CN201638834U - Nanowire heterojunction array based ultraviolet light detector - Google Patents

Nanowire heterojunction array based ultraviolet light detector Download PDF

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Publication number
CN201638834U
CN201638834U CN 201020159386 CN201020159386U CN201638834U CN 201638834 U CN201638834 U CN 201638834U CN 201020159386 CN201020159386 CN 201020159386 CN 201020159386 U CN201020159386 U CN 201020159386U CN 201638834 U CN201638834 U CN 201638834U
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tio
nio
nano
array
wire
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付姚
罗昔贤
彭勇
于涛
冯威
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Dalian Maritime University
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Dalian Maritime University
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    • 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
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    • Y02E10/00—Energy generation through renewable energy sources
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Abstract

The utility model discloses a nanowire heterojunction array based ultraviolet light detector, comprising a glass foundation and a conducting film, wherein the glass base is a quartz glass base; the conducting film is provided with a NiO-TiO2 nanowire heterojunction array and at least one N-shaped ohmic electrode as an ultraviolet-light absorbing layer; and the NiO-TiO2 nanowire heterojunction array is provided with at least one P-shaped ohmic electrode. A preparation method of the utility model comprises the following steps that the NiO-TiO2 nanowire heterojunction array and the N-shaped ohmic electrode are prepared on the conducting film, and the P-shaped ohmic electrode is prepared on the NiO-TiO2 nanowire heterojunction array. The core structure of the utility model is a nanowire heterojunction array structure consisting of the TiO2 nanowire heterojunction array and the NiO nanowire heterojunction array in a line-line abutting manner, and has the advantages of high external quantum efficiency and sensitivity, fast response speed, small dark current, small and exquisite volume and the like.

Description

A kind of nanowire heterojunction array-base ultraviolet light detector
Technical field
The utility model relates to a kind of ultraviolet light detector technology, particularly a kind of TiO that is used for ultraviolet detector 2Nanowire heterojunction array-base ultraviolet light detector.
Background technology
Ultraviolet light detector is a kind of photoelectric detector of all being used widely in the military and civilian field.Wide bandgap semiconductor materials, as (Al) GaN, SiC, ZnO, diamond etc., because of its excellent ultraviolet light is selected absorbability, outstanding thermal conductance, thermal stability and chemical inertness, become substitute cost an arm and a leg, the photomultiplier of restricted application and the preferred material of traditional silicon-based detector.Yet, although the photoelectric properties of monocrystal thin films device are very excellent, prepare high-quality single-crystal semiconductor thin film and exist a lot of difficult problems to need to solve always, as the equipment needed thereby costliness, growth, doping techniques difficulty are high.These factors make that the manufacturing cost of single-crystal semiconductor thin film ultraviolet light detector is still very high, can't be generalizable.
Develop rapidly along with nano material and the sub-technology of nano photoelectric, the appearance of the more easy nano-multicrystal film of preparation technology junction device, opened up brand-new road for manufacturing process low-cost, the high-performance ultraviolet detector, correlative study has also become new research focus.About the research of nano structure membrane ultraviolet light detector mainly concentrates on nano-ZnO and nano-TiO 2On the film.The nano-multicrystal TiO that particularly has been widely used in fields such as DSSC, photocatalysis Decomposition pollutant, self-cleaning film in recent years 2Film has caused the great interest of people especially owing to have very strong UV Absorption characteristic.This material is not only high temperature resistant, durability is strong, physics and chemical property are stable, and preparation technology's difficulty is lower, adopts conventional liquid phase process (as sol-gel process) can make the thin-film material of high-quality, stable performance.Because nano-TiO 2Therefore film has very ripe preparation technology in the extensive use of numerous areas.Above-mentioned these advantages make nano-multicrystal TiO 2Film becomes a kind of ideal material that is used to prepare low cost, high-performance ultraviolet detector.
At present, domestic and international researcher is with nano-multicrystal TiO 2Film the has been basic engineering UV photodetector part of multiple different structure, comprise liquid knot, schottky junction, the ultraviolet light detector of PN junction type, and their photoelectric properties have been carried out comparatively detailed research, delivered " the transparent nano TiO that is used for ultraviolet light transducer of pair Yao, Cao Wang and collaboration as " Science Bulletin " 2006.51 (8) 2The preparation of film ", " functional material and device journal " 2005,11 (2) delivered " TiO that is used for ultraviolet photoconductive detector of collaborations such as Zhang Liwei, Yang Shie, Yao Ning 2Thin film study ".Yet, although relevant nano-multicrystal TiO 2The research of thin film ultraviolet detector has obtained certain progress, but from obtaining device performance, still is in the junior stage.The photoelectric properties of nano-multicrystal thin film ultraviolet detector still can't be caught up with and surpassed single crystal device and be obtained to use.
