CN104445143A - Method for preparing monomolecular film by assembling graphene on amphiphilic ruthenium complex by using spin-coating process - Google Patents
Method for preparing monomolecular film by assembling graphene on amphiphilic ruthenium complex by using spin-coating process Download PDFInfo
- Publication number
- CN104445143A CN104445143A CN201410636632.7A CN201410636632A CN104445143A CN 104445143 A CN104445143 A CN 104445143A CN 201410636632 A CN201410636632 A CN 201410636632A CN 104445143 A CN104445143 A CN 104445143A
- Authority
- CN
- China
- Prior art keywords
- graphene
- ruthenium complexe
- solution
- assembled
- spin
- 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
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 197
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 238000000034 method Methods 0.000 title claims abstract description 71
- 238000004528 spin coating Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title abstract description 13
- 239000012327 Ruthenium complex Substances 0.000 title abstract 7
- 239000000758 substrate Substances 0.000 claims abstract description 112
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 119
- 229910052707 ruthenium Inorganic materials 0.000 claims description 119
- 239000000243 solution Substances 0.000 claims description 73
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 33
- 239000012498 ultrapure water Substances 0.000 claims description 33
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 24
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 24
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 230000009514 concussion Effects 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000001338 self-assembly Methods 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 235000011194 food seasoning agent Nutrition 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- 238000003892 spreading Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 238000000861 blow drying Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000010355 oscillation Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 95
- 239000010410 layer Substances 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000002094 self assembled monolayer Substances 0.000 description 13
- 239000013545 self-assembled monolayer Substances 0.000 description 13
- 125000001165 hydrophobic group Chemical group 0.000 description 10
- 238000010587 phase diagram Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 230000002269 spontaneous effect Effects 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 241000252506 Characiformes Species 0.000 description 1
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing a monomolecular film by assembling graphene on an amphiphilic ruthenium complex by using a spin-coating process, belonging to the technical field of molecular self-assembling chemicals. The method comprises the steps of firstly, self-assembling the amphiphilic ruthenium complex on an ITO substrate, namely preparing an amphiphilic ruthenium complex solution, then, immersing ITO conducting glass into an RCA solution, removing air bubbles by slight oscillation, then transferring the ITO conducting glass into a water bath kettle, washing, blow-drying, then, immersing the ITO conducting glass into the amphiphilic ruthenium complex solution, and taking out after dipping at room temperature for 3-6 hours; preparing a graphene dispersion solution; and fixing the prepared ITO substrate of the amphiphilic ruthenium complex on a spin coater, dropwise adding the graphene dispersion solution on the surface of the substrate, and starting the spin coater, namely assembling graphene on the amphiphilic ruthenium complex to obtain the monomolecular film. The method disclosed by the invention is simple in operation; graphene is uniformly and sufficiently modified on the substrate; and the operation can be carried out at room temperature by using a simple vessel, and no special conditions and equipment are needed.
Description
Technical field
The present invention relates to a kind of spin-coating method that utilizes and Graphene is assembled into method unimolecular film preparing by amphipathic ruthenium complexe, belong to molecular self-assembling technical field of chemistry.
Background technology
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Graphene can be envisioned as the atom grid formed by carbon atom and its covalent linkage, is considered to plane polynuclear aromatics atomic crystal.The structure of Graphene is highly stable, and this stable crystalline network makes Graphene have outstanding thermal conductivity.Graphene is the thinnest in the world is at present the hardest nano material also, and it is almost completely transparent, and only absorb the light of 2.3%, thermal conductivity is up to 5300W/mK, and higher than carbon nanotube and diamond, under normal temperature, its electronic mobility is more than 15000cm
2/ Vs, and resistivity only about 10-6 Ω cm are the material that resistivity is minimum in the world at present.Because its resistivity is extremely low, the speed that electronics runs is exceedingly fast, and is therefore expected to can be used to develop thinner, conduction speed electronic component of new generation or transistor faster.Because Graphene is in fact a kind of transparent, good conductor, be also applicable to for manufacturing transparent touch screen, tabula rasa or even solar cell.
Self-assembling technique refers to the spontaneous a kind of skill being formed with sequence structure of basic structural unit, and this basic structural unit can be molecule, also can be nano material, or the material of more big scale.In the process of self-assembly, basic structural unit spontaneous tissue or gathering under based on the interaction of non covalent bond are a structure stablizing, have certain regular geometric outward appearance.Self assembling process is not the simple superposition of weak force between a large amount of atom, ion, molecule, but between several body, simultaneously spontaneous generation associates and the tight and orderly entirety of the formation one that gathers together, and is a kind of synergy of complexity of entirety.
Spin-coating method (spin-coating) refers to that the substrate surface polymers soln configured being added drop-wise to high speed rotating forms film.Spin-coating method has some superiority in the accurate control etc. of film planeness, compactness extent, firmness that film is connected with substrate and film thickness.The relative permittivity of the film utilizing spin-coating method to prepare is very low (<215), can use in the microelectronic device of super large-scale integration as interlayer ionogen.
The Ordered Film of the molecular self-assembling film Thermodynamically stable that to be molecule formed at solid-liquid or gas/solid interface by chemical bond interaction Spontaneous adsorption and minimum energy.When binding molecule is deposited in case, the established disordered monolayer in local can become more perfect, orderly self-assembled film by self-regeneration.Self-assembled monolayer is the Organized Molecular Films formed in solid surface absorption by organic molecule, it suitable substrate is immersed in after in the solution of molecule to be assembled or atmosphere, molecule is spontaneously adsorbed on solid surface securely by chemical bond and forms a kind of ordered molecular assembly, molecular arrangement is wherein orderly, and defect is few.
