CN110311042B - Preparation method of self-assembled monolayer and perovskite solar cell - Google Patents
Preparation method of self-assembled monolayer and perovskite solar cell Download PDFInfo
- Publication number
- CN110311042B CN110311042B CN201910466109.7A CN201910466109A CN110311042B CN 110311042 B CN110311042 B CN 110311042B CN 201910466109 A CN201910466109 A CN 201910466109A CN 110311042 B CN110311042 B CN 110311042B
- Authority
- CN
- China
- Prior art keywords
- solar cell
- solution
- perovskite
- layer
- perovskite solar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention disclosesA preparation method of the self-assembled monolayer is disclosed, which comprises the following steps: 1) Dissolving carboxylic acid derivative with halogen-like group in organic solvent at 60 o C～70 o C, heating and dissolving to obtain a precursor solution; 2) Spin-coating the precursor solution on a nickel oxide/ITO substrate at room temperature, and then placing the nickel oxide/ITO substrate on a hot table for annealing; 3) After cooling to room temperature, the solution was immediately washed off by spin coating twice with an organic solvent and then annealed once again to obtain a self-assembled monolayer. The invention discloses a preparation method of a perovskite solar cell. The invention also discloses a perovskite solar cell which comprises an ITO (indium tin oxide), a hole transport layer, a self-assembled monolayer, a perovskite layer, an electron transport layer, BCP (barium copper phosphate) and a silver electrode which are sequentially stacked from bottom to top. The invention obviously improves the voltage, the efficiency and the like of the device through the modification of the monomolecular layer, and improves the performance of the battery.
Description
Technical Field
The invention relates to a preparation method of a self-assembled monolayer and a perovskite solar cell and the perovskite solar cell, and belongs to the technical field of perovskite solar cells.
Background
After the industrial revolution, the rapid development of society has prompted the use of a large amount of fossil energy, leading to increased energy crisis and pollution problems. Therefore, people pay attention to the development problem of new energy, and sufficient and environment-friendly solar energy attracts people's attention.
The key to the efficient and widespread utilization of solar energy is the fabrication of inexpensive and efficient solar cells. In the past decades, most of the silicon solar cells found on the market have been high precision silicon solar cells. The manufacturing process of the silicon cell is mature, but the pollution is serious, the prospect is not good, and the efficiency is always kept below 20%, so people urgently need to search for novel materials to prepare the solar cell. In 2009, a new type of perovskite solar cell was proposed, and after a short period of development, the efficiency has reached more than 20%, and now it has reached more than 26%, and the development speed in terms of stability has reached a considerable step. By virtue of the advantages of low cost, excellent performance and strong development, the perovskite solar cell raises a new scientific research heat. The perovskite material has unique properties, excellent charge transport capability, high absorption coefficient and the like in the photoelectric field, but still has the problems of environmental pollution, stability and the like when being used as a battery.
The common perovskite solar cell mainly comprises a conductive glass layer, electrodes, an electron transport layer, a hole transport layer and a perovskite layer (light absorption layer). Since perovskites exhibit two different semiconducting properties, their structures also differ, mainly in three types: mesoscopic structure, planar formal structure, and planar trans-structure. The preparation process of the perovskite film mainly comprises a one-step spin coating method, a double-source gas phase evaporation method, a solution-steam method and the like.
The important breakthroughs in the development history of perovskite solar cells are roughly as follows: in 2009, kojima et al, japan successfully prepared the first perovskite solar cell using two organolead halide perovskite nanocrystals, achieving 3.8% efficiency, but with the use of liquid electrolytes, the stability was extremely low; 2012, kim group et al adopted a (CH) 3 NH 3 ）PbI 3 The perovskite nanocrystal is used as a light absorber and the Spiro-OMeTAD is used as a novel solid mesoscopic solar cell of a hole transport layer, so that the efficiency is improved to 9.7%, and the stability problem is primarily improved; since 2013, various preparation methods are continuously discovered, gratzel et al achieve 15% efficiency by adopting a two-step deposition method, snaith et al achieve 15.4% efficiency by co-evaporation, and the like. The breakthrough can be roughly summarized in the improvement of the methods of adding the solid hole transport layer and the TiO2 dense layer and the preparation process, and the university of Australia national university announces in 2017 and 4 months that scientists of the school realize the photoelectric conversion rate of the perovskite solar cell for the first time and exceeds 26 percent. Except thatBesides the improvement of efficiency and stability, experiments of Snaith groups prove that the perovskite material not only can be used as a light absorption layer, but also can be used as an electron transport layer and a hole transport layer, the structure of the battery can be greatly simplified, and the potential of the perovskite is continuously explored.
