POROUS METAL-ORGANIC STRUCTURE THIN FILM AND PRODUCTION METHOD THEREOF

Hereinafter, with reference to a drawing of the present invention in the embodiment for the present invention in the preface is provided to the person with skill in the art for embodiment is hereinafter to be detailed as follows. But, in the embodiment of the present invention is the valve timing has the number range, this method for assisting in the understanding of the present invention will be interpreted.

As described above, the manufacturing method of a thin film of organic structure of the existing method of organic layer metal - metal - organic structure when a number number times to metal substrates in situ for thin film growth techniques is reported 440 very little corrosion and, in at least some of the existing method manufacturing method in situ metal - organic structure growth is such time or number of diseased or longer than in the sense that his point at the door.

The in the present invention, the manufacturing method of a thin film of porous metal - organic structure (1) organic ligand de-protonated ligand solution, metal oxide and metal ions oxidation number number number additive mixing step number billion diffusion of dye mix solution tank; and (2) said metal mixed solution treating a surface of a substrate; wherein, said (1) and (2) at least in one step during said heating said mixed solution to some or all of the surface of the metal substrate to form a thin film; a porous metal - organic structure including a thin film manufacturing method (Metal provided Organic Framework) number then the number point fixing fitting his [...] enhancer is disclosed.

The number of the existing method of metal - organic structure with trillion processes through simple metal growth process operates directly metal organic structure center, very rapid number trillion processes as well as metal thin film can be copolymer having a spandex.

In hereinafter, the present invention according to such porous metal - organic structure passing of compositions and manufacturing method (Metal provided Organic Framework) described as follows.

First, (1) wherein the organic ligand de-protonated ligand, and addition number number oxide mix solution by mixing step number tank a plurality of hierarchies.

The ligand said mixed solution, solvent added number and oxidation number is added to the high pressure liquid coolant solution by mixing the respective number number number after these high pressure liquid coolant can be high pressure liquid coolant. Hereinafter number part for mixing high pressure liquid coolant solution set up but it is not the number one.

First, metal ions and/or metal atoms carry ligand is de-protonated organic ligand with metal - organic structure of molecular units as, organic ligand de proton that a number bath 1308. The, said de-protonated ligand organic ligand may be provided or organic ligand and said organic ligand after prepared by the number solution mixed solution can be mixed together with solution can be with proton de component.

De-protonated organic ligand solution when mixed solution bath after prepared by the number as a reference number ligand are United, said ligand solution includes an organic ligand and said organic ligand can be de proton which components, can be further includes a solvent capable of dissolving.

Said organic ligand capable of binding the metal ions and/or metal atoms and de-protonated organic coordinated self-acknowledgement number when used without a functional group which can be, as one example, oxalic acid (Oxalic acid), malonic acid (Malonic acid, Succinic acid), the small [phu mask it buys child (Isophthalic acid), terephthalic acid (Terephthalic acid), sheet [lik it buys (Citric Acid), indigo or tree acid (Trimesic acid), 1, 2, 3 - triazole (1, 2, 3 a-Triazole), thiadiazole (Pyrrodiazole) fatigue, imidazole (Imidazole), 2 - methyl imidazole (2 a-Methylimidazole) can be selected from the group consisting of comprising at least more than one.

In addition, de-protonated organic ligand for said components can be using basic organic molecules or inorganic salt.

Said basic molecules or basic ion can be, for example, triethylamine (Triethylamine), it will be burnt amine (n a-decylamine) n -, n - (n-a dodecylamine) deck thread amine, pyrrolidine (pyrrolidine), hexamethylenediamine (Hexamethylene diamine), pyridine (Pyridine), such as basic organic amine (phenylamine), sodium hydroxide (Sodium hydroxide), potassium hydroxide (Potassium hydroxide) can be a basic inorganic salt such as, limited to are not correct.

In addition, added to that said solvent into which said organic ligand said mixed solution to dissolve the cultivation person who burns and it became not one specifically component number and, as an example, said solvent can be water (water), methanol (methanol), ethanol (ethanol), 1 - propanol (1 a-propanol), 2 - propanol (2 a-propanol), 1 - butanol (1 a-butanol), 2 - butanol (2 a-butanol), acetone (acetone), 2 - butane on (2 a-butanone), tetrahydrofuran mixable (tetrahydrofuran), triethylamine (triethyl amine), amide (dimethyl-a formamide) - dimethyl formaldehyde, dimethyl sulfoxide (dimethyl sulfoxide) can be at least one selected from the group consisting of comprising 1.

Wherein, the molar ratio of 1:1 to 1:4 between said rotor and said organic ligand organic proton de components can have more, acidic functional groups such as in the number of hydrogen atoms in organic atoms can be depending on desired conditions. For example, actinic radiation generated when two acidic hydrogen atoms of organic acid (Trimesic acid) tree has a 3, triethylamine (Triethylamine) basic organic molecule is capable of neutralizing acid with actinic radiation to said number of proton 1 mixed solution triethylamine (Triethylamine) (Trimesic acid) and the molar ratio of the morning fair tree implementation being 1:3.

, the content of solvent in said ligand solution into which organic ligand and polarity can be changed properly de polymer which contains content of components the present invention refers to the sound does not specifically define.

In the present invention hereinafter de organic ligand proton a reaction and coordination for specifically and in which the main chain has a sense de-protonated, acidic hydrogen atoms coupled ligand is a stand-alone number de proton microbial acid means that the substrate.

For example, such as to form a reactive, two acidic hydrogen atoms (H) in the case of node 3 is therefore acid (Trimesic acid) 3 of tri-ethyl ammonium tree maul tax [thu is reacted with triethylamine (Triethylamine) (Triethylammonium Trimesate) can be (reactive 1 reference).

[Compound 1]

As above-mentioned as shown with respect to each other protonated ligand is reaction of metal - organic structure constituting units to one ingredient, not organic ligand to form a metal - organic structure through proton de thereof can difficult.

Relative thereto, specifically, at the comparison example 15 Figure 16 of the present invention and also according to manufacturing method not organic coordinated self-acknowledgement H proton₃ BTC containing a solution of SEM pictures and PXRD pattern drawing indicating the reacted copper substrates, crystalline phase came not found any form of octahedron HKUST-a 1, even of Figure 16 PXRD pattern, the phase of the HKUST-a 1 not found yet. In particular, in the case of sample 4 (Sample 4) 15 (c) also shown only a peak in which copper substrate, oxidized copper (I) (Cu₂ O) and HKUST-a 1 powder such as peak applications currently not.

The, rotor means in situ growth method has been de proton of treatment for coordination in 2000.

In addition, hereinafter de-protonated organic self such coordination's dose forming a thin film with an influence on drawing herein disclosed.

Figure 13 the de-protonated BTC and also 12 according to one embodiment of the invention^3- Amount according to SEM pictures and other exhibits PXRD pattern. Wherein, as shown by the SEM photograph of (a) to 12 (i) also 12 also as, de-protonated ligand BTC^3- The relative amounts of (3 ml, 6 ml, 9 ml) by varying the size of the HKUST-a 1 domain, through a quadrature mirror filter domain can be HKUST-a 1, de-protonated BTC^3- Storing the relative amounts within a HKUST-a 1 domain number increase and making sure that the domain size can be uniform.

I.e., BTC de-protonated^3- (F) (d) in the case of 12 - 12 also in 6 ml is also de-protonated BTC^{3 -} (G) 12 - 12 is also in 3 ml (i) domain than the number of processors increases also while a domain in the same area may be liberal have uniform size of, allows more de-protonated BTC^3- The HKUST-a 1 to influence nucleation means other. Thus, according to one embodiment of the present invention, de-protonated BTC^3- By regulating the concentration of HKUST provided 1 film uniformity can be cylindrical. Said under the BTC de-protonated^3- The higher the concentration of the solution state in uniform domain sizes, uniform film with this degree of de-protonated BTC for smaller number 9 ml^3- A third solution preferably enemy. With this smaller number having oppositely relatively non-uniform domain sizes for de-protonated BTC film^3- Preferably about lowering the concentration of the solution.

Second, said metal oxide oxidation number is described as follows.

Said oxidation number added to the elution of the metal ions in the metal surface component, metal surface is oxidized to publicly known components can be used in the case of number grudge without.

As one example for the, (Ammonium persulfate) with sulfuric acid ammonium, [...] (Potassium persulfate), with sulfuric acid natrium (Sodium persulfate), oxygen (Oxygen), ozone (Ozone), hydrogen peroxide (Hydrogen peroxide), benzoyl peroxyde (Benzoyl peroxide), and at least one element selected from the group consisting of tri (Triacetone triperoxide) lung rock side can be 1.

The, said oxidation number has a mixing solution singly morning fair number further comprises directly contacting the solvent solution can be kiln, said solvent is a solvent capable of dissolving said oxidation number using number can be grudge without holes, at least one 2 can be mixed. As an example, said solvent can be water (water), methanol (methanol), ethanol (ethanol), 1 - propanol (1 a-propanol), 2 - propanol (2 a-propanol), 1 - butanol (1 a-butanol), 2 - butanol (2 a-butanol), acetone (acetone), 2 - butane on (2 a-butanone), tetrahydrofuran mixable (tetrahydrofuran), triethylamine (triethyl amine), formaldehyde (dimethyl-a formamide) - dimethyl amide, dimethyl sulfoxide (dimethyl sulfoxide) can be at least one selected from the group consisting 1 comprising. Wherein, the content of oxidation number and solvent solvent in solutions comprising said oxidation number specific colony types can be changed.

Hereinafter, metal - organic structure in said oxidation number hereinafter for forming thin film of an influence on heat substrate.

Oxidation number 17 and Figure 18 also without using a mixed solution of SEM pictures and PXRD pattern according to comparison example reacting time through the copper substrates are disclosed.

17 Shown in the SEM photograph also as shown, if the crystalline oxide mixed solution with sulfuric acid ammonium (Ammonium persulfate) in number of HKUST-a 1 found in the form of a gate and an octahedron, 18 also appears even PXRD pattern, the mixed solution is not added with sulfuric acid ammonium (Ammonium persulfate) in oxidation number, in his not found to have any reaction of copper substrates of HKUST-a 1.

Through these results, the presence of metal ions has been oxidized metal the borad it stands can be know treatment for the elution of the number.

A chemical, metal ion diffusion billion number number additive is described substrate.

Said number added structural stability to the metal - organic structure can be [...] number, said number in the aforementioned oxide dissolved in the mixed solution through diffusion of metal ions can be eluted when using billion number component can be grudge without number. Only, preferably said degree of polarization and the generation number added, the structural stability number can be [...], acetone (Acetone), 2 - butane on (2 a-Butanone) and 3 - [...] (3 a-Pentanone) include at least one selected from the group consisting 1 but, limited to are not correct.

Specifically, adding said number for forming thin film of influence of a kind of metal - organic structure herein disclosed.

According to one embodiment of the invention the addition of PXRD pattern number according to SEM pictures and 6 and Figure 7 each also exhibits different types.

First, in 6 (a) also, added to acetone (sample 1) number when used blue HKUST-a 1 film appears to the naked eyes to the glass substrate and, even when adding number of Figure 7 PXRD pattern consisting of acetone can be identifying HKUST-a 1.

However, the addition of different types as number, sample 2 in MeCN (Sample 2 (number added: Acetonitrile), 6 (b) also), sample 3 (Sample 3 (number added: Ethanol), 6 (c) also) in EtOH, MF (Sample 4 (number added: DMF), 6 (d) also) in sample 4, and sample 5 (of Figure 7 Sample 5 (number added: Water), 6 (e) also) in DDW adding each number when it sells really cannot identify domain appears to adding HKUST-a 1 15, HKUST-a 1 PXRD pattern in tunnel components having cannot confirm disclosed.

The, acetone (Aceton) number to a number added to a copper substrate film impossible number [...] HKUST-a 1 bath can be know. This, other polarization whiteness is lower than the number added acetone (Aceton) diffusion of copper ion eluted copper the borad it stands billion number used for the surface reactions can be expected.

In this regard, adding separate said number according to the polarity of the solvent AB initio, to a relation of (1) removing the solvent from reaction (Reichardt's empirical polarity equation) content via a polarity according to the bill.

E_T (MS)=E_T (LPS)+ E_D Ln (c_p /C^* + 1) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - (1)

Said relational expression (1) in E_T (MS) and E_T (LPS) are each mixed (Mixed Solvents, MS) is of low polarity solvent having polarity and c (Less Polar Solvent)_p The polarity of a tube and with further high concentration, E_D And c^* Has a mixing solvent can be adjustable parameters are disclosed.

In particular, E_D Relative c is_p And c^* By variation of the E_T As with dimensions of energy which affects the degree scale sensitivity parameters (Dimensions of Energy) are disclosed.

Generally a high polarity solvent and ionic liquid (Ionic liquids) number [...] since most water, each the polarity of the solvent water "1" after normalization (Normalize) based on the relative size can be easily compared. (Tetramethylsilane, TMS) mixed solvent and water - 2 - [...][...] normalization ratio of can be calculated through a polarity difference between 2. This, a relational expression (2) can then be mixed to Ziegler-Natta catalysts.

E_T^N =[E_T (Solvent) - E_T (TMS)] / [E_T (Water) - E_T (TMS)]

=[E_T (Solvent) -30. 7]/ 32. 4 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - (2)

Wherein E_T (Water) and E_T (TMS) water and tetra methyl thread column and each polarity, each value is 63. 1 And 30. 7 Are disclosed. Said relational expression (1) calculated through E_T (MS) is said relational expression (2) E through_T^N (MS) simply as normalization can be. The dentist bright mistletoe to 1.

Each solvents and water * - solvent mixture is of [E_T ] Normalized polarity [E_T^N ]

X indicating in said table 1_H2O X and_Solv Each of the loaded solvent with water and sludge Natta volume fraction (number added), the size of the order of the MeCN > > ACE > EtOH normalization polarity can be DMF. Also mixed solvents, E_T^N E > (Water non-EtOH)_T^N (Water-a MeCN) > E_T^N (Water-a DMF) > E_T^N It is order (Water provided ACE), resulting in a low polarity solvent-based polarity may be realized by mixing in addition of number can be cylindrical.

In addition, the aforementioned number (acetone) addition amount influence on forming a thin film heat substrate.

Figure 9 shows a PXRD pattern number according to SEM pictures according to one embodiment of the invention are also the other 8 and also exhibits and addition of amount, through, by adding acetone in number of dose reduction, copper substrates created on the HKSUT provided 1 domain size can be sure that affects the reaction speed.