The research of the domestic method to utilizing spin-coating method to be assembled in unimolecular film by Graphene at present have not been reported.The self-assembling method of disclosed Graphene mainly contains:
Publication number is the Chinese patent disclosed " self-assembly preparation method thereof of noble metal-graphene two-layer compound conducting film " of CN102021573A, with precious metal ion or coordination ion, graphene oxide for raw material, the noble metal-graphene two-layer compound conducting film obtained by solvent-induced self-assembling method.The thickness of the layer of precious metal of two-layer compound conducting film, graphene layer and integral membrane can be regulated and controled by the concentration of precious metal ion solution, graphene oxide solution and volume, and in two-layer compound conducting film, the electroconductibility of silver layer and graphene layer can regulate and control.
Publication number is in the Chinese patent of CN102530929A disclosed " forming the method for graphene oxide patterns and graphene pattern ", hydrophobic self-assembled monolayer is prepared on the surface at least one of substrate, UV-lamp is adopted to expose after covering described hydrophobic self-assembled monolayer with mask, and remove mask after exposure, obtain the substrate of this at least one the self-assembled monolayer template of surface containing patterning, the self-assembled monolayer template of described patterning is covered with the aqueous solution of graphene oxide quantum dot, dry, thus substrate this at least one form graphene oxide patterns on the surface.The method need be carried out in confined conditions, and UV-lamp exposure after needing mask to cover.
Publication number is in the Chinese patent disclosed " a kind of preparation method of titanium alloy surface graphene film " of CN104018145A, medical titanium alloy is carried out put into piranha solution and carry out hydroxylation process, then aminosilane solution self-assembly Silan-based Thin Films is put into, silane-graphene oxide film is prepared with in the titanium alloy immersion graphene oxide colloid of Silan-based Thin Films in surface, finally utilize haloid acid oxidation graphene film, after drying, obtain redox graphene laminated film.The method need be carried out under vacuum seal environment, and need use the dangerous solvents such as the vitriol oil.
At present, unimolecular film self-assembly method is a kind of effective ways being conducive to control group assembling structure and form, can pass through covalent linkage or non covalent bond and the orderly unimolecular layer of spontaneous height of formation on the surface of electrode.Self-assembled film molecular arrangement is tight in order, but assembling process is complicated, and built-up time is long, high to equipment requirements, need carry out at clean, stopping property in good laboratory.And for making reactant and substrate active part react quickly and efficiently, title complex need have good solubleness in a solvent.In addition, the ordinary method of assembling Graphene is generally be scattered in water by Graphene and title complex, long-time ultrasonic mixing, but in this method, Graphene is easily reunited, and the adhesion amount of complex molecule is few.Thus design invention a kind of orientable, self assembling process is simple, stability is high and the method be assembled into by Graphene in unimolecular film of favorable repeatability is very necessary.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of spin-coating method that utilizes and Graphene is assembled into method unimolecular film preparing by amphipathic ruthenium complexe.Hydroxyl in the present invention in amphipathic ruthenium complexe molecule and the surperficial effect by covalent linkage of ITO, ruthenium complexe molecule is fixed on ITO surface, pyrenyl is interacted by π-π with the Graphene with cancellated π-electronic environment, Graphene is fixed in ruthenium complexe unimolecular film, thus realize fixing Graphene on self-assembled monolayer, method of the present invention is simple to operate, Graphene is modified evenly fully in substrate, at room temperature use simple receptacle can operate, without the need to special conditions and equipment.The plurality of advantages such as in invention, specific surface area is large, electroconductibility is high, and the stable Graphene of thermochemical property is assembled in unimolecular film, effectively can improve the electrochemical activity of substrate, and the film of preparation has good machinery and chemical stability, and the thickness of film is controlled.The present invention is achieved through the following technical solutions.
This amphipathic ruthenium complexe [Ru (Py
2g
1meBip) (XPOH)] (PF
6)
2chemical general formula as follows:
。
Utilize spin-coating method Graphene to be assembled into method unimolecular film preparing by amphipathic ruthenium complexe, its concrete steps are as follows:
(1) the amphipathic ruthenium complexe of self-assembly on ITO substrate: add ultrapure water in clean container, with ammoniacal liquor modulation PH to 10, takes amphipathic ruthenium complexe [Ru (Py
2g
1meBip) (XPOH)] (PF
6)
2be dissolved in solution, after regulating PH to 5 with HCl, obtained amphipathic ruthenium complexe solution; ITO conductive glass is immersed in RCA solution, move in water-bath after slight concussion removing bubble, take out ITO conductive glass substrate ultrapure water after heating in water bath to clean, be immersed in amphipathic ruthenium complexe solution after drying up with rare gas element, slight concussion removing bubble, takes out ITO substrate ultrapure water and cleans up rear rare gas element and dry up after at room temperature flooding 3 ~ 6h;
(2) preparation of graphene dispersing solution: sodium lauryl sulphate is dissolved in the water and obtains lauryl sodium sulfate aqueous solution, be that 2 ~ 4:10mg/ml is dispersed in lauryl sodium sulfate aqueous solution by Graphene according to the quality of Graphene and the volume ratio of lauryl sodium sulfate aqueous solution, after ultrasonic wave dispersion treatment, centrifugation removing bottom residues, obtains the graphene dispersing solution that concentration is 0.1 ~ 0.3mg/ml;
(3) Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film: what step (1) prepared has the ITO substrate of amphipathic ruthenium complexe to be fixed on to revolve on Tu instrument, graphene dispersing solution is dripped at substrate surface, start spin coating instrument, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, dry up with rare gas element with after washed with methanol substrate surface removing tensio-active agent, namely Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film.
