CN108922942A - 一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法 - Google Patents
一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法 Download PDFInfo
- Publication number
- CN108922942A CN108922942A CN201810601086.1A CN201810601086A CN108922942A CN 108922942 A CN108922942 A CN 108922942A CN 201810601086 A CN201810601086 A CN 201810601086A CN 108922942 A CN108922942 A CN 108922942A
- Authority
- CN
- China
- Prior art keywords
- preparation
- cspbcl
- zro
- photodetector
- driving
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 52
- 239000002243 precursor Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 15
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 15
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000011565 manganese chloride Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 210000000988 bone and bone Anatomy 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- -1 dimethyl formyl Amine Chemical class 0.000 claims description 5
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000005703 Trimethylamine hydrochloride Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 229940055577 oleyl alcohol Drugs 0.000 claims 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 238000007650 screen-printing Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
-
- 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
- H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—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 in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
- H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PN heterojunction type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
Abstract
本发明公开了一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法。首先采用丝网印刷工艺制备FTO/TiO2/ZrO2/Carbon多孔骨架，然后原位填充Mn:CsPbCl3钙钛矿纳米材料增加紫外线吸收。通过在CsPbCl3钙钛矿中掺杂Mn，可以在钙钛矿带间引入中间掺杂能级，同时由于其属于禁阻跃迁，有较长的激子寿命，可以极大地提高电子向TiO2的注入，从而提高器件光电流响应灵敏度。
Description
技术领域
本发明涉及一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法，属于纳米材料技术领域。
背景技术
近年来，CsPbX3(X=Cl/Br/I)钙钛矿纳米晶由于其独特的光电性质与易于低温溶液生长的特点而倍受关注。相比于传统的半导体纳米晶，CsPbX3钙钛矿纳米晶不仅具有发射波长可调、发射峰半峰宽很窄、荧光强度强、表面可选择地修饰自由官能团等优点，并且可以室温溶液生长，材料本身具有较大的缺陷容忍度。该材料已在照明、激光、探测以及太阳能电池等方面表现出良好的应用前景。基于CsPbX3钙钛矿高的紫外光吸收系数，长的载流子扩散距离，其相关的光电探测器得到了很好的发展。但值得注意的是，其相关的自驱动光探测器却很少见。其原因是要构成自驱动的光探测器，必须形成异质结构，并且材料的能级必须有一定的交错，且形成梯度，更重要的是能级差必须合理。若能级差太小，则不能完成电荷的有效抽取；若能级差太大，则形成绝缘，不会有电荷的定向流动。CsPbX3钙钛矿在自驱动紫外光电探测的失败，就在于较大的能量差。本发明通过掺杂Mn离子在CsPbX3钙钛矿中形成中间能级，并其具有禁阻跃迁的特点，可以作为电荷传输的一个中间过程，极大的提高电荷的抽取，形成较大的光电流。