Specifically, 8 (a)- 8 (b) and also such as acetone also 0. 01 Ml and 0. 10 Ml when cast into the octahedron start forming when the island domain form, (e) 8 - 8 (h) each such as acetone may also 0. 25 Ml and 1. The thickness of the arm is inserted into the number 00 ml when making sure that the domain can be a continuous thin film shape. In addition, 8 - 8 (j) also as identified in (i) also, even when the thickness of the arm is turned on each 2 ml acetone number domain can be sure that the continuous thin film shape.

I.e., the greater the relative amount of mixed solution in acetone adjust HKUST-a 1 domain size is attained, it grows in the form of thin film in the form of island HKUST-a 1 domain not found. This leads to low polarization relative amounts of acetone (Aceton) whiteness degree of polarization according to a solution which changes the copper ion diffusion of the copper substrates be eluted under controlled as a probe substrate.

As a result, the amount of addition of 1 ml of acetone to form a thin continuous film know more can be necessary.

Next, the present invention according to (2) as step, said mixed solution processing metal of the base surface a plurality of hierarchies.

Specifically, the surface of said metal substrate mixed solution represents the metal ions into metal surfaces for forming thin film organic structure by applying a metal metal on surfaces -, 5.0 (open coordination site: OCS) to establish a pre can open coordination sites.

In addition, the metal surface of the substrate processing method (impregnation) impregnating, immersion (soaking), coating (coating), doping (doping), such as a publicly known method of injection (spraying) can be, metal - organic structure grown on said metal substrate can be specially if the number is not one method.

According to one embodiment of the present invention, said metal substrate is immersed in the mixed solution can be said thin film is formed on said metal substrate, said metal substrate immersed time is 3 minutes may be - 180 minutes, preferably 4 minutes may be -8 minutes, more preferably 5 minutes can be 6 minutes.

In this regard, according to one embodiment of the invention Figure 2 shows a PXRD pattern of SEM pictures and therefore mixing produced copper substrates with time and, also 19 to 21 of the PXRD pattern according to one embodiment of the invention exhibits SEM pictures and reaction mixed solution with time-copper substrates.

19 Also through SEM shown in the photograph, 10 minutes reaction time of observing the surface of the sample in 10 seconds after that, said 10 seconds after a reaction time of sample (19 also (b) reference) unlike copper substrate surface of originally start forming domains have small tenths of a nanometer, then by increasing the reaction time 30 S., (c) 4 - 5 micro m size such as 19 also produced with octahedron HKUST-a 1 domain of sweet taste. Then, 19 (d) interaction between growth (Intergrowh) after 1 min. in reaction time also began appearing when the domain, 19 (h) 5 minutes after a reaction time of the metal - organic structure from it stands and eventually also completely angularly continuous form of mutual growth between domain (Intergrowh) detergent can be confirmed.

But, as shown in the SEM 20 also identified in a photograph, a reaction time of about 5 minutes complete film is applied about 3 - 5 micro m additional reaction time applied film thickness even further reacting is not grown and made longer vread, its own termination (Self-a termination) growth of thickness of a film that has been identified.

The, in the form of a continuous film between metal - organic structure domain completely for approximately 5 min or higher than that of a metal substrate immersed time can be.

Then, said (1) and (2) at least in one step during heating said mixed solution is described substrate.

Heating said metal organic structure such mixed solution for the film represents the merging, the point during the phase (Phase) if other non-porous film or metal organic structure created with other material is connected between the door number can be generated.

According to the present invention, said heated dye mix solution, said (1) mix solution prepared by the number in heating or said (1) mix solution in said tank can be heated in a process number.

Specifically, said (1) and (2) at least in one step during a process specifying said mixed solution to a temperature, depending on said metal - organic structure or mixed solution but, 50 - 80 °C can be heated in said temperature. Preferably 60 provided 70 °C implementation being. At this time, in one case to the other said heating temperature is 50 °C hereinafter on other material or metal organic structure created with non-porous film is connected between the door and number occurs, said heating temperature is 80 °C or more with a solvent when rapid evaporation of retentate from the concentration gradient is relatively small number to a non-uniform metal organic structure film number can be door, said range of now.

In this regard, Korean fermented hereinafter said mixed solution to said heating temperature of critical heat substrate.

Figure 11 shows a PXRD pattern according to SEM pictures and other reaction on and therefore also 10 according to one embodiment of the invention are disclosed.

As identified in a of Figure 10 SEM pictures, the number of specific reaction temperature and reaction temperature 25 °C and 45 °C 65 °C [...] HKUST-a 1 non-linear domains simultaneously exist octahedron domain can verify, through 11 shown in the PXRD pattern also, 25 °C, 45 °C, in the case of other than a reaction temperature of 65 °C 25 °C HKUST-a 1 number has been confirmed that the thin film of which can be small. Through, said mixed solution heating temperature 65 °C point can be most efficiently thin film forming temperature can be know.

On the other hand, according to one embodiment of the present invention, said metal - organic structure the gas inlet said metal substrate, as an example, planar substrate, mesh network, tube, capillary, a wire or coating can be, depending on the type of article number applied to various shapes are number can be not.

One embodiment according to the present invention according to example of these materials, such as metal - even when said metal substrate having a structure in which the present invention according to the mesh network including organic structure can be thin film forming.

In this regard, Figure 28 shows a reaction according to one embodiment of the invention therefore is operated optical microscope and copper network before reaction of copper network as SEM pictures HKUST-a 1, 28 (d) having an high such as 8. 0 × 10⁴ m^-1 Voice number HKUST-a 1 copper surface of the copper film work grudge result, in spite of high curvature continuous rigid HKUST-a 1 number of SEM photograph (h) also operable to small film 28 by verifying the first call request.

Through, said method through the high curvature surface of metal such as copper prepared by the number is small at or even HKUST-a 1 film number can be connected.

In addition, in one embodiment of the present invention search, said metal element metal substrate, and an oxide of these metal alloy, e.g., copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), chromium (Cr), vanadium (V), titanium (Ti), scandium (Sc), zirconium (Zr), grade molybdenite concentrates [...] (Mo), ruthenium (Ru), palladium (Pd), cadmium (Cd), half [...] (Hf), magnesium (Mg), and calcium (Ca) 1 species selected from the group consisting of metals, metal alloy and an oxide of a can.

Wherein, in one embodiment of the present invention when said zinc as a metal substrate, a semiconductor thin film according to one embodiment of the invention ZIF-a 8 Figure 4 SEM of zinc, and a Raman spectrum exhibits PXRD (Raman).

As identified in a of Figure 4 PXRD pattern, in addition to zinc zinc are formed on a peak of ZIF-a 8 thin film synthesized ZIF-a 8 can be found in a peak executed by the PXRD pattern shown in powder. (A) such as SEM photograph of ZIF-a 8 4 additionally also in four-way dodecahedron morphology even specific domain can be liberal in connection due to formation of thin film.

With, metal - organic structure in order to identify when the mode of vibration of the unique Raman (Raman) estimating the spectrum, (b) in the case of thin film is generated zinc substrate such as ZIF-a 8 4 also original zinc substrate has been shown in an external view optional additional vibration modes, in particular 176 cm^-1 And 284 cm^-1 Observed at peak (peak) is mounted non-specific Zn-a N ZIF-a 8 structure has been identified. The, said zinc metal substrate even when the four-way dodecahedron morphology ZIF-a 8 - specific domain connection as a mask is enabled and the organic structure can be added instead.