In order to further realize optimization and performance improvement of perovskite solar energy, the invention carries out more intensive research on the perovskite solar energy, and finds that the grain size, smoothness and device performance among layers can be optimized to different degrees by introducing a monomolecular layer method, wherein good expected effects are obtained between a hole transport layer and a perovskite layer in a trans-perovskite solar cell. According to previous researches, the interface of the nickel oxide layer and the perovskite layer can be effectively optimized through the organic compound with carboxyl and halogen, and the performance is greatly improved. The present invention therefore recognizes that there is also the ability of carboxyl and halogen-like organic compounds to optimize the interface.
Therefore, it can be tried to prepare the organic compound with carboxyl and halogen-like into a monomolecular layer by using a self-assembly spin coating method, so as to obtain a solar cell device with better performance and help to realize further production optimization.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a self-assembled monolayer and a perovskite solar cell and the perovskite solar cell.
In order to solve the above technical problems, the present invention provides a method for preparing a self-assembled monolayer, comprising the steps of:
1) Dissolving carboxylic acid derivative with halogen-like group in organic solvent at 60 o C～70 o C, heating and dissolving to obtain a precursor solution;
2) Spin-coating the precursor solution on a nickel oxide/ITO substrate at room temperature, and then placing the nickel oxide/ITO substrate on a hot table for annealing;
3) After cooling to room temperature, the solution is immediately washed off by spin coating twice with an organic solvent and then annealed once again to obtain a self-assembled monolayer.
Further, in the step 1), the halogen-like group is one or more of a cyano group, an isothiocyanato group; the carboxylic acid derivative is a benzoic acid derivative or a linear acid derivative.
Further, in the step 1), the concentration of the precursor solution is 0.01 mg/ml-2 mg/ml; in step 3), the thickness of the monolayer is 1nm to 20nm.
Further, in the step 2) and the step 3), the annealing temperature is 60 DEG o C～80 o And C, annealing for 5-10 min.
Further, in the step 2) and the step 3), the spin-coating rotating speed is 2000 rpm-6000 rpm, and the spin-coating time is 20 s-60 s; before the spin coating is started, the monomolecular layer solution is attached to the surface of the device, and then the monomolecular layer solution is kept still for 10 to 30 seconds.
The invention also provides a preparation method of the perovskite solar cell, which is characterized by comprising the following steps:
1) Spin-coating a nickel oxide solution on the treated ITO, and annealing to obtain a substrate: nickel oxide/ITO;
2) Dissolving carboxylic acid derivative with halogen-like group in organic solvent at 60 o C～70 o C, heating and dissolving to obtain a precursor solution;
3) Spin-coating the precursor solution on a nickel oxide/ITO substrate at room temperature, and then placing the nickel oxide/ITO substrate on a hot bench for annealing;
4) Cooling to room temperature, immediately spin-coating with an organic solvent twice to remove, and then annealing once again to obtain a self-assembled monolayer;
5) Sequentially spin-coating a perovskite solution and a PCBM solution on the self-assembled monolayer, and annealing at a corresponding temperature; then, the device was transferred to an evaporation station, and BCP and silver electrodes were evaporated in sequence.
The invention also provides a perovskite solar cell which comprises an ITO (indium tin oxide), a hole transport layer, a perovskite layer, an electron transport layer, BCP (barium copper phosphate) and a silver electrode which are sequentially stacked from bottom to top, and is characterized in that a self-assembled monomolecular layer prepared by adopting the method is arranged between the hole transport layer and the perovskite layer.
Further, the hole transport layer is a film layer prepared from a deionized water solution of nickel oxide nanoparticles, and the concentration of the solution is 20mg/ml.
