CN102787445A - Method of preparing porous graphene film by using electrostatic spray process - Google Patents
Method of preparing porous graphene film by using electrostatic spray process Download PDFInfo
- Publication number
- CN102787445A CN102787445A CN2012102480288A CN201210248028A CN102787445A CN 102787445 A CN102787445 A CN 102787445A CN 2012102480288 A CN2012102480288 A CN 2012102480288A CN 201210248028 A CN201210248028 A CN 201210248028A CN 102787445 A CN102787445 A CN 102787445A
- Authority
- CN
- China
- Prior art keywords
- film
- graphene
- dispersion liquid
- preparation
- graphite alkene
- 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.)
- Pending
Links
Images
Abstract
The invention relates to a method of preparing a porous graphene film on the surface of a silicon wafer by using an electrostatic spray process combined with a heat treatment process of a substrate silicon wafer, and belongs to the technical field of solid film preparation processes. The method is characterized in that graphene dispersion liquid is prepared by a liquid phase ultrasound stripping method, and the graphene dispersion liquid is used as spinning liquid to prepare the porous graphene film on the surface of the substrate silicon wafer by the electrostatic spray process and a substrate heating method. The method is simple and convenient and has low requirements on equipment; and the prepared film has a porous structure, good adhesiveness with the substrate silicon wafer and a larger specific surface area, and is expected to be applied to the fields of gas sensitive sensors, lithium batteries, catalysts and the like.
Description
Technical field
The present invention relates to utilize electrostatic spray technology and combine heat treatment method, belong to solid film fabricating technology field at silicon substrate surface preparation porous graphite alkene film.
Background technology
Graphene is a kind of carbonaceous material that has only the individual layer atomic thickness, has the two-dimentional carbon atom crystal of honeycomb; Because it has unique band structure and excellent physical property (electricity, machinery, optics and thermal conductance), caused that people pay close attention to widely.Graphene has potential using value in fields such as field-effect transistor, light emitting diode, sensor, catalysis.The graphene film material has also become the focus that people pay close attention to, and these films have been showed excellent characteristic equally, causes emission characteristics, good photoelectric properties, high electrical conductivity and light transmission or the like such as significant electricity.
At present, people can utilize series of physical and chemical method to prepare graphene film, however wherein most methods all with the Graphene dispersion liquid as raw material.Preparation method commonly used mainly contains following several kinds: spray deposited method, filter deposition method, spin coating method, interface construction from part etc.In addition, the CVD method also is usually used in preparing graphene film, but shortcoming such as there is apparatus expensive in this method, cost of material is higher, process is complicated and productive rate is lower.What the present invention adopted is to utilize electrostatic spray technology to combine the silicon chip heating means to prepare graphene film.Primary Study finds that the graphene film of preparation has loose structure and with silicon substrate good tack arranged by this method, has higher specific surface area, is expected to be applied in fields such as lithium battery, gas sensor, catalysis.
Summary of the invention
It is raw material with graphite powder, 1-Methyl-2-Pyrrolidone that the object of the invention provides a kind of, utilizes electrostatic spray to combine the silicon chip heating process in the method for silicon substrate surface preparation porous graphite alkene film.Its preparation process and step are described below:
A. Graphene dispersion liquid preparation
(1) take by weighing 2.5 g graphite powders (99.85%) and place a 250ml beaker, add 100ml 1-Methyl-2-Pyrrolidone (NMP), preparation graphite-NMP suspension is with subsequent use;
(2) above-mentioned suspension is sealed with the multilayer preservative film, at room temperature amount to 72 h, obtain the Graphene dispersion liquid through the discontinuous sonicated of low power ultrasound washer;
(3) leave standstill through 16 h, with dispersion liquid centrifugal treating 30 min: its rotating speed is 8000 r/min; It is subsequent use in clean vial to draw supernatant liquid;
B. the cleaning of silicon substrate
The silicon chip that (1) will contain surface oxide layer is soaking and washing 30 min in ethyl acetate and acetone respectively;
(2) silicon chip that cleans is carried out ultrasonic cleaning respectively in ethanol, distilled water, utilize the infrared lamp baking again;
C. graphene film preparation
(1) pipettes 10 ml Graphene dispersion liquids in 20 ml syringes, syringe is fixed on the computer micro-injection pump, choose the propelling speed of 0.2 ml/h, at the uniform velocity promote dispersion liquid and arrive spinning-nozzle through the polytetrafluoroethylene (PTFE) tubule;
(2) control heating plate and silicon substrate temperature are 200 ° of C, and regulating high-voltage power voltage is 8.6 kV, spins nozzle spray through electricity; The dried that is sprayed onto about 10 h of liquid film process of silicon chip makes solvent evaporates, can obtain porous graphite alkene film; Through the control electron spray time, can prepare film sample with different-thickness.
