KR101195079B1 - METHOD FOR COATING THIN LAYER INCLUDING p-type AND n-type ZINC OXIDE - Google Patents

Abstract

The present invention discloses a coating method of a thin film composition containing a p-type and an enzymatic zinc oxide. The coating method of the thin film composition is a method of coating a thin film composition containing a p-type and enzymatic zinc oxide on the surface of the object, zinc acetate solution, Mn, Li, Pt, Ag, V2O5, WO3, Bi, Ni , Zinc oxide coating composition and zinc acetate solution containing at least one or more selected from the group consisting of CoO, Mg, La, Y, carbon, Cu, N, Se, B2H6, Al, V, Preparing an en-type zinc oxide thin film composition containing at least one selected from the group consisting of Fe, Ti, Ta, Nb, and Ga (step 1); The prepared P-type and en-type zinc oxide thin film composition was put into a rotating drum of a grinding ball mill to further nanoparticles and filtered through a membrane filter of 20 nanometers or less to obtain a P-type and en-type zinc oxide thin film composition (Step 2). ); And a dry film thickness of 1 to 2 µm by mixing the P-type and N-type zinc oxide thin film composition with a water-soluble binder silane (O-Si-O) n. It is characterized in that it comprises a step of heat-treating the heat treatment for 1 to 24 hours at 200 ~ 900 ℃ after coating on the metal as possible.

  P-type zinc oxide, N-type zinc oxide, Zinc Acetate aqueous solution, water-soluble silane (O-Si-O) n

Description

Coating method of thin film composition containing P-type and en-type zinc oxide {METHOD FOR COATING THIN LAYER INCLUDING p-type AND n-type ZINC OXIDE}

        The present invention relates to a coating method of a thin film composition containing a p-type and an enzymatic zinc oxide, and more particularly, containing a p-type and en-type zinc oxide on the surface of an object such as a substrate used in various products A method for coating a thin film composition

       Recently, ZnO has received a very special interest. The research started to write GaN electronic device as a substrate, but ZnO electronic device development is being studied because of its interesting physical properties.

         The most important problems in ZnO are (i) the commonly observed n-type conduction and (ii) p-type doping methods for diode fabrication.

ZnO often exhibits n-type conductivity when O is deficient. For many years O vacancies were thought to be the cause of n-type conduction, but through the study of electronic structure calculation, O vacancies are donors with deep energy levels and cannot give n-type electric conduction. On the other hand, although the Zn gap can give n-type electric conductivity, the formation energy is high and it is thought that the amount is very small. Although there is a claim that the effect of H impurities, the cause of n-type conductivity in ZnO lacking O is still controversial.

For ZnO electronics, there must be a clear way to make p-type ZnO. Due to the deep energy level of O, ZnO forms a deep acceptor level even when implanted with group V, N, P, and As elements and does not become p-type doped. Although some p-type ZnO has been reported experimentally, many processes remain for commercialization. Codoping method of group III Ga and group V N, codoping of Be and N, and electron band bond band of As-2VZn complex have been proposed.

       According to Korean Patent Laid-Open Publication No. 10-2009-0089184, the present invention relates to a method of implementing a p-type semiconductor by simultaneously doping ZnO with Li and Group impurities, and simultaneously co-doping Li and Group impurities in ZnO. Receptors made by impurity complexes combined with group impurities

The technical feature is that the energy level of the acceptor is lower than the pure Li acceptor energy level. Korean Patent Registration No. 10-0857461 relates to a p-type ZnO semiconductor film production method using atomic layer deposition and a thin film transistor including a p-type ZnO semiconductor film manufactured by the method, and more specifically, an oxygen precursor and a zinc precursor. A p-type ZnO semiconductor film manufacturing method comprising a Zn3N2 film or ZnO: N film formed by a surface chemical reaction of a zinc precursor and a nitrogen precursor on a ZnO thin film formed through the surface chemical reaction of p-type ZnO semiconductor prepared by the method A thin film transistor comprising a film.