发明内容
为了实现高电流灵敏度的自驱动紫外光探测器，本发明的目的是提供一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法。
为实现上述目的，本发明采用以下技术方案：
一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法，包括如下步骤：
（1）FTO/TiO2/ZrO2/Carbon的制备：在室温大气环境下，依次在TFO导电玻璃印刷TiO2,然后在马弗炉500℃条件下烧结30-50 min。接着印刷ZrO2和碳浆料，每印一层在70-100 ℃烘干。最后把印好的基片放在350-450 ℃条件下烧结1-2 h, 蒸发掉有机物，形成多孔骨架。
（2）Mn:CsPbCl3钙钛矿的填充：将5-10 ulMn:CsPbCl3纳米晶的前驱体滴到碳电极上，待其溶液挥发10-20 min, 循环滴加5-10 ul氯苯与二甲基甲酰胺（DMF）的混合液2-5次，确保钙钛矿前驱体扩散到片子的底部，为了增加前躯体的渗透，在氯苯与二甲基甲酰胺（DMF）混合液中加1-5 wt.%三甲胺盐酸盐，作为短链配体，帮助扩散。最后把基片在90-100℃条件下加热20-30 min。
进一步的，步骤（1）中，TiO2 (或ZrO2)浆料的制备方法为: TiO2纳米颗粒 (或ZrO2) 和羟乙基纤维素（EC）加入松油醇和乙醇, 然后球磨20-24 h.其中，TiO2 (或ZrO2)，羟乙基纤维素（EC），松油醇，乙醇的投料比为6-8g:4-8g:30-40ml: 15-30ml。
进一步的，碳浆料的制备方法为：炭黑，石墨, 羟乙基纤维素（EC）和ZrO2 纳米颗粒加入到松油醇,然后球磨20-24 h。其中，炭黑，石墨，羟乙基纤维素（EC），ZrO2，松油醇的投料比为2-3g: 6-8g: 1-2g: 1-2g: 30-40ml。
进一步的，步骤（1）中, Mn:CsPbCl3纳米晶前驱体溶液的制备方法如下。A前驱体是CsAc溶于二甲基甲酰胺（DMF）。B前驱体是MnCl2和PbCl2溶于二甲基亚砜（DMSO）。C前驱体是油酸和正辛胺混合溶于正己烷。搅拌情况下，A和B前驱体依次缓慢倒入C前驱体中，形成Mn:CsPbCl3纳米晶前驱体溶液。其中，CsAc, 二甲基甲酰胺（DMF）, MnCl2，PbCl2, 二甲基亚砜（DMSO）,正辛胺, 油酸,正己烷的投料比为1mmol: 1mL: 0-3mmol: 1mmol: 4ml: 6ml:0.8mL: 30-40 mL。
本发明制备的Mn:CsPbCl3自驱动紫外光电探测器，可以通过Mn的掺杂能级，作为中间过渡能级，推动钙钛矿材料吸收光子后产生的电子向TiO2转移，从而提高自驱动光电探测的光电流。
有益效果：
本发明制备的Mn:CsPbCl3自驱动紫外光电探测器，由于采用印刷工艺，所需设备简单、容易操作。另外由于材料的低温生长特性，所以在一般的化学实验室均能完成，易于推广；所制备的Mn:CsPbCl3/TiO2结构，通过Mn掺杂中间能级，有效的促进了电荷向TiO2的定向移动，极大地提高探测器的光电流。
附图说明
图1为不同Mn:CsPbCl3自驱动紫外光电探测器电压电流曲线（AM1.5）；
图2为Mn:CsPbCl3自驱动光电探测器在340nm光照下的电流时间曲线；
图3为Mn:CsPbCl3自驱动紫外光电探测器的单色光转换效率曲线。
具体实施方式
下面结合实施例和附图对本发明做更进一步地解释，下列实施例仅用于说明本发明，但并不用来限定本发明的实施范围。
本实施例中所使用的Cs(Ac)，MnCl2，PbCl2 ，羟乙基纤维素（EC），TiO2, ZrO2, 炭黑，石墨等原材料均为分析纯试剂；溶剂有正己烷，二甲基甲酰胺（DMF），二甲基亚砜（DMSO），正辛胺，油酸；所用的玻璃仪器使用前用去离子水润洗三遍后真空干燥。
实施例1：
Mn:CsPbCl3自驱动紫外光电探测器（MnCl2:PbCl2=1:1）：
1、TiO2 (ZrO2)浆料的制备：8g TiO2纳米颗粒 (或ZrO2) 和 4g 羟乙基纤维素（EC）加入30ml松油醇和15ml乙醇, 然后球磨20-24 h。
2、碳浆料的制备：2g炭黑，6g石墨, 1g羟乙基纤维素（EC）和1g ZrO2 纳米颗粒加入到30ml松油醇, 然后球磨20 h。
3、Mn:CsPbCl3纳米晶前驱体的制备：A前驱体是1mmmol Cs(Ac) 溶于1mL二甲基甲酰胺（DMF）。B前驱体是1mmol MnCl2和1 mmol PbCl2溶于4 mL二甲基亚砜（DMSO）。C前驱体是6 mL油酸和0.8mL正辛胺溶于30 mL正己烷。A和B前驱体依次缓慢倒入C前驱体，形成Mn:CsPbCl3纳米晶前驱体溶液。