Utilize the graphene film of above-mentioned prepared to have following pattern and topological characteristic, and the electromagnetism characteristic:
(1) graphene film is cellular, and Graphene is unordered to be deposited on the silicon chip, and good with the silicon substrate tack.
(2) the Graphene size is between 200 ~ 600 nm, and during through electron spray 70 h, the film average thickness is about 40 μ m.
(3) use comprehensive rerum natura measuring system (the four point probe technique MEASUREMENTS OF THIN magnetic resistance of PPMS-T).Strip shape (10 mm * 5 mm, electrode are Pt silk electrode) graphene film sample, its magnetic resistance are that 80kOe (oersted), temperature are respectively-2.9% and-0.8% when being 6 K and 50 K in magnetic field intensity.
Description of drawings
Fig. 1 main technique flow chart;
Fig. 2 Graphene-NMP dispersion liquid transmission electron microscope (TEM) photo;
Fig. 3 porous graphite alkene film surface SEM (SEM) photo;
Fig. 4 porous graphite alkene thin-membrane section SEM (SEM) photo;
Fig. 5 porous graphite alkene film x-ray photoelectron power spectrum (XPS) figure;
Fig. 6 porous graphite alkene film infrared absorption spectrum;
Fig. 7 porous graphite alkene film and original graphite powder Raman spectrum;
Fig. 8 porous graphite alkene film ultraviolet-visible diffuse reflection spectrum;
Fig. 9 porous graphite alkene thin-film magnetoresistive and temperature, magnetic field intensity graph of a relation.
The specific embodiment
After instantiation of the present invention being specified at present.
Embodiment
The process and the step of preparation porous graphite alkene film are described below:
The silicon chip that will contain surface oxide layer is soaking and washing 30 min in ethyl acetate and acetone respectively, then the silicon chip that cleans are carried out ultrasonic cleaning respectively in ethanol, distilled water, utilize the infrared lamp baking at last.
Take by weighing 2.5 g graphite powders (99.85%) and place a 250ml beaker, add 100ml 1-Methyl-2-Pyrrolidone (NMP), preparation graphite-NMP suspension is with subsequent use.Then above-mentioned suspension is sealed with the multilayer preservative film, at room temperature amount to 72 h, obtain the Graphene dispersion liquid through the discontinuous sonicated of low power ultrasound washer.At last, leave standstill through 16 h, dispersion liquid centrifugal (8000 r/min) is handled 30 min, it is subsequent use in clean vial to draw supernatant liquid.
Pipette 10 ml Graphene dispersion liquids in 20 ml syringes, syringe is fixed on the computer micro-injection pump, choose the propelling speed of 0.2 ml/h, at the uniform velocity promote dispersion liquid and arrive spinning-nozzle through the polytetrafluoroethylene (PTFE) tubule.Control heating plate and silicon substrate temperature are 200 ° of C, and regulating high-voltage power voltage is 8.6 kV, spins nozzle spray through electricity.The dried that is sprayed onto about 10 h of liquid film process of silicon substrate makes solvent evaporates, can obtain porous graphite alkene film.Through the control electron spray time, can prepare film sample with different-thickness.
Technological process of the present invention can be referring to Fig. 1.
