CN103258970A - Preparation method of core-shell type organic/cadmium sulfide nanowire heterojunction array - Google Patents
Preparation method of core-shell type organic/cadmium sulfide nanowire heterojunction array Download PDFInfo
- Publication number
- CN103258970A CN103258970A CN2012103469680A CN201210346968A CN103258970A CN 103258970 A CN103258970 A CN 103258970A CN 2012103469680 A CN2012103469680 A CN 2012103469680A CN 201210346968 A CN201210346968 A CN 201210346968A CN 103258970 A CN103258970 A CN 103258970A
- Authority
- CN
- China
- Prior art keywords
- nano
- organic
- array
- heterojunction
- preparation
- 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
- 239000002070 nanowire Substances 0.000 title claims abstract description 74
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 51
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011258 core-shell material Substances 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000004065 semiconductor Substances 0.000 claims abstract description 22
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 19
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 13
- 239000002071 nanotube Substances 0.000 claims abstract description 11
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000012159 carrier gas Substances 0.000 claims description 40
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011261 inert gas Substances 0.000 claims description 24
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 23
- 238000010926 purge Methods 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 239000003708 ampul Substances 0.000 claims description 16
- 239000010453 quartz Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 15
- 238000002161 passivation Methods 0.000 claims description 13
- 238000005842 biochemical reaction Methods 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 10
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 7
- VQNPSCRXHSIJTH-UHFFFAOYSA-N cadmium(2+);carbanide Chemical compound [CH3-].[CH3-].[Cd+2] VQNPSCRXHSIJTH-UHFFFAOYSA-N 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 4
- 240000005373 Panax quinquefolius Species 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 claims 2
- 125000001741 organic sulfur group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 17
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000003491 array Methods 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- 239000010408 film Substances 0.000 description 6
- 230000004087 circulation Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 acyl dianhydride Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- VVOPUZNLRVJDJQ-UHFFFAOYSA-N phthalocyanine copper Chemical compound [Cu].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 VVOPUZNLRVJDJQ-UHFFFAOYSA-N 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of a core-shell organic cadmium sulfide semiconductor nanowire heterojunction and a cadmium sulfide nanotube, which comprises the steps of growing a monocrystal organic nanowire array by using a physical vapor deposition method, taking the high-density organic nanowire array as a template, and wrapping and growing a cadmium sulfide (CdS) shell layer on the surface layer of the nanowire by using an Atomic Layer Deposition (ALD) technology; by controlling the type of the organic nanowire and the process condition of atomic layer deposition, the controllable preparation of different types of core-shell organic or inorganic heterojunction nanostructure arrays can be conveniently realized; and simultaneously, heating to evaporate the organic nanowires in the core shell to obtain the corresponding hollow inorganic nanotube array. The method has the advantages of simple operation, simple process, uniform product and high controllability, and can control the formation of the heterojunction on the atomic layer level; the heterojunction nanowire and the nanotube array prepared by the method have wide application prospects in the fields of nano electronics and photoelectrons such as solar cells, optical switches, sensors and the like.
Description
Technical field
The present invention relates to semiconductor nano material and heterojunction preparation field thereof, be specifically related to the preparation method of a kind of hud typed organic sulfide cadmium semiconductor nanowires heterojunction and cadmium sulfide nano pipe array.
Background technology
Heterojunction semiconductor is the elementary cell in the various opto-electronic devices, has extensively and important use.Heterojunction can be divided into two kinds of homotype (p-p or n-n) and special-shaped (p-n) heterojunction.Traditional heterojunction semiconductor be by two or many parts combine various heterostructures such as it can be designed to have p-n as required, p-n-p, n-p-n, p-i-n or p-i-p because of composition modulation band gap or the different single crystal semiconductor of conduction type.Fast development of information technology is more and more higher to the requirement of the miniaturization of electronics, opto-electronic device and integrated level, and the individual devices size of large scale integrated circuit has entered sub-micron even Nano grade.As realizing integrated prerequisite and the basis of nano-scale device, how in nano-scale range, to construct the nanometer p-n junction, then become problem demanding prompt solution.
The hybrid nano material can obtain the not available high-performance of single component material by the synergy of effective compound realization organic because of it, thereby becomes one of hot fields of material supply section educational circles research.Inorganic material superior performance, but its component is single, not easy-regulating.And organic semiconducting materials is of a great variety, and it not only has the character of favorable mechanical pliability and wide spectrum, and the molecular configuration of organic semiconducting materials and level structure can also be regulated and control with synthetic flexibly by the design to molecule.Than traditional inorganic semiconductor heterojunction nanostructure, the hybrid nano-heterogeneous structure combines inorganic semiconductor material good stable and good electronic transmission performance, and organic semiconductor is easy to regulate and control by chemical modification the advantage of performance, therefore is expected to show more superior performance.By not only deepening understanding inorganic, organic nano material the research of hybrid nano heterojunction, also help the hybrid nano-device that exploitation makes new advances.