4、FTO/TiO2/ZrO2/Carbon多孔骨架的制备：在室温大气环境下，依次在TFO导电玻璃印刷TiO2, 然后在马弗炉500℃条件下烧结30min。接着印刷ZrO2和碳浆料，每印一层在100 ℃烘干。最后把印好的基片放在350-450℃条件下烧结1h, 蒸发掉有机物，形成多孔骨架。
5、制备Mn掺杂CsPbCl3自驱动紫外光电探测器:将5uL Mn:CsPbCl3纳米晶前驱体溶液滴到碳电极上，待其溶液挥发20min, 接着滴加5ul氯苯/二甲基甲酰胺（DMF）的混合液数次，确保钙钛矿前驱体可以扩散到片子的底部，为了增加前躯体的渗透，可以在氯苯/二甲基甲酰胺（DMF）混合液中加少量（3 wt.%）三甲胺盐酸盐，作为配体，帮助扩散。最后把扩散好的基片在100 ℃条件下合金30 min。
本发明的Mn掺杂CsPbCl3自驱动紫外光电探测器，可以通过Mn杂质的中间能级，有效的提高电荷向TiO2的定向移动（如图1）。并且该自驱动紫外光探测器输出稳定（如图2），其探测波长在300-400nm, 其最大输出波长为340nm（如图3）。
实施例2：
Mn:CsPbCl3自驱动紫外光电探测器（MnCl2:PbCl2=2:1）：
1、TiO2 (ZrO2)浆料的制备：8g TiO2纳米颗粒 (或ZrO2) 和 4g 羟乙基纤维素（EC）加入30ml松油醇和15ml乙醇, 然后球磨20-24 h。
2、碳浆料的制备：2g炭黑，6g石墨, 1g羟乙基纤维素（EC）和1g ZrO2 纳米颗粒加入到30ml松油醇, 然后球磨20 h。
3、Mn:CsPbCl3纳米晶前驱体的制备：A前驱体是1mmmol Cs(Ac) 溶于1mL二甲基甲酰胺（DMF）。B前驱体是2mmol MnCl2和1 mmol PbCl2溶于4 mL二甲基亚砜（DMSO）。C前驱体是6 mL油酸和0.8mL正辛胺溶于30 mL正己烷。A和B前驱体依次缓慢倒入C前驱体，形成Mn:CsPbCl3纳米晶前驱体溶液。
4、FTO/TiO2/ZrO2/Carbon多孔骨架的制备：在室温大气环境下，依次在TFO导电玻璃印刷TiO2, 然后在马弗炉500℃条件下烧结30min。接着印刷ZrO2和碳浆料，每印一层在100 ℃烘干。最后把印好的基片放在350-450℃条件下烧结1h, 蒸发掉有机物，形成多孔骨架。
5、制备Mn掺杂CsPbCl3自驱动紫外光电探测器:将5uL Mn:CsPbCl3纳米晶前驱体滴到碳电极上，待其溶液挥发20min, 接着滴加5ul氯苯/二甲基甲酰胺（DMF）的混合液数次，确保钙钛矿前驱体可以扩散到片子的底部，为了增加前躯体的渗透，可以在氯苯/二甲基甲酰胺（DMF）混合液中加少量（3 wt.%）三甲胺盐酸盐，作为配体，帮助扩散。最后把扩散好的基片在100 ℃条件下合金30 min。
本发明的Mn掺杂CsPbCl3自驱动紫外光电探测器，可以通过Mn杂质的中间能级，有效的提高电荷向TiO2的定向移动（如图1）。并且可以通过Mn的掺杂量来控制电荷转移的程度。当改变锰的投料比从1:1到2:1，探测器光电流从0.11 mA/cm2提高到了0.13mA/cm2。
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (6)
1.一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法，其特征在于,包括以下步骤：
（1）FTO/TiO2/ZrO2/Carbon的制备：在室温大气环境下，依次在TFO导电玻璃印刷TiO2,然后在马弗炉500℃条件下烧结30-50 min，接着印刷ZrO2和碳浆料，每印一层在70-100 ℃烘干，最后把印好的基片放在350-450 ℃条件下烧结1-2 h, 蒸发掉有机物，形成多孔骨架；
（2）Mn:CsPbCl3钙钛矿的填充：将5-10 ulMn:CsPbCl3纳米晶的前驱体滴到碳电极上，待其溶液挥发10-20 min, 循环滴加5-10 ul氯苯与二甲基甲酰胺的混合液2-5次，确保钙钛矿前驱体扩散到片子的底部，为了增加前躯体的渗透，在氯苯与二甲基甲酰胺混合液中加1-5 wt.%三甲胺盐酸盐，作为短链配体，帮助扩散，最后把基片在90-100 ℃条件下加热20-30 min。
2.权利要求1所述的新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法，其特征在于，步骤（1）中，TiO2浆料的制备方法为: TiO2纳米颗粒和羟乙基纤维素加入松油醇和乙醇, 然后球磨20-24h，其中，TiO2，羟乙基纤维素，松油醇，乙醇的投料比为6-8g:4-8g:30-40ml:15-30ml。
3.权利要求1所述的新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法，其特征在于，步骤（1）中，ZrO2浆料的制备方法为: ZrO2纳米颗粒和羟乙基纤维素加入松油醇和乙醇, 然后球磨20-24h，其中，ZrO2，羟乙基纤维素，松油醇，乙醇的投料比为6-8g:4-8g:30-40ml:15-30ml。
