KR101323247B1 - manufacturing method for synthsis of WO3 paste using Polyvinylpyrrolidone mixed solution for photoelectrode fabrication - Google Patents
manufacturing method for synthsis of WO3 paste using Polyvinylpyrrolidone mixed solution for photoelectrode fabrication Download PDFInfo
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- KR101323247B1 KR101323247B1 KR1020110129894A KR20110129894A KR101323247B1 KR 101323247 B1 KR101323247 B1 KR 101323247B1 KR 1020110129894 A KR1020110129894 A KR 1020110129894A KR 20110129894 A KR20110129894 A KR 20110129894A KR 101323247 B1 KR101323247 B1 KR 101323247B1
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- mixed solution
- photoelectrode
- paste composition
- polyvinylpyrrolidone
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- 239000011259 mixed solution Substances 0.000 title claims abstract description 42
- 229920000036 polyvinylpyrrolidone Polymers 0.000 title claims abstract description 42
- 239000001267 polyvinylpyrrolidone Substances 0.000 title claims abstract description 42
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 239000002243 precursor Substances 0.000 claims abstract description 14
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 19
- 238000007650 screen-printing Methods 0.000 claims description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000007606 doctor blade method Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010937 tungsten Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- KVIKMJYUMZPZFU-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O KVIKMJYUMZPZFU-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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Abstract
본 발명은 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법에 관한 것으로, 용매에 폴리비닐파이롤리돈(PVP)를 혼합하여 혼합용액을 형성시키는 제1단계와; 제1단계에서 형성된 혼합용액에 전구체인 AMT(Ammonium metatungstate)를 첨가하여 혼합용액을 반응시킴에 의해 투명한 페이스트 조성물을 형성시키는 제2단계;를 포함하여 형성되는폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법을 기술적 요지로 한다. 이에 따라, 텅스텐 전구체를 폴리비닐파이롤리돈 혼합용액에 분산시켜 페이스트 조성물을 형성시키고, 이를 광전극으로 도포시 투명도가 우수하다는 이점이 있다. The present invention relates to a method for producing a tungsten oxide paste composition for a photoelectrode using a polyvinylpyrrolidone mixed solution, the first step of forming a mixed solution by mixing polyvinylpyrrolidone (PVP) in a solvent; A second step of forming a transparent paste composition by reacting the mixed solution by adding AMT (Ammonium metatungstate) as a precursor to the mixed solution formed in the first step; the light using the polyvinylpyrrolidone mixed solution formed including The manufacturing method of the tungsten oxide paste composition for electrodes is made into a technical summary. Accordingly, the tungsten precursor is dispersed in the polyvinylpyrrolidone mixed solution to form a paste composition, and when applied to the photoelectrode, there is an advantage of excellent transparency.
Description
본 발명은 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법에 관한 것으로, 더욱 상세하게는, 텅스텐 전구체를 폴리비닐파이롤리돈 혼합용액에 분산시켜 페이스트 조성물을 형성시키고, 이를 광전극으로 도포시 투명도가 우수한 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법을 기술적 요지로 한다. The present invention relates to a method for producing a tungsten oxide paste composition for a photoelectrode, and more particularly, to a paste composition by dispersing a tungsten precursor in a polyvinylpyrrolidone mixed solution, and excellent transparency when applied to the photoelectrode The manufacturing method of the tungsten oxide paste composition for photoelectrodes using a polyvinylpyrrolidone mixed solution is made into a technical summary.
일반적으로, 광전극은 금속 산화물 나노입자를 포함하는 조성물을 기판 상에 도포하고, 소결(sintering)하는 방법으로 제조된다.In general, photoelectrodes are prepared by applying a composition comprising metal oxide nanoparticles onto a substrate and sintering.
즉, 기존의 광전극 형성용 조성물은 수열 반응(hydrothermal reaction)을 통해 타이타늄 산화물(TiO2) 등의 금속 산화물 나노입자의 콜로이드 용액을 합성한 후, 상기 콜로이드 용액에 적당량의 고분자 바인더(polymerbinder)를 혼합하는 방법으로 제조된다. That is, the conventional photoelectrode forming composition synthesizes a colloidal solution of metal oxide nanoparticles such as titanium oxide (TiO 2 ) through a hydrothermal reaction, and then adds an appropriate amount of polymer binder to the colloidal solution. It is prepared by the method of mixing.
