CN105506552B - 一种纳米Sn球的制备方法 - Google Patents
一种纳米Sn球的制备方法 Download PDFInfo
- Publication number
- CN105506552B CN105506552B CN201610028075.XA CN201610028075A CN105506552B CN 105506552 B CN105506552 B CN 105506552B CN 201610028075 A CN201610028075 A CN 201610028075A CN 105506552 B CN105506552 B CN 105506552B
- Authority
- CN
- China
- Prior art keywords
- rosin
- preparation
- balls
- substrate
- spheres
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 32
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 32
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000002096 quantum dot Substances 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C23C14/24—Vacuum evaporation
-
- 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
-
- 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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
-
- 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
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Surface Treatment Of Glass (AREA)
- Luminescent Compositions (AREA)
Abstract
本发明提供一种纳米Sn球的制备方法：1)在基板上涂覆一层松香；2)在涂覆的松香上制备一层Sn膜，得到样片；将样片放置在热处理设备内进行热处理，使Sn膜转变为离散分布在松香上的多个纳米Sn球；3)将热处理后的样片放入无水乙醇中，利用无水乙醇将松香溶化，使纳米Sn球与基板分离；4)经过步骤3)后，用无水乙醇清洗纳米Sn球。本发明制备得到的纳米Sn球发光性能较好，可以作为量子点进行应用；本发明采用固体作为原材料，纳米Sn球的直径大小取决于Sn膜的厚度，且所用试剂廉价、无毒，从而使本发明的制备方法具有操作简单、安全性高的优点。
Description
技术领域
本发明属于显示领域，具体涉及一种量子点用的纳米Sn(锡)球的制备方法。
背景技术
量子点是由有限数目的原子组成，三个维度尺寸均在纳米数量级。量子点一般为球形或类球形，是由半导体材料制成的、稳定直径在2～20nm的纳米粒子。作为一种新颖的半导体纳米材料，量子点具有许多独特的纳米性质。
目前，量子点的制备主要有两种方式：有机相制备和水相制备。有机相制备具有荧光量子产率高、较窄的荧光半峰宽、较好的分散性和稳定性；但存在试剂毒性强、实验成本高、操作安全性低等诸多缺点。水相制备具有试剂无毒、廉价、操作简单等优点，但发光性能较差。
发明内容
本发明的目的在于提供一种纳米Sn球的制备方法。
为达到上述目的，本发明采用了以下技术方案：
1)在基板上涂覆一层松香；
2)在涂覆的松香上制备一层厚度≤10μm的Sn膜，得到样片；将样片放置在热处理设备内进行热处理，使Sn膜转变为离散分布在松香上的多个纳米Sn球；
3)将热处理后的样片放入无水乙醇中，利用无水乙醇将松香溶化，使纳米Sn球与基板分离；
4)经过步骤3)后，用无水乙醇清洗纳米Sn球。
所述基板的材料采用玻璃或塑料。
所述基板在涂覆松香前进行清洗，所述清洗的方法为超声清洗、刷洗或高压水流清洗。
所述松香的涂覆方法为印刷、旋涂或喷墨打印。
所述Sn膜的制备方法采用真空蒸镀或离子溅射。
所述热处理设备采用烘箱或马弗炉。
所述热处理的温度为200～400℃，热处理的时间为1～4h。
所述步骤4)具体包括以下步骤：用无水乙醇对步骤3)分离得到的纳米Sn球反复进行离心清洗，直到去除该纳米Sn球表面的松香。
本发明的有益效果体现在：
本发明所述纳米Sn球的制备方法制备得到的纳米Sn球发光性能较好，可以作为量子点进行应用；本发明采用固体作为原材料，纳米Sn球的直径大小取决于Sn膜的厚度，且所用试剂(如松香、无水乙醇)廉价、无毒，从而使本发明的制备方法具有操作简单、安全性高的优点。