Amphipathic ruthenium complexe [Ru (Py in described step (1)
2g
1meBip) (XPOH)] (PF
6)
2strength of solution is 50 μMs.μM representative μm ol/L.
RCA solution in described step (1) is NH
3, H
2o
2with the solution of the ultrapure water mixing of 1:1:5 in mass ratio.
Water bath heating temperature in described step (1) is 90 DEG C, and heat-up time is 0.5 ~ 2h.
In described step (2) lauryl sodium sulfate aqueous solution, the quality of sodium lauryl sulphate and the volume ratio of water are 2:100g/ml.
In described step (2), ultrasonic dispersing time is 0.5 ~ 1.5h, and the centrifugation time is 1 ~ 3h, and rotating speed is 15krpm.
Described step (3) is revolved Tu instrument and is first opened low speed, and low rate start stage speed of rotation is 200rpm, and the time is 3s, and then open at a high speed, high speed rotation rate is 700 ~ 1000rpm, and the time is 70 ~ 120s.
The invention has the beneficial effects as follows:
1, the hydroxyl in this amphipathic ruthenium complexe molecule and the surperficial effect by covalent linkage of ITO, the hydrophilic group of ruthenium complexe molecule is fixed on ITO surface, pyrenyl is interacted by π-π with the Graphene with cancellated π-electronic environment, Graphene is fixed in ruthenium complexe unimolecular film, thus realize fixing Graphene on self-assembled monolayer, and can prevent Graphene self from reuniting, make ruthenium complexe molecule can be attached to graphenic surface uniformly, increase the ruthenium complexe molecule attached amount of graphenic surface.
2, the amphipathic ruthenium complexe [Ru (Py used in the present invention
2g
1meBip) (XPOH)] (PF
6)
2in multi-solvents, there is good solubleness, be conducive to title complex and substrate active part reacts quickly and efficiently, thus improve the efficiency of self-assembly and the quality of self-assembled film.
3, the present invention adopts spin-coating method to be assembled in unimolecular film by Graphene, only needs 70 ~ 120s, greatly shortens built-up time, improve packaging efficiency, and the film of preparation has characteristic optical character.
4, preparation method of the present invention obtains Graphene assembled layers firm in unimolecular film, to the Graphene with optical, electrical character be assembled in ruthenium complexe unimolecular film, form the self assembly molecule film with optical, electrical function, Iy self-assembled layer is evenly distributed in substrate, and has good electrochemical activity and photophysical property.Electrode after modified is anode, has excellent optical, electrical chemical property, can be used for the fields such as dye sensitization solar battery.
5, the present invention at room temperature uses simple receptacle to operate, without the need to plant and instrument and the special conditions of complexity, the whole membrane process technique that is self-assembled into is easy to control, simple to operate, preparation cost is low, and raw material is easy to get, film forming matter is not subject to the restriction of substrate sizes and shape, the film of preparation has good machinery and chemical stability, the thickness of film and structure-controllable, and film forming is reproducible.
Accompanying drawing explanation
Fig. 1 is the AFM height map fix Graphene in the embodiment of the present invention 1 on self-assembled monolayer after;
Fig. 2 is the AFM phase diagram fix Graphene in the embodiment of the present invention 1 on self-assembled monolayer after;
Fig. 3 is the AFM height map fix Graphene in the embodiment of the present invention 2 on self-assembled monolayer after;
Fig. 4 is the AFM phase diagram fix Graphene in the embodiment of the present invention 2 on self-assembled monolayer after;
Fig. 5 is the AFM height map fix Graphene in the embodiment of the present invention 3 on self-assembled monolayer after;
Fig. 6 is the AFM phase diagram fix Graphene in the embodiment of the present invention 3 on self-assembled monolayer after.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
This utilizes spin-coating method Graphene to be assembled into method unimolecular film preparing by amphipathic ruthenium complexe, and its concrete steps are as follows:
(1) the amphipathic ruthenium complexe of self-assembly on ITO substrate: add 20ml ultrapure water in clean beaker, with ammoniacal liquor modulation PH to 10, takes the amphipathic ruthenium complexe of 5.18g [Ru (Py
2g
1meBip) (XPOH)] (PF
6)
2be dissolved in solution, after regulating PH to 5 with HCl, add ultrapure water to 40ml, obtain the ruthenium complexe solution of 50uM; By NH
3, H
2o
2with the ratio mixed preparing RCA solution of ultrapure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, after 90 DEG C of heating 0.5h, take out ITO substrate ultrapure water clean, front is immersed in amphipathic ruthenium complexe solution outwardly after drying up with nitrogen, slight concussion removing bubble, takes out ITO substrate ultrapure water and cleans up rear nitrogen and dry up after at room temperature flooding 3h.