이때 상기 고분자 바인더는 광전극 형성용 조성물에 높은 점도를 부여 함으로써, 조성물이 기판 상에 균일하게 도포될 수 있도록 한다.In this case, the polymer binder provides a high viscosity to the composition for forming a photoelectrode so that the composition can be uniformly applied onto the substrate.
위와 같이 제조된 광전극 형성용 조성물은 전도성 기판 위에 코팅되고, 상기 기판은 약 500 ℃의 온도에서 열처리(소결)된다.The photoelectrode forming composition prepared as described above is coated on a conductive substrate, and the substrate is heat treated (sintered) at a temperature of about 500 ° C.
이때, 기판을 고온에서 열처리 하는 이유는 고분자 바인더를 열분해시킴으로써 전해질이 통과할 수 있는 기공을 형성시킴과 동시에, 금속 산화물 나노입자와 기판과의 접착력을 증대시키고, 금속 산화물 나노입자간 상호 연결(necking, interconnection)을 유도함으로써 전자 전달 효율을 향상시키기 위함이다. At this time, the reason for heat-treating the substrate at a high temperature is to thermally decompose the polymer binder to form pores through which the electrolyte can pass, increase adhesion between the metal oxide nanoparticles and the substrate, and interconnect the metal oxide nanoparticles with each other. In order to improve electron transfer efficiency by inducing interconnection.
상기에서와 같이 광전극 형성용 조성물은 타이타늄 산화물(TiO2)이 대표적으로 사용되고, 다른 금속 산화물 등에 관하여는 활발한 연구가 이루어 지지 않는 실정이다. As described above, titanium oxide (TiO 2 ) is typically used as the composition for forming a photoelectrode, and active research on other metal oxides is not performed.
특히 텅스텐 산화물(WO3)인 경우에는 광전극을 제조하기 위한 시도들이 존재하였으나 사용되는 용액에 따라 투명도 등을 충족시키지 못하는 등의 문제가 발생 되는 경우가 존재하였다. In particular, in the case of tungsten oxide (WO 3 ), there have been attempts to fabricate a photoelectrode, but problems such as inability to satisfy transparency, etc., exist depending on the solution used.
따라서, 본 발명은 상기한 종래기술들의 문제점을 해결하기 위해 안출된 것으로, 텅스텐 전구체를 폴리비닐파이롤리돈 혼합용액에 분산시켜 페이스트 조성물을 형성시키고, 이를 광전극으로 도포시 투명도가 우수한 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법을 제공하는 것을 목적으로 한다. Accordingly, the present invention has been made to solve the above problems of the prior art, a tungsten precursor is dispersed in a polyvinylpyrrolidone mixed solution to form a paste composition, polyvinyl phi excellent when applied to the photoelectrode transparency An object of the present invention is to provide a method for producing a tungsten oxide paste composition for photoelectrodes using a mixed solution of rolidone.
상기한 목적을 달성하기 위한 본 발명은, 용매에 폴리비닐파이롤리돈(PVP)를 혼합하여 혼합용액을 형성시키는 제1단계와; 제1단계에서 형성된 혼합용액에 전구체인 AMT(Ammonium metatungstate)를 첨가하여 혼합용액을 반응시킴에 의해 투명한 페이스트 조성물을 형성시키는 제2단계;를 포함하여 형성됨을 특징으로 하는 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법.The present invention for achieving the above object, a first step of forming a mixed solution by mixing polyvinylpyrrolidone (PVP) in a solvent; A second step of forming a transparent paste composition by reacting the mixed solution by adding AMT (Ammonium metatungstate) as a precursor to the mixed solution formed in the first step; and a polyvinylpyrrolidone mixed solution, characterized in that it comprises a Method for producing a tungsten oxide paste composition for a photoelectrode using the same.
상기 제1단계는, 10℃~50℃의 온도에서 5분 내지 1시간 동안 진행되고, 상기 제2단계는 10℃~50℃온도에서 10분 내지 10시간 진행되는 것이 바람직하다. The first step is performed for 5 minutes to 1 hour at a temperature of 10 ℃ ~ 50 ℃, the second step is preferably 10 minutes to 10 hours at a temperature of 10 ℃ ~ 50 ℃.