Up to the present, fewer about the report of organic/inorganic heterojunction nano-wire in the world, in recent years the preparation method of Bao Dao preparation organic/inorganic heterojunction almost major part concentrate on utilize the AAO(Woelm Alumina) for template, method by electrochemical deposition deposits to inorganic and organic nano line in the AAO nano aperture successively, thereby realize preparation (the Yanbing Guo of organic/inorganic heterojunction nano-wire, Qingxin Tang, Huibiao Liu, Yajie Zhang, Yuliang Li, Wenping Hu, Shu Wang, and Daoben Zhu, Light-Controlled Organic/Inorganic P-N Junction Nanowires, J. AM. CHEM. SOC. 2008,130,9198 –, 9199. Yanbing Guo, Huibiao Liu, Yongjun Li, Guoxing Li, Yingjie Zhao, Yinglin Song, and Yuliang Li, Controlled Core-Shell Structure for Efficiently Enhancing Field-Emission Properties of Organic-Inorganic Hybrid Nanorods, J. Phys. Chem. C, 2009,113,12669 –, 12673. Dezhong Zhang, Liang Luo, Qing Liao, Hao Wang, Hongbing Fu, and Jianniao Yao, Polypyrrole/ZnS Core/Shell Coaxial Nanowires Prepared by Anodic Aluminum Oxide Template Methods, J. Phys. Chem. C, 2011,115,2360 – 2365).Yet synthetic method above-mentioned is subject to the size of AAO template, output is few, and must dissolve alumina formwork when further using, the introducing of organic solvent unavoidably brings infringement to the crystal mass of organic nano line, the controllability of this method is relatively poor, is difficult to the structure of accuracy controlling organic/inorganic heterojunction nano-wire.
Summary of the invention
For overcoming deficiency of the prior art, the invention provides the preparation method of a kind of hud typed organic sulfide cadmium semiconductor nanowires heterojunction and cadmium sulfide nano pipe array.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
The preparation method of a kind of hud typed organic sulfide cadmium semiconductor nanowires heterojunction and cadmium sulfide nano pipe array classifies template as with high density organic nano linear array, at first modifies one deck Al in nanowire surface by ald (ALD)
2O
3Transition zone at this transition zone deposition CdS shell, forms ganoid organic/inorganic nano line heterojunction array, and then by under the uniform temperature organic nano line in the nucleocapsid structure being evaporated, can also conveniently obtain hollow CdS nano-tube array again.
Its concrete steps are as follows:
1) adopts physical gas-phase deposite method, the organic nano linear array of growing high density;
2) classify template as with the high density organic nano linear array of step (1) growth, adopt the grow Al of some nanometer thickness of Atomic layer deposition method
2O
3Transition zone;
3) with the prepared sample of step (2), adopt Atomic layer deposition method at its surface controllable deposition CdS shell;
4) by changing different organic nano lines and changing the presoma that ald uses, realize the controlled preparation of different types of organic/inorganic heterojunction nanostructure;
5) heat in uniform temperature by the organic/inorganic nuclear shell structure nano linear array with step (4) preparation, the organic nano line of evaporation internal layer obtains the hollow inorganic nano-tube array.
Further, the organic semiconductor compound in the described step (1) is CuPc (CuPc) Huo perylene tetracarboxylic acid dianhydride (PTCDA); The condition of the growth CuPc nano-wire array of described physical vapour deposition (PVD) is: the silicon substrate that the porcelain boat that an amount of CuPc powder will be housed according to the flow direction of air-flow is put into the high-temperature region of vacuum tube furnace and will be coated with 6nm Au membrana granulosa is put into the low-temperature space of described vacuum tube furnace, apart from the general 1O-20cm in center, high-temperature region place.Start mechanical pump then and vacuumize, make the interior vacuum degree of furnace chamber of described vacuum tube furnace below 1 Pa, feed inert gas again in quartz ampoule, the maintenance gas flow rate is 30-60sccm; When locating atmosphere of inert gases fully in the quartz ampoule, when keeping the inert gas feeding, the control tube furnace is warming up to 415 ℃ by 20 ℃/min speed, and constant temperature 10min reacts fully and carries out, system naturally cools to room temperature then, can obtain blue CuPc nano-wire array on the surface of silicon chip.