Further, the perovskite layer is a film layer prepared by dissolving lead iodide, lead acetate, methylamine iodide and methylamine bromide in N, N-dimethylformamide according to the following mass ratio of 0.4.
Further, the electron transport layer is a film layer prepared from a solution obtained by dissolving PCBM in chlorobenzene, and the concentration of the solution is 20mg/ml.
The modification principle of the method is as follows: a selected monomolecular layer is dissolved in an organic solvent, a thin film is formed on a nickel oxide layer through high-temperature annealing, the thin film can be washed away through repeated spin coating of an ethanol solvent, the thickness of the thin film can be controlled to be 1-10nm, the interface flatness between nickel oxide and perovskite is effectively improved, the grain size is also influenced to a certain extent, the thin film is smoother and more compact, the nickel oxide layer and a perovskite layer can be matched more, the performance of a solar cell is improved, and particularly the improvement on open-circuit voltage is obvious.
Compared with the prior art, the invention has the following characteristics and effects:
1) Through modification of the monomolecular layer, the nickel oxide and the perovskite layer can be matched more, the interface between the nickel oxide and the perovskite is effectively optimized, the flatness of the perovskite film is improved, and the performance of the device is optimized.
2) The modified material has low price, and the preparation method is simple and stable. The modified material and the preparation method provide new possibility for interface optimization of the perovskite solar cell.
3) Through modification of the monomolecular layer, voltage, efficiency and the like of the device are obviously improved, and the performance of the battery is improved.
Drawings
FIG. 1 is a schematic structural diagram of a perovskite solar cell with monolayer modification;
FIG. 2 is a J-V curve of a cell modified at different concentrations;
FIG. 3 is a scanning electron micrograph of perovskite layers at different concentrations.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The standard part of the perovskite solar cell without modification is prepared by the following steps:
1) The ITO was etched and washed sequentially with a wash solution, deionized water, acetone, ethanol for 20 minutes and treated with uv ozone for 4 minutes. Firstly, nickel oxide nano particles are dissolved into deionized water with the concentration of 20mg/ml, and ultrasonic treatment is carried out for 5 minutes before the use of spin coating.
2) The nickel oxide solution was then spin coated onto the treated ITO at 4000rpm for 30 seconds, then 130 f o Annealing at C for 20 minutes.
3) The device was immediately transferred to a glove box and the perovskite solution was stirred overnight, spin coated onto the nickel oxide layer by rotation at 4000rpm for 30s, and then at 105 o C for 20 minutes.
4) After waiting to cool to room temperature, the PCBM solution was spin-coated onto the perovskite layer at 1250rpm for 30 seconds, then 70 o C for 20 minutes.
5) Then 7nm BCP is evaporated through a vacuum evaporator, and then 100nm silver electrodes are evaporated.
Example 2
Preparing a monomolecular layer modified perovskite solar cell: the preceding steps are the same as steps 1) and 2) of example 1, and the subsequent steps are the same as steps 3) to 5). The difference is that a modification layer is prepared by supplementing a step between the steps 2) and 3), and the specific steps are as follows:
by reacting 4-carboxyl groupsPhenylisothiocyanate was dissolved in ethanol solution to give a 20mg/ml solution, and filtered through a 22um filter. Then diluting to obtain 0.5mg/ml,1mg/ml,2mg/ml monomolecular layer solution, sequentially spin-coating the three concentrations of solution at 2000rpm for 30s, and then 70 rpm o C for 5 minutes. Then after cooling, spin coating twice with ethanol at 2000rpm for 30s, and then 70 deg.C o C for 5 minutes.
The structure of the battery of this embodiment 2 is shown in fig. 1, and the new structure proposed by the present invention mainly introduces a new self-assembled monolayer, so that the interfacial properties of nickel oxide and perovskite are improved. The cell structure of example 1 was the same type of structure that did not contain a monolayer.
The J-V performance curve of the cell tested under AM1.5, 100mW/cm2 standard illumination using the KEITHLEY source table is shown as current density-voltage test, and the test results are shown in FIG. 2, wherein concentration 0 is the result of no modification, concentration 1 is the result of modification of a 0.5mg/ml monolayer solution, and concentration 2 is the J-V curve corresponding to a 1mg/ml monolayer solution.