상기 제1단계에서, 상기 혼합용액은 용매 100중량부에 대하여 폴리비닐파이롤리돈(PVP)이 1 내지 50 중량부 혼합되고, 상기 제2단계에서, 상기 혼합용액 100 중량부에 대하여 AMT(Ammonium metatungstate)가 10 내지 500 중량부 혼합되는 것이 바람직하다.In the first step, 1 to 50 parts by weight of polyvinylpyrrolidone (PVP) is mixed with respect to 100 parts by weight of the solvent, and in the second step, AMT (Ammonium) based on 100 parts by weight of the mixed solution metatungstate) is preferably mixed 10 to 500 parts by weight.
상기 2단계에서, 상기 혼합용액에는 AMT 외에 Bi, V, Si, Mg, Ni, Ru, Fe, W, Sn, Mo, Co, Cu, Zn, Se, Na, Ti 로 구성된 원소 중 하나 이상이 첨가되는 것이 바람직하다. In the second step, at least one of the elements consisting of Bi, V, Si, Mg, Ni, Ru, Fe, W, Sn, Mo, Co, Cu, Zn, Se, Na, Ti is added to the mixed solution. It is desirable to be.
상기 페이스트 조성물은 FTO(F:SnO2) 상면에 도포 되어 광전극으로 형성되고, 상기 도포는 닥터 블레이드법, 스프레이법, 페인팅법, 딥핑법, 스크린프린팅 법 중 하나로 형성되는 것이 바람직하다. The paste composition is applied to the upper surface of the FTO (F: SnO 2 ) to form a photoelectrode, the coating is preferably formed by one of the doctor blade method, spray method, painting method, dipping method, screen printing method.
상기 광전극 도포 후에 400℃~600℃에서 30분 내지 10시간 동안 열처리 되는 것이 바람직하다. After the photoelectrode is applied, heat treatment is preferably performed at 400 ° C. to 600 ° C. for 30 minutes to 10 hours.
이에 따라, 텅스텐 전구체를 폴리비닐파이롤리돈 혼합용액에 분산시켜 페이스트 조성물을 형성시키고, 이를 광전극으로 도포시 투명도가 우수하다는 이점이 있다. Accordingly, the tungsten precursor is dispersed in the polyvinylpyrrolidone mixed solution to form a paste composition, and when applied to the photoelectrode, there is an advantage of excellent transparency.
상기의 구성에 의한 본 발명은, 텅스텐 전구체를 폴리비닐파이롤리돈 혼합용액에 분산시켜 페이스트 조성물을 형성시키고, 이를 광전극으로 도포시 투명도가 우수하다는 효과가 있다. According to the present invention having the above configuration, the tungsten precursor is dispersed in the polyvinylpyrrolidone mixed solution to form a paste composition, and when applied to the photoelectrode, the transparency is excellent.
도1은 본 발명의 제1실시예에 의해 수득된 페이스트 조성물을 24시간 방치한 후의 분산 정도를 나타낸 사진이고,
도2는 광전극이 도포되지 않은 FTO 기판(a) 과 페이스트 조성물을 기판에 스크린 프린팅하여 이를 열처리 한 경우(b)를 나타낸 도이고,
도3은 본 발명의 제1실시예에 따라 형성된 광전극의 광전류밀도(photocurrent density)를 나타낸 도이고,
도4은 본 발명의 제2실시예에 따라 형성된 광전극의 광전류밀도(photocurrent density)를 나타낸 도이고,
도5는 본 발명의 제1실시예에 따른 광전극의 표면 SEM 이미지(a)이고, 제2실시예에 따른 표면 SEM 이미지(b)를 나타낸 도이고,
도6은 본 발명의 제1실시예에 따른 광전극의 측면 SEM 이미지(a)이고, 제2실시예에 따른 측면 SEM 이미지(b)를 나타낸 도이고,
도7은 본 발명의 제1실시예에 따른 광전극의 XRD 분석결과를 나타낸도이고,
도8은 본 발명의 제1실시예에 따른 광투과율 측정결과를 나타낸 도이고,
도9는 본 발명의 제1실시예, 제3실시예, 제4실시예에 따른 광전극의 광전특성 비교를 나타낸 도이다. 1 is a photograph showing the degree of dispersion after leaving the paste composition obtained by the first embodiment of the present invention for 24 hours,
FIG. 2 is a diagram illustrating a case in which an FTO substrate (a) and a paste composition, to which a photoelectrode is not applied, are screen-printed on a substrate and heat treated thereto (b),
3 is a diagram showing a photocurrent density of a photoelectrode formed according to the first embodiment of the present invention.
4 is a diagram showing a photocurrent density of a photoelectrode formed according to a second embodiment of the present invention.
5 is a surface SEM image (a) of the photoelectrode according to the first embodiment of the present invention, a surface SEM image (b) according to the second embodiment,
6 is a side SEM image (a) of a photoelectrode according to a first embodiment of the present invention, a side SEM image (b) according to a second embodiment,
7 is a view showing an XRD analysis result of the photoelectrode according to the first embodiment of the present invention,
8 is a view showing a light transmittance measurement result according to a first embodiment of the present invention,
9 is a diagram showing a comparison of photoelectric characteristics of photoelectrodes according to the first, third and fourth embodiments of the present invention.
이하 첨부된 도면을 참조로 본 발명의 바람직한 실시예를 상세히 설명하기로 한다. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명에 따른 용매에 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법은 폴리비닐파이롤리돈(PVP)를 혼합하여 혼합용액을 형성시키는 제1단계와; 제1단계에서 형성된 혼합용액에 전구체인 AMT(Ammonium metatungstate)를 첨가하여 혼합용액을 반응시킴에 의해 투명한 페이스트 조성물을 형성시키는 제2단계;로 구성된다. A method for preparing a tungsten oxide paste composition for a photoelectrode using a polyvinylpyrrolidone mixed solution in a solvent according to the present invention includes a first step of mixing polyvinylpyrrolidone (PVP) to form a mixed solution; And a second step of forming a transparent paste composition by reacting the mixed solution by adding AMT (Ammonium metatungstate) as a precursor to the mixed solution formed in the first step.
상기 제1단계는, 10℃~50℃의 온도에서 5분 내지 1시간 동안 진행되고, 상기 제2단계는 10℃~50℃온도에서 10분 내지 10시간 진행되며, 상기 혼합용액은 용매 100중량부에 대하여 폴리비닐파이롤리돈(PVP)이 1 내지 50 중량부 혼합된다. 여기서 PVP의 양이 상기 1중량부 보다 적으면 점성이 거의 없어서 후술하는 광전극을 형성시킬 때 도포가 되지 않으며, PVP의 양이 50중량부 보다 많으면 점성이 너무 커 페이스트 형태의 조성물이 되지 못한다. The first step is carried out for 5 minutes to 1 hour at a temperature of 10 ℃ ~ 50 ℃, the second step is 10 minutes to 10 hours at a temperature of 10 ℃ ~ 50 ℃, the mixed solution is 100 wt. To 1 part by weight of polyvinylpyrrolidone (PVP) is mixed. Here, if the amount of PVP is less than 1 part by weight, there is almost no viscosity, so that it is not applied when forming a photoelectrode to be described later. If the amount of PVP is more than 50 parts by weight, the viscosity is too large to form a paste composition.
상기 제2단계에서, 상기 혼합용액 100 중량부에 대하여 AMT(Ammonium metatungstate)가 10 내지 500 중량부 혼합되는 것이 바람직하며, AMT의 양이 10중량부보다 적으면 광전극 형성 시 전극 역할을 거의 하지 못하며, AMT양이 500중량부를 초과하면 AMT가 포화 되어 더 이상 녹아 들어가지 못하게 된다.
In the second step, it is preferable that 10 to 500 parts by weight of Ammonium metatungstate (AMT) is mixed with respect to 100 parts by weight of the mixed solution, and when the amount of AMT is less than 10 parts by weight, the electrode almost does not act as an electrode when forming the photoelectrode. If the amount of AMT exceeds 500 parts by weight, the AMT is saturated and no longer melted.
이하 본 발명의 구체적인 실시예를 상세히 설명하기로 한다.
Hereinafter, specific embodiments of the present invention will be described in detail.