       Zinc oxide is p-en-typed to obtain a p-type and en-type zinc oxide thin film composition, thereby applying energy levels between semiconductors and semiconductors and semiconductors and metals to use light energy as an energy source. By forming electron-hole pairs, efficient surface reactions occur.

       Another object of the present invention is to provide a light-type, en-type zinc oxide thin film composition that can achieve a light weight, simplification of the structure, and capable of rapid processing of a large capacity.

The present invention for achieving the above object is characterized in that to form a P and N type zinc oxide thin film composition to produce a P and N type zinc oxide thin film composition that can use light as an energy source.

         Conventional nanoscale ZnO production methods include organometallic chemical vapor deposition (MOCVD), molecular beam deposition, sol-gel deposition, sputtering, reaction evaporation, spray pyrolysis, pulsed laser deposition, etc. There were many ways. There are various problems in performing such a method, such as controlling the ambient atmosphere such as vacuum state, gas partial pressure, temperature control, purchasing a specimen, and pretreating the specimen.

         Domestic technologies include Photo-MOCVD KAIST: Low cost, highly stable natural surface irregularities ZnO: H technology developed by forced hydrogen doping, Sputter KIER: ZnO: Al fabrication, transparent electrode and window layer of microcrystalline silicon solar cell or CIGS solar cell after chemical etching Used as, low stability in the atmosphere.

         As a foreign technology, LP-MOCVD IMT Neuchatel: A high-quality large-area ZnO: B thin film with natural surface irregularities has been developed and used as a transparent electrode and reflective layer for a-Si: H / μc-Si: H stacked solar cells.

Sputter IPV Julich: ZnO: Al is used as a transparent electrode of high efficiency stacked solar cell through chemical etching. Photo-MOCVD TIT: ZnO: B is used for amorphous silicon solar cell and CIGS solar cell.

         Globally, Korea is recognized for its high technology in the field of semiconductor and ultra-thin liquid crystal display (TFT-LCD). The import dependency rate of raw and subsidiary materials such as gas and wafers, which are used in semiconductor and LCD manufacturing processes, is also over 50%. Knowing which company's equipment or raw materials are used to produce semiconductors and LCDs reveals the overall manufacturing process technology. Therefore, the exact supplier of equipment and raw materials used by LG Philips LCD and Samsung Electronics is not known. However, most of them belong to Japanese firms with original technology, according to industry officials. Although the price of the equipment is kept secret, ULVAC is known to supply sputtering equipment for about $ 10 million. Chemical vapor deposition equipment (CVD), which functions similar to sputtering, also costs $ 10.5 million. In the global market, semiconductor and LCD-related products of domestic companies are sold in huge quantities, but a large portion of them are returned to Japanese companies.

In the present invention, the solution is mixed with a water-soluble binder silane (O-Si-O) n and heat-treated by solution coating to complete the invention.

It is an object of the present invention to provide a coating method of a thin film composition containing a p-type and en-typed zinc oxide.

Accordingly, the present invention provides a method for coating a thin film composition containing a p-type and en-typed zinc oxide on the surface of an object,
Zinc Acetate Aqueous Solution, Mn, Li, Pt, Ag, V2O5, WO3, Bi, Ni, CoO Type Zinc Oxide Coating Composition and Zinc Acetate Aqueous Solution Containing At least One or One Or More Types, Mg En type zinc oxide containing at least one selected from the group consisting of La, Y, carbon, Cu, N, Se, B2H6, Al, V, Fe, Ti, Ta, Nb, and Ga Preparing a thin film composition (step 1);
The prepared P-type and en-type zinc oxide thin film composition was put into a rotating drum of a grinding ball mill to further nanoparticles and filtered through a membrane filter of 20 nanometers or less to obtain a P-type and en-type zinc oxide thin film composition (Step 2). ); And
The P-type and N-type zinc oxide thin film composition is mixed with a water-soluble binder silane (O-Si-O) n to dry film thickness of 1 to 2㎛. It provides a coating method of a thin film composition containing the p-type and en-typed zinc oxide, including; the step of coating the metal surface as possible and heat-treated at 200 to 900 ° C. for 1 to 24 hours (step 3).