In addition, according to one embodiment of the present invention, the thickness of said metal substrate formed in a continuous manner for thin metal - organic structure like a film may be 450 nm or more, more preferably 0. 40 Micro m - 500 micro m implementation being. If less than 450 nm thickness of metal - metal substrate even when the protrusions organic structure continuous film-like the former into a difficult up, said range of now.

Specifically, according to one embodiment of the invention therefore also 24 Figure 26 shows a film thickness on a glass substrate to a semiconductor sample of SEM pictures and PXRD pattern and the film is formed by HKUST-a 1, 27 according to one embodiment of the invention 500 nm thin copper shaped to the glass board SEM photograph, picture and EDS spectrum exhibits EXD mapping.

Figure 25 shows a thin copper thickness is operated also HKUST-a 1 24 and also shaped to SEM photograph of the PXRD pattern of Figure 26 and glass board reaction, different thickness copper thin film glass substrate (25 (a): 100 nm, (d): 200 nm, (g): 300 nm, (j): 400 nm, (m): 500 nm,) is used as the precursor of a catalyst metal are disclosed. In Figure 25 24 also studied to confirm, reaction of the respective thicknesses of the PXRD pattern is shown in Figure 26 is a sliding of a copper thin film representing HKUST-a 1, also 24 (a), 24 (b) and (c) as shown in the variation also 24 also, with the case of using copper thin film thickness 100 nm cannot precision continuous thin film form. But, 200 nm or more copper thin film for use in copper thin film is formed continuously with the presence of domains HKUST-a 1 approximately 93 nm thickness occurring but, appears to be the degree of empty spaces as signal peptides.

However, as can be also 24 by selecting a (m), with the case of using copper thin film thickness 500 nm for all HKUST-a 1 domains substantially approximately 393 nm thickness of copper thin film is formed continuously present can be molecules. The, operation 500 nm or more copper thin film necessary number HKUST-a 1 film can be know.

On the other hand, the present invention refers to, metal substrate; said metal substrate and at least a portion of said organic thin film is de-protonated ligand ligand surface thin film is formed, metal oxide oxidation number, number additive including a porous metal - organic structure of a metal ion diffusion billion number (Metal provided Organic Framework) thin film number [...] substrate.

Wherein, said thin film is represented by the formula 1 units to form a continuous structure including bar, said oxide of said metal ingredient "M" formula 1 to the metal substrate are arranged to combine said number de protonated organic metal ions or metal-containing metal represents, "L" is said to form a structure molecules capable of organic metal as organic - which, the open coordination sites "SOL" metal - organic structure engageable with metal ions and molecules, this is mainly ascribable devoted greater possibility solvent composed of synthetic process. In addition, open coordination sites of the metal by applying heat and vacuum SOL number is associated with the wetting ability can be, when exposed to other solvent can be exchanged.

[Formula 1]

[M_x (L)_y (SOL)_z ]

The Cu M in formula 1⁺ , Cu²⁺ , Cu³⁺ , Zn²⁺ , Ni²⁺ , Ni³⁺ , Co²⁺ , Co³⁺ , Fe²⁺ , Fe³⁺ , Mn^{2 +} , Mn³⁺ , Cr²⁺ , Cr³⁺ , VO^{2 +} , Ti⁴⁺ , Sc²⁺ , Zr²⁺ , Mo²⁺ , Ru²⁺ , Ru³⁺ Pd²⁺ , Cd²⁺ , Hf⁴⁺ , Mg²⁺ , And Ca²⁺ 1 Species can be selected from the group consisting more.

Said L of formula 1 the oxalate (Oxalate), malonic acid (Malonate), three sour this [thu (Succinate), isophthalate (Isophthalate), terephthalate (Terephthalate), sheet with it buys the salt (Citrate), tree maul tax [thu (Trimesate), 1, 2, 3 - triazole (1, 2, 3 a-Triazole), fatigue d oh the [ley which will doze the [thu (Pyrrodiazolate), 2 - methyl imidazole rate (Imidazolate) and imidazole rate (2 a-Methylimidazolate) can be at least one selected from the group consisting 1 comprising.

SOL of formula 1 with an open coordination sites as solvent molecules, preferably open coordination sites with soil or any solvent molecules to metal - organic structure which, as an example, said solvent water molecules (water), methanol (methanol), ethanol (ethanol), 1 - propanol (1 a-propanol), 2 - propanol (2 a-propanol), 1 - butanol (1 a-butanol), 2 - butanol (2 a-butanol), acetone (acetone), 2 - butane on (2 a-butanone), tetrahydrofuran mixable (tetrahydrofuran), triethylamine (triethyl amine), amide (dimethyl-a formamide) - dimethyl formaldehyde, dimethyl sulfoxide (dimethyl sulfoxide) can be at least one selected from the group consisting of comprising 1.

The integer number of 1 to 6 of formula 1 x, y is integer number of 1 to 12, z is an integer 0 to 24.

Such as repeated units represented by said formula 1 units of said organic ligand is a continuous-structure said thin film metal ions or metallic atoms and strong binding by using a metal substrate, said thin film having strong binding capability is equal to said metal.

According to the present invention, organic metal substrate comprising said identifier is said metal atom or organic groups can be combined, such functional groups are, e.g., and polyester, hydroxy, amine (amine group), [...] Sues (mercapto group) consisting of at least one selected from the group consisting (azole group) and can be more. The, said metal ions or said metallic atoms and by combining functional groups is, equal to or higher than said metal thin film is also more coupled to mating forces.

Said porous metal - organic structure such as a thin film including a crystalline form of number produced therewith may have (crystalline structure), the shape of the crystalline substance are placed in a grid (lattice) arranged regularly repeated (repetition) indicates a shape having structure, typically X - ray diffraction pattern analysis (X-a ray diffraction pattern: XRD pattern) can be identified.

In addition, said porous metal - organic structure thin film may have its own vibration mode. This guest molecules, solvent molecules, ligand, metal, and metal can be up the coordination between a coupling, the metal - organic structure thin film is different from the metal precursor or other material which can exhibit a Raman vibration (Raman vibration), through analysis and identification can be Raman spectrum (Raman spectrum).

In addition, porous metal - organic structure - ultraviolet (UV-a vis) visible in said thin film can exhibit a unique electronic transitions (Electronic transition). For example, transition metal ion can be observing specific spectrum due to d a-d, this ultraviolet - visible light spectrum (UV-a vis spectrum) can through analysis and identification.

Hereinafter, preferred embodiment of the present invention to aid in understanding a number decodes (example). But, in the embodiment of the present invention is to form a pavement for aiding understanding only, not the limited portion in which a testing process by the present invention.

[Preparation example]

1. Number of bath copper substrates

Copper substrates is cut into a 25 mm x 15 mm and Royal. Then, 10% Alconox cells 30 minutes and ultrasonic treatment the number which has been toasted copper substrate placed in an aqueous solution, and unreacted acetone bath copper substrate (Acetone, purity 99%, Duksan yarn) and distilled water deionization (Distilled deionized water, Merck Millipore, use MQ Direct 8) good for repulsion, nitrogen atmosphere was stored.