< 제1실시예 >≪ Embodiment 1 >
본 발명의 제1실시예는 폴리비닐파이롤리돈(이하 'PVP'라 함) 1g을 10㎖의 증류수에 첨가한 다음 PVP가 다 용해될 때까지 10분 동안 기다려 혼합용액을 형성시킨다. In a first embodiment of the present invention, 1 g of polyvinylpyrrolidone (hereinafter referred to as 'PVP') is added to 10 ml of distilled water, and then waited for 10 minutes until the PVP is completely dissolved to form a mixed solution.
그런 다음, 용해된 상기 혼합용액에 WO3 광전극의 전구체인 AMT(Ammonium metatungstate)를 9g 첨가하여 다시 완전히 용해된 상태의 투명용액이 될 때까지 1시간 동안 방치시키면 페이스트 조성물이 형성된다. Thereafter, 9 g of AMT (Ammonium metatungstate), which is a precursor of the WO 3 photoelectrode, was added to the dissolved solution and left for 1 hour until it became a transparent solution in a completely dissolved state, thereby forming a paste composition.
상기 수득된 페이스트 조성물을 이용하여 FTO기판에 스핀코터(Spin coater)를 이용하여 500rpm 10초 동안 FTO 기판을 고정 후 2000rpm 회전시, 페이스트 조성물을 도포한다. The paste composition is applied to the FTO substrate using a spin coater to fix the FTO substrate for 10 seconds at 500 rpm and then rotated at 2000 rpm.
그런 다음, 500℃에서 1시간 동안 열처리하면, FTO기판에 WO3 투명 광전극이 형성된다.
Then, after heat treatment at 500 ° C. for 1 hour, a WO 3 transparent photoelectrode is formed on the FTO substrate.
< 제2실시예 >≪
본 발명의 제2실시에는 PVP 1g을 10㎖의 증류수에 첨가한 다음 PVP가 다 용해될 때까지 10분 동안 기다려 혼합용액을 형성시킨다. In a second embodiment of the present invention, 1 g of PVP is added to 10 ml of distilled water, and then waits 10 minutes until the PVP is completely dissolved to form a mixed solution.
그런 다음, 용해된 상기 혼합용액에 WO3 광전극의 전구체인 AMT(Ammonium metatungstate)를 9g 첨가하여 다시 완전히 용해된 상태의 투명용액이 될 때까지 1시간 동안 방치시키면 페이스트 조성물이 형성된다. Thereafter, 9 g of AMT (Ammonium metatungstate), which is a precursor of the WO 3 photoelectrode, was added to the dissolved solution and left for 1 hour until it became a transparent solution in a completely dissolved state, thereby forming a paste composition.
상기 수득된 페이스트 조성물은 70℃의 오븐에서 1시간 동안 건조하여 수분을 일부 증발시킨다. 이는 후술하는 스크린 프린팅 시 균일한 프린팅을 위해 수분의 일부를 증발시키는 과정이다. The paste composition obtained is dried in an oven at 70 ° C. for 1 hour to partially evaporate the moisture. This is a process of evaporating a part of moisture for uniform printing during screen printing, which will be described later.
상기 오븐에서 건조된 페이스트 조성물을 이용하여 FTO기판에 스크린 프린팅법을 이용하여 페이스트 조성물을 도포한다. The paste composition is applied to the FTO substrate by screen printing using the paste composition dried in the oven.
그런 다음, 500℃에서 1시간 동안 열처리하면, FTO기판에 WO3 투명 광전극이 형성된다.
Then, after heat treatment at 500 ° C. for 1 hour, a WO 3 transparent photoelectrode is formed on the FTO substrate.
< 제3실시예 >≪ Third Embodiment >
본 발명의 제3실시에는 PVP 1g을 10㎖의 증류수에 첨가한 다음 PVP가 다 용해될 때까지 10분 동안 기다려 혼합용액을 형성시킨다. In a third embodiment of the present invention, 1 g of PVP is added to 10 ml of distilled water, and then waited for 10 minutes until the PVP is completely dissolved to form a mixed solution.
그런 다음, 용해된 상기 혼합용액에 WO3 광전극의 전구체인 AMT(Ammonium metatungstate)를 8.82g 첨가하고, Zn 도핑을 위해 Zinc nitrate hexahydrate 0.18g을 첨가하여 완전히 용해된 상태의 투명용액이 될 때까지 1시간 방치시키면 페이스트 조성물이 형성된다. Then, 8.82 g of AMT (Ammonium metatungstate), which is a precursor of the WO 3 photoelectrode, was added to the dissolved solution, and 0.18 g of zinc nitrate hexahydrate was added for Zn doping until the solution was completely dissolved. If left for 1 hour, a paste composition is formed.
상기 수득된 페이스트 조성물은 70℃의 오븐에서 1시간 동안 건조하여 수분을 일부 증발시킨다. 이는 후술하는 스크린 프린팅 시 균일한 프린팅을 위해 수분의 일부를 증발시키는 과정이다. The paste composition obtained is dried in an oven at 70 ° C. for 1 hour to partially evaporate the moisture. This is a process of evaporating a part of moisture for uniform printing during screen printing, which will be described later.
상기 오븐에서 건조된 페이스트 조성물을 이용하여, FTO기판에 스크린 프린팅법을 이용하여 페이스트 조성물을 도포한다. Using the paste composition dried in the oven, the paste composition is applied to the FTO substrate by screen printing.
그런 다음, 500℃에서 1시간 동안 열처리하면, FTO기판에 Zn이 도핑된 WO3 투명 광전극이 형성된다.
Then, after heat treatment at 500 ° C. for 1 hour, a Zn-doped WO 3 transparent photoelectrode is formed on the FTO substrate.
< 제4실시예 >Fourth Embodiment
본 발명의 제4실시에는 PVP 1g을 10㎖의 증류수에 첨가한 다음 PVP가 다 용해될 때까지 10분 동안 기다려 혼합용액을 형성시킨다. In a fourth embodiment of the present invention, 1 g of PVP is added to 10 ml of distilled water and then waited for 10 minutes until the PVP is completely dissolved to form a mixed solution.
그런 다음, 용해된 상기 혼합용액에 WO3 광전극의 전구체인 AMT(Ammonium metatungstate)를 8.96g 첨가하고, Ti 도핑을 위해 Titanium diisopropoxide bis(acac)2 -propanol 75% 0.04g을 첨가하여 완전히 용해된 상태의 황색용액이 될 때까지 1시간 방치시키면 페이스트 조성물이 형성된다. Then, 8.96 g of AMT (Ammonium metatungstate), which is a precursor of the WO 3 photoelectrode, was added to the dissolved solution, and Titanium diisopropoxide bis (acac) 2 -propanol 75% 0.04 g was added to completely dissolve the mixture. It is left to stand for 1 hour until it becomes the yellow solution of a state, and a paste composition is formed.
상기 수득된 페이스트 조성물은 70℃의 오븐에서 1시간 동안 건조하여 수분을 일부 증발시킨다. 이는 후술하는 스크린 프린팅 시 균일한 프린팅을 위해 수분의 일부를 증발시키는 과정이다. The paste composition obtained is dried in an oven at 70 ° C. for 1 hour to partially evaporate the moisture. This is a process of evaporating a part of moisture for uniform printing during screen printing, which will be described later.
상기 오븐에서 건조된 페이스트 조성물을 이용하여, FTO기판에 스크린 프린팅법을 이용하여 페이스트 조성물을 도포한다. Using the paste composition dried in the oven, the paste composition is applied to the FTO substrate by screen printing.
그런 다음, 500℃에서 1시간 동안 열처리하면, FTO기판에 Ti이 도핑된 WO3 투명 광전극이 형성된다.
Then, after heat treatment at 500 ° C. for 1 hour, a WO 3 transparent photoelectrode doped with Ti is formed on the FTO substrate.
상기 실시예에서 수득된 페이스트 조성물 및 광전극의 물리화학적 성질을 측정하였는바, 이하 구체적으로 살펴보기로 한다.
The physical and chemical properties of the paste composition and photoelectrode obtained in the above example were measured, and will be described in detail below.
도1은 본 발명의 제1실시예에 의해 수득된 페이스트 조성물을 24시간 방치한 후의 분산 정도를 나타낸 사진으로 투명한 페이스트 조성물이 형성되어 분산이 양호함을 알 수 있다. 그리고 제2실시예, 및 제3실시예에 의한 페이스트 조성물도 상기 제1실시에와 같이 분산되어 투명하였으며, 제4실시예인 경우 분산은 양호하였으며 황색용액이 형성되었다. 1 is a photograph showing the degree of dispersion after leaving the paste composition obtained by the first embodiment of the present invention for 24 hours, it can be seen that the dispersion is good because a transparent paste composition is formed. The paste compositions according to the second and third embodiments were also dispersed and transparent as in the first embodiment. In the fourth embodiment, the dispersion was good and a yellow solution was formed.
도2는 광전극이 도포되지 않은 FTO 기판(a) 과 페이스트 조성물을 기판에 스크린 프린팅하여 이를 열처리 한 경우(b)를 나타낸 도로 본 발명의 제2실시예에 따른 페이스트 조성물은 투명하여 광전극으로의 이용이 가능함을 나타내고 있다. FIG. 2 is a diagram illustrating a case in which an FTO substrate (a) and a paste composition to which a photoelectrode is not applied are screen printed on a substrate and heat-treated to it (b). Indicates that can be used.
도3은 본 발명의 제1실시예에 따라 형성된 광전극의 광전류밀도(photocurrent density)를 나타내고, 도4은 본 발명의 제2실시예에 따라 형성된 광전극의 광전류밀도(photocurrent density)를 나타내었다. FIG. 3 shows the photocurrent density of the photoelectrode formed according to the first embodiment of the present invention, and FIG. 4 shows the photocurrent density of the photoelectrode formed according to the second embodiment of the present invention. .
도3 및 도4에 나타나 바와 같이, 양호한 광전 특성이 나타남을 알 수 있다. As shown in Figs. 3 and 4, it can be seen that good photoelectric properties are exhibited.
도5는 본 발명의 제1실시예에 따른 광전극의 표면 SEM 이미지(a)이고, 제2실시예에 따른 표면 SEM 이미지(b)를 나타낸 도이다. 5 is a surface SEM image (a) of the photoelectrode according to the first embodiment of the present invention, and a surface SEM image (b) according to the second embodiment.
도시된 바와 같이, 입자기 크기가 나노사이즈이고, 입자의 분산이 양호함을 알 수 있다. As shown, it can be seen that the particle size is nanosize and the dispersion of the particles is good.
도6은 본 발명의 제1실시예에 따른 광전극의 측면 SEM 이미지(a)이고, 제2실시예에 따른 측면 SEM 이미지(b)를 나타낸 도이다.6 is a side SEM image (a) of the photoelectrode according to the first embodiment of the present invention, and a side SEM image (b) according to the second embodiment.
도시된 바와 같이, 본 발명에 따른 광전극은 기판상면에 양호하게 접착되어 있음을 알 수 있다. As shown, it can be seen that the photoelectrode according to the present invention is well bonded to the upper surface of the substrate.
도7은 본 발명의 제1실시예에 따른 광전극의 XRD 분석결과를 나타낸도로써, WO3 물성이 나타난바, WO3 광전극이 양호하게 형성되어 있음을 알 수 있고, T(주석 산화물, tin oxide) 인 경우 기판에 의한 것으로 추정된다. 7 is a view showing the XRD analysis results of the photoelectrode according to the first embodiment of the present invention, WO 3 physical properties are shown, WO 3 It can be seen that the photoelectrode is formed well, and in the case of T (tin oxide), it is presumed to be due to the substrate.
도8은 본 발명의 제1실시예에 따른 광투과율 측정결과를 나타낸 도이다. 8 is a view showing a light transmittance measurement result according to a first embodiment of the present invention.
도시된 바와 같이, 본 발명에서, UV 영역을 포함하는 가시광성 영역에서 투과도가 일정하며 투과도가 우수함을 알 수 있다. As shown, in the present invention, it can be seen that the transmittance is constant and excellent in the visible region including the UV region.
도9는 본 발명의 제1실시예, 제3실시예, 제4실시예에 따른 광전극의 광전특성 비교를 나타낸 도로써, 제3실시예 및 제4실시예인 경우도 광전특성이 양호하게 나타남을 알 수 있다. 9 is a view showing a comparison of the photoelectric characteristics of the photoelectrode according to the first, third and fourth embodiments of the present invention. In the case of the third and fourth embodiments, the photoelectric characteristics are well represented. It can be seen.
