CN105655414A - Method for cation exchange in-situ deposition of Ag2S quantum dots - Google Patents
Method for cation exchange in-situ deposition of Ag2S quantum dots Download PDFInfo
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- CN105655414A CN105655414A CN201610039477.XA CN201610039477A CN105655414A CN 105655414 A CN105655414 A CN 105655414A CN 201610039477 A CN201610039477 A CN 201610039477A CN 105655414 A CN105655414 A CN 105655414A
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- 238000000034 method Methods 0.000 title claims abstract description 16
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical group [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 title claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 title abstract description 8
- 230000008021 deposition Effects 0.000 title abstract description 7
- 238000005341 cation exchange Methods 0.000 title abstract description 4
- 239000002096 quantum dot Substances 0.000 claims abstract description 31
- 229910052946 acanthite Inorganic materials 0.000 claims abstract description 10
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 5
- 150000004763 sulfides Chemical class 0.000 claims abstract description 5
- 239000010405 anode material Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims 2
- 238000011010 flushing procedure Methods 0.000 claims 1
- 229910001961 silver nitrate Inorganic materials 0.000 claims 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 230000005693 optoelectronics Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 229910004613 CdTe Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011066 ex-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a method for in-situ deposition of Ag2S quantum dots on a photo-anode through a cation exchange mode. Specifically the method comprises the following steps of: 1) preparing a soluble salt solution of a certain concentration, including Ag+; and 2) immersing an photo-anode with grown metal sulfide quantum dots into the salt solution including Ag+ for a certain time, and exchanging metal cations to obtain an Ag2S quantum dot sensitized photo-anode. The photo-anode is applicable to an optoelectronic chemical device. The method for in-situ deposition of the Ag2S quantum dots on the photo-anode through the cation exchange mode has advantages that the operation is safe and convenient, the material is saved, the cost is reduced, and the industrialized popularization and application are facilitated.
Description
Technical field
The present invention relates to a kind of by the mode of cation replacement on light anode in-situ deposition Ag2S quantum dot method, its application is mainly in Optical Electro-Chemistry association area.
Background technology
Due to many merits such as quantum size effect and many exciton effects, the quantum dot sensitized solar cell based on technology of quantum dots obtains bigger concern in recent years. CdS/CdSe is widely studied as classical efficient sensitization system altogether at present, but the absorption long wavelength threshold of this system is about 700nm, it is impossible to realize absorption and the conversion of major part HONGGUANG and near infrared band light, to such an extent as to the sunlight of about 40% is not utilized. Limit red shift is absorbed so that sensitizer band gap is better mated with sunlight power spectrum, CuInS for realizing sensitizer2��PbS��CdTe��Ag2S quantum dot is used as efficiency light sensitizer.
Ag2S is band gap width is the direct band-gap semicondictor of 1.1eV, its optical band gap in photovoltaic device the best band gap (1.0-1.5eV) scope, near infrared region spectral response range can widened to 1100nm wave band. Relative to CuInS2This ternary compound inorganic semiconductor quantum dot, Ag2S is easier to preparation as a kind of binary compound, and the raw material needed for its preparation is also more cheap. Relative to PbS, CdTe quantum, Ag2S is more friendly to environment. The band gap of PbS is 0.37eV, and at the bottom of conduction band, position is relatively low, can be with matrix material and PbS quantum that sunlight power spectrum matching is good to obtain, it is desirable to its particle diameter is less than other quantum dot, and this is that the preparation of PbS quantum adds difficulty. CdTe quantum is except link is polluted by Cd, and Te is rare element, and in preparation process, Te source is expensive and unstable, and this also greatly limit the use of CdTe quantum. So Ag2S quantum dot has huge application potential in photoelectrochemicalcell cell.