The present invention utilizes TEM and SEM that the porous graphite alkene film of examples preparation is carried out microstructure analysis; And further study its structure through XPS, infrared absorption spectroscopy and Raman spectrum and form and change; Then through its optical property of ultraviolet spectra test, use the four point probe technique of comprehensive rerum natura measuring system (PPMS-T) to measure magnetic resistance at last and concern with temperature, magnetic field intensity.
Its test result shows:
Fig. 2 is Graphene-NMP dispersion liquid TEM photo.We can see folding multi-layer graphene sheet among the figure, and a spot of single-layer graphene film is also arranged simultaneously.By observing a spot of single-layer graphene film edge clear among Fig. 2 (b), its microstructure can further be verified by electron diffraction diagram.
Fig. 3 is a porous graphite alkene film surface SEM photo: (multiplication factor is respectively 5.0 k to the field emission scanning electron microscope photo of different resolution; 10.0 k; 20.0 k; 40.0 k), can find out graphene film structure porous, continuous the (a) and (b), and from figure (c), (d), can find out do not have graphite granule in the film of preparation and have only graphene film from figure.
Fig. 4 is a porous graphite alkene thin-membrane section SEM photo: (multiplication factor is respectively 1.0 k to the field emission scanning electron microscope photo of different resolution; 2.0 k; 5.0 k; 30.0 k), can find out the graphene film thickness average out to 40 μ m that prepare the (a) and (b), demonstrate and silicon chip tack preferably from figure.Can see the graphene film structure of porous among figure (c), (d) equally.
Fig. 5 is porous graphite alkene film x X-ray photoelectron spectroscopy X figure (XPS).Can find out from (a) and mainly to contain C, two kinds of elements of O the sample; Also have the peak of Si element to occur; At the oxygen element peak at 532eV place is because our the graphene film part of preparation is oxidized; We can obtain checking from figure (b) for this, and we find to have the existence of C-O and C=O near 286eV, 287eV.We also find to have the existence of C-N in addition, and this is that the illustration among the figure (b) is the molecular structure of NMP because unnecessary NMP is due to residual in the experimentation.
Fig. 6 is a porous graphite alkene film infrared absorption spectrum.Absworption peak is at 3470 cm
-1Be since graphene film surface-the OH vibration due to, absworption peak is at 2920 cm
-1Absworption peak is at 2850 cm corresponding to the antisymmetric stretching vibration of C-H
-1Corresponding to the symmetrical stretching vibration of C-H, it is residual to explain that NMP exists, and this analysis result with XPS is consistent.Absworption peak appears at 1620 cm
-1With 1460 cm
-1C=C vibration corresponding to aromatic rings is stretched and 1270 cm
-1With 987 cm
-1Then corresponding to the vibration of bridging oxygen key in the graphene film.
Fig. 7 is porous graphite alkene film and original graphite powder Raman spectrum.Graphite D peak position is in 1340 cm
-1Place, and 1570 cm
-1The place is the G peak, the symmetry and the degree of order of reflection graphene film material, 2700 cm
-1Near 2D peak then is biphonon resonance raman peak, the degree of piling up of its intensity reflects Graphene.The D peak compares I with the integrated intensity at G peak
D/ I
GCan be used for the detection of the degree of order and the crystallite dimension of material with carbon element crystal structure.I
D/ I
GIntegration ratio increases, and then the defective of sample is many more, and degree of graphitization is low more.Learn the I of original graphite powder through calculating like Fig. 7
D/ I
GBe 0.103, and the I of porous graphite alkene film
D/ I
GBe 0.272, reflect that porous graphite alkene film has the part defective, prepares graphene film (I but compare oxidation-reduction method
D/ I
GBe more than 1) lower defective arranged.2D peak (the 2690cm of porous graphite alkene film
-1) with the 2D peak (2700cm of powdered graphite
-1) compare, shift to low frequency, judge that thus porous graphite alkene film is to be piled up by few layer graphene sheet to form, and is less than about 5 layers greatly.