이상에서와 같이, 텅스텐 전구체를 폴리비닐파이롤리돈 혼합용액에 분산시켜 페이스트 조성물을 형성시키고, 이를 광전극으로 도포시 분산성이 양호하여 투명도가 우수함을 알 수 있었다. As described above, it was found that the tungsten precursor was dispersed in the polyvinylpyrrolidone mixed solution to form a paste composition, and when it was applied to the photoelectrode, the dispersibility was good and the transparency was excellent.
Claims (10)
제1단계에서 형성된 혼합용액에 전구체인 AMT(Ammonium metatungstate)를 첨가하여 혼합용액을 반응시킴에 의해 투명한 페이스트 조성물을 형성시키는 제2단계;를 포함하여 구성되되,
상기 페이스트 조성물은 FTO(F:SnO2) 상면에 도포 되어 광전극으로 형성됨을 특징으로 하는 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법.A first step of forming a mixed solution by mixing polyvinylpyrrolidone (PVP) with a solvent;
A second step of forming a transparent paste composition by reacting the mixed solution by adding AMT (Ammonium metatungstate) as a precursor to the mixed solution formed in the first step;
The paste composition is a method of manufacturing a tungsten oxide paste composition for a photoelectrode using a polyvinylpyrrolidone mixed solution, characterized in that formed on the upper surface of the FTO (F: SnO 2 ) to form a photoelectrode.
상기 혼합용액은 용매 100중량부에 대하여 폴리비닐파이롤리돈(PVP)이 1 내지 50 중량부 혼합됨을 특징으로 하는 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법.The method of claim 1, wherein in the first step,
The mixed solution is a method for producing a tungsten oxide paste composition for a photoelectrode using a polyvinylpyrrolidone mixed solution, characterized in that 1 to 50 parts by weight of polyvinylpyrrolidone (PVP) is mixed with respect to 100 parts by weight of a solvent.
상기 혼합용액 100 중량부에 대하여 AMT(Ammonium metatungstate)가 10 내지 500 중량부 혼합됨을 특징으로 하는 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법.The method of claim 1, wherein in the second step,
Method for producing a tungsten oxide paste composition for a photoelectrode using a polyvinylpyrrolidone mixed solution, characterized in that 10 to 500 parts by weight of AMT (Ammonium metatungstate) is mixed with respect to 100 parts by weight of the mixed solution.
상기 혼합용액에는 AMT 외에 Bi, V, Si, Mg, Ni, Ru, Fe, W, Sn, Mo, Co, Cu, Zn, Se, Na, Ti 로 구성된 원소 중 하나 이상이 첨가됨을 특징으로 하는 폴리비닐파이롤리돈 혼합용액을 사용한 광전극용 텅스텐옥사이드 페이스트 조성물의 제조방법.The method of claim 1, wherein in the second step,
In addition to the AMT, at least one of the elements consisting of Bi, V, Si, Mg, Ni, Ru, Fe, W, Sn, Mo, Co, Cu, Zn, Se, Na, Ti is added to the mixed solution. Method for producing a tungsten oxide paste composition for a photoelectrode using a vinylpyrrolidone mixed solution.
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| KR100724814B1 (en) * | 1999-09-15 | 2007-06-04 | 아이엠알에이 아메리카, 인코포레이티드. | Electrode composition comprising doped tungsten oxides and method of preparation |
| KR20080114202A (en) * | 2007-06-27 | 2008-12-31 | 동우 화인켐 주식회사 | Conductive paste composition, electrode including the same and fabrication method of the electrode |
| KR100879767B1 (en) | 2007-01-12 | 2009-01-21 | 한국과학기술연구원 | Electrode for supercapacitor having heat-treated titanium dioxide layer and the fabrication method thereof |
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| KR100724814B1 (en) * | 1999-09-15 | 2007-06-04 | 아이엠알에이 아메리카, 인코포레이티드. | Electrode composition comprising doped tungsten oxides and method of preparation |
| KR100879767B1 (en) | 2007-01-12 | 2009-01-21 | 한국과학기술연구원 | Electrode for supercapacitor having heat-treated titanium dioxide layer and the fabrication method thereof |
| KR20080114202A (en) * | 2007-06-27 | 2008-12-31 | 동우 화인켐 주식회사 | Conductive paste composition, electrode including the same and fabrication method of the electrode |
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