Prepare Ag at present2The method of S quantum dot mainly has Ex-situ sythesis method, Photodeposition and SILAR method. Ex situ method is first to synthesize Colloidal Quantum Dots, then passes through the mode (such as directly absorption or bridging agent auxiliary absorption) of ex situ, is deposited to by quantum dot in wide bandgap semiconductor materials (photo anode base material). Directly during absorption, the surface of quantum dot is surrounded by the organic molecule of one layer of long-chain, the mode that this dependence long-chain molecule directly adsorbs makes quantum dot coverage rate reduce, and these long-chain molecules can reduce the charge transfer rate between quantum dot and semiconductor optical anode, and then reduces electricity conversion.During auxiliary absorption, quantum dot surface is generally coated with by water solublity bifunctional molecules, they can as the surface of bridging agent Molecular Adsorption to semiconductor optical anode, but bridging agent molecule not only affects the load capacity of quantum dot, also can affect the transmission of electric charge, separation and compound, thus reducing photoelectric transformation efficiency. Light anode is immersed Ag by having main steps that of Photodeposition+In the solution of source, and clean with taking out after high intensity Hg lamp irradiation certain time and dry, then light anode is immersed S2-Source solution is incubated a few hours prepared Ag in a heated condition2S quantum dot. This preparation process is loaded down with trivial details, and preparation condition is wayward, and preparation time is long, is unfavorable for industry production application. SILAR method deposition Ag2During S, Ag2S quantum dot not easily adsorbs at photoanode surface, and along with the increase of frequency of depositing, inevitably generates precipitation in the solution so that precursor solution cannot re-use, and causes a large amount of wastes of source solution. Silver itself belongs to noble metal, is unfavorable for the reduction of production cost. For this kind of situation, we first introduce one on light anode and are relatively easy to absorption, raw material sources metal sulfide quantum dots wide, low-cost, then metal ion is replaced as Ag+, thus on light anode material growth in situ Ag2S quantum dot. The method is easy and simple to handle, with low cost, reproducible, it is simple to industrialized production is applied.
Summary of the invention
The invention provides a kind of growth in situ Ag on light anode material2The method of S quantum dot, and applied it to photoelectrochemicalcell cell. The method is simple to operate, reproducible, it is not necessary to linking agent is assisted, and decreases the waste of Ag source solution.
Present invention aim at providing a kind of in-situ deposition Ag on light anode material2The method of S quantum dot, is accomplished by:
1. smooth anode material such as SnO2Porous membrane, ZnO nano post array, TiO2The preparation of nano column array
2. the synthesis of quantum dot
1) on light anode material, metal sulfide quantum dots is grown;
2) being equipped with concentration is that 0.01 ~ 0.1M contains Ag+Soluble salt solutions;
3) by step 1) the light anode that obtains immerses step 2) 5 ~ 10min in the saline solution prepared, take out by corresponding solvent clean totally, and dry. On light anode material, then form Ag2The quantum dot sensitized oxidant layer of S.
Detailed description of the invention:
Hereinafter implement to be intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1:
1) at SnO2Porous membrane light anode material grows CdS quantum dot;
2) being equipped with concentration is the AgNO of 0.1M3Aqueous solution;
3) by step 1) the light anode material that obtains immerses step 2) provisioned AgNO3Aqueous solution soaks 2 minutes, cleans with deionized water after taking-up and dry, finally at light anode material SnO2Porous membrane is formed Ag2The quantum dot sensitized oxidant layer of S.
Embodiment 2:
1) at TiO2Nano column array light anode material grows ZnS quantum dot;
2) being equipped with concentration is the AgNO of 0.1M3Aqueous solution;
3) by step 1) the light anode material that obtains immerses step 2) provisioned AgNO3Aqueous solution soaks 5 minutes, then takes out and clean with deionized water and dry, finally at light anode material TiO2Nano column array is formed Ag2The quantum dot sensitized oxidant layer of S.
Embodiment 3:
1) on ZnO nano post array photo-anode material, ZnS quantum dot is grown;
2) being equipped with concentration is the AgNO of 0.1M3Aqueous solution;
3) by step 1) the light anode material that obtains immerses step 2) provisioned AgNO3Aqueous solution soaks 10 minutes, then takes out and clean with deionized water and dry, on light anode material ZnO nano post array, finally form Ag2The quantum dot sensitized oxidant layer of S.