附图说明
图1为本发明所述样片的示意图；
图2为本发明所述样片经过热处理后的示意图；
图中：1为基板，2为松香，3为Sn膜，4为Sn球。
具体实施方式
下面结合附图和实施例对本发明作详细说明。
1)基板清洗：
将1英寸的玻璃基板分别采用刷洗、在无水乙醇中超声清洗10min、用纯水超声清洗10min后，待用。刷洗主要是用来清洗基板表面的微粒，无水乙醇中超声清洗主要是为了清洗基板表面的有机物，纯水中超声清洗是为了清洗基板表面残留的乙醇；清洗有利于松香在玻璃表面的铺展，可以得到均匀平整的膜；
2)松香的涂覆：
将松香加热软化，然后采用印刷法在玻璃基板1表面上涂敷一层松香2，厚度为1μm；
3)Sn膜的制备：
待涂敷的松香2自然冷却至室温后，采用真空蒸镀的方法在松香2上制备一层Sn膜3，真空蒸镀的条件为：真空度为4×10-3Pa，蒸发时电流为100A，蒸发厚度为100nm，最终制备得到的样片结构如图1所示；
4)样片的热处理：
采用马弗炉对样片进行热处理，热处理温度为300℃、时间为2h；样片经热处理，使松香表面的Sn熔化，松香没有太大变化，Sn熔化后，由于与松香不浸润，依靠自身的表面张力形成Sn球4，如图2所示；
5)Sn球分离：
将热处理后的样片放入无水乙醇中(热处理后直接放入或者冷却一段时间后放入都可以)，利用无水乙醇将玻璃基板上的松香溶化，使Sn球与玻璃基板剥离，取出玻璃基板，即得到分散有Sn球的松香无水乙醇溶液；
6)Sn球清洗：
将分散有Sn球的松香无水乙醇溶液进行离心处理，使Sn球在试管底部形成团聚，然后去除上层液体；然后用无水乙醇对Sn球进行10次离心清洗(即用无水乙醇分散，然后离心，弃去上清，反复进行10次)，从而去除Sn球表面的松香(显微镜观察)。
将上述步骤6)得到的Sn球加入无水乙醇中，经超声分散，形成Sn球无水乙醇分散系；然后按以下步骤进行性能检测：
发光性能的检测：采用波长为450nm的蓝光照射本实施例所制备的所有Sn球，可以检测到绿光和红光。
粒径的检测：本实施例制备得到的Sn球的粒径为50～120nm，使用时可以根据需要进行筛选，直径较大的Sn球在450nm蓝光照射下可以得到红光，直接较小的Sn球在450nm蓝光照射下可以得到绿光。
其他实施例表明，增加Sn膜的厚度(例如，1μm左右)，则可以得到粒径更大的Sn球(在450nm蓝光照射下得到相应红光)，减小Sn膜的厚度，则可以得到粒径更小的Sn球(在450nm蓝光照射下可以得到相应绿光甚至蓝光)。
Claims (8)
1.一种Sn球的制备方法，其特征在于：包括以下步骤：
1)在基板上涂覆一层松香；
2)在涂覆的松香上制备一层厚度≤10μm的Sn膜，得到样片；将样片放置在热处理设备内进行热处理，使Sn膜转变为离散分布在松香上的多个Sn球；
3)将热处理后的样片放入无水乙醇中，利用无水乙醇将松香溶化，使Sn球与基板分离；
4)经过步骤3)后，用无水乙醇清洗Sn球。
2.根据权利要求1所述一种纳米Sn球的制备方法，其特征在于：所述基板的材料采用玻璃或塑料。
3.根据权利要求1所述一种Sn球的制备方法，其特征在于：所述基板在涂覆松香前进行清洗，所述清洗的方法为超声清洗、刷洗或高压水流清洗。
4.根据权利要求1所述一种Sn球的制备方法，其特征在于：所述松香的涂覆方法为印刷、旋涂或喷墨打印。
5.根据权利要求1所述一种Sn球的制备方法，其特征在于：所述Sn膜的制备方法采用真空蒸镀或离子溅射。
6.根据权利要求1所述一种Sn球的制备方法，其特征在于：所述热处理设备采用烘箱或马弗炉。
7.根据权利要求1所述一种Sn球的制备方法，其特征在于：所述热处理的温度为300～400℃，热处理的时间为1～4h。
8.根据权利要求1所述一种Sn球的制备方法，其特征在于：所述步骤4)具体包括以下步骤：用无水乙醇对步骤3)分离得到的Sn球反复进行离心清洗，直到去除该Sn球表面的松香。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610028075.XA CN105506552B (zh) | 2016-01-15 | 2016-01-15 | 一种纳米Sn球的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610028075.XA CN105506552B (zh) | 2016-01-15 | 2016-01-15 | 一种纳米Sn球的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105506552A CN105506552A (zh) | 2016-04-20 |
| CN105506552B true CN105506552B (zh) | 2017-12-29 |