Fig. 8 is a porous graphite alkene film ultraviolet-visible diffuse reflection spectrum.Porous graphite alkene film is that 375 nm and 635 nm have lower reflection respectively at wavelength, corresponding to it bigger absorption should be arranged.At wavelength is that 375 nm have bigger absorption to be because fragrance is in bad due to a large amount of C=C key and C=O De π – π * transition in the graphene film, and is that 635nm has bigger absorption to be because due to the n – π * transition of the lone electron pair of C=O at wavelength.Simultaneously, the 235-375 nm and in the black light district at visible region 440-635 nm, the absorption of porous graphite alkene film strengthens with the increase of wavelength.
Fig. 9 is porous graphite alkene thin-film magnetoresistive and temperature, magnetic field intensity graph of a relation.Porous graphite alkene film (6K and 50K) at low temperatures presents the phenomenon of negative magnetoresistance, and when 50K, magnetic resistance presents the trend of monotone decreasing with the increase that applies magnetic field; When being 80kOe in magnetic field; Its magnetic resistance is-0.8%, and when 6K, magnetic resistance also presents the trend of successively decreasing with the increase that applies magnetic field; When being 50kOe in magnetic field, its maximum magnetic resistance reaches-2.9%.
Claims (1)
1. method of utilizing electrostatic spray prepared porous graphite alkene film is characterized in that this method has following preparation process and step:
A. Graphene dispersion liquid preparation
(1) take by weighing 2.5 g graphite powders (99.85%) and place a 250ml beaker, add 100ml 1-Methyl-2-Pyrrolidone (NMP), preparation graphite-NMP suspension is with subsequent use;
(2) above-mentioned suspension is sealed with the multilayer preservative film, at room temperature amount to 72 h, obtain the Graphene dispersion liquid through the discontinuous sonicated of low power ultrasound washer;
(3) leave standstill through 16 h, with dispersion liquid centrifugal treating 30 min: its rotating speed is 8000 r/min; It is subsequent use in clean vial to draw supernatant liquid;
B. the cleaning of silicon substrate
The silicon chip that (1) will contain surface oxide layer is soaking and washing 30 min in ethyl acetate and acetone respectively;
(2) silicon chip that cleans is carried out ultrasonic cleaning respectively in ethanol, distilled water, utilize the infrared lamp baking again;
C. graphene film preparation
(1) pipettes 10 ml Graphene dispersion liquids in 20 ml syringes, syringe is fixed on the computer micro-injection pump, choose the propelling speed of 0.2 ml/h, at the uniform velocity promote dispersion liquid and arrive spinning-nozzle through the polytetrafluoroethylene (PTFE) tubule;
(2) control heating plate and silicon substrate temperature are 200 ° of C, and regulating high-voltage power voltage is 8.6 kV, spins nozzle spray through electricity; The dried that is sprayed onto about 10 h of liquid film process of silicon substrate makes solvent evaporates, can obtain porous graphite alkene film; Through the control electron spray time, can prepare film sample with different-thickness.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012102480288A CN102787445A (en) | 2012-07-18 | 2012-07-18 | Method of preparing porous graphene film by using electrostatic spray process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012102480288A CN102787445A (en) | 2012-07-18 | 2012-07-18 | Method of preparing porous graphene film by using electrostatic spray process |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102787445A true CN102787445A (en) | 2012-11-21 |
Family
ID=47153023