4.权利要求1所述的新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法，其特征在于，步骤（1）中的碳浆料的制备方法为：炭黑，石墨, 羟乙基纤维素和ZrO2 纳米颗粒加入到松油醇,然后球磨20-24h，其中，炭黑，石墨，羟乙基纤维素，ZrO2，松油醇的投料比为2-3g: 6-8g: 1-2g: 1-2g: 30-40ml。
5.权利要求1所述的新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法，其特征在于，步骤（1）中，Mn:CsPbCl3纳米晶前驱体溶液的制备方法为:A前驱体是CsAc溶于二甲基甲酰胺；B前驱体是MnCl2和PbCl2溶于二甲基亚砜；C前驱体是油酸和正辛胺混合溶于正己烷；搅拌情况下，A和B前驱体依次缓慢倒入C前驱体中，形成Mn:CsPbCl3纳米晶前驱体溶液；其中，CsAc, 二甲基甲酰胺, MnCl2，PbCl2, 二甲基亚砜,正辛胺, 油酸,正己烷的投料比为1mmol: 1mL: 0-3mmol: 1mmol: 4ml: 6ml: 0.8mL: 30-40 mL。
6.权利要求5所述的新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法，其特征在于：Mn的掺杂方式是采用在室温环境下过饱和结晶生长。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810601086.1A CN108922942A (zh) | 2018-06-12 | 2018-06-12 | 一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810601086.1A CN108922942A (zh) | 2018-06-12 | 2018-06-12 | 一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108922942A true CN108922942A (zh) | 2018-11-30 |
Family
ID=64419203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810601086.1A Pending CN108922942A (zh) | 2018-06-12 | 2018-06-12 | 一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108922942A (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416333A (zh) * | 2019-07-11 | 2019-11-05 | 华中科技大学 | 一种紫外光电探测器及其制备方法 |
| CN112071984A (zh) * | 2020-02-11 | 2020-12-11 | 吉林大学 | 一种基于稀土离子掺杂钙钛矿纳米晶体的深紫外光电探测器及其制备方法 |
| CN113707818A (zh) * | 2021-08-27 | 2021-11-26 | 南京工程学院 | 一种快速制备全印刷钙钛矿太阳能电池的方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753358A (zh) * | 2017-01-24 | 2017-05-31 | 东南大学 | 一种双发射Mn掺杂CsPb(Cl/Br)3钙钛矿纳米晶及其制备方法 |
| EP3168278B1 (en) * | 2015-10-28 | 2018-08-01 | Samsung Electronics Co., Ltd. | Quantum dots, production methods thereof, and electronic devices including the same |
-
2018
- 2018-06-12 CN CN201810601086.1A patent/CN108922942A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3168278B1 (en) * | 2015-10-28 | 2018-08-01 | Samsung Electronics Co., Ltd. | Quantum dots, production methods thereof, and electronic devices including the same |
| CN106753358A (zh) * | 2017-01-24 | 2017-05-31 | 东南大学 | 一种双发射Mn掺杂CsPb(Cl/Br)3钙钛矿纳米晶及其制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| QIAN WANG等: "Energy-Down-Shift CsPbCl3：Mn Quantum Dots for Boosting the Efficiency and Stability of Perovskite Solar Cells", 《ACS ENERGY LETTERS》 * |