Further, the condition of the Chang perylene tetracarboxylic acid dianhydride of the Sheng of described physical vapour deposition (PVD) nano-wire array is: the porcelain boat that Shi Liang perylene tetracarboxylic acid dianhydride powder will be housed according to the flow direction of air-flow is put into the high-temperature region of vacuum tube furnace; And the silicon substrate that cleans up put into the low-temperature space of described vacuum tube furnace, apart from the general 1O-20cm in center, high-temperature region place; Start mechanical pump and vacuumize, make the interior vacuum degree of furnace chamber of described vacuum tube furnace below 1 Pa, feed inert gas then in quartz ampoule, gas flow rate is 30-60sccm; When locating atmosphere of inert gases fully in the quartz ampoule, when keeping inert gas to flow into, the control tube furnace is warming up to 415 ℃ by 20 ℃/min speed, and constant temperature 30min reacts fully and carries out, system cools naturally then, can obtain red De perylene tetracarboxylic acid dianhydride nano-wire array on the surface of silicon chip.
Further, the Al in the described step (2)
2O
3The growth conditions of the Atomic layer deposition method of transition zone is: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm, the burst length of presoma trimethyl aluminium is 0.015s, and the purge time of carrier gas for the first time is 10s, and the burst length of presoma water is 0.015s, the purge time of carrier gas for the second time is 10s, and presoma adsorbs concurrent biochemical reaction and forms described Al in organic nano line surface chemistry
2O
3Transition zone.
Further, the growth conditions of the Atomic layer deposition method of the CdS shell in the described step (3) is: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the presoma thioacetamide need be heated to 120 ℃, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm in the growth chamber, the burst length of presoma dimethyl cadmium is 0.015s, the purge time of carrier gas for the first time is 10s, the burst length of presoma thioacetamide is 0.015s, the purge time of carrier gas for the second time is 10s, and the CdS presoma is modified with Al again
2O
3The concurrent biochemical reaction of chemisorbed on the CuPc nano wire of passivation layer finally forms the CdS shell on its surface.
Compared with prior art, the present invention has following beneficial effect:
Effectively avoided introducing the influence that organic solvent may bring organic nano line crystal mass in the nanowire heterojunction growth course, and can be on the atomic level accurate control nanowire heterojunction synthetic.By changing the presoma of different organic nano line templates and replacing ald, realize the controlled preparation of different types of organic/inorganic heterojunction nanostructure.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Description of drawings
The optical photograph of the CuPc nano-wire array that Fig. 1 prepares for invention example 1;
The sem photograph of the CuPc nano-wire array that Fig. 2 prepares for invention example 1;
The sem photograph of the CdS-CuPc heterojunction nano-wire array that Fig. 3 prepares for invention example 1;
The transmission electron microscope picture of the CdS-CuPc heterojunction nano-wire that Fig. 4 prepares for invention example 1;
The radially X ray energy dispersion spectrogram of the CdS-CuPc heterojunction nano-wire that Fig. 5 prepares for invention example 1;
The optical photograph of the PTCDA nano-wire array that Fig. 6 prepares for invention example 2;
The sem photograph of the PTCDA nano-wire array that Fig. 7 prepares for invention example 2;
The sem photograph of the CdS-PTCDA heterojunction nano-wire that Fig. 8 prepares for invention example 2;
The transmission electron microscope picture of the CdS-PTCDA heterojunction nano-wire that Fig. 9 prepares for invention example 2.
Embodiment
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
A kind of hud typed organic/preparation method of CdS semiconduct nanowire heterojunction and cadmium sulfide nano pipe array, classify template as with high density organic nano linear array, at first modify one deck Al in nanowire surface by ald (ALD)
2O
3Transition zone at this transition zone deposition CdS shell, forms ganoid organic/inorganic nano line heterojunction array, and then by under the uniform temperature organic nano line in the nucleocapsid structure being evaporated, can also conveniently obtain hollow CdS nano-tube array again.
Further, describedly classify template as with high density organic nano linear array, at the inorganic shell of nanowire surface parcel growth, can obtain nano-tube array by heating evaporation organic nano line by ald (ALD), its concrete steps are as follows:
1) adopts physical gas-phase deposite method, the organic nano linear array of growing high density;
2) classify template as with the high density organic nano linear array of step (1) growth, adopt the grow Al of some nanometer thickness of Atomic layer deposition method
2O
3Transition zone;
3) with the prepared sample of step (2), adopt Atomic layer deposition method at its surface controllable deposition CdS shell;
4) by changing different organic nano lines and changing the presoma that ald uses, realize the controlled preparation of different types of organic/inorganic heterojunction nanostructure;
5) heat in uniform temperature by the organic/inorganic nuclear shell structure nano linear array with step (4) preparation, the organic nano line of evaporation internal layer obtains the hollow inorganic nano-tube array, and the bore of cadmium sulfide nano pipe can be by diameter and the Al of organic nano line
2O
3The control of transition zone layer thickness.