2. Thereby the copper thin film glass substrate number bath

The glass substrate 25 mm x 15 mm and cut into the work through. Then, the 30 minutes and ultrasonic treatment number 10% Alconox cells placed in an aqueous solution which has been toasted glass substrate, glass substrate coated with a ultrasonic treatment (Distilled deionized water) distilled water deionization and acetone (Acetone) good for repulsion, sulfuric acid and hydrogen peroxide solution mix the 3:1 30 minutes immersion-gate. Then, sulfuric acid and hydrogen peroxide water treatment is good for a glass substrate coated with a distilled water deionization (Distilled deionized water) is carried out after nitrogen the wind very dry. Dried glass substrate via sputter deposition method (sputter deposition method) 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 800 nm copper thin film made from the height and produce, thereby the copper thin film was stored in a nitrogen ambient under glass.

3. Number of zinc bath

Zinc substrate is hand grinder (rotating polisher) through oxidation polished aluminum powder, and cut into a 25 mm × 15 mm was prepared. Then, 10% Alconox cells 30 minutes and ultrasonic treatment the number which has been toasted zinc substrate placed in an aqueous solution, and deionization (Distilled deionized water) distilled water bath zinc substrate is acetone (Acetone) good for repulsion, nitrogen atmosphere was stored.

4. A polymer which contains de a BTC^3- Ligand Solution number bath

21. 4 G tree with actinic radiation acid (1, 3, 5 a-benzenetricarboxylic acid: H₃ BTC, purity 98%, Alfa yarn) after solvent bottle packed, distilled water was added 100 g of deionization (Distilled deionized water). Tree with actinic radiation acid (1, 3, 5 a-benzenetricarboxylic acid, H₃ BTC) of volcanic ash 30 and includes a synthetic resin material. 4 G of triethylamine (Triethylamine, purity 99%, Alfa yarn) into solvent bottle is carried out after 30 minutes after solvent bottle closing one phase with stirring until the solution and ultrasonic treatment (Phase) chains.

5. A polymer which contains de a MIm^- Ligand Solution number bath

8. 3 G of methyl imidazole (2 a-Methylimidazole, HMIm, purity 99%, Aldrich yarn) after solvent bottle packed, 100 g of distilled water deionization (Distilled deionized water) through the main body. Methyl imidazole (2 a-Methylimidazole, HMIm) powder in relation to element being 10. 1 G of triethylamine (Triethylamine, purity 99%, Alfa yarn) was added to the solvent bottle. Next solvent bottle after closing, and ultrasonic treatment 30 minutes with stirring until the solution one phase (Phase) chains.

6. APS Number bath solution

4 G of (Ammonium persulfate, purity 98%, Aldrich yarn) after solvent bottle packed with sulfuric acid ammonium, distilled water was added 5 g of deionization (Distilled deionized water). Next solvent bottle after closing, one phase (Phase) solution with stirring until chains.

[In the embodiment]

<In the embodiment 1> HKUST-1 Number bath is operated copper substrates

Such as for table 2, prepared in example 4 de-protonated BTC number produced therewith^3- Ligand solution 9 ml 3 ml distilled water deionization on (Distilled deionized water), as prepared in example 1 ml acetone (Acetone) number added with sulfuric acid ammonium (Ammonium persulfate, purity 98%, Aldrich yarn) to number 6 and number prepared by the oxidation solution 0. 5 Ml glass reactor pressure is lowered after enemy in preparing his high pressure liquid coolant mix solution number.

Then, mix solution prepared by the number 65 °C to about 20 minutes in example 1 to prepare a mixed solution heated by a heated copper substrates prepared by the number 5 minutes have been immersed in a ((RS component codeL 159 - 5773) Copper non-clad laminate board). To provide a copper substrate is (Distilled deionized water) distilled water deionization substances while using HKUST-a 1 film on ethanol (Ethanol, purity 99. 9%, Duksan yarn) in a volume ratio of 1:1 is blended solution after washing argon (Ar) filled with a glove box for archiving substrate.

<In the embodiment 2 - 23>

Said table 2 and table 3 - 4 as shown in the bright, copper substrates of the same method in the embodiment 1 and the early morning gun number differently point number [...] HKUST-a 1 the film is formed copper substrate number was high pressure liquid coolant.

<In the embodiment 24> HKUST-1 Number bath is operated including copper thin glass substrate

As shown in the table 5 a, prepared in example 4 de-protonated BTC number produced therewith^3- Ligand solution 9 ml 3 ml distilled water deionization on (Distilled deionized water), as prepared in example 1 ml acetone (Acetone) prepared with sulfuric acid ammonium oxidation number 6 and number added to 0 (Ammonium persulfate) solution. 5 Ml glass reactor pressure is lowered after enemy in preparing his high pressure liquid coolant mix solution number.

Then, mix solution prepared by the number 65 °C to about 20 minutes to prepare a mixed solution prepared in example 2 is heated heated cigarettes but 5 minutes a 800 nm copper thin film glass substrate (Marienfeld) immersing the substrate. To provide a copper thin film he HKUST-a 1 substances while using the glass substrate (Marienfeld) on ethanol (Ethanol) is 1:1 volume ratio mix the distilled water deionization (Distilled deionized water) solution after washing (Ar) was filled with argon glove box for archiving.

<In the embodiment 25 - 29>

As shown in the to table 5, the same method in the embodiment 24 [...] point number in order to make a thickness thin film of glass substrate and the glass substrate is operated including copper thin HKUST-a 1 number was high pressure liquid coolant.

<In the embodiment 30> ZIF-8 Number bath zinc substrate is formed on the substrate

Such as to table 6, example 5 prepared in de-protonated MIm number produced therewith^- Ligand solution 3 ml distilled water deionization (Distilled deionized water) on 7 ml, 1 ml and oxidation number number added as acetone (Acetone) hydrogen peroxide (Hydrogen peroxide: H₂ O₂ ,28 Weight % in H2O, Duksan yarn) solution 0. 5 Ml glass reactor pressure is lowered after enemy in preparing his high pressure liquid coolant mix solution number. Then, mix solution prepared by the number 65 °C to about 20 minutes heating, zinc substrate heated mixed solution ((0. 25 Mm thick): purity 99. 98%, Alfa yarn) have been immersed in a 30 minutes. ZIF-a 8 substances while using distilled water (Distilled deionized water) with thin film on volume ratio 1:1 methanol (Methanol) zinc substrate is deionization is filled with argon (Ar) mix the solution after washing was stored in the glove box.

<In the embodiment 31 - 38>

As shown in the to table 6, and the same method in the embodiment 30 the number of dipping time point different zinc [...] ZIF-a 8 high pressure liquid coolant are formed zinc substrate his number.

<In the embodiment 39> HKUST-1 Is operated Copper network Number bath

Such as to table 7, prepared in example 4 de-protonated BTC number produced therewith^3- Ligand on 3 ml 9 ml distilled water deionization (Distilled deionized water) solution, prepared as in example 1 ml acetone (Acetone) added as number 6 (Ammonium persulfate) solution with sulfuric acid ammonium oxidation number 0 and prepared. 5 Ml glass reactor pressure is lowered after enemy in preparing his high pressure liquid coolant mix solution number. Then, mix solution prepared by the number 65 °C to about 20 minutes heating, heated mixed solution 20 mm x 20 mm copper network area 5 minutes immersion chains. In case substances while using HKUST-a 1 to provide a copper film on ethanol 1:1 volume ratio mix the solution is distilled water deionization (Distilled deionized water) (Ethanol) argon (Ar) after washing was filled with a glove box for archiving.

[Comparison example]

<Comparison example 1 - 6>

Such as of the following table 8, copper substrates of different number and early morning gun point number [...], example 1 was prepared with copper substrate film in the embodiment 1 according to HKUST-a 1 number and high pressure liquid coolant.