| 王亢: "无空穴传输层介观钙钛矿太阳能电池的印刷制备及优化", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416333A (zh) * | 2019-07-11 | 2019-11-05 | 华中科技大学 | 一种紫外光电探测器及其制备方法 |
| CN112071984A (zh) * | 2020-02-11 | 2020-12-11 | 吉林大学 | 一种基于稀土离子掺杂钙钛矿纳米晶体的深紫外光电探测器及其制备方法 |
| CN113707818A (zh) * | 2021-08-27 | 2021-11-26 | 南京工程学院 | 一种快速制备全印刷钙钛矿太阳能电池的方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107204379B (zh) | 一种高质量无机钙钛矿薄膜及其制备方法和在太阳能电池中的应用 | |
| Li et al. | Carbon and graphene quantum dots for optoelectronic and energy devices: a review | |
| CN108922942A (zh) | 一种新型Mn:CsPbCl3自驱动紫外光电探测器的制备方法 | |
| Tian et al. | Interfacial linkage and carbon encapsulation enable full solution‐printed perovskite photovoltaics with prolonged lifespan | |
| CN105702864B (zh) | 一种高质量钙钛矿薄膜、太阳能电池及其制备方法 | |
| Hou et al. | Efficient quasi-mesoscopic perovskite solar cells using Li-doped hierarchical TiO2 as scaffold of scattered distribution | |
| CN106622323B (zh) | 一种具有可见光响应的多功能光电催化膜的制备方法 | |
| CN102368537B (zh) | 一种具有高稳定性的有机太阳能电池 | |
| CN107369770B (zh) | 一种低温碳基钙钛矿太阳能电池用碳电极层的制备方法 | |
| Barichello et al. | The effect of water in Carbon-Perovskite Solar Cells with optimized alumina spacer | |
| Chen et al. | Stabilizing and scaling up carbon-based perovskite solar cells | |
| Zhang et al. | Upconversion Er-doped TiO2 nanorod arrays for perovskite solar cells and the performance improvement | |
| CN109065727A (zh) | 一种钙钛矿太阳能电池的制备方法 | |
| CN107266337A (zh) | 钙钛矿发光材料甲脒溴化铅纳米晶的低温快速制备方法 | |
| CN107706308A (zh) | 一种钙钛矿太阳能电池及制备方法 | |
| KR101113658B1 (ko) | 표면안정제로 개질된 이산화티탄 나노 입자, 이를 포함하는 이산화티탄 나노 잉크, 이를 사용하여 제조되는 태양전지, 및 그의 제조방법 | |
| CN104112793A (zh) | 一种低温全溶液法制备钙钛矿太阳能电池的方法 | |
| CN101777430B (zh) | 一种染料敏化太阳能电池光阳极用二氧化钛膜的制备方法 | |
| CN109192860A (zh) | 一种三元混合溶剂的钙钛矿太阳电池制备方法 | |
| CN110368962A (zh) | 一种BiOI/WO3异质结高效光电催化电极的制备方法、产品及应用 | |
| CN108039412A (zh) | 一种硫化复合电子传输层结构的钙钛矿太阳能电池 | |
| CN108649125A (zh) | 一种提高钙钛矿材料湿度稳定性的方法 | |
| CN111525036B (zh) | 一种自驱动钙钛矿光电探测器及其制备方法 | |
| Yan et al. | CsPbBr 3 quantum dots photodetectors boosting carrier transport via molecular engineering strategy | |
| CN110194780B (zh) | 一种具有光电导效应的有机无机杂化材料晶体及其应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181130 |