According to the above method of the present invention, using zinc acetate (Zn (CH3COO) 2) aqueous solution as the first material of ZnO, it is mixed with water-soluble binder silane (O-Si-O) n, and the solution is coated and heat-treated. The large-area solar cell unit can be produced by the production of N-type zinc oxide thin film composition and the reduction of production cost because it does not use expensive equipment and the production of low-priced high-purity ZnO glass substrate.

1 is a film type zinc oxide (10) thin film composition containing at least one selected from the group consisting of an aqueous zinc acetate solution, Mn, Li, Pt, Ag, V2O5, WO3, Bi, Ni, and CoO; And zinc acetate solution, Mg, La, Y, carbon, Cu, N, Se, B2H6, Al, V, Fe, Ti, Ta, Nb, and at least one selected from the group consisting of An en type zinc oxide thin film composition 20 is prepared. The p-type and en-type zinc oxide thin film composition is installed on one side of the cylindrical or cylindrical cone type, the inlet and outlet 130 is installed to operate the belt 120 by the motor 110 to operate the fine nano-pulverization. The support chamber 100 is provided at both sides of the grinding chamber with respect to the horizontal axis, and the inlet of the rotating drum is used to insert and grind the p-type and en-typed zinc oxide thin film composition by using the cylindrical grinding mill (140). Through the 130, a plurality of ceramic balls 150 and the P-type 10 and N-type zinc oxide thin film composition to be pulverized into the rotating drum 140, together with water, and then as an inlet as a stopper. Membrane, and the motor 110 is rotated to be pulverized and nano-filtered, and filtered through membrane filters 210 and 220 to obtain p-type and en-type zinc oxide thin film compositions. A water-soluble polysiloxane polymer, which is a binder, and a mixture of finely divided particles in a cylindrical rotating drum were mixed at a weight ratio of 100: 120 to 150 to obtain a zinc oxide thin film composition having a dry coating thickness of 1 to 2㎛. After coating the metal 300 as much as possible, it is a flowchart showing that the final fibrous zinc oxide thin film composition 510 is obtained by heating in a high temperature oven 400 at 200 to 900 ° C. for 1 to 24 hours.

        According to the method of manufacturing a photocatalyst coating film as shown in FIG. 1, when the metal surface is coated with P or N type, ohmic contact or Schottky barrier bonding is performed according to a work function between the metal and the coating. When light is applied to this, electromagnetic breakdown occurs due to its properties, and thus the conduction electrons are excited. At this time, excitation due to ionization collision occurs in the zinc oxide particles, and thus the electron-hole pair formed is involved in the redox reaction.

In other words, electron-hole pairs are formed in the individual particles of zinc oxide from the micro perspective, but the p-enzymatic injection of the minority carrier from the macro perspective results in p- and enzymatic coating. As the whole takes the form of an electron-hole pair, the efficiency of the surface chemical reaction of zinc oxide is rapidly increased.

 (a) Surface of the type zinc oxide

H2O + h ⁺ → 2H ⁺ + ½ O2

H2O + h ⁺ → H ⁺ +? OH Radical

? OH + h ⁺ → OH

 2OH → (O) + H2O

h ⁺ → h ⁺ trap (h ⁺ trap: holes captured on the surface)

 (b) The surface of en-type zinc oxide

2H ⁺ + e- → H2

 Surface adsorption O2 + e- →? O2-

? O2 ^{- +} H + → HO2? (peroxo radical)

      The present invention relates to a thin film composition and coating method for the type and enzymatic zinc oxide, more specifically, consisting of a zinc acetate solution, Mn, Li, Pt, Ag, V2O5, WO3, Bi, Ni, CoO Thin film composition and zinc acetate solution, Mg, La, Y, carbon, Cu, N, Se, B2H6, Al, V, Fe, A step (step 1) of preparing an en-type zinc oxide thin film composition containing at least one or one or more selected from the group consisting of Ti, Ta, Nb, and Ga is as follows.

Example 1 Type Zinc Oxide

① Zinc Acetate ((CH3COO) 2Zn) is mixed with two solutions with water / alkoxide molar ratio of 5 to 55 and stirred for 1 to 8 hours to undergo hydrolysis reaction. In this case, 0.11 to 9 wt% aqueous hydrochloric acid or sulfuric acid solution is used instead of neutral water.

