KR0176291B1 - Method for fabricating transparent conductive film of zno and zno/sno2 double later using ultrasonic spraying method - Google Patents
Method for fabricating transparent conductive film of zno and zno/sno2 double later using ultrasonic spraying method Download PDFInfo
- Publication number
- KR0176291B1 KR0176291B1 KR1019950025877A KR19950025877A KR0176291B1 KR 0176291 B1 KR0176291 B1 KR 0176291B1 KR 1019950025877 A KR1019950025877 A KR 1019950025877A KR 19950025877 A KR19950025877 A KR 19950025877A KR 0176291 B1 KR0176291 B1 KR 0176291B1
- Authority
- KR
- South Korea
- Prior art keywords
- transparent conductive
- conductive film
- zinc oxide
- glass substrate
- zinc
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000005507 spraying Methods 0.000 title description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 239000011787 zinc oxide Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 14
- 229910001887 tin oxide Inorganic materials 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 5
- 239000005361 soda-lime glass Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 4
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021472 group 8 element Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 43
- 239000000243 solution Substances 0.000 abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 7
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1666—Ultrasonics
Abstract
투명전도막은 비정질 규소 태양전지나 액정표시장치 등의 박막표시장치에서 투명전극으로 사용되므로 가시광 투과율이 높고, 전기 저항이 작고, 화학적으로 안정되어 있어야 하며, 태양전지용 투명전도막의 경우 입사된 태양광의 다중 산란에 의한 반사 손실을 줄이기 위하여 요철구조의 표면형상을 가지고 있어야 한다.Since the transparent conductive film is used as a transparent electrode in a thin film display device such as an amorphous silicon solar cell or a liquid crystal display device, it has to have high visible light transmittance, small electrical resistance and chemical stability. In the case of a transparent conductive film for solar cells, multiple scattering of incident sunlight In order to reduce the reflection loss caused by this, the surface shape of the uneven structure should be used.
본 발명은 원료인 아연 화합물, Ⅲ족 원소의 화합물, 물 및 메탄올의 혼합용액을 초음파를 이용하여 무화시키고, 이를 반송가스에 실어 가열된 기판 위에서 열분해·산화 시킴으로써 산화아연계 박막을 투명한 기판에 입혀 투명전도막을 제조하는 방법이다.According to the present invention, a zinc oxide-based thin film is coated on a transparent substrate by atomizing a mixed solution of a zinc compound, a compound of a group III element, water, and methanol using ultrasonic waves, and pyrolyzing and oxidizing it on a heated substrate. It is a method of manufacturing a transparent conductive film.
산화아연계 투명전도막은 산화아연의 에너지 간격(금지대의 폭)이 크므로 가시광 투과율이 높으며, 불순물로서 Ⅲ족 원소를 미량 함유하기 때문에 전기 저항이 작고, 산화아연의 결합 에너지가 매우 크르모 화학적으로 안정되어 있다.The zinc oxide transparent conductive film has a high visible light transmittance because of the large zinc oxide energy gap (the width of the prohibition zone), and because it contains a small amount of group III elements as impurities, the electrical resistance is small, and the bonding energy of zinc oxide is very large. It is stable.
또한 본 발명에서는 원료 혼합용액을 초음파를 이용하여 무화시키는 방법을 사용하므로 CVD 법과는 달리 박막 제조장치의 구성과 조작이 간편하고, 원료의 투입을 물질별로 독립적으로 해야되는 번거로움을 피할 수 있다.In addition, the present invention uses a method of atomizing the raw material mixture solution using ultrasonic waves, unlike the CVD method, the configuration and operation of a thin film manufacturing apparatus is simple, and the trouble of having to independently input raw materials for each material can be avoided.
Description
제1도는 본 발명에 따른 방법을 실현시키기 위해 사용된 장치의 개략도.1 is a schematic diagram of an apparatus used to realize the method according to the invention.
제2도는 본 발명에서 얻은 산화아연(ZnO)계 또는 산화아연/산화주석(ZnO/SnO2) 이중층 투명전도막의 응용 사례인 비정질 규소 태양전지의 개략도.2 is a schematic diagram of an amorphous silicon solar cell which is an application example of a zinc oxide (ZnO) -based or zinc oxide / tin oxide (ZnO / SnO 2 ) double layer transparent conductive film obtained in the present invention.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
1 : 반응실 2 : 노즐1: reaction chamber 2: nozzle
3 : 유리기판 4 : 가열판3: glass substrate 4: heating plate
5 : 원료용액 6 : 초음파 진동자5: raw material solution 6: ultrasonic vibrator
7 : 초음파 진동자 냉각수 8 : 반송가스7: ultrasonic oscillator cooling water 8: carrier gas
9 : 태양광 10 : 유리기판9: solar 10: glass substrate
11 : 투명전극 12 : 비정질 규소층11 transparent electrode 12 amorphous silicon layer
14 : 이면금속전극14 back metal electrode
본 발명은 용매인 메탄올을 순수(deionized water)와 함께 적정 함량비의 원료와 혼합하여 용액으로 만들고, 이를 초음파 진동자를 이용하여 안개 모양의 미세한 입자로 무화시킨 다음, 반송가스에 실어 가열된 유리기판 위로 보내서 열분해·산화 반응시키는 초음파 용액 분무법에 의해 비정질 규소 태양전지용 산화아연(Ⅲ족 원소를 함유한 것 포함)계 투명전도막 또는 산화아연(Ⅲ족 원소를 함유한 것 포함)과 산화주석(Ⅶ족 원소를 함유한 것 포함)의 이중 구조(ZnO/SnO2)를 가진 투명전도막을 제조하기 위한 용액조성과 제조 기법에 관한 것이다.According to the present invention, a solvent is mixed with deionized water with a raw material having an appropriate content ratio to make a solution, and atomized into mist-like fine particles by using an ultrasonic vibrator, and then loaded on a carrier gas and heated on a glass substrate. Zinc oxide (including group III element) transparent conductive film or zinc oxide (including group III element) and tin oxide (A) for amorphous silicon solar cells The present invention relates to a solution composition and a manufacturing technique for producing a transparent conductive film having a double structure (including ZnO / SnO 2 ) containing a group element.
제2도와 같은 구조를 가진 비정질 규소 태양전지에서 유리기판 위의 투명 전극으로 사용되는 투명전도막은 가시광에 대한 투과율이 높아야 하는 동시에 저항이 작아야 한다. 산화아연을 소재로 하는 투명전도막은 이와같은 조건을 만족시키는 동시에 화학적·물리적 내구성이 매우 우수하다고 알려져 있다.In the amorphous silicon solar cell having the structure as shown in FIG. 2, the transparent conductive film used as the transparent electrode on the glass substrate should have high transmittance to visible light and low resistance. It is known that a transparent conductive film made of zinc oxide satisfies these conditions and has excellent chemical and physical durability.
이와같은 투명전도막의 제조방법으로는 진공증착(vacuum evaporation), 스퍼터링(sputtering), 이온도금(ion plating)등의 물리적인 방법과 화학 증기증착(chemicla vapor deposition ; CVD)같은 화학적인 방법이 있으며, 생산원가 측면에서는 화학적인 방법이 물리적인 방법보다 훨씬 경제적이다.As a method of manufacturing such a transparent conductive film, there are physical methods such as vacuum evaporation, sputtering, ion plating, and chemical methods such as chemical vapor deposition (CVD). In terms of production costs, chemical methods are much more economical than physical methods.
투명전도막에 대한 특허증 스퍼터링에 의한 단일층(single layer)산화아연 투명전도막에 대해서는 일본 특허(공개번호 6-345426)가 출원·공개되어 있으며, 산화아연계는 아니나 CVD 법에 의한 산화주석계 투명전도막에 대해서도 여러편의 특허(일본 ; 일본 61-225714, 61-227946, 63-89657, 64-91959)가 출원·공개되어 있다. 그러나 아직 스퍼터링법 이외의 제조방법에 의한 단일층 산화아연 투명전도막이나 산화아연/산화주석(ZnO/SnO2)의 이중층 구조의 투명전도막에 대해서는 어떤 특허도 출원·공개된 바 없다.Japanese Patent (Publication No. 6-345426) for a single layer zinc oxide transparent conductive film by sputtering of a transparent conductive film has been filed and disclosed, and not a zinc oxide system, but a tin oxide system by CVD method Several patents (Japan; Japan; 61-225714, 61-227946, 63-89657, and 64-91959) have also been filed and published for transparent conductive films. However, no patent has been filed or disclosed for a single layer zinc oxide transparent conductive film or a double layer zinc oxide / tin oxide (ZnO / SnO 2 ) transparent conductive film by a production method other than sputtering.
CVD 법을 이용하여 투명전도막을 제조할 경우에는 출발 물질로서 기체를 사용하거나 또는 액체상태의 원료와 용매를 각각 별도의 장치를 사용하여 기화시키고, 조성비에 맞게 각각의 증기 투입량을 조정하여 이를 반송가스에 실어 가열된 유리기판 위에서 열분해·산화 반응시켜 막을 기판에 입히게 된다.When manufacturing a transparent conductive film by CVD method, gas is used as a starting material, or a liquid raw material and a solvent are vaporized by using a separate device, and each steam input amount is adjusted according to the composition ratio, and this is returned to the carrier gas. The film is coated on the substrate by pyrolysis and oxidation reaction on the heated glass substrate.
그러나 본 발명에서는 원료를 용매인 메탄올, 물과 함께 적정함량 비로 혼합하여 초음파를 이용해서 안개 모양의 미세한 입자로 무화시키고, 이를 반송가스에 실어 가열된 유리기판 위에서 열분해·산호 반응에 의해 투명전도막을 제조하는 초음파 용액 분무법이므로 제조 기술면에서 CVD 법과는 근본적으로 다른 방법이다.However, in the present invention, the raw material is mixed with a solvent of methanol and water at an appropriate content ratio and atomized into fine mist-like particles by using ultrasonic waves, and the transparent conductive film is formed by pyrolysis and coral reaction on a heated glass substrate loaded with carrier gas. Since it is the ultrasonic solution spray method to manufacture, it is fundamentally different from the CVD method from a manufacturing technique.
또한 CVD 법과는 달리 필요한 원료의 투입량을 각각 조절하는 번거로움이 없이 적절한 용액의 조성과 제조조건 및 제조 장치만으로도 우수한 전기적·광학적 특성과 요철 표면 형상을 가진 산화아연계 투명전도막을 얻을 수 있다.In addition, unlike the CVD method, a zinc oxide-based transparent conductive film having excellent electrical and optical properties and uneven surface shape can be obtained only with an appropriate solution composition, manufacturing conditions, and manufacturing equipment, without the hassle of controlling the input amount of raw materials.
또한 이미 국내특허(공개번호 92 - 7251호)를 취득한 불소함유 산화주석 투명전도막과 산화아연 투명전도막의 이중층을 형성함으로써 비정질 규소 태양전지의 제조분위기인 수소 플라즈마에 대한 내구성을 갖게 할 수 있으며, 단일층 투명전도막보다 낮은 저항을 나타내는 투명전도막을 제조할 수 있다.In addition, by forming a double layer of a fluorine-containing tin oxide transparent conductive film and a zinc oxide transparent conductive film, which have already obtained a domestic patent (Publication Nos. 92-7251), it can provide durability against hydrogen plasma, which is a manufacturing atmosphere of amorphous silicon solar cells. A transparent conductive film having a lower resistance than a single layer transparent conductive film can be produced.
초음파 용액 분무법에 의한 박막제조에 대해서는 이미 여러편의 특허(미국 3880112, 일본 61-69961, 63-69968, 64-28378, 국내 073457)가 출원·공개되어 있다. 그러나 미국특허와 일본특허는 제조장치의 구성과 노즐장와 용액 분무법을 이용하는 창연(Sb, 안티몬)함유 산화주석 투명전도막 제조를 위한 용액 조성 및 제조방법에 관한 것으로서 산화아연계 투명전도막을 제조하기 위한 용액조성과 제조방법에 관한 특허는 출원되어 있지 않다. 그리고 국내 특허는 용액 분무법에 의한 불소함유 산화주석 투명전도막의 제조에 관한 것이다.A number of patents (US 3880112, Japan 61-69961, 63-69968, 64-28378, Korea 073457) have already been filed and published for thin film production by the ultrasonic solution spray method. However, the US and Japanese patents are concerned with the composition of the manufacturing apparatus and the composition and method for preparing the tin oxide transparent conductive film containing bismuth (Sb, antimony) using the nozzle field and the solution spraying method. There is no patent for solution composition and preparation method. And the domestic patent relates to the production of fluorine-containing tin oxide transparent conductive film by a solution spray method.
또한 일본특허공개공보 제05152213호가 있으나 이는 자외선 흡수막의 제조에 관한 것으로 대상물질이 산화티탄, 질화규소, 산화아연이다. 하지만 본 발명의 제조방법은 CVD(Chemical Vapor Dcposition)이다. CVD 방법은 반응하기전 원료물질의 상태가 반드시 기체이어야 한다. 물론 액체상태로도 사용할 수 있지만 사전에 가열(별도의 장치 필요)하여 반드시 기체상태로 변환시켜야 한다.There is also Japanese Patent Application Laid-Open No. 05152213, which relates to the manufacture of an ultraviolet absorbing film, wherein the target materials are titanium oxide, silicon nitride, and zinc oxide. However, the manufacturing method of the present invention is CVD (Chemical Vapor Dcposition). The CVD method requires that the state of the raw material be a gas before reacting. Of course, it can also be used in liquid form, but must be converted to gaseous state by heating in advance (separate device required).
본 발명의 초음파분무법은 초음파를 이용하여 액체 상태의 원료 물질을 무화시켜 사용하는 점에서 상기 선행기술과 근본적인 차이가 있다. 따라서 기존 기술에서 언급된 조건으로는 결코 본 발명에서 획득하는 양질의 투명전도막을 얻을 수 없다.The ultrasonic atomization method of the present invention is fundamentally different from the prior art in that atomization of a raw material material in a liquid state using an ultrasonic wave is used. Therefore, under the conditions mentioned in the prior art, it is never possible to obtain a high quality transparent conductive film obtained in the present invention.
본 발명은 전기광학적 특성이 우수한 산화아연계 투명전도막의 제조에는 반드시 제3의 첨가물(불순물)을 의도적으로 첨가하였다.In the present invention, a third additive (impurity) is intentionally added to the production of a zinc oxide transparent conductive film having excellent electro-optical properties.
위와 같이 산화아연 및 산화주석/산화아연 이중층을 기본으로 하는 투명진도막을 초음파분무법으로 제조하는 방법, 특히 출발용액의 조성에 관한 것이 본 발명의 요지이다.As described above, a method for preparing a transparent progressive film based on zinc oxide and tin oxide / zinc oxide bilayers by ultrasonic spraying, in particular, regarding the composition of the starting solution is the gist of the present invention.
이하 발명의 요지를 간략하여 그 실시예에 의하여 자세히 설명하면 다음과 같다.Hereinafter, the gist of the invention will be described in detail by way of examples.
유리기판 위에 투명전도막을 형성시키는 방법에 있어서, 메탄올을 주 용매로 하고 순수와 아연 화합물 및 Ⅲ족 원소 화합물의 혼합용액을 초음파로 진동시켜 무화시킨 후 이를 반송가스와 함께 가열된 유리기판 또는 산화주석(Ⅶ족 원소를 함유한 것 포함)의 막이 입혀진 유리기판과 접촉시켜 열분해·산화 반응에 의한 불순물로서 Ⅲ족 원소가 함유된 산화아연을 주성분으로 하는 투명전도막을 얻는 것을 특징으로 하는 산화아연을 주성분으로 하는 투명전도막을 얻는 것을 특징으로 하는 산화아연 단일층 투명전도막 또는 산화아연/산화주석 이중구조 투명전도막을 제조하는 것이고 이 기술중 유리 기판은 코닝 7059 바륨붕사유리, 소다석회유리, 소다석회유리 위에 알칼리 이온의 확산을 억제하기 위한 산화규소(SiO2) 막이 입혀진 유리 또는 이와같은 유리위에 산화주석(Ⅶ족 원소를 함유한 것 포함)막이 입혀진 기판을 이용하며, 아연 화합물은 ZnCl2, Zn(CH3COO)2·nH2O 중의 하나이고, Ⅲ족 원소의 화합물은 AlCl3나 InCl3중의 하나이며, 혼합용액 중에서 아연에 대한 Ⅲ족 원소의 무게비가 0.1%이상이며, 혼합용액중 몰에 대한 메탄올의 몰(mole)비가 0.1이상이며, 초음파 진동자의 발생 주파수가 1 ∼ 2㎒이며, 반송가스는 공기, 산소(O2), 질소(N2), 수소(H2)중의 하나이며 열분해·산화 반응을 위한 유리기판의 온도가 300 ∼ 500℃범위이며, 산화아연의 막은 두께가 0.3 ∼ 3㎛의 범위로 표면요철 구조를 가진 투명전도막의 제조방법인 것이다.In the method of forming a transparent conductive film on a glass substrate, a glass substrate or tin oxide heated with a carrier gas after methanol is a main solvent and the mixed solution of pure water, zinc compound and group III element compound is ultrasonically vibrated and atomized. Zinc oxide, the main component of which is obtained by contacting a glass substrate coated with a film (including a group VIII element) to obtain a transparent conductive film mainly composed of zinc oxide containing group III elements as impurities by thermal decomposition and oxidation reactions. To prepare a zinc oxide single layer transparent conductive film or a zinc oxide / tin oxide double structure transparent conductive film, characterized in that the transparent conductive film is obtained, wherein the glass substrate is Corning 7059 barium borax glass, soda lime glass, soda lime glass Glass coated with silicon oxide (SiO 2 ) film to suppress diffusion of alkali ions or the like A substrate coated with a tin oxide film (including one containing a Group VIII element) on glass is used. The zinc compound is one of ZnCl 2 and Zn (CH 3 COO) 2 nH 2 O, and the Group III element is AlCl 3. Or one of InCl 3 , the weight ratio of the group III element to zinc in the mixed solution is 0.1% or more, the mole ratio of methanol to mole in the mixed solution is 0.1 or more, and the generation frequency of the ultrasonic vibrator is 1 to 2 ㎒, the carrier gas is one of air, oxygen (O 2 ), nitrogen (N 2 ) and hydrogen (H 2 ), and the temperature of the glass substrate for pyrolysis and oxidation reaction ranges from 300 to 500 ° C. It is a manufacturing method of the transparent conductive film which has a surface asperity structure in the range of thickness 0.3-3 micrometers.
[실시예]EXAMPLE
CH3OH 100 cc, H2O 7 cc에 Zn(CH3COO)2·2H2O 15g, InCl34g을 녹인 용액을 초음파 진동자(주파수 1.7㎒)로 무화시켜 이를 공기에 실어 약 400℃로 가열된 코닝 7059 바륨붕사유리 또는 두께 1,000Å의 SiO2막을 입힌 소다석회유리 기판위에서 열분해·산화시켜 성장속도 약 300Å/초로 두께 6,000Å의 In 함유 산화아연 투명전도막을 얻었다. 투명전도막의 가시광 투과율은 약 80%, 비저항은 4 ×10-4Ω㎝였다.15 g of Zn (CH 3 COO) 2 · 2H 2 O and 4 g of InCl 3 were dissolved in 100 cc of CH 3 OH, 2 h of 7 cc, and 4 g of InCl 3 was atomized with an ultrasonic vibrator (frequency 1.7 MHz) and loaded into air at about 400 ° C. Pyrolysis and oxidation were performed on a heated Corning 7059 barium borax glass or a soda-lime glass substrate coated with a SiO 2 film having a thickness of 1,000 Å to obtain an In-containing zinc oxide transparent conductive film having a thickness of 6,000 Å at a growth rate of about 300 Å / sec. The visible light transmittance of the transparent conductive film was about 80% and the specific resistance was 4x10 -4 Ωcm.
그리고 주사 전자 현미경(scanning electron microscope ; SEM)으로 관찰한 투명전도막의 표면은 크기 약 0.2 ∼ 0.3㎛의 입자가 치밀하게 들어찬 요철 구조를 가지고 있었다.The surface of the transparent conductive film observed with a scanning electron microscope (SEM) had a concavo-convex structure in which particles of about 0.2 to 0.3 µm in size were densely packed.