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2012102480288A Pending CN102787445A (en) | 2012-07-18 | 2012-07-18 | Method of preparing porous graphene film by using electrostatic spray process |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102787445A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103556240A (en) * | 2013-11-22 | 2014-02-05 | 苏州大学张家港工业技术研究院 | Electrostatic spinning device for preparing nano-porous fibers |
WO2014114081A1 (en) * | 2013-01-24 | 2014-07-31 | 东南大学 | Method for preparing graphene film |
CN103972511A (en) * | 2013-01-24 | 2014-08-06 | 黄炳照 | Surface modified powder |
US9117652B2 (en) | 2013-06-18 | 2015-08-25 | International Business Machines Corporation | Nanoporous structures by reactive ion etching |
CN107117604A (en) * | 2017-06-19 | 2017-09-01 | 成都新柯力化工科技有限公司 | A kind of method that utilization electrostatic accelerating medium stream stripping prepares graphene |
CN107314921A (en) * | 2017-06-12 | 2017-11-03 | 常州第六元素材料科技股份有限公司 | Graphene oxide detection method for making sample, detection method, detection sample preparation device and its operating method |
CN109179385A (en) * | 2018-09-27 | 2019-01-11 | 青岛大学 | A kind of multichannel graphene film and preparation method thereof |
CN110067081A (en) * | 2018-01-24 | 2019-07-30 | 新材料与产业技术北京研究院 | The processing method of static spinning membrane |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7790242B1 (en) * | 2007-10-09 | 2010-09-07 | University Of Louisville Research Foundation, Inc. | Method for electrostatic deposition of graphene on a substrate |
CN102134067A (en) * | 2011-04-18 | 2011-07-27 | 北京大学 | Method for preparing single-layer graphene |
KR20110115539A (en) * | 2010-04-15 | 2011-10-21 | 국립대학법인 울산과학기술대학교 산학협력단 | Preparation method of graphene transparent thin film using layer-by-layer assembly process of reduced graphene oxide |
WO2011139173A1 (en) * | 2010-05-04 | 2011-11-10 | Kogan Andrey Yakovlevich | Electrostatic method for producing graphene from graphite |
JP2012031024A (en) * | 2010-08-02 | 2012-02-16 | Fuji Electric Co Ltd | Method for manufacturing graphene thin film |
CN102398900A (en) * | 2010-09-19 | 2012-04-04 | 东丽纤维研究所(中国)有限公司 | Single-layer graphene capable of dispersing stably and preparation method thereof |
CN102557020A (en) * | 2011-12-31 | 2012-07-11 | 上海大学 | Simple method for preparing high-quality graphene with stable solution |
CN102557728A (en) * | 2012-02-17 | 2012-07-11 | 上海大学 | Method for preparing graphene film and graphene composite carbon film |
-
2012
- 2012-07-18 CN CN2012102480288A patent/CN102787445A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7790242B1 (en) * | 2007-10-09 | 2010-09-07 | University Of Louisville Research Foundation, Inc. | Method for electrostatic deposition of graphene on a substrate |
KR20110115539A (en) * | 2010-04-15 | 2011-10-21 | 국립대학법인 울산과학기술대학교 산학협력단 | Preparation method of graphene transparent thin film using layer-by-layer assembly process of reduced graphene oxide |
WO2011139173A1 (en) * | 2010-05-04 | 2011-11-10 | Kogan Andrey Yakovlevich | Electrostatic method for producing graphene from graphite |
JP2012031024A (en) * | 2010-08-02 | 2012-02-16 | Fuji Electric Co Ltd | Method for manufacturing graphene thin film |
CN102398900A (en) * | 2010-09-19 | 2012-04-04 | 东丽纤维研究所(中国)有限公司 | Single-layer graphene capable of dispersing stably and preparation method thereof |
CN102134067A (en) * | 2011-04-18 | 2011-07-27 | 北京大学 | Method for preparing single-layer graphene |
CN102557020A (en) * | 2011-12-31 | 2012-07-11 | 上海大学 | Simple method for preparing high-quality graphene with stable solution |
CN102557728A (en) * | 2012-02-17 | 2012-07-11 | 上海大学 | Method for preparing graphene film and graphene composite carbon film |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014114081A1 (en) * | 2013-01-24 | 2014-07-31 | 东南大学 | Method for preparing graphene film |
CN103972511A (en) * | 2013-01-24 | 2014-08-06 | 黄炳照 | Surface modified powder |
US9117652B2 (en) | 2013-06-18 | 2015-08-25 | International Business Machines Corporation | Nanoporous structures by reactive ion etching |