<Comparison example 7> HKUST-1 Synthesis

As shown in the table 9 to, each container Copper nitrate trihydrate (Cu (NO₃ )₂ It 3H₂ O (0. 87 G, 3. 6 Mmol), purity 98. 0 - 103%, Alfa yarn) 10 ml distilled water deionization of a dissolving (Distilled deionized water), BTC (0. 22 G, 1. 0 Mmol) dissolved in 10 ml of ethanol (Ethanol) with respect to a. Then, Cu (NO₃ )₂ BTC is dissolved in the solution is dissolved quickly adding solution container, 10 minutes is mixed uniformly at room temperature. Then, 1 ml of dimethyl N-a N the form probably the id (N, N-a dimethylformamide: DMF, purity 99. 5%, Duksan yarn) adding solution mixing, PTFE tape securely sealing limit after a container, said container 80 °C 20 hours reaction to proceed been heated in an oven to a mixed solution. After this the, cooling said heated in an oven at room temperature was taken out of the container. Distilled water deionization (Distilled deionized water) and ethanol (Ethanol) reaction using the undesirable materials are number after wetting ability, blue water in powder form (H₂ O) and ethanol (Ethanol) is coordinated HKUST-a 1 solvates ([Cu₃ (BTC)₂ (H₂ O)_x (EtOH)_{3 A-x} ], X=1. 0 - 2. 0) Obtained a.

<Comparison example 8> ZIF-8 Synthesis

As shown in the table 9 to, each container Zinc acetate dehydrate (Zn (CH₃ COO)₂ 2H-like₂ O (0. 175 G, 7. 9 Mmol), 98% purity, Aldrich yarn) and 2 - methyl imidazole (2 a-Methylimidazole, HMIm) (0. 263 G, 3. 2 Mmol) dissolved in 40 ml of methanol (MeOH) with respect to a. Then, 10 minutes is mixed uniformly at room temperature. Then, PTFE (Polytetrafluoroethylene) using the sealing container was rigid. Next, a mixed solution container 50 °C 24 hours in an oven to said reaction of abortion. Then, cooling said heated in an oven at room temperature was taken out of the container. (Distilled deionized water) and methanol (MeOH) reaction using distilled water deionization undesirable materials after a number of special paper, white powder form ZIF-a 8 powder [Zn (MIm)₂ ] Obtained a.

[Experiment example] HKUST-1 The film is formed copper substrate via

<Experiment example 1>Of copper substrates HKUST-1 Identifying film production

In the embodiment 1 in number of PXRD pattern for generating high pressure liquid coolant copper substrate placed on SEM observation photograph HKUST-a 1 and 2 also shown to fig. 19.

Specifically, measuring said PXRD pattern is 2 θ is 4. In 5° 55. Have been measured between 5°, PANalytical diffractometer yarn Empyrean with a monochromatic nickel non-filtered Cu K α beam) it has been determined that by. Said SEM - platinum alloy (Au-a Pt alloys) and is saved in the gold coated sample expected to have a 3 nm, 3 kv acceleration voltage has been measured under measuring conditions, it has been determined that by Hitachi yarn FE-a SEM S-a 4800. As shown by the experiment examples and is even applied to the same.

By using a small sample number when such as in the embodiment 1, as shown in the PXRD pattern of (i) of Figure 2, generation of the naked eyes were blue HKUST-a 1 film. In addition, (b) to (d) as shown in the variation also 19 19 also, each reaction time 10 seconds, 30 seconds, 1 minute, 2 minutes, 4 minutes and 3 minutes when maintained for growing an indirectly-cream, reaction time 5 minutes 10 minutes (e) to 2 (f) and each also 2 as shown in the (i) also 19 and also, SEM photograph HKUST-a 1 through specific octahedron's morphology with identifying domain coupling results in a method of forming thin due first call request.

In addition, in order to identify whether or not a further metal - organic structure, UV-a vis absorption spectrum in the range of 350 nm - 1250 nm using a Cary 5000 UV-a VIS-a NIR spectrophotometer Agilent yarn were measured. As shown in the 2 (j) also, as compared to the original copper substrates (bare Cu0 plate) HKUST-a 1 film is generated copper substrate in an external additional 590 nm or more wavelengths of visible light absorption region has been measured, this HKUST-a 1 of Cu²⁺ Ion by d a-d transition to her.

In addition, metal - organic structure in order to identify when the mode of vibration of the unique Raman (Raman) estimating the spectrum, this Thermo Scientific yarn has been measured by Nicolet Almega XR dispersive Raman spectrometer. As shown by the experiment examples and is even applied to the same. (K) also 2 such as compared to the original copper substrates with an additional vibration modes of HKUST-a 1 film is generated copper substrate have been an external view, in particular 178 cm^-1 The specific structure of binding observed at an upper surface of a flexible vibration HKUST-a 1 Cu-a Cu as signal peptides.

The, method of said in the embodiment 1 is to provide a copper substrate of the washing tank 5 HKUST-a 1 film successfully at a number has been confirmed.

<Experiment example 2>Added according to number type HKUST-1 Film production method for checking

In the embodiment 6 - 9 in the embodiment 1 and high pressure liquid coolant in number in order to identify whether PXRD pattern of copper substrate HKUST-a 1 film production units SEM photograph of him.

(A) sample 1 of Figure 7 (Sample 1: acetone (Acetone)) are symmetrically 6 as shown in the variation, adding acetone (Aceton) saturation of blue HKUST-a 1 film number appears to the naked eyes and to selectively generation of film, even when identifying HKUST-a 1 PXRD pattern of cream, SEM photograph HKUST-a 1 through specific octahedron's morphology may be liberal in formation of films were.

The, number added to acetone (Aceton) when used with copper substrates has been confirmed that the number of the washing tank HKUST-a 1 film successfully.

However, in the embodiment 6 in process for addition of knight reel number (MeCN (of Figure 7 Sample 2 (Acetonitrile), 6 (b) also), in ethanol (Ethanol) in the embodiment 7 (of Figure 7 Sample 3 (ethanol (Ethanol), also 6 (c)), in the embodiment 8 in dimethyl the form probably the id (N, N-a dimethylformamide: DMF), of Figure 7 Sample 4 (DMF), 6 (d) also), and in the embodiment 9 (Distilled deionized water, of Figure 7 Sample 5 (Water), 6 (e) also) in distilled water deionization when adding, 5 also are symmetrically 6 as shown in the variation, it sells really identifying HKUST-a 1 15 domain appears to room, PXRD pattern in HKUST-a 1 components having been pattern cannot confirm it.

The, a number added to acetone (Aceton) number [...] impossible when the substrate is also used for a copper film HKUST-a 1 number tank, through, other polarization is lower than the number added acetone (Aceton) whiteness number billion through diffusion of copper ion eluted copper the borad it stands used for surface reactions can be found.

<Experiment example 3 Added>number dose according to HKUST-1 Film production method for checking

In high pressure liquid coolant in the embodiment 1 - in the embodiment 5 PXRD patterns in order to identify whether number of copper substrate HKUST-a 1 generating units SEM photograph of him.

As shown in the variation also 9, PXRD pattern consisting of adding another amount of acetone (Aceton) number in the case of other products in the embodiment 2 - in the embodiment 5 HKUST-a 1 film has been confirmed that the other is not.

Further, as shown in the variation also 8, other volumes of acetone (Aceton) SEM in a photograph number added by making the copper substrates created on the HKSUT provided 1 thin film domain size has been confirmed that the reaction speed control device. Through, the greater the relative amount of mixed solution in acetone (Aceton) adjust HKUST-a 1 domain size is attained, it grows in the form of form of a non-island by HKUST-a 1 domain has been confirmed.

Through, the relative amounts of acetone (Aceton) whiteness low polarization variation according to polarization solution according to control copper be eluted under ion conductive copper substrates can be confirmed.

<Experiment example 4>According to reaction temperature HKUST-1 Film production method for checking

In the embodiment 10 - 11 in the embodiment 1 and high pressure liquid coolant in number in order to identify whether PXRD patterns of copper substrate HKUST-a 1 generating units SEM photograph of him.

As shown in the 11 also, in PXRD pattern 25 °C, 45 °C, 25 °C reaction temperature of 65 °C and during other than thin film on small number which in the case of including in the embodiment 10 HKUST-a 1 has been confirmed.

Further, as shown in the 10 also, in the case of the 25 °C and 45 °C 65 °C in a photograph number [...] SEM reaction temperature and reaction temperature including in the embodiment 10 - 11 non-linear domains concurrently present domain specific octahedron HKUST-a 1 has been confirmed. This number has been identified and a reaction temperature 65 °C [...] an amorphous polymer is created.

<Experiment example 5> De-protonatedBTC^3-According to copper substrates tendency of dose

In the embodiment 12 - 13 in the embodiment 1 and high pressure liquid coolant in number in order to identify whether PXRD patterns of copper substrate HKUST-a 1 generating units SEM photograph of him.

As shown in the 13 also, BTC protonated at the PXRD pattern^3- HKUST-a 1 phase relative small amount without affecting the have a relatively large number used to confirm, as shown in the variation also 12, SEM photograph at the protonated BTC^3- The relative amounts of the HKUST-a 1 for automatically adjusting size of domain may be confirmed. In the embodiment 12 - 13 de-protonated BTC in solution mixed in^3- The greater the relative amount extends HKUST-a 1 domain size has been confirmed from the base plate. Through, more de-protonated BTC^3- The HKUST-a 1 affecting nucleation can be confirmed.

<Experiment example 6>Steel number DiffusedLigand Solution according to copper substrates via

In the embodiment 14 in form of copper substrates prepared by the number generating excessive copper ion diffusion in SEM photograph of his units in order to identify HKUST-a 1.

Further, as shown in 14 (a) also, the copper ion diffusion of steel number conducting experiments. The support of the original copper color initially before reaction with copper substrates, wherein the stirred reaction tank into the same magnetic rod 1150 rpm reaction of abortion. After reaction, also as shown in the (b) 14, the HKUST-a 1 film is assumed is a region of the blue copper substrates depending on the direction distribution by having the reaction for diffusion of solutions containing other optical microscope has been confirmed. (C)- (g) as shown in the variation 14 also, depending on the direction for diffusion of solutions containing each regions of the wafer positioned such as not having any form of example 1 experiment result said continuous film has been confirmed.

Through, low polarization degrees due to copper ion diffusion billion in situ growth method is essential conditions in a reaction solution number can be predetermined position.

<Experiment example 7> A polymer which contains de Not Ligand Solution according to copper substrates via

Comparison example 1 - 4 in number in order to identify whether the patterns of high pressure liquid coolant copper substrate HKUST-a 1 generating units PXRD SEM photograph of him.

Also 16 as shown in the variation, in the PXRD pattern of linseed (Triethylamine) basic molecular reactive solution added ethyl tree by not including in the case of comparison example 1 - 4 of de proton not ligand HKUST-a 1 didn't found. In particular Sample 4 [Abs. TEA 360 min (DMF)] in the case of copper (I) oxide film of copper oxide (Cu₂ O) of been found.

In addition 15 on a SEM photograph also as shown, the form of octahedron of didn't found any HKUST-a 1. This method of treatment for in situ growth has been in coordination's de proton exhibit substrate.

<Experiment example 8>Oxidation number is mixed solution in the copper substrate via-free

In comparison example 5 - 6 PXRD patterns in order to identify whether number of generating high pressure liquid coolant copper substrate HKUST-a 1 SEM photograph of his units.

As shown in the variation also 18, a reactive solution with sulfuric acid ammonium (Ammonium persulfate) PXRD pattern in the case of example 5 - 6 in number compared to the crystalline oxide, copper substrates of HKUST-a 1 in the phase of the reaction pressure was not found, of Figure 17 SEM photograph as identified, of the form of octahedron didn't found any HKUST-a 1.

Through, and the elution of the metal ions is also used for condition number oxide has been the presence of metal the borad it stands can be.

<Experiment example 9>According to reaction time HKUST-1 Film production method for checking

In the embodiment 15 - 23 in number in order to identify whether the patterns of high pressure liquid coolant copper substrate HKUST-a 1 generating units PXRD SEM photograph of him.

As identified in a photograph of Figure 19 SEM, reaction time of 10 seconds to 10 minutes with his observing the surface of a sample. 10 Seconds with the reaction time of the surface of a sample (19 also (b) reference) of the original copper substrates relatively small unlike some ten nanometers formed small domains as signal peptides.

However, when increasing the reaction time, 4 - 5 micro m with generation of the octahedron HKUST-a 1 domain size of cream, approximately 1 min. after interaction between growth (Intergrowth) by compressing the reaction time domain has been confirmed. 5 Minutes then metal - organic structure after a lapse time responses are performed completely mutual growth (Intergrowth) domain and a continuous film were confirmed in the form of the pass. Further, also 2 (j) PXRD pattern of a metal thin film as, reaction time 10 seconds after each sample is of HKUST-a 1 liquid crystal layer has been confirmed.

In addition, metal - organic structure form a dielectric thin film growth Volmer-a Weber (Island growth) verify (after approximately 5 minutes reaction time) for finished thin film thereafter additional SEM photograph of the reaction time was further applied reaction degree units. As identified in a photograph of Figure 20 SEM, critical thickness between about 3 - 5 micro m at least correspondingly thin film growth, growth of thickness of thin film that terminates its own (Self-a termination) has been identified. This also 23 as shown in the variation, HKUST-a 1 cage (Cage) window (Window) size (Ammonium persulfate) with sulfuric acid ammonium, hydrogen atoms bonded to one tri-ethyl ammonium (Triethylammonium (HTEA⁺ )), BTC^3- (22 Also reference) is smaller than that, they react with exposed copper substrates in solution penetrates into the pores of the metal - organic structure oxidation number, and ligand are not react with copper can be caused in the developing interprets. Further, as identified in Figure 21, HKUST-a 1 and a copper PXRD pattern even after additional reaction in another pattern is not yet.

<Experiment example 10> Copper layer Glass out of the Copper film Thickness measurement

Such as shown in the to table 2, the density of the copper atoms in each volume of metal copper HKUST-a 1 84. 69 Atoms/nm³ And 2. 63 Atoms/nm³ About 32. 26 Times been show differences in density copper atoms. This information calculated based on the area of a specific thickness in HKUST-a 1 film thickness of metallic copper link is generated by computing, 4000 nm thickness of film thickness HKUST-a 1 124 nm copper, the thickness of the film thickness of 5000 nm HKUST-a 1 155 nm copper, and 6000 nm thickness of copper is required HKUST-a 1 186 nm film thickness is also used for can be.

