KR20090025520A - Method for synthesizing zinc hydroxide nitrate having relaxed layer distance and fabricating method zno thin films using the same - Google Patents
Method for synthesizing zinc hydroxide nitrate having relaxed layer distance and fabricating method zno thin films using the same Download PDFInfo
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- KR20090025520A KR20090025520A KR1020070090440A KR20070090440A KR20090025520A KR 20090025520 A KR20090025520 A KR 20090025520A KR 1020070090440 A KR1020070090440 A KR 1020070090440A KR 20070090440 A KR20070090440 A KR 20070090440A KR 20090025520 A KR20090025520 A KR 20090025520A
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- zinc
- zinc oxide
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- 239000010409 thin film Substances 0.000 title claims abstract description 47
- QAOTYOGEQAZIFQ-UHFFFAOYSA-M zinc;hydroxide;nitrate Chemical compound [OH-].[Zn+2].[O-][N+]([O-])=O QAOTYOGEQAZIFQ-UHFFFAOYSA-M 0.000 title claims abstract description 42
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 139
- 239000011787 zinc oxide Substances 0.000 claims abstract description 68
- 239000011701 zinc Substances 0.000 claims abstract description 59
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 150000003751 zinc Chemical class 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract 2
- 238000007254 oxidation reaction Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 8
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 claims description 2
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 claims description 2
- -1 screen printing Substances 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 2
- 238000010189 synthetic method Methods 0.000 abstract 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 239000013078 crystal Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
Abstract
Description
본 발명은 층간 거리가 이완된 산화아연 전구체의 합성 방법 및 이를 이용한 산화아연 박막의 제조방법에 관한 것으로, 더욱 상세하게는 금속-산소 중합반응(metal-oxygen polymerization)에 의하여 층간 거리가 이완된(relaxed) 산화아연 전구체를 합성하는 것을 특징으로 하는 산화아연 전구체의 합성 방법 및 이를 이용한 산화아연 박막의 제조방법에 관한 것이다.The present invention relates to a method for synthesizing a zinc oxide precursor having a relaxed interlayer distance and a method for producing a zinc oxide thin film using the same. More particularly, the interlayer distance is relaxed by a metal-oxygen polymerization ( The present invention relates to a method for synthesizing a zinc oxide precursor and a method for producing a zinc oxide thin film using the same.
Ⅱ-Ⅳ족 산화물인 산화아연(ZnO)은 육방정계 우르차이트형(hexagonal wurtzite) 결정 구조를 가지며 약 3.3eV의 넓은 광학적 밴드갭을 가지는 반도체 물질이다. 산화아연 박막은 강한 압전성과 광전 효과를 가지고 있어서 기존의 자외선/청색 발광 다이오드(LED) 및 레이저 다이오드(LD) 소자의 재료인 GaN과 유사한 광학적 특성을 가지고 있다. 특히, 상온에서 GaN의 3배나 되는 여기 구속 에너 지(excition binding energy)를 가져서, 고효율의 발광이 가능하고, 레이저 펌핑에 의한 자발적 발광(stimulated spontaneous emission)시 문턱에너지가 매우 낮다는 좋은 특성을 가지고 있는 것으로 보고되어 있다. 또한 산화아연계 박막은 적외선 및 가시광선 영역에서의 투과성 및 전기 전도성과 플라즈마에 대한 내구성이 우수하며, 원료 가격이 저렴하여 TFT, 도핑에 의한 투명 전극, 광촉매제, 에너지 절약형 창유리 코팅재료, 음향 광학 소자, 강유전체 메모리, 태양전지, 환원가스검출센서 등 그 응용범위가 매우 광범위하다.Zinc oxide (ZnO), a group II-IV oxide, is a semiconductor material having a hexagonal wurtzite crystal structure and having a wide optical bandgap of about 3.3 eV. Zinc oxide thin films have strong piezoelectric and photoelectric effects, and have similar optical properties to GaN, which is a material of conventional ultraviolet / blue light emitting diode (LED) and laser diode (LD) devices. In particular, it has an excitation binding energy that is three times higher than GaN at room temperature, which enables high efficiency light emission, and has a good characteristic that the threshold energy is very low during stimulated spontaneous emission by laser pumping. Reported to be present. In addition, the zinc oxide thin film has excellent transmittance in the infrared and visible light region, electrical conductivity, and durability against plasma, and the raw material is low in cost, so that TFT, doping transparent electrode, photocatalyst, energy-saving window glass coating material, and acoustic optics Applications such as devices, ferroelectric memories, solar cells and reducing gas detection sensors are very broad.
상기 산화아연 박막을 성장시키는 일반적인 방법으로는 화학 기상 도포법, 금속 유기 화학 기상 도포법, 분자선 적층법, 금속 유기 분자선 적층법, 펄스 레이저 도포법, 원자층 도포법, 스퍼터링법, RF 마그네트론 스퍼터링법(RF magnetron sputtering), 졸-겔 재료를 이용한 용액 코팅법 등과 같은 여러 가지 도포 방법이 알려져 있다. 그러나 이러한 방법 중 용액 코팅법을 제외한 방법들은 사용되는 장비가 고가이고 사용이 간단하지 않으며, 대면적 크기의 기판에 도포할 경우 크기에 대한 한계가 있다. 따라서 인쇄 및 다양한 용액 코팅 방법을 이용하여 산화아연 박막을 형성하는 방법이 요구된다.As a general method for growing the zinc oxide thin film, chemical vapor deposition, metal organic chemical vapor deposition, molecular beam deposition, metal organic molecular beam deposition, pulse laser coating, atomic layer coating, sputtering, RF magnetron sputtering Various application methods are known, such as RF magnetron sputtering and solution coating using a sol-gel material. However, among these methods, except for the solution coating method, the equipment used is expensive and not easy to use, and there is a limit on the size when applied to a large-area substrate. Therefore, there is a need for a method of forming a zinc oxide thin film using printing and various solution coating methods.
이와 같은 용액 방법에 사용되는 산화아연 박막의 전구체 용액 제조시 Zn 공급원으로 아세트산 아연(Zinc acetate), 염화 아연(Zinc chloride), 질산 아연(Zinc nitrate) 등을 사용하는데, 이러한 아연 공급원들의 높은 분해 온도(보통 500℃ 이상)로 인하여 플렉시블 기판용 디바이스나 투명전극용 유리 기판에의 적용에 있어 어려움이 있다. 이를 위하여 제시된 방법이 300℃ 미만의 분해 온도를 갖 는 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate) 전구체를 이용하는 것이다. 그러나 이 경우 전구체의 용매에 대한 용해도가 높지 않아 막을 어느 정도 두껍게 형성하기 위하여 코팅을 여러 번 반복해야 하는 단점이 있다.Zinc acetate, zinc chloride, zinc nitrate, etc. are used as Zn sources in preparing the precursor solution of the zinc oxide thin film used in such a solution method. (Usually, 500 ° C. or more), there is a difficulty in application to a device for a flexible substrate or a glass substrate for a transparent electrode. The proposed method is to use a Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) precursor having a decomposition temperature of less than 300 ° C. However, in this case, the solubility of the precursor in the solvent is not high, so the coating must be repeated several times to form a thick film to some extent.
본 발명의 하나의 목적은 층간 거리가 이완되어 용해도가 증가한 산화아연 전구체의 합성방법을 제공하는 것이다.One object of the present invention is to provide a method for synthesizing a zinc oxide precursor having increased solubility due to a relaxed interlayer distance.
본 발명의 다른 목적은 상기 산화아연 전구체를 아연 공급원으로 하는 산화아연 전구체 용액을 이용한 산화아연 박막의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing a zinc oxide thin film using a zinc oxide precursor solution using the zinc oxide precursor as a zinc source.
본 발명의 다른 목적은 상기 방법에 의하여 수득된 산화아연 박막을 포함하는 전자부품용 기재를 제공하는 것이다.Another object of the present invention is to provide a substrate for an electronic component comprising a zinc oxide thin film obtained by the above method.
아연염을 유기 용매에 용해시키는 단계;Dissolving zinc salt in an organic solvent;
상기 아연염 용액에 산을 첨가하여 금속-산소 중합반응(metal-oxygen polymerization) 시키는 단계; 및Adding acid to the zinc salt solution to perform metal-oxygen polymerization; And
상기 금속-산소 중합반응 후 염기를 첨가하여 중화시켜 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)를 합성하는 단계를 포함하는 층간 거리가 이완 된(relaxed) 산화아연 전구체의 합성방법에 관한 것이다.Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) comprising the step of neutralizing by the addition of a base after the metal-oxygen polymerization reaction relaxes the zinc oxide (relaxed) It relates to a method for synthesizing a precursor.
본 발명의 다른 양상은Another aspect of the invention
아연염을 유기 용매에 용해시키는 단계;Dissolving zinc salt in an organic solvent;
상기 아연염 용액에 산을 첨가하여 금속-산소 중합반응(metal-oxygen polymerization) 시키는 단계;Adding acid to the zinc salt solution to perform metal-oxygen polymerization;
상기 금속-산소 중합반응 후 염기를 첨가하여 층간 거리가 이완된(relaxed) Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)를 수득하는 단계;Adding a base after the metal-oxygen polymerization to obtain Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) having a relaxed interlayer distance;
상기Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)를 안정제 또는 개질제와 극성 용매에서 혼합 및 교반하여 산화아연 박막용 전구체 용액을 제조하는 단계; 및Preparing a zinc oxide thin film precursor solution by mixing and stirring the Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) with a stabilizer or a modifier in a polar solvent; And
상기 산화아연 박막용 전구체 용액을 기판 위에 도포한 후 건조 및 소성시키는 단계를 포함하는 산화아연 박막의 제조방법에 관한 것이다.It relates to a method for producing a zinc oxide thin film comprising the step of coating the zinc oxide thin film precursor solution on a substrate, followed by drying and baking.
본 발명의 다른 양상은 상기 방법에 의해 수득된 산화아연 박막을 포함하는 전자부품용 기재에 관한 것이다.Another aspect of the invention relates to a substrate for an electronic component comprising a zinc oxide thin film obtained by the above method.
본 발명에 의한 Zn5(OH)8(NO3)2·2H2O (zinc hydroxide nitrate)는 층간 거리가 이완되어 용매에 대한 용해도가 높으므로 용액 방법을 이용하여 산화아연 박막을 형성하는데 유용하다. 본 발명에 의한 산화아연 박막은 졸의 우수한 화학적 균 질성, 유동성, 반응성에 의하여 균질할뿐 아니라, 진공을 필요로 하지 않아 장치가 비교적 간단하고 공정 비용이 저렴하다. 또한 낮은 공정 온도에서 산화아연 박막을 형성시킬 수 있어 사용되는 기판에 무리를 주지 않으므로 플렉시블 기판용 디바이스나 투명전극용 유리 기판에의 적용이 용이하고, 기존의 도포 방법을 사용할 수 있어 제조 공정성이 우수하다.Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) according to the present invention is useful for forming a zinc oxide thin film using a solution method because the interlayer distance is relaxed and high solubility in a solvent. . The zinc oxide thin film according to the present invention is not only homogeneous due to the excellent chemical homogeneity, flowability, and reactivity of the sol, but also does not require a vacuum, so the device is relatively simple and the process cost is low. In addition, it is possible to form a zinc oxide thin film at a low process temperature, so that it is easy to apply to devices used for flexible substrates or glass substrates for transparent electrodes, and it is easy to apply the conventional coating method. Do.
이하에서 첨부 도면을 참고하여 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.
본 발명의 일 구현예에 의하면 층간 거리가 이완된(relaxed) Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate) 를 합성하기 위하여 먼저 아연염을 유기 용매에 용해시킨 후 산을 첨가하여 금속-산소 중합반응(metal-oxygen polymerization) 을 시킨다. 이어서 상기 용액에 염기를 첨가하여 중화시킨다.According to one embodiment of the present invention, in order to synthesize a Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) in which the distance between layers is relaxed, first, zinc salt is dissolved in an organic solvent. Acid is added to the metal-oxygen polymerization. The solution is then neutralized by addition of base.
본 발명에서는 상기 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)를 알루미늄(Al), 주석(Sn), 인듐(In), 갈륨(Ga), 철(Fe), 안티몬(Sb) 및 리튬(Li)으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 도핑(doping) 할 수 있다. 상기 금속을 도핑하기 위하여 상기 도핑금속을 함유하는 금속염을 상기 아연염 용해시 유기용매에 용해시킨다.In the present invention, the Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) is aluminum (Al), tin (Sn), indium (In), gallium (Ga), iron (Fe), It may be doped with one or more metals selected from the group consisting of antimony (Sb) and lithium (Li). In order to dope the metal, a metal salt containing the doped metal is dissolved in an organic solvent when the zinc salt is dissolved.
도 1은 본 발명의 일 실시예에 의한 Zn5(OH)8(NO3)22·H2O(zinc hydroxide nitrate) 합성방법을 나타내는 공정 흐름도이다. 도 1을 참조하면, 본 발명에 의 해서 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate) 를 합성하기 위하여 먼저 아연염을 유기용매에 용해시킨다. 이 때 도핑이 필요할 경우 도핑금속의 금속염을 함께 용해시킨다. 이어서 금속-산소 중합반응(metal-oxygen polymerization)이 일어나도록 산을 첨가하고 전체 부피가 1/5이 되도록 60 ~ 100 ℃ 에서 1 ~ 5시간 동안 교반한다. 상기 용액을 실온으로 냉각시킨 후 염기를 첨가하여 중화시킨다. 침전된 물질인 Zn5(OH)8(NO3)2·2H2O 을 필터링하고 이를 초순수 물로 수차례 세정한 후 50 ~ 80℃에서 건조시킨다.1 is a process flow diagram illustrating a method for synthesizing Zn 5 (OH) 8 (NO 3 ) 2 2 .H 2 O (zinc hydroxide nitrate) according to an embodiment of the present invention. Referring to FIG. 1, zinc salts are first dissolved in an organic solvent in order to synthesize Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) according to the present invention. At this time, when doping is required, the metal salt of the doping metal is dissolved together. The acid is then added to allow metal-oxygen polymerization to occur and stirred at 60-100 ° C. for 1-5 hours to bring the total volume to 1/5. The solution is cooled to room temperature and then neutralized by addition of base. The precipitated material, Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O, is filtered and washed several times with ultrapure water and dried at 50-80 ° C.
본 발명의 합성방법에 의해서 합성되는 산화아연 전구체는 상기 금속-산소 중합반응(metal-oxygen polymerization)에 의하여 Zn-O-Zn 결합이 형성된다. 이와 같이 중합체화된 부분들은 유기용매 안에 용해되어 있다가 염기의 첨가로 인하여 급속히 침전되는데 화합물 결정구조를 형성할 때 미처 빠져나가지 못한 유기용매 분자들이 불순물로 남아 합성되는 화합물의 층간 거리를 증가시키는 것으로 예상된다.In the zinc oxide precursor synthesized by the synthesis method of the present invention, Zn—O—Zn bonds are formed by the metal-oxygen polymerization. These polymerized parts are dissolved in the organic solvent and then precipitated rapidly due to the addition of a base, which increases the interlayer distance of the compound where organic solvent molecules remaining as impurities remain as impurities when forming the compound crystal structure. It is expected.
본 발명에 사용되는 아연염은 염화아연, 황산아연, 질산아연, 산화아연, 인산아연, 플루오르화아연, 브롬화아연, 요오드화아연으로 이루어진 군으로부터 선택되는 1종 이상이나 반드시 이에 제한되는 것은 아니다.The zinc salt used in the present invention is one or more selected from the group consisting of zinc chloride, zinc sulfate, zinc nitrate, zinc oxide, zinc phosphate, zinc fluoride, zinc bromide, and zinc iodide, but is not necessarily limited thereto.
본 발명에 사용되는 유기용매는 알코올계 용매로 에탄올, 이소프로필알콜, n-부탄올, 메탄올, 1-메톡시-2-프로판올, 디아세톤알콜, 이소부틸알콜, t-부틸알콜 중에서 선택되는 1종 이상이나 반드시 이에 제한되는 것은 아니다.The organic solvent used in the present invention is an alcohol solvent, one selected from ethanol, isopropyl alcohol, n-butanol, methanol, 1-methoxy-2-propanol, diacetone alcohol, isobutyl alcohol and t-butyl alcohol. The above is not necessarily limited thereto.
본 발명의 다른 양상은 본 발명의 산화아연 전구체를 이용한 산화아연 박막의 제조방법에 관한 것이다. 본 발명의 일구현예에 의하면, Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)를 아연의 공급원으로 하는 산화아연 박막을 제조하기 위하여 먼저 아연염을 유기 용매에 용해시킨 후 상기 아연염 용액에 산을 첨가하여 금속-산소 중합반응(metal-oxygen polymerization) 을 시킨다. 이어서 염기를 첨가하여 상기 금속-산소 중합반응을 거친 용액을 중화시킴으로써 격자거리가 이완된(relaxed) Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)를 수득한다.Another aspect of the present invention relates to a method for producing a zinc oxide thin film using the zinc oxide precursor of the present invention. According to one embodiment of the present invention, zinc salt is first dissolved in an organic solvent to prepare a zinc oxide thin film containing Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) as a source of zinc. After the acid is added to the zinc salt solution to the metal-oxygen polymerization (metal-oxygen polymerization). Subsequent neutralization of the metal-oxygen polymerized solution by addition of a base yields a relaxed lattice distance Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate).
이어서Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)를 안정제 또는 개질제와 극성 용매에서 혼합 및 교반하여 산화아연 박막용 전구체 용액을 제조한다.Subsequently, Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) is mixed and stirred with a stabilizer or modifier in a polar solvent to prepare a precursor solution for a zinc oxide thin film.
상기 방법에 의하여 제조된 균질하고 투명한 졸 형태의 산화아연 박막용 전구체 용액을 스핀코팅(spin coating)이나 딥코팅(dip coating)등의 방법으로 기판 위에 도포한 후 건조시킨다. 이어서 300℃ 미만의 핫 플레이트(hot plate) 또는 전기로에서 소성하면 하기 반응식 1의 반응에 의하여 산화아연 박막이 형성된다.The homogeneous and transparent sol form precursor solution for zinc oxide thin film prepared by the above method is coated on a substrate by spin coating or dip coating and then dried. Subsequently, firing in a hot plate or an electric furnace below 300 ° C. forms a zinc oxide thin film by the reaction of
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본 발명에서는 상기 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)를 알루미늄(Al), 주석(Sn), 인듐(In), 갈륨(Ga), 철(Fe), 안티몬(Sb) 및 리튬(Li)으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 도핑(doping) 할 수 있다.In the present invention, the Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) is aluminum (Al), tin (Sn), indium (In), gallium (Ga), iron (Fe), It may be doped with one or more metals selected from the group consisting of antimony (Sb) and lithium (Li).
본 발명에 사용되는 아연염은 염화아연, 황산아연, 질산아연, 산화아연, 인산아연, 플루오르화아연, 브롬화아연, 요오드화아연으로 이루어진 군으로부터 선택되는 1종 이상이나 반드시 이에 제한되는 것은 아니다. The zinc salt used in the present invention is one or more selected from the group consisting of zinc chloride, zinc sulfate, zinc nitrate, zinc oxide, zinc phosphate, zinc fluoride, zinc bromide, and zinc iodide, but is not necessarily limited thereto.
본 발명에 사용되는 유기용매는 알코올계 용매로 에탄올, 이소프로필알콜, n-부탄올, 메탄올, 1-메톡시-2-프로판올, 디아세톤알콜, 이소부틸알콜, t-부틸알콜 중에서 선택되는 1종 이상이나 반드시 이에 제한되는 것은 아니다.The organic solvent used in the present invention is an alcohol solvent, one selected from ethanol, isopropyl alcohol, n-butanol, methanol, 1-methoxy-2-propanol, diacetone alcohol, isobutyl alcohol and t-butyl alcohol. The above is not necessarily limited thereto.
상기 안정제 또는 개질제는 균일한 용액을 제조하기 위해 포함될 수 있으며, 안정제의 예로는 모노에탄올아민(monoethanolamine), 디에탄올아민(diethanolamine) 및 트리에탄올아민(triethanolamine)등과 같은 아민계 안정제가 있으나 반드시 이에 제한되는 것은 아니다. 또한 상기 개질제의 예로는 아세토 인(acetoin), 디메틸아민보란(dimethylamineborane), 글리신(glycine), 아세톨(acetol)등의 유기계 분산제 또는 무기계 분산제가 있으나 반드시 이에 제한되는 것은 아니다.The stabilizer or modifier may be included to prepare a uniform solution, and examples of the stabilizer include amine stabilizers such as monoethanolamine, diethanolamine, and triethanolamine, but are not limited thereto. It is not. In addition, examples of the modifier include, but are not limited to, organic dispersants or inorganic dispersants such as acetoin, dimethylamineborane, glycine, acetol, and the like.
상기 극성 용매는 2-메톡시에탄올(2-methoxyethanol), 에탄올(ethanol), 이소프로판올(isopropanol)과 같은 알코올(alcohol)계 용매, 아세토니트릴(acetonitrile) 및 증류수(H2O)를 포함하고, 바람직하게는 코팅중에 휘발되지 않도록 끓는점이 다소 높은 2-메톡시에탄올(2-methoxyethanol)이 사용될 수 있으나 반드시 이에 제한되는 것은 아니다.The polar solvent includes an alcohol solvent such as 2-methoxyethanol, ethanol, isopropanol, acetonitrile and distilled water (H 2 O). Preferably, the boiling point of 2-methoxyethanol may be used to prevent volatilization, but the present invention is not limited thereto.
상기 산화아연 박막용 전구체 용액 중의 아연 농도는 바람직하게는 0.0005 ~ 1 M이나 반드시 이에 제한되는 것은 아니다. 상기 농도가 0.0005M보다 낮은 경우, 형성되는 박막의 두께를 조절할 수 없고, 1M보다 높은 경우 투명하고 균일한 전구체 용액을 얻기 어렵게 될 우려가 있다.The zinc concentration in the zinc oxide thin film precursor solution is preferably 0.0005 to 1 M, but is not necessarily limited thereto. When the concentration is lower than 0.0005M, the thickness of the formed thin film cannot be adjusted, and when the concentration is higher than 1M, it is difficult to obtain a transparent and uniform precursor solution.
상기 안정제 또는 개질제의 농도는 산화아연 박막용 전구체 용액 중의 아연 농도에 따라서 조절되며, 바람직하게는 산화아연 박막용 전구체 용액 중의 아연 농도의 약 1 ~ 10배이나 반드시 이에 제한되는 것은 아니다. 상기 농도가 아연 농도의 1배보다 작을 경우 용해가 일어나지 않고, 10배보다 큰 경우 부반응이 생길 수 있다.The concentration of the stabilizer or modifier is adjusted according to the zinc concentration in the zinc oxide thin film precursor solution, preferably about 1 to 10 times the zinc concentration in the zinc oxide thin film precursor solution, but is not necessarily limited thereto. If the concentration is less than 1 times the zinc concentration does not occur dissolution, if greater than 10 times a side reaction may occur.
기존의 합성방법을 통한 산화아연 전구체는 투명하고 균질한 용액의 제조를 위하여 안정제 또는 개질제를 다량 첨가하여야 하지만 본 발명에 의하면 소량의 안 정제 또는 개질제를 첨가하여도 0.1M 이상의 농도를 가진 산화아연 전구체 용액을 제조할 수 있다.The zinc oxide precursor through the conventional synthesis method should be added a large amount of stabilizers or modifiers to prepare a transparent and homogeneous solution, but according to the present invention zinc oxide precursor having a concentration of 0.1M or more even if a small amount of eye tablets or modifiers are added Solutions can be prepared.
상기 산화아연 전구체 용액의 도포 방법으로는 스핀코팅(spin coating), 딥코팅(dip coating), 롤코팅(roll coating), 스크린 코팅(screen coating), 분무코팅(spray coating), 스핀 캐스팅(spin casting), 흐름코팅(flow coating), 스크린 인쇄(screen printing), 잉크젯(ink jet) 또는 드롭캐스팅(drop casting)등이 있으나, 반드시 이에 제한되는 것은 아니다.The coating method of the zinc oxide precursor solution is spin coating, dip coating, roll coating, screen coating, spray coating, spin casting. ), Flow coating, screen printing, ink jet or drop casting, but are not necessarily limited thereto.
상기 기판은 웨이퍼 기판, ITO 기판, 석영유리 기판, 플라스틱 기판으로 이루어진 군으로부터 선택되는 1종 이상일 수 있으나, 반드시 이에 제한되는 것은 아니다.The substrate may be at least one selected from the group consisting of a wafer substrate, an ITO substrate, a quartz glass substrate, and a plastic substrate, but is not limited thereto.
본 발명의 다른 양상은 본 발명의 방법에 의해 수득된 산화아연 박막을 포함하는 전자부품용 기재에 관한 것이다. 본 발명에 의한 전자부품용 기재는 투명전극, 태양전지, 광센서, TFT, 산화아연 나노와이어(nanowire), 발광 재료를 포함하나, 반드시 이에 제한되는 것은 아니다.Another aspect of the invention relates to a substrate for an electronic component comprising a zinc oxide thin film obtained by the method of the invention. The substrate for an electronic component according to the present invention includes, but is not necessarily limited to, a transparent electrode, a solar cell, an optical sensor, a TFT, a zinc oxide nanowire, and a light emitting material.
이하에서, 실시예 및 비교예를 통하여 본 발명을 보다 상세하게 설명하고자 하나, 하기의 실시예는 단지 설명의 목적을 위한 것으로 본 발명의 보호범위를 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the following examples are for illustrative purposes only and should not be construed as limiting the protection scope of the present invention.
[실시예 1]Example 1
금속-산소 중합반응(metal-oxygen polymerization) 을 이용한 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 합성Synthesis of Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) by metal-oxygen polymerization
50ml의 2-프로판올(2-propanol) 용매에 1.0M의 Zn(NO3)2 를 용해시키고 60%의 HNO3 10g을 첨가하였다. 상기 용액을 100℃에서 3시간 동안 부피가 약 1/5 정도로 감소될 때까지 교반하면서 반응시켰다. 용액을 실온으로 식힌 후 염화암모늄을 pH7이 될 때까지 첨가하여 흰색 침전물 형태의 Zn5(OH)8(NO3)2·2H2O를 수득하였다.수득된 Zn5(OH)8(NO3)2·2H2O를 필터로 여과하여 수 차례 세정한 후 약 50℃에서 밤새 건조시켰다.1.0 M of Zn (NO 3 ) 2 was dissolved in 50 ml of 2-propanol solvent and 10 g of 60% HNO 3 was added. The solution was reacted with stirring at 100 ° C. for 3 hours until the volume was reduced to about 1/5. Zn 5 (OH) of a white precipitate form by the addition of ammonium chloride until a pH7 was cooled to room temperature, a solution 8 (NO 3) 2 · the 2H 2 O was obtained. The obtained Zn 5 (OH) 8 (NO 3 ) 2. 2H 2 O was filtered through a filter, washed several times, and dried at about 50 ° C. overnight.
[실시예 2]Example 2
산화아연 전구체 용액의 제조Preparation of Zinc Oxide Precursor Solution
실시예 1에서 합성된Zn5(OH)8(NO3)2·2H2O, 모노에탄올아민(MEA)을 2-메톡시에탄올(2-methoxyethanol)에서 혼합, 교반하여 균질하고 안정된 산화아연 전구체 용액을 만들었다.A homogeneous and stable zinc oxide precursor obtained by mixing and stirring Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O and monoethanolamine (MEA) synthesized in Example 1 in 2-methoxyethanol. A solution was made.
[실시예 3]Example 3
산화아연 박막 제조Zinc Oxide Thin Film Manufacturing
실시예 2에서 제조된 산화아연 전구체 용액을 1000rpm에서 30초간 스핀-코 팅(spin-coating)하고 110℃의 핫플레이트에서 5분간 중간 열처리한 후, 결정화를 위하여 150~500℃의 공기 하에서 1시간 동안 열처리하였다.The zinc oxide precursor solution prepared in Example 2 was spin-coated at 1000 rpm for 30 seconds and subjected to an intermediate heat treatment on a hot plate at 110 ° C. for 5 minutes, followed by 1 hour in air at 150 ° C. to 500 ° C. for crystallization. Heat treatment for
[비교예 1]Comparative Example 1
수용액상 NaOH를 이용한 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 합성Synthesis of Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) using NaOH in aqueous solution
3.5M의 Zn(NO3)2·6H2O 수용액 20ml와 0.75M의 NaOH 수용액 50 ml를 상온에서 혼합, 교반하여 형성된 백색의 침전물을 필터로 여과하였다. 여과된 Zn5(OH)8(NO3)2·2H2O를 수 차례 세정한 후 약 50℃에서 밤새 건조시켰다.A white precipitate formed by mixing and stirring 20 ml of 3.5 M aqueous Zn (NO 3 ) 2 .6H 2 O solution and 50 ml of 0.75 M NaOH aqueous solution at room temperature was filtered with a filter. The filtered Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O was washed several times and then dried at about 50 ° C. overnight.
[비교예 2]Comparative Example 2
수용액상 KOH를 이용한 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 합성 Synthesis of Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) using KOH in aqueous solution
3.5M의 Zn(NO3)2·6H2O 수용액 20ml와 0.75M의 KOH 수용액 50 ml를 상온에서 혼합, 교반하여 형성된 백색의 침전물을 필터로 여과하였다. 여과된 Zn5(OH)8(NO3)2·2H2O를 수 차례 세정한 후 약 50℃에서 밤새 건조시켰다.A white precipitate formed by mixing and stirring 20 ml of a 3.5 M aqueous Zn (NO 3 ) 2 .6H 2 O solution and 50 ml of a 0.75 M KOH aqueous solution at room temperature was filtered with a filter. The filtered Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O was washed several times and then dried at about 50 ° C. overnight.
도 2는 종래 방법에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 결정구조이고 도 3은 종래 방법에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 결정 격자 거리 측정 결과를 나타낸다.FIG. 2 is a crystal structure of Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized by a conventional method, and FIG. 3 is Zn 5 (OH) 8 (NO synthesized by a conventional method. 3 ) The crystal lattice distance measurement results of 2 · 2H 2 O (zinc hydroxide nitrate) are shown.
도 4는 실시예 1, 비교예 1 및 비교예 2에 의하여 합성된 각각의Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 XRD 패턴이고 도 5는 이들의 TEM 사진이다.4 is an XRD pattern of each Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized by Example 1, Comparative Example 1 and Comparative Example 2 and FIG. 5 is their TEM It is a photograph.
도 4를 참조하면, 2-프로판올(2-propanol)에서 염화암모늄(NH4OH)을 첨가하여 합성된 실시예 1에 의한 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate) 의 결정구조는 NaOH 및 KOH 를 사용하여 합성된 비교예 1 및 2에 의한 것과 유사한 층상 구조(layered structure)임을 알 수 있다. 이와 같이 기본 결정 구조가 유사하다는 전제하에 도 3의 (400) hkl index를 이용하여 각각의 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)에 대한 격자 파라미터 a를 계산하면 기존의 방법에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 격자 파라미터 a는 19.46Å 이고, 본 발명에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 격자 파라미터 a는 19.60Å으로 본 발명에 의한 경우 층간 거리가 증가하였음은 알 수 있다. 이와 같은 결정 구조의 차이로 인하여 본 발명에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 용매에 대한 용해도가 증가한다.4, Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide) according to Example 1 synthesized by the addition of ammonium chloride (NH 4 OH) in 2-propanol It can be seen that the crystal structure of nitrate) is a layered structure similar to that according to Comparative Examples 1 and 2 synthesized using NaOH and KOH. The lattice parameter a for each Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) is calculated using the (400) hkl index of FIG. 3 on the assumption that the basic crystal structures are similar. The lattice parameter a of Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) synthesized by the conventional method is 19.46Å, and Zn 5 (OH) 8 ( The lattice parameter a of NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) is 19.60 Hz, which means that the distance between layers increased according to the present invention. Due to such a difference in crystal structure, the solubility of Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized by the present invention increases.
또한 도 6은 실시예 1, 비교예 1 및 비교예 2에 의하여 합성된 각각의 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 전자회절 사진으로, 본 발명에 의한 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)는 비정질(amophorous) 특성 경향을 보이는 형태임을 알 수 있다.6 is an electron diffraction photograph of each of Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized in Example 1, Comparative Example 1 and Comparative Example 2, It can be seen that Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) is in the form of an amorphous (anophorous) characteristic tendency.
[산화아연 전구체의 분해 온도 측정][Measurement of decomposition temperature of zinc oxide precursor]
실시예 1에 의하여 제조된 산화아연 전구체의 분해 온도를 측정하여 비교예 1에 의하여 제조된 산화아연 전구체의 분해 온도와 비교하였다. 측정 장비는 TA instrument사의 TGA 2050으로, 속도 5℃/min으로 공기분위기 하에서 상온에서 600 ℃까지 상승시키면서 질량변화를 측정하였다.The decomposition temperature of the zinc oxide precursor prepared in Example 1 was measured and compared with the decomposition temperature of the zinc oxide precursor prepared in Comparative Example 1. The measuring instrument was TGA 2050, manufactured by TA instrument, and the mass change was measured while rising from room temperature to 600 ° C. under an air atmosphere at a rate of 5 ° C./min.
도 7a 및 도 7b는 각각 실시예 1 및 비교예 1에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 열분석 결과이다. 예상되는 열분해 반응식은 각각 하기 반응식 2 및 반응식 3으로 나타낼 수 있다.7A and 7B show thermal analysis results of Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized in Example 1 and Comparative Example 1, respectively. The expected pyrolysis schemes can be represented by the following
[반응식 2]
[반응식 3]
상기 반응식 2 및 반응식 3에 의하면 실시예 1 및 비교예 1에 의하여 합성된 화합물은 각각 분해되는 경향이 다르고, 따라서 결정구조적으로 서로 다른 구조를 가질것으로 예상된다. According to
[산화아연 전구체를 적용하여 형성된 박막의 특성][Characteristics of Thin Film Formed by Applying Zinc Oxide Precursor]
도 8은 실시예 3에 의하여 제조된 산화아연 박막의 소성 후의 SEM 사진으로 형성된 박막의 두께는 약 60nm 이다. 도 9는 실시예 3에 의하여 제조된 산화아연 박막의 XRD 분석 결과로 형성된 산화아연 박막은 ZnO 단일상 구조를 가짐을 알 수 있다.8 is a thickness of the thin film formed by SEM photograph after firing of the zinc oxide thin film prepared in Example 3 is about 60nm. FIG. 9 shows that the zinc oxide thin film formed as a result of XRD analysis of the zinc oxide thin film prepared in Example 3 has a ZnO single phase structure.
도 1은 본 발명의 일 실시예에 의한 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate) 합성방법을 나타내는 공정흐름도,1 is a process flow diagram showing a method for synthesizing Zn 5 (OH) 8 (NO 3 ) 2 · 2H 2 O (zinc hydroxide nitrate) according to an embodiment of the present invention,
도 2는 종래 방법에 의하여 합성된 Zn5(OH)8(NO3)·22H2O(zinc hydroxide nitrate)의 결정구조,2 is a crystal structure of Zn 5 (OH) 8 (NO 3 ). 2 2H 2 O (zinc hydroxide nitrate) synthesized by a conventional method,
도 3은 종래 방법에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 결정 구조 PDF 파일,3 is a crystal structure PDF file of Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized by a conventional method,
도 4는 실시예 1, 비교예 1 및 비교예 2에 의하여 합성된 각각의 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 XRD 패턴,4 is an XRD pattern of each of Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized by Example 1, Comparative Example 1 and Comparative Example 2,
도 5는 실시예 1, 비교예 1 및 비교예 2에 의하여 합성된 각각의 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 TEM 사진,5 is a TEM photograph of each of Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized by Example 1, Comparative Example 1 and Comparative Example 2,
도 6은 실시예 1, 비교예 1 및 비교예 2에 의하여 합성된 각각의 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 전자회절 사진,6 is an electron diffraction photograph of each of Zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized by Example 1, Comparative Example 1 and Comparative Example 2,
도 7a 는 실시예 1 에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 열분석 결과를 나타내는 그래프,7A is a graph showing a thermal analysis result of zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized in Example 1,
도 7b 는 비교예 1 에 의하여 합성된 Zn5(OH)8(NO3)2·2H2O(zinc hydroxide nitrate)의 열분석 결과를 나타내는 그래프,7B is a graph showing a thermal analysis result of zn 5 (OH) 8 (NO 3 ) 2 .2H 2 O (zinc hydroxide nitrate) synthesized in Comparative Example 1;
도 8 은 실시예 3 에 의하여 형성된 ZnO 박막의 SEM 사진, 및8 is a SEM photograph of the ZnO thin film formed by Example 3, and
도 9 는 실시예 3 에 의하여 합성된 ZnO 박막의 XRD 분석 패턴을 나타내는 그래프이다.9 is a graph showing an XRD analysis pattern of a ZnO thin film synthesized in Example 3. FIG.
Claims (19)
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| CN102583509A (en) * | 2012-02-22 | 2012-07-18 | 浙江大学 | Method for manufacturing zinc oxide material with coralliform macropore - mesoporous structure |
| KR20230025323A (en) * | 2021-08-13 | 2023-02-21 | 연세대학교 산학협력단 | A method of manufacturing metal-organic frameworks nanosheets, metal-organic frameworks manufactured using the method and gas separation membrane comprising the same |
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| CN102583509A (en) * | 2012-02-22 | 2012-07-18 | 浙江大学 | Method for manufacturing zinc oxide material with coralliform macropore - mesoporous structure |
| KR20230025323A (en) * | 2021-08-13 | 2023-02-21 | 연세대학교 산학협력단 | A method of manufacturing metal-organic frameworks nanosheets, metal-organic frameworks manufactured using the method and gas separation membrane comprising the same |
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