이와같이 본 발명은 필요한 원료 투입량을 조정하는 번거로움이 없고, 장치를 간단히 할 수 있으면서도 CVD 법보다 우수한 투명전도막을 얻을 수 있어 비정질 규소 태양전지의 실용화를 앞당길 수 있다.As described above, the present invention is not cumbersome to adjust the required raw material input amount, and the device can be simplified, and a transparent conductive film superior to the CVD method can be obtained, which can accelerate the practical use of the amorphous silicon solar cell.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950025877A KR0176291B1 (en) | 1995-08-22 | 1995-08-22 | Method for fabricating transparent conductive film of zno and zno/sno2 double later using ultrasonic spraying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950025877A KR0176291B1 (en) | 1995-08-22 | 1995-08-22 | Method for fabricating transparent conductive film of zno and zno/sno2 double later using ultrasonic spraying method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR970012993A KR970012993A (en) | 1997-03-29 |
| KR0176291B1 true KR0176291B1 (en) | 1999-04-15 |
Family
ID=19424035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019950025877A KR0176291B1 (en) | 1995-08-22 | 1995-08-22 | Method for fabricating transparent conductive film of zno and zno/sno2 double later using ultrasonic spraying method |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR0176291B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101355236B1 (en) * | 2010-07-30 | 2014-01-27 | 히타치 긴조쿠 가부시키가이샤 | Oxide semiconductor target and mehtod for manufacturing oxide semiconductor film |
| WO2016137233A1 (en) * | 2015-02-24 | 2016-09-01 | 한양대학교 산학협력단 | Method for forming zinc-doped tin oxide thin film |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100626822B1 (en) * | 2004-06-24 | 2006-09-20 | 김용성 | Manufacturing method of zinc oxide thin film |
| CN101887849B (en) * | 2010-06-29 | 2011-12-21 | 上海大学 | Method and device for preparing ZnO film by two-step deposition method |
| CN103177800B (en) * | 2011-12-22 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of high transmittance transparent conductive film and preparation method thereof |
-
1995
- 1995-08-22 KR KR1019950025877A patent/KR0176291B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101355236B1 (en) * | 2010-07-30 | 2014-01-27 | 히타치 긴조쿠 가부시키가이샤 | Oxide semiconductor target and mehtod for manufacturing oxide semiconductor film |
| WO2016137233A1 (en) * | 2015-02-24 | 2016-09-01 | 한양대학교 산학협력단 | Method for forming zinc-doped tin oxide thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970012993A (en) | 1997-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH02503615A (en) | Substrate for solar cells | |
| WO2002016679A1 (en) | Polycrystalline semiconductor material and method of manufacture thereof | |
| KR20000049201A (en) | Chemical vapor deposition of aluminum oxide | |
| US6761986B2 (en) | Thin film infrared transparent conductor | |
| JPH04506505A (en) | Zinc oxyfluoride transparent conductor | |
| JPH01145350A (en) | Method for agglutinating tin oxide of aggregated construction form | |
| KR0176291B1 (en) | Method for fabricating transparent conductive film of zno and zno/sno2 double later using ultrasonic spraying method | |
| JPS61227946A (en) | Electroconductive glass | |
| WO1984002229A1 (en) | Photovoltaic cell | |
| AU2007290844B2 (en) | Method of forming a zinc oxide coated article | |
| JP2001059175A (en) | Tin oxide film, its production and device for producing tin oxide film | |
| Gaikwad et al. | Nanocrystalline ZnO films deposited by spray pyrolysis: Effect of gas flow rate | |
| KR940001291B1 (en) | Manufacturing method of trasparent conducting film for amorphous silicon solar cell | |
| JPH0421638B2 (en) | ||
| JPH0438147B2 (en) | ||
| JPS62213281A (en) | Transparent conductive film | |
| JPH0413301B2 (en) | ||
| JP3558519B2 (en) | Method for manufacturing transparent conductive film and method for manufacturing photovoltaic element | |
| JPS6269405A (en) | Transparent conductive substrate for photoelectric element | |
| JP2853125B2 (en) | Method for producing transparent conductive film | |
| SU890907A1 (en) | Method for preparing photosensitive cadmium sulfide films | |
| JPH03104871A (en) | Production of thin film by magnetic field microwave plasma cvd method | |
| US4931308A (en) | Process for the preparation of functional tin oxide thin films | |
| JPS6147227B2 (en) | ||
| JPS58115020A (en) | Preparation of amorphous silicon film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20121114 Year of fee payment: 15 |
|
| FPAY | Annual fee payment |
Payment date: 20131108 Year of fee payment: 16 |
|
| FPAY | Annual fee payment |
Payment date: 20140923 Year of fee payment: 17 |
|
| EXPY | Expiration of term |