② Zinc oxide is mixed with MeOH solution on the basis of 100molwt%, and then 0.1 ~ 5.7molwt% of manganese chloride solution with 12.5wt% aqueous solution of manganese chloride as an oxygen activator, and 0.5 ~ 7.5molwt% of bismuth with solution of 7wt% bismuth chloride, 11.7wt Mix 0.1% to 5.5molwt% of nickel chloride solution.

③ 0.1 to 5.5 molwt% of 0.5wt% platinum chloride solution in 10% ammonia water and 12wt% vanadium pentoxide and 5wt% WO3 dissolved in 0.5wt% silver chloride and 7.5wt% lithium hydroxide aqueous solution as hydrocarbon adsorbents. Mix 0.5–2 molwt%, 0.5–2.0 molwt%.

④ Adjust the energy band gap of zinc oxide, and mix 1 ~ 5molwt% of cobalt oxide, an oxidatio type with oxygen carrier function. (10)

Example 2 En-type Zinc Oxide

① Zinc Acetate ((CH3COO) 2Zn) is mixed with two solutions with water / alkoxide molar ratio of 5 to 55 and stirred for 1 to 8 hours to undergo hydrolysis reaction. In this case, 0.11 to 9 wt% aqueous hydrochloric acid or sulfuric acid solution is used instead of neutral water. Based on 100 molwt% zinc oxide

② Mix 0.5 ~ 1.0molwt% 18.7wt% magnesium chloride solution as hydrogen activator.

③ In the transition metal group IIIB, lanthanum or yttrium, which is a negative electroactive material, is mixed with 100 to 10 to 100 weight molar ratio of zinc oxide.

④ Adjust the band gap of zinc oxide, capture OH radicals and mix 1.5 ~ 5.5molwt% of carbon with electron transfer catalyst function. (20)

Example 3 Type Zinc Oxide

① Zinc Acetate ((CH3COO) 2Zn) is mixed with two solutions with water / alkoxide molar ratio of 5 to 55 and stirred for 1 to 8 hours to undergo hydrolysis reaction. In this case, 0.11 to 9 wt% aqueous hydrochloric acid or sulfuric acid solution is used instead of neutral water.

② Mix zinc oxide with MeOH solution based on 100 molwt% zinc oxide and mix 1.1 ~ 9.5molwt% manganese with 12.5wt% manganese chloride as an oxygen activator.

③ 0.5 ~ 1.5m olwt of 0.1wt% platinum chloride solution dissolved in 0.1 ~ 5.5molwt%, 10% aqueous ammonia water and 12wt% vanadium pentoxide dissolved in 7.5wt% lithium hydroxide aqueous solution as hydrocarbon adsorbent. %, 4 to 5 molwt% to mix.

Example 4 En-type Zinc Oxide

① Zinc Acetate ((CH3COO) 2Zn) is mixed with two solutions with water / alkoxide molar ratio of 5 to 55 and stirred for 1 to 8 hours to undergo hydrolysis reaction. In this case, 0.11 to 9 wt% aqueous hydrochloric acid or sulfuric acid solution is used instead of neutral water. Based on 100 molwt% zinc oxide

② Mix 0.5 ~ 1.0molwt% 18.7wt% magnesium chloride solution as hydrogen activator.

③ In the transition metal group IIIB, lanthanum or yttrium, which is a negative electroactive material, is mixed at a ratio of 100: 10 to 100% by weight of zinc oxide.

④ Adjust band gap of zinc oxide, capture OH radicals, carbon 1.5 ~ 5.5molwt%, Cu 0.5 ~ 1.5molwt%, N 0.1 ~ 2.5molwt%, Se 0.1 ~ 2.5 5molwt%, B2H6 0.1 to 2.5 molwt%, Al 0.1 to 2.5 molwt%, Fe 0.1 to 2.5 molwt%, Ti 1.5 to 5.5 molwt%, Ta 1.5 to 5.5 molwt% Nb 0.1 to 2.5 molwt%, Ga 1.5 to 5.5 molwt%. 20)

        The prepared thin film composition was put into a rotating drum 140 of a grinding ball mill to further nanoparticles, and filtered through a filter network 220 of a membrane filter 210 of 20 nanometers or less, thereby filtering a p-type and en-type zinc oxide thin film composition. The obtaining step (step 2) is as follows.

