preferred embodiments only illustrate the present invention and its technical characteristics, and the technology of this embodiment can still be implemented in various substantially equivalent modifications and/or replacements; therefore, the scope of rights of the present invention depends on the appended patent application The scope defined by the scope shall prevail. The copyright in this case is restricted to be used for patent applications in the Republic of China.

1: Perovskite element

10: Substrate

11: Hole transport layer

12: Perovskite layer

13: Electron transport layer

14: electrode

Claims (10)

A method for manufacturing organic elements with nanostructure modification, which includes: performing a pretreatment operation on a substrate to obtain a treated surface; using a conductive polymer solution to perform a first coating on the treated surface and heating operations to form a conductive polymer film; use an inorganic material solution to perform a second coating and heating operation on the conductive polymer film to form a hole transport layer, and the inorganic material solution is selected from a a nanoscale inorganic material solution, and the inorganic material solution has a nanostructure; using a perovskite material solution to perform a third coating and heating operation on the hole transport layer, so as to form a perovskite layer, And using the pore characteristics of the nanostructure of the inorganic material solution to increase the contact area with the perovskite layer; using a polymer material solution to perform a fourth coating and heating operation on the perovskite layer, In order to form an electron transport layer; and performing an evaporation operation on the electron transport layer with an electrode material, so as to form several electrodes. According to the method for manufacturing organic devices with nanostructure modification described in claim 1 of the patent application, the conductive polymer solution is selected from a styrene sulfonic acid solution or a solution containing styrene sulfonic acid. According to the method for manufacturing organic elements with nanostructure modification described in item 1 of the scope of the patent application, the inorganic material solution is selected from a nanoscale nickel monoxide solution, a solution containing nanoscale nickel monoxide, or a nanoscale nickel monoxide containing solution. Solutions of meter-scale transition metal materials. According to the method for manufacturing organic devices with nanostructure modification described in item 1 of the scope of the patent application, an anti-solvent can be optionally added to the perovskite material solution, and the anti-solvent is selected from a toluene solvent or a toluene-containing solvent. According to the method for manufacturing organic devices with nanostructure modification described in item 1 of the scope of the patent application, wherein the polymer material solution is selected from a fullerene derivative solution or a solution containing fullerene derivatives. A nano-structure modified organic device structure, which includes: a substrate, which performs a pre-treatment operation on the substrate to obtain a treated surface; a conductive polymer film, which uses a conductive polymer solution on the processed surface The conductive polymer film is formed by performing a first coating and heating operation on the treated surface; a hole transport layer is formed by performing a second coating and heating operation on the conductive polymer film using an inorganic material solution The hole transport layer, and the inorganic material solution is selected from a nanoscale inorganic material solution, and the inorganic material solution has a nanostructure; a perovskite layer, which utilizes a perovskite material solution in the hole Perform a third coating and heating operation on the transport layer to form the perovskite layer, and use the pore characteristics of the nanostructure of the inorganic material solution to increase its contact area with the perovskite layer; an electron transport layer, which uses a polymer material solution to perform a fourth coating and heating operation on the perovskite layer to form the electron transport layer; and at least one electrode, which performs an evaporation of an electrode material on the electron transport layer The electrode is formed by plating operation; wherein the inorganic material of the inorganic material solution is used to replace the organic polymer of the conductive polymer solution. According to the nanostructure-modified organic device structure described in claim 6 of the patent application, the conductive polymer solution is selected from a styrene sulfonic acid solution or a solution containing styrene sulfonic acid. According to the nanostructure-modified organic element structure described in item 6 of the scope of the patent application, wherein the inorganic material solution is selected from a nano-scale nickel monoxide solution, a solution containing nano-scale nickel monoxide, or a nano-scale nickel monoxide-containing solution Solutions of grade transition metal materials. According to the nanostructure modified organic device structure described in item 6 of the scope of the patent application, an anti-solvent can be optionally added to the perovskite material solution, and The anti-solvent is selected from a toluene solvent or a toluene-containing solvent. According to the nanostructure-modified organic device structure described in claim 6 of the patent application, the polymer material solution is selected from a solution of a fullerene derivative or a solution containing a fullerene derivative.

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