Claims (7)
1. an efficient preparation Ag2S quantum dot is to the method on light anode, it is characterised in that comprise the following steps:
(1) on light anode material, metal sulfide quantum dots is grown;
(2) soluble silver salt is dissolved in liquid medium, makes containing Ag+Source solution;
(3) the light anode of preparation in (1) is immersed Ag described above+In solution, take out flushing after a period of time, dry.
2. in claim 1, light anode material includes nano column array (ZnO nano post array, SnO2Nano column array, TiO2Nano column array etc.) and porous membrane (SnO2��TiO2, ZnO etc.).
3. in claim 1, metal sulfide quantum dots includes ZnS, CdS, SnS, is wherein preferably ZnS.
4. Ag selected in claim 1+Source is selected from silver nitrate.
5. liquid medium selected in claim 1 is water.
6. Ag in claim 1+Concentration is 0.01 ~ 1mol/L.
7. the time soaked in claim 1 is 2 ~ 10min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610039477.XA CN105655414A (en) | 2016-01-21 | 2016-01-21 | Method for cation exchange in-situ deposition of Ag2S quantum dots |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610039477.XA CN105655414A (en) | 2016-01-21 | 2016-01-21 | Method for cation exchange in-situ deposition of Ag2S quantum dots |
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| Publication Number | Publication Date |
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| CN105655414A true CN105655414A (en) | 2016-06-08 |
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| CN201610039477.XA Pending CN105655414A (en) | 2016-01-21 | 2016-01-21 | Method for cation exchange in-situ deposition of Ag2S quantum dots |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018120515A1 (en) * | 2016-12-30 | 2018-07-05 | Tcl集团股份有限公司 | Quantum dot material, preparation method therefor, and semiconductor device |
| CN110713201A (en) * | 2019-12-16 | 2020-01-21 | 桑顿新能源科技(长沙)有限公司 | Preparation method of fluoride quantum dots |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014081419A2 (en) * | 2012-11-20 | 2014-05-30 | The Board Of Trustees Of The Leland Stanford Junior University | High resolution imaging using near-infrared-ii fluorescence |
| CN104377036A (en) * | 2014-10-31 | 2015-02-25 | 东华大学 | Method for preparing AgInS2 quantum dot sensitized TiO2 photoelectrode with In2S3 used as buffer layer |
-
2016
- 2016-01-21 CN CN201610039477.XA patent/CN105655414A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014081419A2 (en) * | 2012-11-20 | 2014-05-30 | The Board Of Trustees Of The Leland Stanford Junior University | High resolution imaging using near-infrared-ii fluorescence |
| CN104377036A (en) * | 2014-10-31 | 2015-02-25 | 东华大学 | Method for preparing AgInS2 quantum dot sensitized TiO2 photoelectrode with In2S3 used as buffer layer |
Non-Patent Citations (1)
| Title |
|---|
| DONG HEE SON，STEVEN M. HUGHES，YADONG YIN，A. PAUL ALIVISATOS: "Cation Exchange Reactions in Ionic Nanocrystals", 《SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018120515A1 (en) * | 2016-12-30 | 2018-07-05 | Tcl集团股份有限公司 | Quantum dot material, preparation method therefor, and semiconductor device |
| US11121338B2 (en) | 2016-12-30 | 2021-09-14 | Tcl Technology Group Corporation | Quantum dot material, preparation method, and semiconductor device |
| CN110713201A (en) * | 2019-12-16 | 2020-01-21 | 桑顿新能源科技(长沙)有限公司 | Preparation method of fluoride quantum dots |
| CN110713201B (en) * | 2019-12-16 | 2020-04-17 | 桑顿新能源科技(长沙)有限公司 | Preparation method of fluoride quantum dots |
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Application publication date: 20160608 |