Further, organic semiconductor compound in the described step (1) is that (condition of the growth CuPc nano-wire array of the described physical vapour deposition (PVD) of CuPc) Huo perylene tetracarboxylic acid dianhydride (PTCDA) is: the silicon substrate that the porcelain boat that an amount of CuPc powder will be housed according to the flow direction of air-flow is put into the high-temperature region of vacuum tube furnace and will be plated 6nmAu is put into the low-temperature space of described vacuum tube furnace to CuPc, starting mechanical pump apart from the general 1O-20cm in center, high-temperature region place vacuumizes, make the interior vacuum degree of furnace chamber of described vacuum tube furnace below 1 Pa, feed inert gas then in quartz ampoule, gas flow rate is 30-60sccm; When locating atmosphere of inert gases fully in the quartz ampoule, when keeping inert gas to flow into, the control tube furnace is warming up to 415 ℃ by 20 ℃/min speed, constant temperature 10min reacts fully and carries out then, system cools naturally then, obtains the CuPc nano-wire array of blueness at the basal plane of silicon chip.
Further, the condition of the Chang perylene tetracarboxylic acid dianhydride of the Sheng of described physical vapour deposition (PVD) nano-wire array is: the porcelain boat that Shi Liang perylene tetracarboxylic acid dianhydride powder will be housed according to the flow direction of air-flow is put into the high-temperature region of vacuum tube furnace; And the silicon substrate that cleans up put into the low-temperature space of described vacuum tube furnace, apart from the general 1O-20cm in center, high-temperature region place; Start mechanical pump and vacuumize, make the interior vacuum degree of furnace chamber of described vacuum tube furnace below 1 Pa, feed inert gas then in quartz ampoule, gas flow rate is 30-60sccm; When locating atmosphere of inert gases fully in the quartz ampoule, when keeping inert gas to flow into, the control tube furnace is warming up to 415 ℃ by 20 ℃/min speed, constant temperature 30min reacts fully and carries out then, system cools naturally then, obtains red De perylene tetracarboxylic acid dianhydride nano-wire array at the basal plane of silicon chip.
Further, the Al in the described step (2)
2O
3The growth conditions of the Atomic layer deposition method of transition zone is: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm, the burst length of presoma trimethyl aluminium is 0.015s, and the purge time of carrier gas for the first time is 10s, and the burst length of presoma water is 0.015s, the purge time of carrier gas for the second time is 10s, and presoma adsorbs concurrent biochemical reaction and forms described Al in organic nano line surface chemistry
2O
3Transition zone.
Further, the growth conditions of the Atomic layer deposition method of the CdS shell in the described step (3) is: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the presoma thioacetamide need be heated to 120 ℃, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm in the growth chamber, the burst length of presoma dimethyl cadmium is 0.015s, the purge time of carrier gas for the first time is 10s, the burst length of presoma thioacetamide is 0.015s, for the second time the carrier gas purge time is 10s, and the CdS presoma is modified with the concurrent biochemical reaction of chemisorbed on the CuPc nano wire of Al2O3 passivation layer again, finally forms the CdS shell on its surface.
Embodiment 1: preparation CdS-CuPc heterojunction nano-wire
Adopt electron beam evaporation process in the gold thin film of silicon chip substrate deposition 6nm, with physical vaporous deposition growth CuPc nano-wire array.Concrete growth parameter(s) is as follows: the porcelain boat that the CuPc powder will be housed according to the flow direction of air-flow is put into the high-temperature region of vacuum tube furnace; And the silicon substrate that will plate 6nmAu puts into the low-temperature space of described vacuum tube furnace, apart from the about 1O-20cm in warm area center; Start mechanical pump and vacuumize, make the interior vacuum degree of furnace chamber of described vacuum tube furnace below 1Pa, feed inert gas then in quartz ampoule, gas flow rate is 30-60sccm; When locating atmosphere of inert gases fully in the quartz ampoule, when keeping inert gas to flow into; The control tube furnace is warming up to 415 ℃ by 20 ℃/min speed, and constant temperature 30min reacts fully and carries out then; After the system for the treatment of naturally cools to room temperature, obtain the CuPc nano-wire array of blueness at the basal plane of silicon chip.
Product is directly taken out from furnace chamber, can see from its optical photograph (see figure 1), the direction of falling along temperature obtains to the right of low temperature that larger area product and resulting product area only are subject to the size of vacuum chamber and in the difference of growth warm area temperature by the left side of high temperature.Resulting one-dimensional nano line array is observed under SEM (as Fig. 2 (a, b) shown in), the array that the CuPc nano wire that can be observed length and be the pattern homogeneous about 5 microns epitaxial growth from the gold nano grain comes out to form.