The perovskite layers with different concentrations are observed through a scanning electron microscope, the obtained result is shown in figure 3, and the flatness and the grain size of the film are improved to a certain extent.
In conclusion, the new self-assembled monolayer introduced by the invention enables the film forming quality of the perovskite on the nickel oxide layer to be better, the flatness of the film to be obviously improved, the open-circuit voltage and the efficiency to be improved to a certain extent, and the device performance of the perovskite solar cell to be improved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a perovskite solar cell is characterized by comprising the following steps:
1) Spin-coating a nickel oxide solution on the treated ITO, and annealing to obtain a substrate: nickel oxide/ITO;
2) Dissolving carboxylic acid derivative with halogen-like group in organic solvent at 60 o C～70 o C, heating and dissolving to obtain a precursor solution;
3) Spin-coating the precursor solution on a nickel oxide/ITO substrate at room temperature, and then placing the nickel oxide/ITO substrate on a hot table for annealing;
4) Cooling to room temperature, immediately spin-coating with an organic solvent twice to remove, and then annealing once again to obtain a self-assembled monolayer;
5) Sequentially spin-coating a perovskite solution and a PCBM solution on the self-assembled monolayer, and annealing at a corresponding temperature; then, the device was transferred to an evaporation station, where BCP and silver electrodes were evaporated in sequence.
2. The method for preparing a perovskite solar cell as claimed in claim 1, wherein in the step 2), the halogen-like group is one or more of a cyano group, a cyano group and an isothiocyanato group; the carboxylic acid derivative is a benzoic acid derivative or a linear acid derivative.
3. The method according to claim 1, wherein in step 2), the concentration of the precursor solution is 0.01mg/ml to 2mg/ml; in the step 4), the thickness of the monolayer is 1nm to 20nm.
4. The method of claim 1, wherein the annealing temperature in step 3) and step 4) is 60 ℃ o C～80 o And C, annealing for 5-10 min.
5. The method for preparing the perovskite solar cell according to claim 1, wherein in the step 3) and the step 4), the spin coating speed is 2000rpm to 6000rpm, and the spin coating time is 20s to 60s; before the spin coating is started, the monomolecular layer solution is attached to the surface of the device, and then the monomolecular layer solution is kept still for 10 to 30 seconds.
6. A perovskite solar cell comprising ITO, a hole transport layer, a perovskite layer, an electron transport layer, BCP, a silver electrode, stacked in sequence from bottom to top, characterized in that a self-assembled monolayer prepared according to any one of claims 1 to 5 is provided between the hole transport layer and the perovskite layer.
7. The perovskite solar cell according to claim 6, wherein the hole transport layer is a film prepared from a deionized water solution of nickel oxide nanoparticles, and the concentration of the solution is 20mg/ml.
8. The perovskite solar cell according to claim 6, wherein the perovskite layer is a film prepared by dissolving lead iodide, lead acetate, methylamine iodide and methylamine bromide in N, N-dimethylformamide in an amount of 0.4.