        The inlet and outlet 130 is installed at one side of the cylindrical or cylindrical cone shape and is operated by moving the belt 120 by the motor 110 to finely pulverize the nanoparticles. The support chamber 100 is provided at both sides of the grinding chamber with respect to the horizontal axis, and the inlet of the rotating drum is used to insert and grind the p-type and en-typed zinc oxide thin film composition by using the cylindrical grinding mill (140). Through the 130, a plurality of ceramic balls 150 and the P-type 10 and N-type zinc oxide thin film composition to be pulverized into the rotating drum 140, together with water, and then as an inlet as a stopper. And the motor 110 is rotated to rotate the rotating drum 140 through the belt 120 to pulverize and atomize the particles.

        In detail, a plurality of ceramic balls 150 and a pulverized type 10 and an en-type zinc oxide thin film composition to be pulverized are introduced into a new rotating drum, respectively, inside the rotating drum 140 having a cylindrical shape. When rotated at a speed of 5 to 500 rpm for 1 hour to 24 hours in a state, a plurality of ceramic balls 150 collide with each other, and the P-type and en-typed zinc oxide thin film compositions injected with the ceramic balls are different from each other. It collides with each other and pulverizes. At the same time, it collides with a plurality of ceramic balls and alumina ceramic inner wall plate attached to the inner surface of the rotating drum, and further nano-structures the film type and enzymatic zinc oxide thin film composition therebetween. It is filtered through a filter network 220 of 20 nm or less membrane filter 210 to obtain a P-type and en-type zinc oxide thin film composition.

        Mixing with the water-soluble binder silane (O-Si-O) n and heat-treating by solution coating (step 3) are as follows.

        The coating method currently used is CVD method and SPUTTER method. The equipment price required for CVD and SPUTTER method is 300 ~ 1 billion won per unit, and the coating area is about 10 * 10cm, so the production cost per unit is very high, vacuum and plasma Energy consumption is very high, but solution coating method can save 80% in terms of energy saving. In the present invention, a solution coating method was used.

        NaF is used as the surface cleaner of the substrate to thin-film coating a mixture of thin film composition of zinc oxide type and entype and water-soluble polysiloxane polymer on sapphire substrate (Al2O3) or silicon substrate (Si). F is due to etching and surface melting of the substrate.

A water-soluble polysiloxane polymer, which is a binder, and a mixture of finely divided particles in a cylindrical rotating drum were mixed at a weight ratio of 100: 120 to 150 to obtain a zinc oxide thin film composition having a dry coating thickness of 1 to 2㎛. After coating the metal 300 as much as possible, and then heated in a 200 ~ 900 ℃ high temperature oven (400) for 1 to 24 hours to obtain a final film-type zinc oxide thin film composition (510).

N-type zinc oxide thin film composition was dried by mixing the composition of water-soluble polysiloxane polymer as a binder and the mixture pulverized into fine particles in a cylindrical rotating drum at a weight ratio of 100: 120-150. After coating the metal 300 as much as possible, and then heated in a 200 ~ 900 ℃ high temperature oven (400) for 1 to 24 hours to obtain a final en-type zinc oxide thin film composition (520).

               High temperature heat treatment above 200 ℃ results in coating thickness of 1 ~ 2㎛ and water and organic components (carbon chain) are released.

                      CO2 ↑ + H2O ↑ + ZnO? dop

Target technology Measure Example 1 Example 2 Example 3 Example 4 Assessment Methods Securing subsidies optimal optimal optimal optimal optimal experience Resistivity <8.0 * 10 ^-4 Ωcm <8.0 * 10 ^-4 <8.0 * 10 ^-4 <8.0 * 10 ^-4 <8.0 * 10 ^-4 Conductivity Test Permeability 〉 85% 〉 85% 〉 85% 〉 85% 〉 85% Transmittance meter Adhesion 100% 100% 100% 100% 100% Tape test Uniformity <10% <10% <10% <10% <10% Surface biopsy
(Smoothness) Organization chart ZnO configuration ZnO configuration ZnO configuration ZnO configuration ZnO configuration Fog rate 10% 10% 10% 10% 10% Fog test

Claims (21)

In the method for coating a thin film composition containing the type and zinc oxide enzymatically on the surface of the object, Zinc Acetate Aqueous Solution, Mn, Li, Pt, Ag, V2O5, WO3, Bi, Ni, CoO Type Zinc Oxide Coating Composition and Zinc Acetate Aqueous Solution Containing At least One or One Or More Types, Mg En type zinc oxide containing at least one selected from the group consisting of La, Y, carbon, Cu, N, Se, B2H6, Al, V, Fe, Ti, Ta, Nb, and Ga Preparing a thin film composition (step 1); The prepared P-type and en-type zinc oxide thin film composition was put into a rotating drum of a grinding ball mill to further nanoparticles and filtered through a membrane filter of 20 nanometers or less to obtain a P-type and en-type zinc oxide thin film composition (Step 2). ); And The P-type and N-type zinc oxide thin film composition is mixed with a water-soluble binder silane (O-Si-O) n to dry film thickness of 1 to 2㎛. Coating the metal surface as much as possible and then performing heat treatment at 200 to 900 ° C. for 1 to 24 hours (step 3); Coating method of a thin film composition containing a p-type and entyped zinc oxide comprising a. delete delete delete The method of claim 1, Coating method of the thin film composition containing the p-type and en-typed zinc oxide that Zinc Acetate ((CH3COO) 2Zn) is used to prepare the type and the oxidized zinc oxide thin film composition. The method of claim 1, In order to prepare the P-type and the en-typed zinc oxide thin film composition, P-type and en-typed zinc oxide, in which Zinc Acetate ((CH 3 COO) 2 Zn) and a water-soluble polysiloxane polymer (O-Si-O) n are used. Coating method of the thin film composition containing. delete delete delete delete The method of claim 1, The substrate for thin-film coating a mixture of the thin film composition containing the type-type and the enzymatic zinc oxide and a water-soluble polysiloxane polymer (O-Si-O) n on a sapphire substrate (Al 2 O 3) or a silicon substrate (Si) The coating method of the thin film composition containing a p-type and an oxidized zinc oxide which NaF is used as a surface cleaner of the. delete delete The method of claim 1, The thin film composition is a thin film containing the p-type and enzymatic zinc oxide which further contains at least one selected from the group consisting of an aqueous solution of manganese chloride, bismuth chloride and nickel chloride as an oxygen generating activator. Coating method of the composition. The method of claim 1, The thin film composition further comprises at least one kind or at least one kind selected from the group consisting of platinum chloride aqueous solution, silver chloride dissolved in ammonia water, vanadium pentoxide dissolved in aqueous lithium hydroxide solution and WO3 as an adsorbent. Coating method of thin film composition containing typed zinc oxide. delete The method of claim 1, The thin film composition is a coating method of the thin film composition containing the p-type and en-typed zinc oxide to adjust the energy band gap of zinc oxide and further contain cobalt oxide having an oxygen carrier (oxygen carrier) function. The method of claim 1, The thin film composition is a coating method of a thin film composition containing the type P and entyped zinc oxide which further contains an aqueous magnesium chloride solution as a hydrogen generating activator. The method of claim 1, The thin film composition may contain a p-type and en-type zinc oxide further containing at least one or more selected from the group consisting of lanthanum or yttrium, which are negative electroactive materials. Coating method of the thin film composition. The method of claim 1, The thin film composition further contains at least one or one or more selected from the group consisting of carbon, Cu, N, Se, B 2 H 6, Al, Fe, Ti, Ta, Nb, and Ga having an electron transfer catalyst function. Coating method of thin film composition containing P-type and en-typed zinc oxide. delete