(2) preparation of graphene dispersing solution: the sodium lauryl sulphate (SDS) of 0.2g is dissolved in 10ml water and obtains 2%(w/c) the SDS aqueous solution, by 4mg Graphene (Graphene,-325mesh) be dispersed in the SDS aqueous solution of 10ml, move to after ultrasonic wave dispersion treatment 0.5h in whizzer, centrifugation 1h under 15krpm rotating speed, removing bottom residues, obtains the graphene dispersing solution that concentration is 0.3mg/ml.
(3) Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film: be fixed on there being the ITO substrate of amphipathic ruthenium complexe in step (1) and revolve on Tu instrument, graphene dispersing solution is dripped at substrate surface, start spin coating instrument, low rate start stage speed of rotation is 200r/min, time is 3s, high speed rotation rate is 700r/min, time is 120s, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, dry up with nitrogen with after the promoting agent of washed with methanol ITO surface removing substrate surface, namely Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film.
The surface contact angle test of the substrate after what the present embodiment prepared fix Graphene in ruthenium complexe unimolecular film: the contact angle of the ITO substrate surface after cleaning is 87.2 °, illustrates that clean ITO surface is hydrophobicity; The contact angle of the ITO substrate surface after the process of RCA surface hydrophilic is 64.7 °, demonstrates the wetting ability that RCA hydrophilic treatment method of the present invention improves ITO surface; The surface contact angle of the ITO substrate after assembling ruthenium complexe unimolecular film is 81.3 °, surface hydrophilicity reduces, this is because the hydrophilic group in ruthenium complexe molecule is fixed to ITO interface, hydrophobic group is exposed to surface, makes the ITO substrate surface after assembling ruthenium complexe unimolecular film present hydrophobicity; After ruthenium complexe unimolecular film fixes Graphene, the contact angle of substrate surface is 61.3 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complexe, substrate surface is Graphene, reduces the hydrophobicity of substrate surface; Meanwhile, the change of contact angle to also demonstrate on ITO assembling ruthenium complexe unimolecular film on successfully assembling gone up Graphene.
The AFM test of the substrate after what the present embodiment prepared fix Graphene in ruthenium complexe unimolecular film: because single-layer graphene is difficult to be observed under scanning electronic microscope (SEM), only could observe clearly under atomic force microscope (AFM).Atomic force microscope characterizes Graphene the most direct means.In order to can the surface topography size of clearer research Graphene and height, by atomic force microscope, further research have been carried out to it, Fig. 1 be obtaining of preparing of the implementation case in ruthenium complexe unimolecular film, fix Graphene after the AFM figure of substrate.Clearly can see the laminated structure of graphene layer from afm image, can see that Graphene thickness is 1-11nm from data plot, the Graphene number of plies of that is assembling is 1-11 layer.
For determining the assembling area of graphene layer, still characterize graphene layer prepared by two schemes by atomic force microscope, setting scan size is 10 μm × 10 μm, obtains the AFM phase diagram of graphene layer, as shown in Figure 2.Can find out roughly from Fig. 2 that graphene layer is evenly distributed in substrate, fully, for clearly concrete Graphene area coverage, the area of application area software for calculation to the graphene layer in AFM phase diagram in Fig. 2 calculates, the fraction of coverage obtaining graphene layer is 97.11%, illustrate that graphene layer is comparatively large at suprabasil assembling area, assemble more abundant.
Embodiment 2
This utilizes spin-coating method Graphene to be assembled into method unimolecular film preparing by amphipathic ruthenium complexe, and its concrete steps are as follows:
(1) the amphipathic ruthenium complexe of self-assembly on ITO substrate: add 20ml ultrapure water in clean beaker, with ammoniacal liquor modulation PH to 10, takes the amphipathic ruthenium complexe of 5.18g [Ru (Py
2g
1meBip) (XPOH)] (PF
6)
2be dissolved in solution, after regulating PH to 5 with HCl, add ultrapure water to 40ml, obtain the amphipathic ruthenium complexe solution of 50uM; By NH
3, H
2o
2with the ratio mixed preparing RCA solution of ultrapure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, after 90 DEG C of heating 1h, take out ITO substrate ultrapure water clean, front is immersed in amphipathic ruthenium complexe solution outwardly after drying up with nitrogen, slight concussion removing bubble, takes out ITO substrate ultrapure water and cleans up rear nitrogen and dry up after at room temperature flooding 4h.
(2) preparation of graphene dispersing solution: the sodium lauryl sulphate (SDS) of 0.2g is dissolved in 10ml water and obtains 2%(w/c) the SDS aqueous solution, by 3.5mg Graphene (Graphene,-325mesh) be dispersed in the SDS aqueous solution of 10ml, move to after ultrasonic wave dispersion treatment 1h in whizzer, centrifugation 2h under 15krpm rotating speed, removing bottom residues, obtains the graphene dispersing solution that concentration is 0.26mg/ml.
(3) Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film: be fixed on there being the ITO substrate of amphipathic ruthenium complexe in step (1) and revolve on Tu instrument, graphene dispersing solution is dripped at substrate surface, start spin coating instrument, low rate start stage speed of rotation is 200r/min, time is 3s, high speed rotation rate is 800r/min, time is 100s, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, dry up with nitrogen with after the promoting agent of washed with methanol ITO surface removing substrate surface, namely Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film.
The surface contact angle test of the substrate after what the present embodiment prepared fix Graphene in ruthenium complexe unimolecular film: the contact angle of the ITO substrate surface after cleaning is 86.1 °, illustrates that clean ITO surface is hydrophobicity; The contact angle of the ITO substrate surface after the process of RCA surface hydrophilic is 66.6 °, demonstrates the wetting ability that RCA hydrophilic treatment method of the present invention improves ITO surface; The surface contact angle of the ITO substrate after assembling ruthenium complexe unimolecular film is 81.9 °, surface hydrophilicity reduces, this is because the hydrophilic group in ruthenium complexe molecule is fixed to ITO interface, hydrophobic group is exposed to surface, makes the ITO substrate surface after assembling ruthenium complexe unimolecular film present hydrophobicity; After ruthenium complexe unimolecular film fixes Graphene, the contact angle of substrate surface is 60.5 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complexe, substrate surface is Graphene, reduces the hydrophobicity of substrate surface; Meanwhile, the change of contact angle to also demonstrate on ITO assembling ruthenium complexe unimolecular film on successfully assembling gone up Graphene.
The AFM test of the substrate after what the present embodiment prepared fix Graphene in ruthenium complexe unimolecular film: because single-layer graphene is difficult to be observed under scanning electronic microscope (SEM), only could observe clearly under atomic force microscope (AFM).Atomic force microscope characterizes Graphene the most direct means.In order to can the surface topography size of clearer research Graphene and height, by atomic force microscope, further research have been carried out to it, Fig. 3 be obtaining of preparing of the implementation case in ruthenium complexe unimolecular film, fix Graphene after the AFM figure of substrate.Clearly can see the laminated structure of graphene layer from afm image, can see that Graphene thickness is 1-10nm from data plot, the Graphene number of plies of that is assembling is 1-10 layer.
For determining the assembling area of graphene layer, still characterize graphene layer prepared by two schemes by atomic force microscope, setting scan size is 10 μm × 10 μm, obtains the AFM phase diagram of graphene layer, as shown in Figure 4.Can find out roughly from Fig. 4 that graphene layer is evenly distributed in substrate, fully, for clearly concrete Graphene area coverage, the area of application area software for calculation to the graphene layer in AFM phase diagram in Fig. 4 calculates, the fraction of coverage obtaining graphene layer is 95.68%, illustrate that graphene layer is comparatively large at suprabasil assembling area, assemble more abundant.
Embodiment 3
This utilizes spin-coating method Graphene to be assembled into method unimolecular film preparing by amphipathic ruthenium complexe, and its concrete steps are as follows:
(1) the amphipathic ruthenium complexe of self-assembly on ITO substrate: add 20ml ultrapure water in clean beaker, with ammoniacal liquor modulation PH to 10, takes the amphipathic ruthenium complexe of 5.18g [Ru (Py
2g
1meBip) (XPOH)] (PF
6)
2be dissolved in solution, after regulating PH to 5 with HCl, add ultrapure water to 40ml, obtain the amphipathic ruthenium complexe solution of 50uM; By NH
3, H
2o
2with the ratio mixed preparing RCA solution of ultrapure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, after 90 DEG C of heating 2h, take out ITO substrate ultrapure water clean, front is immersed in amphipathic ruthenium complexe solution outwardly after nitrogen dries up, slight concussion removing bubble, takes out ITO substrate ultrapure water and cleans up rear nitrogen and dry up after at room temperature flooding 6h.
(2) preparation of graphene dispersing solution: the sodium lauryl sulphate (SDS) of 0.2g is dissolved in 10ml water and obtains 2%(w/c) the SDS aqueous solution, by 3mg Graphene (Graphene,-325mesh) be dispersed in the SDS aqueous solution of 10ml, move to after ultrasonic wave dispersion treatment 1.5h in whizzer, centrifugation 3h under 15krpm rotating speed, removing bottom residues, obtains the graphene dispersing solution that concentration is 0.19mg/ml.
(3) Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film: be fixed on there being the ITO substrate of amphipathic ruthenium complexe in step (1) and revolve on Tu instrument, graphene dispersing solution is dripped at substrate surface, start spin coating instrument, low rate start stage speed of rotation is 200r/min, time is 3s, high speed rotation rate is 1000r/min, time is 70s, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, dry up with nitrogen with after the promoting agent of washed with methanol ITO surface removing substrate surface, namely Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film.
The surface contact angle test of the substrate after what the present embodiment prepared fix Graphene in ruthenium complexe unimolecular film: the contact angle of the ITO substrate surface after cleaning is 87.1 °, illustrates that clean ITO surface is hydrophobicity; The contact angle of the ITO substrate surface after the process of RCA surface hydrophilic is 65.9 °, demonstrates the wetting ability that RCA hydrophilic treatment method of the present invention improves ITO surface; The surface contact angle of the ITO substrate after assembling ruthenium complexe unimolecular film is 82.5 °, surface hydrophilicity reduces, this is because the hydrophilic group in ruthenium complexe molecule is fixed to ITO interface, hydrophobic group is exposed to surface, makes the ITO substrate surface after assembling ruthenium complexe unimolecular film present hydrophobicity; After ruthenium complexe unimolecular film fixes Graphene, the contact angle of substrate surface is 61.9 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complexe, substrate surface is Graphene, reduces the hydrophobicity of substrate surface; Meanwhile, the change of contact angle to also demonstrate on ITO assembling ruthenium complexe unimolecular film on successfully assembling gone up Graphene.
The AFM test of the substrate after what the present embodiment prepared fix Graphene in ruthenium complexe unimolecular film: because single-layer graphene is difficult to be observed under scanning electronic microscope (SEM), only could observe clearly under atomic force microscope (AFM).Atomic force microscope characterizes Graphene the most direct means.In order to can the surface topography size of clearer research Graphene and height, by atomic force microscope, further research have been carried out to it, Fig. 5 be obtaining of preparing of the implementation case in ruthenium complexe unimolecular film, fix Graphene after the AFM figure of substrate.Clearly can see the laminated structure of graphene layer from afm image, can see that Graphene thickness is 1-10nm from data plot, the Graphene number of plies of that is assembling is 1-10 layer.
For determining the assembling area of graphene layer, still characterize graphene layer prepared by two schemes by atomic force microscope, setting scan size is 10 μm × 10 μm, obtains the AFM phase diagram of graphene layer, as shown in Figure 6.Can find out roughly from Fig. 6 that graphene layer is evenly distributed in substrate, fully, for clearly concrete Graphene area coverage, the area of application area software for calculation to the graphene layer in AFM phase diagram in Fig. 6 calculates, the fraction of coverage obtaining graphene layer is 94.17%, illustrate that graphene layer is comparatively large at suprabasil assembling area, assemble more abundant.
Embodiment 4
This utilizes spin-coating method Graphene to be assembled into method unimolecular film preparing by amphipathic ruthenium complexe, and its concrete steps are as follows:
(1) the amphipathic ruthenium complexe of self-assembly on ITO substrate: add 20ml ultrapure water in clean beaker, with ammoniacal liquor modulation PH to 10, takes the amphipathic ruthenium complexe of 5.18g [Ru (Py
2g
1meBip) (XPOH)] (PF
6)
2be dissolved in solution, after regulating PH to 5 with HCl, add ultrapure water to 40ml, obtain the amphipathic ruthenium complexe solution of 50uM; By NH
3, H
2o
2with the ratio mixed preparing RCA solution of ultrapure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, after 90 DEG C of heating 1.5h, take out ITO substrate ultrapure water clean, front is immersed in amphipathic ruthenium complexe solution outwardly after nitrogen dries up, slight concussion removing bubble, takes out ITO substrate ultrapure water and cleans up rear nitrogen and dry up after at room temperature flooding 5h.
(2) preparation of graphene dispersing solution: the sodium lauryl sulphate (SDS) of 0.2g is dissolved in 10ml water and obtains 2%(w/v) the SDS aqueous solution, by 2.5mg Graphene (Graphene,-325mesh) be dispersed in the SDS aqueous solution of 10ml, move to after ultrasonic wave dispersion treatment 1.5h in whizzer, centrifugation 3h under 15krpm rotating speed, removing bottom residues, obtains the graphene dispersing solution that concentration is 0.15mg/ml.
(3) Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film: be fixed on there being the ITO substrate of amphipathic ruthenium complexe in step (1) and revolve on Tu instrument, graphene dispersing solution is dripped at substrate surface, start spin coating instrument, low rate start stage speed of rotation is 200r/min, time is 2s, high speed rotation rate is 900r/min, time is 80s, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, dry up with nitrogen with after the promoting agent of washed with methanol ITO surface removing substrate surface, namely Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film.
The surface contact angle test of the substrate after what the present embodiment prepared fix Graphene in ruthenium complexe unimolecular film: the contact angle of the ITO substrate surface after cleaning is 87.3 °, illustrates that clean ITO surface is hydrophobicity; The contact angle of the ITO substrate surface after the process of RCA surface hydrophilic is 65.5 °, demonstrates the wetting ability that RCA hydrophilic treatment method of the present invention improves ITO surface; The surface contact angle of the ITO substrate after assembling ruthenium complexe unimolecular film is 82.1 °, surface hydrophilicity reduces, this is because the hydrophilic group in ruthenium complexe molecule is fixed to ITO interface, hydrophobic group is exposed to surface, makes the ITO substrate surface after assembling ruthenium complexe unimolecular film present hydrophobicity; After ruthenium complexe unimolecular film fixes Graphene, the contact angle of substrate surface is 61.6 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complexe, substrate surface is Graphene, reduces the hydrophobicity of substrate surface; Meanwhile, the change of contact angle to also demonstrate on ITO assembling ruthenium complexe unimolecular film on successfully assembling gone up Graphene.
Embodiment 5
This utilizes spin-coating method Graphene to be assembled into method unimolecular film preparing by amphipathic ruthenium complexe, and its concrete steps are as follows:
(1) the amphipathic ruthenium complexe of self-assembly on ITO substrate: add 20ml ultrapure water in clean beaker, with ammoniacal liquor modulation PH to 10, takes the amphipathic ruthenium complexe of 5.18g [Ru (Py
2g
1meBip) (XPOH)] (PF
6)
2be dissolved in solution, after regulating PH to 5 with HCl, add ultrapure water to 40ml, obtain the amphipathic ruthenium complexe solution of 50uM; By NH
3, H
2o
2with the ratio mixed preparing RCA solution of ultrapure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, after 90 DEG C of heating 1.2h, take out ITO substrate ultrapure water clean, front is immersed in amphipathic ruthenium complexe solution outwardly after nitrogen dries up, slight concussion removing bubble, takes out ITO substrate ultrapure water and cleans up rear nitrogen and dry up after at room temperature flooding 4.5h.
(2) preparation of graphene dispersing solution: the sodium lauryl sulphate (SDS) of 0.2g is dissolved in 10ml water and obtains 2%(w/v) the SDS aqueous solution, by 2.0mg Graphene (Graphene,-325mesh) be dispersed in the SDS aqueous solution of 10ml, move to after ultrasonic wave dispersion treatment 1.5h in whizzer, centrifugation 3h under 15krpm rotating speed, removing bottom residues, obtains the graphene dispersing solution that concentration is 0.10mg/ml.
(3) Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film: be fixed on there being the ITO substrate of amphipathic ruthenium complexe in step (1) and revolve on Tu instrument, graphene dispersing solution is dripped at substrate surface, start spin coating instrument, low rate start stage speed of rotation is 200r/min, time is 1s, high speed rotation rate is 950r/min, time is 75s, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, dry up with nitrogen with after the promoting agent of washed with methanol ITO surface removing substrate surface, namely Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film.
The surface contact angle test of the substrate after what the present embodiment prepared fix Graphene in ruthenium complexe unimolecular film: the contact angle of the ITO substrate surface after cleaning is 87.1 °, illustrates that clean ITO surface is hydrophobicity; The contact angle of the ITO substrate surface after the process of RCA surface hydrophilic is 66.0 °, demonstrates the wetting ability that RCA hydrophilic treatment method of the present invention improves ITO surface; The surface contact angle of the ITO substrate after assembling ruthenium complexe unimolecular film is 81.8 °, surface hydrophilicity reduces, this is because the hydrophilic group in ruthenium complexe molecule is fixed to ITO interface, hydrophobic group is exposed to surface, makes the ITO substrate surface after assembling ruthenium complexe unimolecular film present hydrophobicity; After ruthenium complexe unimolecular film fixes Graphene, the contact angle of substrate surface is 61.2 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complexe, substrate surface is Graphene, reduces the hydrophobicity of substrate surface; Meanwhile, the change of contact angle to also demonstrate on ITO assembling ruthenium complexe unimolecular film on successfully assembling gone up Graphene.
By reference to the accompanying drawings the specific embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (7)
1. utilize spin-coating method Graphene to be assembled into method unimolecular film preparing by amphipathic ruthenium complexe, it is characterized in that concrete steps are as follows:
(1) the amphipathic ruthenium complexe of self-assembly on ITO substrate: add ultrapure water in clean container, with ammoniacal liquor modulation PH to 10, takes amphipathic ruthenium complexe [Ru (Py
2g
1meBip) (XPOH)] (PF
6)
2be dissolved in solution, after regulating PH to 5 with HCl, obtained amphipathic ruthenium complexe solution; ITO conductive glass is immersed in RCA solution, move in water-bath after slight concussion removing bubble, take out ITO conductive glass substrate ultrapure water after heating in water bath to clean, be immersed in amphipathic ruthenium complexe solution after drying up with rare gas element, slight concussion removing bubble, takes out ITO substrate ultrapure water and cleans up rear rare gas element and dry up after at room temperature flooding 3 ~ 6h;
(2) preparation of graphene dispersing solution: sodium lauryl sulphate is dissolved in the water and obtains lauryl sodium sulfate aqueous solution, be that 2 ~ 4:10mg/ml is dispersed in lauryl sodium sulfate aqueous solution by Graphene according to the quality of Graphene and the volume ratio of lauryl sodium sulfate aqueous solution, after ultrasonic wave dispersion treatment, centrifugation removing bottom residues, obtains the graphene dispersing solution that concentration is 0.1 ~ 0.3mg/ml;
(3) Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film: what step (1) prepared has the ITO substrate of amphipathic ruthenium complexe to be fixed on to revolve on Tu instrument, graphene dispersing solution is dripped at substrate surface, start spin coating instrument, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, dry up with rare gas element with after washed with methanol substrate surface removing tensio-active agent, namely Graphene is assembled on amphipathic ruthenium complexe and prepares unimolecular film.
2. Graphene is assembled into method unimolecular film preparing by amphipathic ruthenium complexe by the spin-coating method that utilizes according to claim 1, it is characterized in that: the amphipathic ruthenium complexe [Ru (Py in described step (1)
2g
1meBip) (XPOH)] (PF
6)
2strength of solution is 50 μMs.
3. Graphene is assembled into method unimolecular film preparing by amphipathic ruthenium complexe by the spin-coating method that utilizes according to claim 1, it is characterized in that: the RCA solution in described step (1) is NH
3, H
2o
2with the solution of the ultrapure water mixing of 1:1:5 in mass ratio.
4. Graphene is assembled into method unimolecular film preparing by amphipathic ruthenium complexe by the spin-coating method that utilizes according to claim 1, it is characterized in that: the water bath heating temperature in described step (1) is 90 DEG C, and heat-up time is 0.5 ~ 2h.
5. Graphene is assembled into method unimolecular film preparing by amphipathic ruthenium complexe by the spin-coating method that utilizes according to claim 1, it is characterized in that: in described step (2) lauryl sodium sulfate aqueous solution, the quality of sodium lauryl sulphate and the volume ratio of water are 2:100g/ml.
6. Graphene is assembled into method unimolecular film preparing by amphipathic ruthenium complexe by the spin-coating method that utilizes according to claim 1, it is characterized in that: in described step (2), ultrasonic dispersing time is 0.5 ~ 1.5h, the centrifugation time is 1 ~ 3h, and rotating speed is 15krpm.
7. Graphene is assembled into method unimolecular film preparing by amphipathic ruthenium complexe by the spin-coating method that utilizes according to claim 1, it is characterized in that: described step (3) is revolved Tu instrument and first opened low speed, low rate start stage speed of rotation is 200rpm, time is 3s, then open at a high speed, high speed rotation rate is 700 ~ 1000rpm, and the time is 70 ~ 120s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410636632.7A CN104445143A (en) | 2014-11-13 | 2014-11-13 | Method for preparing monomolecular film by assembling graphene on amphiphilic ruthenium complex by using spin-coating process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410636632.7A CN104445143A (en) | 2014-11-13 | 2014-11-13 | Method for preparing monomolecular film by assembling graphene on amphiphilic ruthenium complex by using spin-coating process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104445143A true CN104445143A (en) | 2015-03-25 |
Family
ID=52892007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410636632.7A Pending CN104445143A (en) | 2014-11-13 | 2014-11-13 | Method for preparing monomolecular film by assembling graphene on amphiphilic ruthenium complex by using spin-coating process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104445143A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107104078A (en) * | 2017-06-06 | 2017-08-29 | 深圳市华星光电技术有限公司 | Graphene electrodes and its patterning preparation method, array base palte |
-
2014
- 2014-11-13 CN CN201410636632.7A patent/CN104445143A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| LI YANG ET AL.: ""Janus-type" Ruthenium Complex Bearing Both Phosphonic Acids and Pyrene Groups for Functionalization of ITO and HOPG Surfaces", 《THE CHEMICAL SOCIETY OF JAPAN》 * |
| SHUWEN LI ET AL.: "Noncovalent modified graphene sheets with ruthenium(II) complexes used as electrochemiluminescent materials and photosensors", 《CARBON》 * |
| YUQI YU ET AL.: "Synthesis of electrochemiluminescent graphene oxide functionalized with a ruthenium(II) complex and its use in the detection of tripropylamine", 《CARBON》 * |
| 孙颖: "钌配合物修饰石墨烯的制备及光谱性质", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107104078A (en) * | 2017-06-06 | 2017-08-29 | 深圳市华星光电技术有限公司 | Graphene electrodes and its patterning preparation method, array base palte |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | MXene derived metal–organic frameworks | |
| Gao et al. | Ingenious artificial leaf based on covalent organic framework membranes for boosting CO2 photoreduction | |
| Xiao et al. | Layer-by-layer self-assembly of CdS quantum dots/graphene nanosheets hybrid films for photoelectrochemical and photocatalytic applications | |
| Rolison et al. | Multifunctional 3D nanoarchitectures for energy storage and conversion | |
| Dao et al. | Graphene-based nanohybrid materials as the counter electrode for highly efficient quantum-dot-sensitized solar cells | |
| Barpuzary et al. | Two-dimensional growth of large-area conjugated polymers on ice surfaces: high conductivity and photoelectrochemical applications | |
| Wang et al. | van der Waals epitaxial growth of 2D metal–porphyrin framework derived thin films for dye‐sensitized solar cells | |
| TW201210113A (en) | Manufacturing method for porous material | |
| CN108866561A (en) | A kind of preparation method and applications of electro-catalysis carbon dioxide reduction electrode | |
| CN102332356A (en) | DSSC and manufacturing approach thereof | |
| KR100945742B1 (en) | The method for producing of the photo-electrode of dye-sensitized solar cell | |
| Ishihara et al. | Semiconducting Langmuir–Blodgett Films of Porphyrin Paddle-Wheel Frameworks for Photoelectric Conversion | |
| Gu et al. | Facile synthesis of metal-loaded porous carbon thin films via carbonization of surface-mounted metal–organic frameworks | |
| Park et al. | Facile graft copolymer template synthesis of mesoporous polymeric metal-organic frameworks to produce mesoporous TiO2: Promising platforms for photovoltaic and photocatalytic applications | |
| TW201101556A (en) | Method and device for dye adsorption for photosensitizing dye, process and apparatus for producing dye-sensitized solar cell, and dye-sensitized solar cell | |
| Shi et al. | Hydrophilic hydrogen-bonded organic frameworks/g-C3N4 all-organic Z-scheme heterojunction for efficient visible-light photocatalytic hydrogen production and dye degradation | |
| Zhang et al. | Rapid synthesis of covalent organic frameworks with a controlled morphology: an emulsion polymerization approach via the phase transfer catalysis mechanism | |
| Tang et al. | In situ growth of zeolitic imidazolate frameworks nanocrystals on ordered macroporous carbon for hydroquinone and catechol simultaneous determination | |
| Shrivastav et al. | Recent advances on surface mounted metal-organic frameworks for energy storage and conversion applications: Trends, challenges, and opportunities | |
| Wei et al. | Mesoporous Poly (3, 4-Ethylenedioxythiophene): Poly (Styrenesulfonate) as Efficient Iodine Host for High-Performance Zinc–Iodine Batteries | |
| JP2005235757A (en) | Metal oxide electrode film and dye sensitized solar cell | |
| Emani et al. | Organophilicity of graphene oxide for enhanced wettability of ZnO nanorods | |
| Zhong et al. | Metal–organic frameworks on versatile substrates | |
| Huang et al. | In-situ carbonization of zeolitic imidazolate framework-67 on Ni foam as binder-free electrode for energy storage | |
| CN100533850C (en) | Counter electrode for photoelectric converter and photoelectric converter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150325 |
|
| RJ01 | Rejection of invention patent application after publication |