Be not difficult by analysis to find traditional polycrystalline TiO 2Why the film photoelectric performance can't obtain tremendous raising, its basic reason is: too high crystal boundary and defect concentration seriously hindered the diffusion of light induced electron to conductive substrates or metal electrode in the polycrystal film, the life-span that simultaneously a large amount of defectives have also seriously reduced photo-generated carrier as right complex centre, light induced electron-hole.Therefore, even make junction device, its photoelectric properties also are difficult to obtain significantly to promote.And these problems and traditional polycrystalline TiO 2The degree of disorder that the film intercrystalline is bigger has much relations.If can be with nano-TiO 2Line up the crystal grain high-sequential of polycrystal film, even the designated lane of formation photo-generated carrier transmission in film, the obstruction that photo-generated carrier is subjected in transmission in the film is significantly reduced, thereby the photoelectric properties that are expected to make the nano-multicrystal film obtain significant the raising, make its near in addition reach the level of single crystal device.
In fact, utilize the nano-multicrystal film preparation opto-electronic device of high-sequentialization to become one of popular in recent years research topic.Relevant nano-tube array, nano-wire array, photonic crystal applications have all obtained good effect in the research in fields such as solar cell, gas sensor, photocatalysis." Applied PhysicsLetters " 2008.93:133107 has delivered C.J.Lin, " the Roughconical-shaped TiO that W.Y.Yu and S.H.Chien collaborates 2-nanotube arrays for flexible backilluminated dye-sensitizedsolar cells ", their result of study confirms that the nano-multicrystal film with high-sequential structure can obtain amazing performance really than traditional polycrystal film and improve.Though yet the nanostructure that it should be noted that high-sequentialization the transmission rate that improves photo-generated carrier is had very great help, it does not have direct effect to the right separation in light induced electron-hole.Therefore, only with TiO 2The simple substance material constitutes the ordering film and is difficult to obtain desirable high photoelectric properties.Though, by some simple measures,, can improve the film photoelectric performance to a certain extent as ion doping, semiconductor sensitization etc., its action effect can obtain 50% left and right sides performance at most and improve, and this is far from being enough.
Summary of the invention
Be to solve the problems referred to above that prior art exists, the utility model will design a kind of with low cost, nanowire heterojunction array-base ultraviolet light detector with high photoelectric properties and stable performance.
To achieve these goals, the technical solution of the utility model is as follows: a kind of nanowire heterojunction array-base ultraviolet light detector, comprise substrate of glass, conductive film, and described conductive film is positioned on the substrate of glass; Described substrate of glass is the quartz glass substrate, and the NiO-TiO as the UV Absorption layer is arranged on the described conductive film 2Nanowire heterojunction array and at least one N type Ohmic electrode, described NiO-TiO 2At least one P type Ohmic electrode is arranged on the nanowire heterojunction array.
Conductive film described in the utility model is ITO conductive film or FTO conductive film.
NiO-TiO described in the utility model 2Nanowire heterojunction array is TiO 2Nano-wire array and NiO nano-wire array constitute described TiO by line-line butt joint 2Nano-wire array is by the TiO of the direction of growth perpendicular to conductive film 2Nano wire be arranged in parallel formation and each root TiO 2There is a NiO nano wire nano wire upper end all growth; Described NiO nano-wire array is by being grown in TiO 2Nano wire upper end, the direction of growth and TiO 2The NiO nano wire of the nano wire direction unanimity formation that is arranged in parallel; Equal and the TiO of each root NiO nano wire in the described NiO nano-wire array 2An identical TiO of position with it in the nano-wire array 2Nano wire links to each other, and constitutes NiO-TiO 2Nanowire heterojunction.
P type Ohmic electrode described in the utility model and N type Ohmic electrode are dots structure or loop configuration or curvilinear structures.
Compared with prior art, the utlity model has following beneficial effect:
1, since core texture of the present utility model by TiO 2Nano-wire array and NiO nano-wire array constitute the nanowire heterojunction array structure by the butt joint of line-line, have external quantum efficiency and highly sensitive, plurality of advantages such as response speed is fast, dark current is little, volume is small and exquisite.
2, preparation method described in the utility model has following feature: the easy maturation of nano-wire array preparation technology, can adopt the template-electrophoretic deposition technique that generally is used at present to prepare nano wire to make, the titanium source is comparatively cheap butyl titanate, titanium tetrachloride or titanyl sulfate, and the nickel source is nickel nitrate cheap and that be easy to buy.Prepared detector is not only with low cost, and long service life, and the ultraviolet light that only wavelength is shorter than 380nm has highly sensitive response output, and to infrared and visible light without any response, can prevent other interference of light sources except that ultraviolet light.
3, the utility model adopts wide bandgap semiconductor materials (Eg＞3.0) NiO nano wire and TiO 2Nano wire is made nanowire heterojunction as P, n type material respectively, and a large amount of nanowire heterojunctions are arranged in parallel make nanowire heterojunction array, utilizes this NiO-TiO 2Nanowire heterojunction array prepares ultraviolet light detector as photosensitive layer.Because the transmission channel that nano wire provided can improve the transmission rate of photo-generated carrier greatly, and the nanowire heterojunction internal electric field can significantly reduce the right recombination probability in light induced electron-hole to the right pressure separation in light induced electron-hole, therefore, the detector speed of photoresponse is fast, the responsiveness height, good stability.
4, NiO-TiO described in the utility model 2Nanowire heterojunction array has following feature: NiO-TiO 2TiO in the nanowire heterojunction array 2The thickness of nano-wire array and NiO nano-wire array is adjustable, can guarantee that light absorption mainly occurs in the space charge region, guarantees that simultaneously the depletion layer electric field is enough strong, thereby effectively suppresses the compound of photo-generated carrier, improves the response speed of detector.
Description of drawings
3 in the total accompanying drawing of the utility model, wherein:
Fig. 1 is the nanowire heterojunction array-base ultraviolet light detector generalized section.
Fig. 2 is the nanowire heterojunction array-base ultraviolet light detector floor map that does not prepare P type Ohmic electrode.
Fig. 3 is NiO-TiO 2The nanowire heterojunction array generalized section
Among the figure, 1, substrate of glass, 2, conductive film, 3, NiO-TiO 2Nanowire heterojunction array, 4, P type Ohmic electrode, 5, N type Ohmic electrode, 31, TiO 2Nano-wire array, 32, the NiO nano-wire array, 311, TiO 2Nano wire, 321, the NiO nano wire.
Embodiment
Below in conjunction with accompanying drawing the utility model is described further.As Figure 1-3, a kind of nanowire heterojunction array-base ultraviolet light detector comprises substrate of glass 1, conductive film 2, and described conductive film 2 is positioned on the substrate of glass 1; Described substrate of glass 1 is quartz glass substrate 1, and the NiO-TiO as the UV Absorption layer is arranged on the described conductive film 2 2Nanowire heterojunction array 3 and at least one N type Ohmic electrode 5, described NiO-TiO 2At least one P type Ohmic electrode 4 is arranged on the nanowire heterojunction array 3.Described conductive film 2 is ITO conductive film 2 or FTO conductive film 2.Described NiO-TiO 2Nanowire heterojunction array 3 is TiO 2Nano-wire array 31 and NiO nano-wire array 32 constitute described TiO by line-line butt joint 2Nano-wire array 31 is by the TiO of the direction of growth perpendicular to conductive film 2 2 Nano wire 311 be arranged in parallel formation and each root TiO 2All growing in nano wire 311 upper ends has a NiO nano wire 321; Described NiO nano-wire array 32 is by being grown in TiO 2Nano wire 311 upper ends, the direction of growth and TiO 2The NiO nano wire 321 of the nano wire 311 direction unanimities formation that is arranged in parallel; Each root NiO nano wire 321 equal and TiO in the described NiO nano-wire array 32 2An identical TiO of position with it in the nano-wire array 31 2 Nano wire 311 links to each other, and constitutes NiO-TiO 2Nanowire heterojunction.Described P type Ohmic electrode 4 and N type Ohmic electrode 5 are dots structure or loop configuration or curvilinear structures.