US9977002B2 (en) | 2013-06-18 | 2018-05-22 | Globalfoundries Inc. | Nanoporous structures by reactive ion etching |
CN103556240A (en) * | 2013-11-22 | 2014-02-05 | 苏州大学张家港工业技术研究院 | Electrostatic spinning device for preparing nano-porous fibers |
CN103556240B (en) * | 2013-11-22 | 2016-08-17 | 苏州大学张家港工业技术研究院 | For preparing the electrostatic spinning apparatus of nano-porous fiber |
CN107314921A (en) * | 2017-06-12 | 2017-11-03 | 常州第六元素材料科技股份有限公司 | Graphene oxide detection method for making sample, detection method, detection sample preparation device and its operating method |
CN107117604A (en) * | 2017-06-19 | 2017-09-01 | 成都新柯力化工科技有限公司 | A kind of method that utilization electrostatic accelerating medium stream stripping prepares graphene |
CN110067081A (en) * | 2018-01-24 | 2019-07-30 | 新材料与产业技术北京研究院 | The processing method of static spinning membrane |
CN110067081B (en) * | 2018-01-24 | 2021-06-11 | 新材料与产业技术北京研究院 | Method for treating electrostatic spinning membrane |
CN109179385A (en) * | 2018-09-27 | 2019-01-11 | 青岛大学 | A kind of multichannel graphene film and preparation method thereof |
CN109179385B (en) * | 2018-09-27 | 2021-08-31 | 青岛大学 | Multi-channel graphene film and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102787445A (en) | Method of preparing porous graphene film by using electrostatic spray process | |
US20200227631A1 (en) | Multilayer coatings formed on aligned arrays of carbon nanotubes | |
Narimani et al. | Fabrication, modeling and simulation of high sensitivity capacitive humidity sensors based on ZnO nanorods | |
Shan et al. | Excellent toluene sensing properties of SnO2–Fe2O3 interconnected nanotubes | |
Yoon et al. | Design of a highly sensitive and selective C2H5OH sensor using p-type Co3O4 nanofibers | |
Wu et al. | Electrospun ZnO nanowires as gas sensors for ethanol detection | |
Aziz et al. | Core–shell electrospun polycrystalline ZnO nanofibers for ultra-sensitive NO2 gas sensing | |
Han et al. | Sunlight‐Reduced Graphene Oxides as Sensitive Moisture Sensors for Smart Device Design | |
Tang et al. | Conductive polymer nanowire gas sensor fabricated by nanoscale soft lithography | |
Wongchoosuk et al. | Carbon doped tungsten oxide nanorods NO2 sensor prepared by glancing angle RF sputtering | |
Abachi et al. | Highly flexible, conductive and transparent MoO3/Ag/MoO3 multilayer electrode for organic photovoltaic cells | |
Shen | Properties of SnO2 based gas-sensing thin films prepared by ink-jet printing | |
Chen et al. | Gas sensing properties of surface acoustic wave NH3 gas sensor based on Pt doped polypyrrole sensitive film | |
Muhammad et al. | Cadmium selenide quantum dots: Synthesis, characterization and their humidity and temperature sensing properties with poly-(dioctylfluorene) | |
CN103675078B (en) | Preparation method for acetone gas sensor | |
Park et al. | Surface-area-controlled synthesis of porous TiO2 thin films for gas-sensing applications | |
CN103469202A (en) | Method for manufacturing gas-sensitive composite nanometer film | |
Ali et al. | H 2 S gas sensitivity of PAni nano fibers synthesized by hydrothermal method | |
Liu et al. | Micromachined catalytic combustion type gas sensor for hydrogen detection | |
Wang et al. | One‐dimensional electrospun ceramic nanomaterials and their sensing applications | |
Li et al. | Wafer-level patterning of SnO nanosheets for MEMS gas sensors | |
Zhang et al. | Roles of inter-SWCNT junctions in resistive humidity response | |
Mi et al. | Multifunctional devices based on SnO2@ rGO-coated fibers for human motion monitoring, ethanol detection, and photo response | |
Imran et al. | Effect of different electrodes on the transport properties of ZnO nanofibers under humid environment | |
Batool et al. | Comparative analysis of Ti, Ni, and Au electrodes on characteristics of TiO2 nanofibers for humidity sensor application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121121 |