9. The perovskite solar cell according to claim 6, wherein the electron transport layer is a layer prepared from a solution of PCBM dissolved in chlorobenzene at a concentration of 20mg/ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910466109.7A CN110311042B (en) | 2019-05-31 | 2019-05-31 | Preparation method of self-assembled monolayer and perovskite solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910466109.7A CN110311042B (en) | 2019-05-31 | 2019-05-31 | Preparation method of self-assembled monolayer and perovskite solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110311042A CN110311042A (en) | 2019-10-08 |
| CN110311042B true CN110311042B (en) | 2022-10-14 |
Family
ID=68075766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910466109.7A Active CN110311042B (en) | 2019-05-31 | 2019-05-31 | Preparation method of self-assembled monolayer and perovskite solar cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110311042B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116171053B (en) * | 2023-03-21 | 2023-11-21 | 四川大学 | Full perovskite laminated solar cell and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104465992A (en) * | 2014-11-30 | 2015-03-25 | 浙江大学 | Perovskite planar heterojunction solar battery based on self-assembled monolayer |
| CN106531888A (en) * | 2016-08-04 | 2017-03-22 | 南京工业大学 | Porphyrin derivative for interface modification of hole transport layer/perovskite layer in inverted perovskite solar cell |
| CN109244249A (en) * | 2018-10-15 | 2019-01-18 | 南京邮电大学 | The perovskite solar cell device and preparation method thereof that hole transmission layer is modified |
| CN109244245A (en) * | 2018-09-10 | 2019-01-18 | 武汉大学深圳研究院 | A kind of plane perovskite solar battery and preparation method thereof |
-
2019
- 2019-05-31 CN CN201910466109.7A patent/CN110311042B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104465992A (en) * | 2014-11-30 | 2015-03-25 | 浙江大学 | Perovskite planar heterojunction solar battery based on self-assembled monolayer |
| CN106531888A (en) * | 2016-08-04 | 2017-03-22 | 南京工业大学 | Porphyrin derivative for interface modification of hole transport layer/perovskite layer in inverted perovskite solar cell |
| CN109244245A (en) * | 2018-09-10 | 2019-01-18 | 武汉大学深圳研究院 | A kind of plane perovskite solar battery and preparation method thereof |
| CN109244249A (en) * | 2018-10-15 | 2019-01-18 | 南京邮电大学 | The perovskite solar cell device and preparation method thereof that hole transmission layer is modified |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110311042A (en) | 2019-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Improved interface of ZnO/CH 3 NH 3 PbI 3 by a dynamic spin-coating process for efficient perovskite solar cells | |
| CN105789444B (en) | A kind of perovskite solar cell and preparation method thereof based on vacuum evaporatation | |
| CN109904318B (en) | Perovskite thin film preparation method based on anti-solution bath and solar cell | |
| CN112802965B (en) | Interface modification-based perovskite solar cell preparation method | |
| CN109802041B (en) | Non-fullerene perovskite planar heterojunction solar cell and preparation method thereof | |
| CN106531888A (en) | Porphyrin derivative for interface modification of hole transport layer/perovskite layer in inverted perovskite solar cell | |
| CN111909169A (en) | Hole transport material with benzodithiophene diketone as core, synthesis method and application in perovskite solar cell | |
| Chan et al. | High-performance perovskite solar cells based on low-temperature processed electron extraction layer | |
| CN115332454A (en) | Perovskite solar cell and preparation method thereof | |
| CN112993167B (en) | Application of organic ammonium salt modified metal oxide nanoparticles in positive perovskite solar cell and preparation method of device | |
| CN113416213B (en) | Application of organic phosphonium salt molecule in perovskite solar cell and preparation method of device thereof | |
| CN114784193A (en) | Organic photoelectric device based on metal-induced organic interface layer and preparation method thereof | |
| CN110311042B (en) | Preparation method of self-assembled monolayer and perovskite solar cell | |
| CN109851571B (en) | Conjugated organic small molecule interface modification material, preparation method and organic solar cell formed by conjugated organic small molecule interface modification material | |
| CN114447234B (en) | Organic-inorganic hybrid perovskite surface interface treatment method, material and application | |
| CN113903862B (en) | SnO modified based on phenylboronic acid derivative 2 Perovskite solar cell preparation method | |
| CN116056469A (en) | Perovskite solar cell based on ionic liquid interface modification | |
| CN115347120A (en) | Perovskite quantum dot solar cell and preparation method thereof | |
| CN115275020A (en) | High-efficiency all-polymer organic solar cell structure and preparation method thereof | |
| Manseki et al. | Current Advances in the Preparation of SnO2 Electron Transport Materials for Perovskite Solar Cells | |
| CN114725291B (en) | Preparation method of high-quality stable all-inorganic perovskite solar cell | |
| CN113690373B (en) | Based on HfS 2 Organic solar cell as hole transport layer and method for manufacturing the same | |
| CN220307715U (en) | Perovskite solar cell with double light absorption layer structure | |
| Lal | CH3NH3PbI3: A Potential Candidate for Perovskite Based Solar Cells | |
| CN115377291B (en) | Bottom-up 2D/3D perovskite heterojunction, preparation method thereof and application thereof in perovskite solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |