Production of organic thin film

[Detailed Description of the Invention]

[Field of the Invention] In the present invention, about a manufacturing method of an organic thin film, a micell-ized agent specific in detail is used, and the electrochemical technique is devised. therefore, an organic thin film which can be used for an electronic industry material etc. -- efficiency (related with a method of manufacturing.). [ -- as the method of manufacturing organic thin films, such as pigment, from the problem] former which prior art and an invention tend to solve -- a vacuum evaporation method, a heat CVD method, a plasma CVD method, and an ultrahigh vacuum (an ion beam, molecular beam epitaxy) -- law, the LB removing method cast method, etc. are known. However, since each of these methods needed operation of dissolving materials, such as pigment, in an organic solvent, or heating, they was not able to thin-film-ize a weak hydrophobic organic substance with heat. these artificers need to cancel the fault of the above-mentioned conventional technology, and also need to thin-film-ize a weak hydrophobic organic substance easily with heat -- research was repeated wholeheartedly that How to do should be developed. [Means for Solving the Problem] As a result, when a ferrocene derivative was used as a micell-ized agent, various kinds of hydrophobic organic substances could be underwater taken in into micell, and it found out that a desired organic thin film could be formed on an electrode by carrying out electrolytic treatment of this. The present invention is completed based on this knowledge. That is, a manufacturing method of an organic thin film, wherein the present invention electrolyzes a micellar solution obtained by solubilizing a hydrophobic organic substance in a micell-ized agent which consists of ferrocene derivatives in a water medium and forms a thin film of the hydrophobic organic substance on an electrode is provided. A method of the present invention advances according to a Like principle shown in Drawing 1, and an organic thin film is formed on an electrode (anode). That is, when a micell-ized agent and a hydrophobic organic substance consisting of ferrocene derivative 1 are added, mixed churning is fully carried out and a water medium which added a supporting electrolyte etc. to water if needed, and adjusted electrical conductivity is distributed, If micell 3 which took hydrophobic owner 89 substances 2 into an inside is formed and electrolytic treatment of this is carried out, micell 3 can draw near to anode 5, and a ferrocene derivative in micell will lose electronic e- on the anode (Fe" in ferrocene oxidizes to Fe"), With it, micell collapses, and internal hydrophobic organic substance 2 deposits on anode 5, and forms a thin film. On the other hand, it can draw near to negative pole 6, Acceptance takes electronic e-, and oxidized ferrocene derivative 4 forms micell again, and takes hydrophobic organic substance 2 into an inside. It is a process in which formation and collapse of such micell are repeated, and particles of hydrophobic organic substance 2 deposit on the anode, it will become filmy, and an organic thin film made into the object will be formed. A micell-ized agent used by a method of the present invention consists of ferrocene derivatives. Although some are [ various kinds of ] as a ferrocene derivative here, Usually, it is a ferrocene compound (suitable substitution machine for ferrocene or ferrocene (Alkyl machine)) to a Armonium type (preferably the fourth class Armonium type) cationic surface-active agent which has a main chain of carbon number 4~16 (preferably 8~14). What what an acetyl group etc. combined combined is raised. Micell is not formed and there is inconvenience that it will not dissolve in water here, by some too many are what has a few carbon number of a main chain. A mode which a ferrocene compound combines with this surface-active agent is various, and modes, such as what was divided roughly and combined with an end of a main chain of a surface-active agent, a thing combined via a direct or Alkyl machine in the middle of a main chain, and a thing incorporated into the main End, are raised. When a general formula of such a ferrocene derivative is shown, it is a general formula (R' and R" show hydrogen or a Alkyl machine of carbon number 1~4 (however, the below-mentioned integer m is not exceeded) among a formula, respectively, Y and Z show hydrogen or a substitution machine, respectively, and X shows halogen.). m and n show an integer with which it is m>=O and n>=O and fills 4 <=m+n<=16. . General formula R', Rt, X, Y, and Z are that it is the same (however, a carbon number of R1 and R2 -- the after-mentioned -- ready -- it does not exceed several persons.) with the above among a formula. An integer with which it is h>=O1j>=0 *k>=1 and fills <=15 to 3 <=h+j+ is shown in h and j, and p shows an integer with which -1 is filled to 0 <=p<=. . General formula (R', R2, X, Y, and Z are that it is the same (however, RI and a carbon number of R2 do not exceed the below-mentioned integer r.) with the above among a formula.) r, s, and t show an integer with which it is r>=0.s>=0*t>=1, and fills 4 <=r+S+t<=16. or General formula (R', R", X, Y, Z, r, s, and t are the same as the above among a formula.) -- what is expressed is raised. It will be a formula if concrete of a ferrocene derivative as this micell-ized agent is shown. Such is raised. If it is insolubility thru/or poor solubility and the particle may moreover be taken in in micell to water (namely, what is meltable in micell), various kinds of things of a hydrophobic organic substance which, on the other hand, serves as materials of an organic thin film manufactured by a method of the present invention are usable, and there is no restriction in particular. For example, there are various things, such as pigment, a paint, photosensitive materials, an organic electric conduction material, and an electrical insulation material, Specifically, they are 1 and 1'-diheptyl 4 and 4'-Vibilidinium dibromide, Erection good comic materials, such as 1 or 1 degree-didodecyl 4 and 4 *-Vibilidinium dibromide, Photosensitive materials, such as 6-nitroglycerine 1 and 3 and 3-Trimethyl spiro (2"H-1"-benzopyran 2, 2 *-indoline) (common name spiro Piran) (photochromic material), Organic electric conduction materials, such as 1:1 complexes of pigment for liquid crystal display, such as p-Abciani sole, 7, 7.8.8-tetra-Butyrospermum parkii Non-job methane (TCNQ), and tetra-thia full Baren (TTF), Diazo type photosensitive materials, paints, etc., such as organic colors, such as insulating materials, such as optical hardenability paints, such as Penta erythritol diacrylate, and stearic acid, and phthalocyanine, and 1-phenylazo 2-naphthol, can be raised. In addition, protein, such as histone and a lysozyme, etc. can also be used as a hydrophobic organic substance. Although an above-mentioned micell agent and a hydrophobic organic substance are added into a water medium which makes water or water the main ingredients and mixed churning is carried out in a method of the present invention, in order to adjust that electrical conductivity in this water medium, support salt (supporting electrolyte) is added if needed. Addition shaking of this support salt usually makes a standard an about [ a 10~3oO time ] concentration of the above-mentioned micell-ized agent, preferably about 50~200-time concentration. Without a kind of this support salt barring formation of micell, and precipitation of a hydrophobic organic substance to an electrode, electrical conductivity of a water medium is adjusted, and if it is that of nonglutinous rice, there will be no restriction in particular. Sulfate specifically used as support salt widely generally (lithium, potassium, sodium.) Salt, such as kana Jeum and aluminum, acetate (lithium, potassium, sodium, kana Jeum.) Salt, such as beryllium, magnesium, calcium, strontium, barium, and aluminum, is preferred. The electrode used by a method of the present invention should just be a metal more Blame than oxidation potential (-)-0 and 15 V pair saturated calomel electrode or an electric conduction object of ferrocene. Specifically, ITO (mixed oxide of indium oxide and tin oxide), platinum, gold, Grudge, Gradi- carbon, conductive metallic oxide, an organic polymer electric conduction object, etc. are raised. In a method of the present invention, an above-mentioned micell-ized agent, support salt, and a hydrophobic organic substance are first put in a water medium, Make an ultrasonic wave, a homogenizer, or a stirrer fully distribute, and micell is made to form, and electrolytic treatment is carried out using an above-mentioned electrode, adding some churning with a micellar solution settled obtained by removing a superfluous hydrophobic organic substance if needed after that. Supplement addition of the hydrophobic organic substance may be carried out during electrolytic treatment at a micellar solution, or a hydrophobic organic substance may be added to a micellar solution which extracted and extracted a micellar solution near the anode out of a system, mixed churning may fully be carried out, and a circulation circuit which returns this liquid near the negative pole after an appropriate time may be put side by side. although electrolysis conditions in this case may be suitably selected according to various situations, 0~70 degrees of solution temperature usually make them into C1, preferably 20~30 degreeC1 voltage 0.03~1■, preferably 0.1~0.5■ -- current density 10mA/cm" -- the following desirable considers it as 50~300 uA/cm." If this electrolytic treatment is performed, a Like reaction shown with having mentioned above in Drawing 1 will advance. If its attention is paid to this at an action of Fe ion in a ferrocene derivative, in the anode, Fe"° of ferrocene will become Fe", micell will collapse and particles (600~900lambda grade) of a hydrophobic organic substance will deposit on the anode. On the other hand, in the negative pole, it will return to micell of even if Fe" which oxidized by the anode is returned to Fe", and a hydrophobic organic substance which is floating in a water medium at the time of this micell formation will be taken into an inside. Of such electrolytic treatment, a thin film by about 600~900 persons' particles of a hydrophobic organic substance for which it asks is formed on the