Preparation method of the present utility model may further comprise the steps:
A, substrate of glass 1 is carried out clean;
B, on the substrate of glass after the clean 1 preparation conductive film 2, obtain electro-conductive glass substrate 1, and preliminary treatment carried out in electro-conductive glass substrate 1;
C, on conductive film 2, prepare NiO-TiO 2Nanowire heterojunction array 3, described NiO-TiO 2The area of nanowire heterojunction array 3 is less than the area of conductive film 2;
D, at NiO-TiO 2Preparation P type Ohmic electrode 4 on the nanowire heterojunction array 3;
E, on conductive film 2, make N type Ohmic electrode 5.
Described electro-conductive glass substrate 1 preliminary treatment may further comprise the steps:
B1, do mask with tinfoil paper, will shelter from through the edge of pretreated ITO electro-conductive glass, cover width is 2mm;
B2, employing vacuum evaporation technology, the thick high-purity Al film of preparation 20-25 μ m on quartzy conductive substrates;
B3, the good high-purity Al film of evaporation is carried out surface clean, remove degrease; Utilize perchloric acid and absolute ethyl alcohol mixed liquor to carry out electrobrightening, obtain the clean Al film of light as electrolyte;
B4, be anode with gained Al film, platinized platinum is a negative electrode, and 5% phosphoric acid is electrolyte, in the water-bath Al film is carried out a high-voltage anode oxidation;
B5, employing phosphoric acid and chromic acid mixture are removed the relatively poor once oxidation layer of order, and under the same conditions the Al film are carried out secondary oxidation, make the thick quartzy electro-conductive glass base anodised aluminium AAO template of 10-15 μ m.
Described NiO-TiO 2The preparation method of nanowire heterojunction array 3 may further comprise the steps:
C1, on conductive film 2, at first prepare a series of TiO perpendicular to plane, conductive film 2 place based on substrate of glass 1 2 Nano wire 311 makes prepared TiO 2 Nano wire 311 is arranged in parallel and constitutes TiO 2Nano-wire array 31;
C2, at TiO 2Every TiO in the nano-wire array 31 2Prepare a NiO nano wire 321 on the nano wire 311 respectively, make the direction of growth and the TiO of NiO nano wire 321 2 Nano wire 311 unanimities, prepared NiO nano wire 321 are arranged in parallel and promptly constitute NiO nano-wire array 32.
Described substrate of glass 1 thickness is 0.5-2mm; Conductive film 2 is semiconductor conductive film 2 or conductive metal film 2, and thickness is 0.5-1 μ m; NiO-TiO 2Nanowire heterojunction array 3 thickness are 0.5-11 μ m, wherein TiO 2The thickness of nano-wire array 31 is 0.05-10 μ m, and electron concentration is greater than 1 * 10 18Cm -3, the thickness of NiO nano-wire array 32 is 0.05-10 μ m, free carrier concentration is less than 1 * 10 16Cm -3TiO 2Nano wire 311 length are 0.05-10 μ m, and NiO nano wire 321 length are 0.05-10 μ m.
Described P type Ohmic electrode 4 and N type Ohmic electrode 5 are dots structure or loop configuration or curvilinear structures, are made by Au or Pd or Pt or Ni or Al material, and thickness is 0.1-5 μ m.
Described TiO 2The preparation method of nano-wire array 31 and NiO nano-wire array 32 comprises sol-gel process, template, template-electrophoretic deposition, vapour deposition process and magnetron sputtering method, and the preparation method of described P type Ohmic electrode 4 and N type Ohmic electrode 5 comprises sputtering technology, gas-phase deposition, ion plating, evaporation process.
Described template-electrophoretic deposition prepares TiO 2The step of nano-wire array 31 and NiO nano-wire array 32 is as follows: at TiO 2In the colloidal sol, be negative electrode with electro-conductive glass substrate 1 bilateral AAO template, graphite rod is an anode, applies 10-15V voltage.Make positively charged TiO 2Micelle moves to negative electrode, and enters the template micropore by capillarity, constantly deposits at electronegative electro-conductive glass substrate 1 one ends, forms the long nano wire 311 of 1-2 μ m behind the 10min; Template is removed unnecessary organic principle through 100 ℃ of dry 30min, makes TiO through 400 ℃ of roasting 1h again 2 Nano wire 311 internal capillaries shrink, crystallization, and with the conductive substrates strong bonded; Adopt above-mentioned electrophoretic deposition technique, depositing the long TiO of 1-2 μ m 2Continue deposition NiO micelle in the AAO micropore of nano wire 311, make the long NiO nano wire 321 of 5-6 μ m behind the 30min; Then, through 100 ℃ of dry 30min, 400 ℃ of roasting 1h, remove unnecessary organic principle respectively and make NiO nano wire 321 crystallization; With 3mol/LNaOH solution dissolving AAO template, make the thick NiO-TiO of 6-8 μ m 2Nanowire heterojunction array 3.