In order to compare the theoretical information which correlates empirical measures, such as to table 10, in the embodiment 24 - 28 in 100 nm, 200 nm, 300 nm, 400 nm, 500 nm copper thin film glass substrate HKUST-a 1 thereby the metal ions as precursors to his database. In Figure 25 thereby the copper thin film such as glass substrate (also 25 (a): 100 nm, also 25 (d): 200 nm, also 25 (g): 300 nm, 25 (j) also: 400 nm, also 25 (m): 500 nm,) when metal is used as the precursor of a catalyst, such as the illustrated form layer 24 of Figure 25 and also to gain. In addition, copper thin films are also 26 as shown in the PXRD pattern but the reaction is measured thickness of HKUST-a 1, also 24 (a)- (c) such as copper thin film thickness 100 nm also 24 for use in the form of a film corresponding to the condition has been continuous. Also, a thickness of at least 200 nm copper thin film for use in the presence of an identifying but continuously domains HKUST-a 1, some empty spaces are not present but, all of 500 nm thickness with the case of using copper thin HKUST-a 1 domains 24 by selecting a continuously the presence (m) also can be. As well, such as in the embodiment 29, even in the use of copper thin film using copper thin film thickness 800 nm 500 nm thickness with less HKUST-a 1 domains of continuous present can be expected.

Through, the reference experiment example 9 together, in the form of islands (island) generated in an initial reaction solution HKUST-a 1 domain with sulfuric acid ammonium (Ammonium persulfate) or BTC below metals are HKUST-a 1 domain^3- Number by supply of metal head is relayed removal were expected. The, outer peripheral metal has been exhausted HKUST-a 1 domain not peripherally and extending horizontally are generated new HKUST-a 1 domain were each domain.

As a result, such as at least 500 nm or more copper thin film in the embodiment 24 - 28 HKUST-a 1 condition identifying number operation can be necessary.

Ratio^a:The ratio of the parameters of metallic Cu over the parameters of HKUST-a 1

Example 11><experiments using copper network checking HKUST-a 1 film production

In high pressure liquid coolant in the embodiment 39 copper network number in order to identify whether SEM photograph of his HKUST-a 1 generating units.

General method in that it is difficult to thin film high surface curvature smaller number, in case copper used experiments, 3 (a) to 3 (d) and (d) also 28 also appears also as, copper with a surface shape and high curvature. In the embodiment 39 8 used in a high curvature. 0 × 10⁴ m^-1 Copper voice number HKUST-a 1 film work grudge result, as shown in the (h) 28 also, in spite of high curvature continuous rigid HKUST-a 1 film number is also used for capable of an output transistor can be small.

This is effected by insuring, copper metal on a surface of high curvature method using neural HKUST-a 1 can be is also used for forming a film.

<Experiment example 12>Of copper substrates HKUST-1 Film for bonding between the substrate and the confirming

In high pressure liquid coolant in the embodiment 1 number of mechanical stability generated copper substrate reaction after HKUST-a 1 film units in order to identify whether SEM photograph of him.

Metal - organic structure practical for use as a thin film of a thin film substrate adhesion force between a must be high substrate. Such a mechanical bond certification for ethanol in the embodiment 1 to a beaker is put in a sample ultrasonic treatment whereupon the texturing. Adhesion between the thin film and second mode is generally can be separated from the substrate.

Just, as identified in a photograph of Figure 30 SEM, 60 minutes despite ultrasonic treatment, most of the gas to adhere over the copper substrate HKUST-a 1 domain.

This is effected by insuring, identifying a strong adhesive metal copper substrates can be inter - organic structure, BTC coordination's and polyester reaction surface includes or copper ions (Carboxylate group) of copper atoms can be coupled is also used for generation ratio.

<Experiment example 13>Zinc substrate ZIF-8 Checking thin film deposition

In the embodiment 30 of generating high pressure liquid coolant in number in order to identify whether a reacted zinc PXRD pattern SEM photograph was observing HKUST-a 1.

In the embodiment 30 equal to when performing, the naked eyes were colorless ZIF-a 8 to the glass substrate. (B) 4 also identified in a PXRD pattern of as, in addition to the metallic zinc cream PXRD pattern ZIF-a 8 thin film identifying additional PXRD pattern been cannot confirm it. In addition, as also identified in a photograph (a) SEM of 4, put in connection with four-way dodecahedron morphology of ZIF-a 8 domain identifying method of forming thin due first call request.

On the other hand, metal - organic structure in order to identify when the estimating the spectrum of Raman specific vibration mode, as shown in the 4 (b) also, as compared to the original zinc substrate with an additional vibration modes of ZIF-a 8 thin film is generated zinc have been an external view, in particular 176 cm^-1 And 284 cm^-1 Observed at peak (peak) is mounted non-specific Zn-a N ZIF-a 8 structure has been identified.

The, method of thin film having a film on a substrate to said in the embodiment 30 ZIF-a 8 zinc has been confirmed that the number of the washing tank successfully.

<Experiment example 14>Zinc substrate according to reaction time ZIF-8 Checking thin film deposition

In the embodiment 30 - 38 high pressure liquid coolant in number in order to identify whether reaction copper substrate generating SEM photograph was observing HKUST-a 1.

(C) 29 also as shown in the variation, the service cannot be executed after confirming from 1 minutes reaction time of phase are made to the start but, since approximately 5 minutes (island) are generated in a form of thin film appears to a four-way dodecahedron determining ZIF-a 8 starts when the island, approximately 30 minutes to produce a ZIF-a 8 continuous film has been confirmed.

<Experiment example 15>Zinc substrate exposed to iodine HKUST-1 Film measuring electric conductivity

To provide a copper substrate film in the embodiment 1 in number prepared by the HKUST-a 1 iodine (Iodine: I₂ , Purity 99. 5%, Aldrich yarn) for measuring the electrical conductivity of film exposed HKUST-a 1, 2 in the form of a copper electrode in an electrode current - voltage curve and HKUST-a 1 electrode electrochemical impedance spectrum observing her.

This current - voltage curve (V) in the range of - 1000 mV - 1000 mV voltage is measured. Using CHI 604E electrochemical potentiostat CH Instruments yarn were measured.

AC 600 mV electrochemical impedance spectrum measuring conditions, in frequency DC 50 mV 30 × 10⁶ Hz - 0. 1 Hz were measured between. Solartron Analytical yarn were measured using SI1260 Impedance/Gain provided Phase analyzer.

(A) as shown in the 5 also, current - voltage curve but the original HKUST-a 1 film (pristine HKUST-a 1 film) of "0" or near cathode-ray-tube properties, iodine vapor HKUST-a 1 - voltage curve slope when the exposed film specific mistletoe.

Through, iodine vapor exposed conductive film determining HKUST-a 1 cream, about 5. 1 ΜS system of mistletoe.

Further, as shown in the (b) also 5, such as sample exposed to iodine vapor HKUST-a 1 film electrochemical impedance spectrum result, conduct through a predetermined position at the end of the resistance value in the form of semi-right cream, iodine vapor exposed HKUST-a 1 film is about 3. Conductivity of 3 μS mistletoe.

Through, in the case of iodine with identifying point exposed HKUST-a 1 film conductivity cream, this film exhibits by iodine electrochemical sensor may be used as said HKUST-a 1.

Or more, the present invention embodiments detailed but a preferred embodiment and experiment example, the present invention refers to said in the embodiment and process by the experiment without limit, technical idea and scope of the present invention in person with skill in the art in was found by several modified change is pivotably.