Concrete growth parameter(s) with Atomic layer deposition method growth Al2O3 passivation layer is as follows: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm, the burst length of presoma trimethyl aluminium is 0.015s, the purge time of carrier gas for the first time is 10s, and the burst length of presoma water is 0.015s, and the purge time of carrier gas for the second time is 10s.Presoma adsorbs concurrent biochemical reaction and forms the Al2O3 passivation layer in nanowire surface chemistry.The deposition rate of Al2O3 passivation layer is 0.9A/cycle, and growth 2nmAl2O3 passivation layer needs 23 circulations.
Concrete growth parameter(s) with Atomic layer deposition method growth CdS shell is as follows: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the presoma thioacetamide need be heated to 120 ℃, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm, and the burst length of presoma dimethyl cadmium is 0.015s, and the purge time of carrier gas for the first time is 10s, the burst length of presoma thioacetamide is 0.015s, and the purge time of carrier gas for the second time is 10s.The CdS presoma is modified with the concurrent biochemical reaction of chemisorbed on the CuPc nano wire of Al2O3 passivation layer again, finally forms the CdS shell on its surface.The deposition rate of CdS shell is 0.85A/cycle, sets period 800 circulations of deposition.
Product is directly taken out from reaction chamber, resulting one-dimensional nano line array is observed (as shown in Figure 3) under SEM, can be observed one-dimensional phthalocyanine copper nano-wire array surface and be wrapped in uniformly by the CdS film.Figure can confirm that the CuPc nanowire surface is wrapped in uniformly by the CdS film, and the CdS film is polycrystalline structure from TEM(such as Fig. 4 (a, b) shown in).X ray energy dispersion stave is levied as Fig. 5 (a, b) shown in) and has been proved that further the prepared nano wire of this method is is inner core with the CuPc nano wire, the nucleocapsid heterostructure of surface parcel nano CdS (Cadmium Sulfide) film.
Embodiment 2: preparation CdS-PTCDA heterojunction nano-wire
With the Chang perylene tetracarboxylic acid dianhydride of physical vaporous deposition Sheng nano-wire array.Concrete growth parameter(s) is as follows: the porcelain boat that Shi Liang perylene tetracarboxylic acid dianhydride powder will be housed according to the flow direction of air-flow is put into the high-temperature region of vacuum tube furnace; And the silicon substrate that cleans up put into the low-temperature space of described vacuum tube furnace, apart from the about 10-20cm in warm area center; Start mechanical pump and vacuumize, make the interior vacuum degree of furnace chamber of described vacuum tube furnace below 1Pa, feed inert gas then in quartz ampoule, gas flow rate is 30-60sccm; When locating atmosphere of inert gases fully in the quartz ampoule, when keeping inert gas to flow into, the control tube furnace is warming up to 415 ℃ by 20 ℃/min speed, and constant temperature 30min reacts fully and carries out then; After the system for the treatment of naturally cools to room temperature, obtain red De perylene tetracarboxylic acid dianhydride nano-wire array at the basal plane of silicon chip.
Product is directly taken out from reaction chamber, can see from its optical photograph (see figure 6), the direction of falling along temperature obtains to the right of low temperature that larger area product and resulting product area only are subject to the size of vacuum chamber and in the difference of growth warm area temperature by the left side of high temperature.Resulting one-dimensional nano line array is observed under SEM (as Fig. 7 (a, b) shown in), be can be observed length and be the epitaxial growth on the monocrystalline substrate of 10 microns left and right sides De perylene tetracarboxylic acid dianhydride nano-wire arrays and come out to form.
Concrete growth parameter(s) with Atomic layer deposition method growth Al2O3 passivation layer is as follows: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm, the burst length of presoma trimethyl aluminium is 0.015s, the purge time of carrier gas for the first time is 10s, and the burst length of presoma water is 0.015s, and the purge time of carrier gas for the second time is 10s.Presoma adsorbs concurrent biochemical reaction and forms the Al2O3 passivation layer in nanowire surface chemistry.The deposition rate of Al2O3 passivation layer is 0.9A/cycle, and growth 2nmAl2O3 passivation layer needs 23 circulations.
Concrete growth parameter(s) with Atomic layer deposition method growth CdS shell is as follows: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the presoma thioacetamide need be heated to 120 ℃, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm, and the burst length of presoma dimethyl cadmium is 0.015s, and the purge time of carrier gas for the first time is 10s, the burst length of presoma thioacetamide is 0.015s, and the purge time of carrier gas for the second time is 10s.The CdS presoma is modified with the concurrent biochemical reaction of chemisorbed on the Al2O3 passivation layer De perylene tetracarboxylic acid dianhydride nano wire again, finally forms the CdS shell on its surface.The deposition rate of CdS shell is 0.85A/cycle, sets period 500 circulations of deposition.
Product is directly taken out from reaction chamber, resulting one-dimensional nano line array is observed (as Fig. 8 (a, b) shown in), can be observed Yi Wei perylene four acyl dianhydride nano-wire array surfaces and being wrapped in uniformly by the CdS film under SEM.Evenly wrapped up by the CdS film with Kan Chu perylene tetracarboxylic acid dianhydride nanowire surface from TEM(such as Fig. 9 (a, b) shown in) figure Ke.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. the preparation method of a hud typed organic sulfide cadmium semiconductor nanowires heterojunction and cadmium sulfide nano pipe array classifies template as with high density organic nano linear array, at first modifies one deck Al in nanowire surface by ald (ALD)
2O
3Transition zone at this transition zone deposition CdS shell, forms ganoid organic or inorganic nanowire heterojunction array, and then by under the uniform temperature organic nano line in the nucleocapsid structure being evaporated, can also conveniently obtain hollow CdS nano-tube array again.
2. the preparation method of hud typed organic sulfide cadmium semiconductor nanowires heterojunction according to claim 1 and cadmium sulfide nano pipe array, it is characterized in that, describedly classify template as with high density organic nano linear array, wrap up the inorganic shell of growth by ald (ALD) in nanowire surface, can obtain nano-tube array by heating evaporation organic nano line, its concrete steps are as follows:
1) adopts physical gas-phase deposite method, the organic nano linear array of growing high density;
2) classify template as with the high density organic nano linear array of step (1) growth, adopt the grow Al of some nanometer thickness of Atomic layer deposition method
2O
3Transition zone;
3) with the prepared sample of step (2), adopt Atomic layer deposition method at its surface controllable deposition CdS shell;
4) by changing different organic nano lines and changing the presoma that ald uses, realize the controlled preparation of different types of organic/inorganic heterojunction nanostructure;
5) heat in uniform temperature by the organic/inorganic nuclear shell structure nano linear array with step (4) preparation, the organic nano line of evaporation internal layer obtains the hollow inorganic nano-tube array.
3. the preparation method of hud typed organic sulfide cadmium semiconductor nanowires heterojunction according to claim 2 and cadmium sulfide nano pipe array, it is characterized in that, organic semiconductor compound in the described step (1) is that (condition of the growth CuPc nano-wire array of the described physical vapour deposition (PVD) of CuPc) Huo perylene tetracarboxylic acid dianhydride (PTCDA) is: the silicon substrate that the porcelain boat that an amount of CuPc powder will be housed according to the flow direction of air-flow is put into the high-temperature region of vacuum tube furnace and will be plated 6nmAu is put into the low-temperature space of described vacuum tube furnace to CuPc, apart from the general 1O-20cm in center, high-temperature region place, starting mechanical pump subsequently vacuumizes, make the interior vacuum degree of furnace chamber of described vacuum tube furnace below 1 Pa, feed inert gas again in quartz ampoule, gas flow rate is 30-60sccm; When being in atmosphere of inert gases fully in the quartz ampoule, when keeping inert gas to flow into, the control tube furnace is warming up to 415 ℃ by 20 ℃/min speed, and constant temperature 10min reacts fully and carries out, naturally cool then, obtain the CuPc nano-wire array of blueness at the basal plane of silicon chip.
4. according to the preparation method of claim 2,3 described hud typed organic sulfide cadmium semiconductor nanowires heterojunction and cadmium sulfide nano pipe array, it is characterized in that the condition of the Chang perylene tetracarboxylic acid dianhydride of the Sheng of described physical vapour deposition (PVD) nano-wire array is: the porcelain boat that Shi Liang perylene tetracarboxylic acid dianhydride powder will be housed according to the flow direction of air-flow is put into the high-temperature region of vacuum tube furnace; And the silicon substrate that cleans up is put into the low-temperature space of described vacuum tube furnace, apart from the general 1O-20cm in center, high-temperature region place, starting mechanical pump subsequently vacuumizes, make the interior vacuum degree of furnace chamber of described vacuum tube furnace below 1 Pa, feed inert gas then in quartz ampoule, gas flow rate is 30-60sccm; When locating atmosphere of inert gases fully in the quartz ampoule, when keeping inert gas to flow into, the control tube furnace is warming up to 415 ℃ by 20 ℃/min speed, and constant temperature 30min reacts fully and carries out, naturally cool then, obtain red De perylene tetracarboxylic acid dianhydride nano-wire array at the basal plane of silicon chip.
5. the preparation method of hud typed organic sulfur according to claim 2/change cadmium semiconductor nanowires heterojunction and cadmium sulfide nano pipe array is characterized in that, the Al in the described step (2)
2O
3The growth conditions of the Atomic layer deposition method of transition zone is: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm, the burst length of presoma trimethyl aluminium is 0.015s, and the purge time of carrier gas for the first time is 10s, and the burst length of presoma water is 0.015s, the purge time of carrier gas for the second time is 10s, and presoma adsorbs concurrent biochemical reaction and forms described Al in organic nano line surface chemistry
2O
3Transition zone.
6. the preparation method of hud typed organic sulfide cadmium semiconductor nanowires heterojunction according to claim 2 and cadmium sulfide nano pipe array, it is characterized in that, the growth conditions of the Atomic layer deposition method of the CdS shell in the described step (3) is: compressed air pressure is 2-5MPa, carrier gas pressure is 0.1-0.3MPa, the presoma thioacetamide need be heated to 120 ℃, the cavity growth temperature is 150 ℃, carrier gas flux is 20sccm in the growth chamber, the burst length of presoma dimethyl cadmium is 0.015s, the purge time of carrier gas for the first time is 10s, the burst length of presoma thioacetamide is 0.015s, the purge time of carrier gas for the second time is 10s, and the CdS presoma is being modified with Al
2O
3The concurrent biochemical reaction of chemisorbed on the CuPc nano wire of passivation layer finally forms the CdS shell on its surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103469680A CN103258970A (en) | 2012-09-19 | 2012-09-19 | Preparation method of core-shell type organic/cadmium sulfide nanowire heterojunction array |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103469680A CN103258970A (en) | 2012-09-19 | 2012-09-19 | Preparation method of core-shell type organic/cadmium sulfide nanowire heterojunction array |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103258970A true CN103258970A (en) | 2013-08-21 |
Family
ID=48962776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103469680A Pending CN103258970A (en) | 2012-09-19 | 2012-09-19 | Preparation method of core-shell type organic/cadmium sulfide nanowire heterojunction array |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103258970A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104952703A (en) * | 2015-05-20 | 2015-09-30 | 安阳师范学院 | Production method of IIB-VIB semiconductor/CdS nano P-N junction |
| CN104992840A (en) * | 2014-12-29 | 2015-10-21 | 中国科学院物理研究所 | Quantum dot sensitized solar cell and preparation method thereof |
| CN105720197A (en) * | 2016-02-19 | 2016-06-29 | 暨南大学 | Self-driven wide-spectral-response silicon-based hybrid heterojunction photoelectric sensor and preparation method therefor |
| CN105883903A (en) * | 2014-09-12 | 2016-08-24 | 中南大学 | Preparation method of one-dimensional II-VI semiconductor core-shell nanostructure |
| CN106057931A (en) * | 2016-07-05 | 2016-10-26 | 安阳师范学院 | Large open-circuit voltage nano heterojunction solar energy cell and manufacturing method |
| CN108745400A (en) * | 2018-05-31 | 2018-11-06 | 福州大学 | The preparation and application of the porous silicon nanowires of nucleocapsid-cadmiumsulfide quantum dot composite photocatalyst material |
| CN109742184A (en) * | 2018-12-11 | 2019-05-10 | 厦门大学 | A kind of preparation method of semiconductor package metal nanometer line |
| CN113838980A (en) * | 2021-08-13 | 2021-12-24 | 武汉理工大学 | Polyhedral CsPbBr3@CsPbX3Core-shell perovskite heterojunction and preparation method thereof |
| CN115275107A (en) * | 2022-09-28 | 2022-11-01 | 四川启睿克科技有限公司 | Silicon-based negative electrode with integrated structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101026203A (en) * | 2006-02-22 | 2007-08-29 | 中国科学院半导体研究所 | Semiconductor nano structure and its preparing method |
| CN102412369A (en) * | 2011-10-14 | 2012-04-11 | 中国科学院等离子体物理研究所 | Organic/inorganic hybrid solar cell and preparation method thereof |
-
2012
- 2012-09-19 CN CN2012103469680A patent/CN103258970A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101026203A (en) * | 2006-02-22 | 2007-08-29 | 中国科学院半导体研究所 | Semiconductor nano structure and its preparing method |
| CN102412369A (en) * | 2011-10-14 | 2012-04-11 | 中国科学院等离子体物理研究所 | Organic/inorganic hybrid solar cell and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHIH-CHIEH WANG ET AL: "Organic Nanowire-Templated Fabrication of Alumina Nanotubes by Atomic Layer Deposition", 《NANO LETTERS》, vol. 7, no. 6, 23 May 2007 (2007-05-23), pages 1566 - 1569 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883903A (en) * | 2014-09-12 | 2016-08-24 | 中南大学 | Preparation method of one-dimensional II-VI semiconductor core-shell nanostructure |
| CN104992840A (en) * | 2014-12-29 | 2015-10-21 | 中国科学院物理研究所 | Quantum dot sensitized solar cell and preparation method thereof |
| CN104952703A (en) * | 2015-05-20 | 2015-09-30 | 安阳师范学院 | Production method of IIB-VIB semiconductor/CdS nano P-N junction |
| CN105720197A (en) * | 2016-02-19 | 2016-06-29 | 暨南大学 | Self-driven wide-spectral-response silicon-based hybrid heterojunction photoelectric sensor and preparation method therefor |
| CN105720197B (en) * | 2016-02-19 | 2018-10-09 | 暨南大学 | It is a kind of to respond silicon-based hybrid heterojunction photovoltaic sensor and preparation method thereof from driving wide spectrum |
| CN106057931A (en) * | 2016-07-05 | 2016-10-26 | 安阳师范学院 | Large open-circuit voltage nano heterojunction solar energy cell and manufacturing method |
| CN106057931B (en) * | 2016-07-05 | 2023-07-07 | 安阳师范学院 | Large open-circuit voltage nano heterojunction solar cell and preparation method thereof |
| CN108745400A (en) * | 2018-05-31 | 2018-11-06 | 福州大学 | The preparation and application of the porous silicon nanowires of nucleocapsid-cadmiumsulfide quantum dot composite photocatalyst material |
| CN108745400B (en) * | 2018-05-31 | 2020-09-15 | 福州大学 | Preparation and application of core-shell structure porous silicon nanowire-cadmium sulfide quantum dot composite photocatalytic material |
| CN109742184A (en) * | 2018-12-11 | 2019-05-10 | 厦门大学 | A kind of preparation method of semiconductor package metal nanometer line |
| CN113838980A (en) * | 2021-08-13 | 2021-12-24 | 武汉理工大学 | Polyhedral CsPbBr3@CsPbX3Core-shell perovskite heterojunction and preparation method thereof |
| CN115275107A (en) * | 2022-09-28 | 2022-11-01 | 四川启睿克科技有限公司 | Silicon-based negative electrode with integrated structure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103258970A (en) | Preparation method of core-shell type organic/cadmium sulfide nanowire heterojunction array | |
| Huang et al. | Single crystalline wurtzite ZnO/zinc blende ZnS coaxial heterojunctions and hollow zinc blende ZnS nanotubes: synthesis, structural characterization and optical properties | |
| US7354871B2 (en) | Nanowires comprising metal nanodots and method for producing the same | |
| O'Regan et al. | Recent advances in the growth of germanium nanowires: synthesis, growth dynamics and morphology control | |
| CN103952682A (en) | Method for growing single-layer molybdenum disulfide by chemical vapor deposition | |
| CN105239156A (en) | Method for preparing plane semiconductor nanowire through epitaxial orientated growth, transfer and integration | |
| CN103526297A (en) | Method for preparing topological insulator Bi2Se3 film | |
| Li et al. | Zinc oxide nanostructures and high electron mobility nanocomposite thin film transistors | |
| CN102040187B (en) | Method for growing core-shell structure ZnO nanowire array | |
| CN105481002B (en) | Autocatalysis growth method for large-dimension beta-Ga2O3 microwire | |
| Sun et al. | Synthesis of germanium nanowires on insulator catalyzed by indium or antimony | |
| Sahoo et al. | Evolution of GaN nanowire morphology during catalyst-induced growth process | |
| CN104805409B (en) | Method for preparing Ag nanowire array electrode according to magnetron sputtering-masking assisted deposition | |
| KR101538742B1 (en) | Synthesis method for nanowires | |
| CN110079787B (en) | Method for surfactant-assisted vapor phase growth of III-V semiconductor nanowire | |
| CN106185897A (en) | A kind of controlled method preparing graphene nanobelt in multiple substrate | |
| Wang et al. | A systematic study on self-catalyzed growth of InAs/GaSb axial heterostructured nanowires by MOCVD | |
| EP2261402B1 (en) | Method for producing germanium semiconductor nanowires | |
| CN105529242B (en) | A kind of method for preparing bead string shape monocrystalline silicon nano line | |
| Li et al. | Epitaxial growth of horizontally aligned single-crystal arrays of perovskite | |
| Li et al. | Growth of InAs nanowires with the morphology and crystal structure controlled by carrier gas flow rate | |
| CN103498190B (en) | The preparation method of high purity dendrite FeWO4/FeS nanometer nuclear shell nano-structure | |
| CN102162135A (en) | Preparation method of ZnS/Si core-shell nanowire or nanoribbon and polycrystalline Si tube | |
| Umar et al. | Hierarchical ZnO nanostructures: growth and optical properties | |
| Hu et al. | Synthesis and Photoluminscence Properties of Morphology-and Microstructure-Controlled S-Doped ZnO Nanostructures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130821 |