Utilize bias voltage circuit to provide reverse bias voltage to ultraviolet light detector.When ultraviolet lighting is mapped to detector quartz glass one side, TiO 2It is right to produce light induced electron-hole in the nano-wire array 31, and under the effect of internal electric field, light induced electron, hole are respectively to NiO nano-wire array 32 and TiO 2Nano-wire array 31 drifts about fast, and imports external circuit respectively into through P type Ohmic electrode 4 and N type Ohmic electrode 5, produces photo-signal, thereby reaches the purpose of ultraviolet detector.

Claims (4)

1. a nanowire heterojunction array-base ultraviolet light detector comprises substrate of glass (1), conductive film (2), and described conductive film (2) is positioned on the substrate of glass (1); It is characterized in that: described substrate of glass (1) is quartz glass substrate (1), and the NiO-TiO as the UV Absorption layer is arranged on the described conductive film (2) 2Nanowire heterojunction array (3) and at least one N type Ohmic electrode (5), described NiO-TiO 2At least one P type Ohmic electrode (4) is arranged on the nanowire heterojunction array (3).
2. a kind of nanowire heterojunction array-base ultraviolet light detector according to claim 1 is characterized in that: described conductive film (2) is ITO conductive film (2) or FTO conductive film (2).
3. a kind of nanowire heterojunction array-base ultraviolet light detector according to claim 1 is characterized in that: described NiO-TiO 2Nanowire heterojunction array (3) is TiO 2Nano-wire array (31) and NiO nano-wire array (32) constitute described TiO by line-line butt joint 2Nano-wire array (31) is by the TiO of the direction of growth perpendicular to conductive film (2) 2Nano wire (311) be arranged in parallel formation and each root TiO 2There is a NiO nano wire (321) nano wire (311) upper end all growth; Described NiO nano-wire array (32) is by being grown in TiO 2Nano wire (311) upper end, the direction of growth and TiO 2The NiO nano wire (321) of nano wire (311) the direction unanimity formation that is arranged in parallel; Equal and the TiO of each root NiO nano wire (321) in the described NiO nano-wire array (32) 2An identical TiO of position with it in the nano-wire array (31) 2Nano wire (311) links to each other, and constitutes NiO-TiO 2Nanowire heterojunction.
4. a kind of nanowire heterojunction array-base ultraviolet light detector according to claim 1 is characterized in that: described P type Ohmic electrode (4) and N type Ohmic electrode (5) are dots structure or loop configuration or curvilinear structures.
CN 201020159386 2010-04-14 2010-04-14 Nanowire heterojunction array based ultraviolet light detector Expired - Fee Related CN201638834U (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102437229A (en) * 2011-11-29 2012-05-02 吉林大学 Titanium-zirconium oxide solid solution nanowire array ultraviolet detector and preparation method thereof
CN103745585A (en) * 2014-01-03 2014-04-23 北京工业大学 Self-driven nano ultraviolet detection system employing smart responder wireless transmission
CN104810425A (en) * 2014-01-24 2015-07-29 中国科学院上海微系统与信息技术研究所 Ultraviolet detector and manufacturing method thereof
CN106159093A (en) * 2015-04-20 2016-11-23 北京纳米能源与系统研究所 Flexible light sensor and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102437229A (en) * 2011-11-29 2012-05-02 吉林大学 Titanium-zirconium oxide solid solution nanowire array ultraviolet detector and preparation method thereof
CN103745585A (en) * 2014-01-03 2014-04-23 北京工业大学 Self-driven nano ultraviolet detection system employing smart responder wireless transmission
CN103745585B (en) * 2014-01-03 2017-12-19 北京工业大学 The self-driven nano ultraviolet detection system that intelligent response formula is wirelessly transferred
CN104810425A (en) * 2014-01-24 2015-07-29 中国科学院上海微系统与信息技术研究所 Ultraviolet detector and manufacturing method thereof
CN106159093A (en) * 2015-04-20 2016-11-23 北京纳米能源与系统研究所 Flexible light sensor and preparation method thereof
CN106159093B (en) * 2015-04-20 2018-10-16 北京纳米能源与系统研究所 Flexible optical sensor and preparation method thereof

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