anode. [Example] Next, an example explains the present invention in more detail. Example 1 0.02 mol of lithium sulfate as support salt is melted in 100-cc water, as a micell-ized agent, 0.2 millimoles of compounds of the formula were added to this, it was distributed according to the ultrasonic wave, and micell was made to form in it. Next, this pigment was made to take into this micellar solution into micell the pigment (1-phenylazo 2-naphthol) which is a hydrophobic organic substance according to an ultrasonic wave after 0.2 millimole added. Superfluous pigment was removed by filtration after that, and the micellar solution was obtained. By having used this micellar solution as the electrolysis solution, ITO was used for the anode, the To saturate Coe electrode was used for platinum and a reference electrode at the negative pole, and electrolytic treatment was performed on condition of temperature [ of 25 degrees ] C1 impressed-electromotive-force 0.3■, and current density [ of 35micro ] A /c+n 2. The pigment thin film with the primary particle of 700 average particle diameter was obtained on ITO 20 minutes afterward. The scanning electron microscope (SEM) photograph (product JSM-Tmade from one [ 35000 times the magnification of this ] JEOL [ 1 ] ■ 220 use) of the generated pigment thin film is shown in Drawing 2. The ultraviolet absorption spectrum which melted this thin film in ethanol is shown in Curved line of Drawing 5. Although the ultraviolet absorption spectrum of what only melted the above-mentioned pigment in ethanol was shown in curve C of Drawing 5, since the absorption peak of curves C and D corresponds, it turns out that the thin film on ITO is what consists of the above-mentioned pigment. Example 2 In Example 1, the same operation as Example 1 was performed except having changed the anode into platinum and having changed current density into 3 old muA /cm Z. The ultraviolet absorption spectrum of what melted the generated thin film in ethanol is shown in curve B of Drawing 5. Example 3 In Example 1, the same operation as Example 1 was performed except having changed the anode into Gradi- carbon and having changed current density into 40microA / cm." The ultraviolet absorption spectrum of what melted the generated thin film in ethanol is shown in curve A of Drawing 5. Example 4 In Example 1, the same operation as Example 1 was performed except having changed current density into 30microA / cm", using the compound of a formula as a micell-ized agent. The SEM photograph (one 35000 times the magnification of this) of the generated thin film Product JSM-Tmade from JEOL @ 220 use is shown in Drawing 3. Example 5 In Example 1, using 1. Engineering °-didodecyl 4 and 4 degree-bipyridinium dibromide as pigment, except having changed current density into 58microA/cI112, the same operation as Example 1 was performed, and the thin film was generated on ITO. The ultraviolet absorption spectrum which melted the generated thin film in methanol is shown in curve B of Drawing 6. The ultraviolet absorption spectrum of what (concentration 0.042 millimole /2) melted the above-mentioned pigment in methanol is shown in curve A of Drawing 6. Since the absorption peak of curves A and B corresponds, it turns out that the thin film on ITO is what consists of the above-mentioned pigment. Example 6 In Example 5, the same operation as Example 5 was performed except having changed the anode into Gradi- carbon and having changed current density into 60microA / cm." The SEM photograph (one 500 times the magnification of this, ■ Hitachi S-800 use) of the obtained thin film is shown in Drawing 4. [Effect of the Invention] According to [ like / the above statement ] the method of the present invention, the thin film of various kinds of hydrophobic organic substances can be efficiently manufactured at the temperature about room temperature, without using the organic solvent. And it is also easy to also large-area-ize the thin film formed and to adjust film thickness. Therefore, the method of the present invention begins paint and coloring of various products, and are electronic industry materials, such as optical electric conduction object material 5 electric-power-machinery material 9 display device material, and also photosensitive materials. It is used for manufacture of an insulating material etc. broadly and effectively.

[Brief Description of the Drawings]

The explanatory view in which Drawing 1 shows the principle of the method of the present invention typically, and the 2~4th figure are electron microscopic pictures in which Example L4 and the surface structure of the thin film formed by 6 are shown, respectively. Drawing 5 shows the ultraviolet absorption spectrum of the ethanol solution of the thin film formed in Example 1~3, and Drawing 6 shows the ultraviolet absorption spectrum of the methanol solution of the thin film formed in Example 5. The ferrocene derivative in which, as for one, a ferrocene derivative and 2 oxidized among the 1st figure, and, as for a hydrophobic organic substance and 3, micell and 4 oxidized, and 5 show the anode, 6 shows the negative pole, Fc shows ferrocene and e- shows an electron. Drawing j Drawing 6 Front length (nm)