Family
ID=55714843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610028075.XA Active CN105506552B (zh) | 2016-01-15 | 2016-01-15 | 一种纳米Sn球的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105506552B (zh) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930001513B1 (ko) * | 1988-01-14 | 1993-03-02 | 니혼 일렉트로 플레이팅 엔지니어스 가부시끼 가이샤 | 금속파우더 및 그 페이스트와, 금속파우더의 제조장치 |
| CN100537082C (zh) * | 2005-10-26 | 2009-09-09 | 财团法人工业技术研究院 | 纳米金属球的制造装置及方法与纳米金属粉末 |
| CN104607648B (zh) * | 2015-01-15 | 2017-03-01 | 太原理工大学 | 一种制备纳米或亚微米级锡或锡合金微球的方法 |
-
2016
- 2016-01-15 CN CN201610028075.XA patent/CN105506552B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105506552A (zh) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103499847B (zh) | 一种具有光学增透功能的中空纳米锥阵列膜的制备方法 | |
| CN105542641B (zh) | 一种强附着力、高透光度、低面电阻的碳纳米管抗静电薄膜及其制备工艺 | |
| CN101519278A (zh) | 一种制备透明超疏水自清洁涂层的方法 | |
| CN107121714B (zh) | 一种呈色具有低角度依赖性的无裂缝光子晶体及其制备方法 | |
| CN106752462A (zh) | 一种超疏水材料及其制备方法 | |
| CN104112544A (zh) | 一种防硫化氢气体腐蚀的银纳米线透明导电薄膜的制备方法 | |
| CN104528709A (zh) | 一种强拉曼散射强度的石墨烯的制备方法 | |
| CN102974839B (zh) | 化学沉积法制备纳米厚度片状银粉的方法 | |
| CN103710685B (zh) | 一种直接在柔性基底上制备石墨烯透明导电薄膜的喷涂方法 | |
| CN110093141A (zh) | 用于柔性基板剥离的组合材料及其制备方法、柔性面板的制作方法 | |
| CN103484821A (zh) | 一种具有响应性纯色显示功能的纳米火山型阵列薄膜的制备方法 | |
| CN104226977B (zh) | 金属纳米线的定向有序排列的方法 | |
| CN105506552B (zh) | 一种纳米Sn球的制备方法 | |
| CN104353507B (zh) | 一种基于纳米半锥壳阵列实时控制水流方向的方法 | |
| CN102653862A (zh) | 一种氧化铟锡纳米涂层的制备方法 | |
| CN106329306A (zh) | 一种基于纳米孔隙结构的无序增益介质的制备方法 | |
| CN103130527B (zh) | 一种超疏水硫化锑涂层的制备方法 | |
| CN105061798A (zh) | 超疏水线性低密度聚乙烯薄膜及其制备方法 | |
| CN106746725B (zh) | 一种新型ZnO纳米片状结构涂层的制备方法 | |
| Rentería-Tapia et al. | Silver nanoparticles dispersed on silica glass for applications as photothermal selective material | |
| CN108610730A (zh) | 银修饰的氧化锌纳米棒阵列及制备的树脂复合涂层和应用 | |
| CN105425266A (zh) | 一种光子晶体塑料闪烁体的制备方法 | |
| CN112028011A (zh) | 一种手性纳米火山阵列薄膜和手性中空纳米球壳结构及其平行制备方法 | |
| CN104299721B (zh) | 一种通过清洗处理提高金属纳米线透明导电薄膜光学性质的方法 | |
| CN102515558B (zh) | 一种以组合法制备透明导电碳纳米管薄膜的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |