CN103500703B - Improve the method for CdS and CdSe nano material conductivity and photoelectric current - Google Patents

Improve the method for CdS and CdSe nano material conductivity and photoelectric current Download PDF

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CN103500703B
CN103500703B CN201310470086.XA CN201310470086A CN103500703B CN 103500703 B CN103500703 B CN 103500703B CN 201310470086 A CN201310470086 A CN 201310470086A CN 103500703 B CN103500703 B CN 103500703B
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electron beam
cds
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conductivity
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CN103500703A (en
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张礼杰
朱大鸣
戴宁
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Shanghai Institute of Technical Physics of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/34Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
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Abstract

The invention discloses a kind of method improving CdS and CdSe nano material conductivity and photoelectric current, it utilizes electron beam irradiation to improve CdS and CdSe low-dimension nano material conductivity and photoelectric current.Method of the present invention is simple, controlled, and required electron beam energy low (0.2-30keV), can realize by scanning electron microscopy.(1 × 10 is better than in high vacuum environment -3pa), the method is utilized can to increase substantially conductivity (the & gt of CdS and CdSe low-dimension nano material in pole; 10 5times) and photoelectric current (reaching 5 times).

Description

Improve the method for CdS and CdSe nano material conductivity and photoelectric current
Technical field
The present invention relates to nano material technology, be specifically related to a kind of method improving CdS and CdSe low-dimension nano material conductivity as isostructural in nano wire, band and sheet and photoelectric current.It is applicable to nanometer science and technology field, is especially having important application prospect based in the electronics of CdS or CdSe low-dimensional nano structure, opto-electronic device.
Background technology
Nano ZnO regulation and control are one of most important research fields in the development of current nanoscale science and technology.Through the development of two more than ten years, scientists has developed vertical multi-method for improving the physical property of nano material.Wherein chemical method as: improve the electron transport ability of nano material by doping; By changing the skin effect of material at Surface-modification of Nanoparticles functional molecular or group, thus improve its physical property.Also nano ZnO can be regulated and controled by Physical, as ion implantation and the heat utilizing laser irradiation to produce are used for changing nano ZnO.Along with the development of science and technology, electron beam is one of most important means of research nano material.Scanning electron microscopy (SEM) is such as usually needed to observe pattern and understand component; Need to study nano material internal structure with transmission electron microscope (TEM).In addition, it has been found that high-power electron beam (MeV magnitude) exposed material can change the physical property of material.Such as, with 1MeV electron beam irradiation InP crystal, crystals can be made to produce deep energy level [A.SibilleandJ.C.Bourgoin, Appl.Phys.Lett., 41 (1982), 956-958].Along with the development of TEM technology, can more clearly home position observation to change [D.Golberg, the PedroM.F.J.Costa of nano material internal structure when electron beam irradiation, M.Wang, X.Wei, D.Tang, Z.Xu, Y.Huang, U.K.Gautam, B.Liu, H.Zeng, N.Kawamoto, C.Zhi, M.MitomeandY.Bando, 24 (2013) 177-194].
CdS and CdSe is important II-VI group compound semiconductor materials, is widely used in electronics, field of optoelectronic devices.Its low-dimension nano material as nano wire, band, sheet etc. at nano-device as having wide practical use in field-effect transistor, solar cell, photodetector and photodiode etc.But, intrinsic CdS and CdSe nano material resistance huge, have a strong impact on its application in some nano-device.Doping is important channel [Z.He, J.Jie, W.Zhang, W.Zhang, L.Luo, X.Fan, G.Yuan, I.BelloandS.-T.Lee, Small, 2009,5,345. of improving its conductivity; Z.Hu, X.Zhang, C.Xie, C.Wu, X.Zhang, L.Bian, Y.Wu, L.Wang, Y.ZhangandJ.Jie, Nanoscale, 2011,3,4798.; C.Liu, P.Wu, T.Sun, L.Dai, Y.Ye, R.MaandG.Qin, J.Phys.Chem.C, 2009,113,14478.].Obviously, doping is difficult to adulterate to certain single nano wire, band or the sheet of specifying, i.e. poor selectivity.Therefore, if find a kind of method, optionally can improve the conductivity of certain single nano wire, band or sheet, will have great importance.Mention the performance that electron beam can be utilized to change nano material above, because interact with extranuclear electron after high energy electron enters material, destroy original equilibrium state, change band structure, and regional area likely causes its structural deterioration because producing excessive heat.Such as, CdSe polycrystal film is by after 7MeV electron beam irradiation, and Fermi level moves to conduction band, thus its electron mobility declines [S.Antohe, L.IonandV.Ruxandra, J.Appl.Phys., 90 (2001), 5928-5932.].The result of study of forefathers shows to utilize high energy electron beam to be difficult to improve the conductivity of nano material.At present, yet there are no and utilize electron beam to improve the conductivity of CdS and CdSe low-dimension nano material and the document of photoelectric current aspect.Total institute is known, when electron beam (usual <30keV) and the material of SEM interact, produces backscattered electron, auger electrons and secondary electron etc.Obviously, secondary electron and injection electronics likely will remain in material internal, and these inject electronics may enter conduction band increase conductivity.In addition, material may produce temporary crystal defect when SEM electron beam irradiation, and defect improves the key factor of electron transport ability.Experimentally, we confirm that CdS and CdSe low-dimension nano material is after SEM electron beam irradiation, and conductivity obtains and increases substantially.And because electron beam irradiation causes the change of material electronics structure, thus the photoelectric current of material also obtains raising.
Summary of the invention
The object of the present invention is to provide a kind of method improving CdS and CdSe low-dimension nano material conductivity and photoelectric current, the method utilizes electron beam irradiation material to be achieved, simple, controlled.Correlative study of the present invention finds, can be changed the electronic structure of CdS and CdSe low-dimension nano material by electron beam irradiation, and then improves conductivity and the photoelectric current of material.
The present invention is achieved through the following technical solutions:
CdS and CdSe nano wire, band or sheet are put into vacuum degree and is better than 1 × 10 -3in the vacuum system of Pa, CdS and the CdSe nano wire of electron beam to required process of 30pA, band or sheet irradiation more than 30 seconds is greater than with energy 0.2-30keV, line, close electron beam, being placed in vacuum system by material after irradiation makes material property tend towards stability in more than 3 hours, is greatly improved before the conductivity of now processed nano material and photocurrent ratio irradiation.
In order to prove that electron beam irradiation can improve conductivity and the photoelectric current of these materials, need material to make device so that test.Device preparation and method of testing as follows:
The dispersion of CdS and the CdSe low dimensionality of nano-wires of synthesis, band or sheet in ethanol, mixed liquor is added drop-wise to SiO 2/ Si substrate surface, utilizes ultraviolet photolithographic, electron beam lithography or the technique such as other method and metal deposition to draw metal microelectrode on nano wire, band or sheet.The device prepared is inserted in SEM sample room, and device two ends are connected to electrical characterization equipment.(1 × 10 is better than when SEM sample room is evacuated to ultimate vacuum -3pa), close electron beam with electron beam exposed material after 30 seconds, after 3 hours, device performance is in stable state.Record the current-voltage relation curve after predose respectively by electrical characterization equipment, and after predose and illumination time current-voltage curve.Experimental provision schematic diagram is as Fig. 1.
The mechanism that electron beam irradiation improves CdS and CdSe low-dimension nano material conductivity and photoelectric current may be: (1) is after the electronics (0.2-30kV) with certain energy enters material, generation secondary electron and incident electron major part enter material conduction band, thus increase the carrier concentration of material, and then improve conductive capability; (2), after incident electron enters material, material itself is made to produce temporary defect, from being with angle analysis, vertical many defect levels are produced in forbidden band, the electronics being in this energy level more easily transits to conduction band after illumination, forms electron hole pair, thus improves photoelectric response performance.By the characterization result of single CdSe nanobelt field-effect transistor before and after contrast electron beam irradiation, the electron concentration in the material that confirms that electron beam irradiation can increase substantially (100 times).
The present invention's CdS and CdSe low-dimension nano material used can use chemical vapour deposition technique (CVD) to prepare, also can with wet chemistry method or the preparation of other method.Material itself has complete mono-crystalline structures, but to the not special requirement such as the thickness of the diameter of the pattern such as nano wire of material, nanobelt and sheet.
In a word, the present invention proposes and utilize relative low energy electrons bundle irradiation CdS and CdSe low-dimension nano material, thus increase the electron concentration of this material, and then improve the thought of its conductivity and photoelectric current.
According to its principle, the present invention has two major advantages: (1) is simple to operate, only needs SEM or similar devices to provide electron beam irradiation CdS and the CdSe low-dimension nano material of appropriate energy, can improve conductivity and the photoelectric current of material; (2) there is selectivity, select target nano material can carry out electron beam irradiation, thus improve conductivity and the photoelectric current of this nano material.
Accompanying drawing explanation
Fig. 1. the experimental provision schematic diagram of its conductivity is improved with SEM electron beam irradiation CdS and CdSe low-dimension nano material.
Fig. 2. the current-voltage characteristic curve of single CdSe nanobelt device before and after electron beam irradiation; Embedding the SEM photo that figure is this two terminal device, is electron beam irradiation region in red boxes.
Fig. 3. this CdSe nanobelt device is by electric current (bias voltage 1V) change curve in time after electron beam irradiation.
Fig. 4. a CdSe nanobelt FET, before electron beam irradiation, (a) (figure is b) with transfer characteristic curve for figure for aerial curve of output.
Fig. 5. this FET by after electron beam irradiation, in vacuum (5 × 10 -4pa) (a) (figure b) with transfer characteristic curve for figure for the curve of output in environment.
Fig. 6. a SEM photo based on the two poles of the earth device of single CdS nanobelt.
Fig. 7. this CdS nanobelt device, before and after electron beam irradiation, light, dark current are with voltage change curve.Light source is 532nm semiconductor laser, and power density is 0.81mW/cm 2.
Embodiment
Below in conjunction with accompanying drawing, further describe situation of the present invention by embodiment, but do not limit the present invention in any way.
Embodiment 1: the conductive capability being improved CdSe nanobelt material by electron beam irradiation.
Concrete steps are as follows:
(1) CVD synthesis CdSe nanobelt.
(2) prepared CdSe nanobelt is dispersed in ethanolic solution, drips this mixed liquor to SiO 2/ Si substrate surface, allows ethanol natural evaporation do.
(3) by spin-coating method spin coating one deck PMMA(4000r/min), dry through 1min at 160 degree.
(4) scribble the techniques such as the substrate electron beam lithography of PMMA, metal deposition and stripping, prepare microelectrode (In/Au) at selected single nanobelt two ends.
(5) this device is inserted in SEM sample room, CdSe nanobelt two ends metal electrode is connected to the electrical characterization equipment outside sample room by silver-colored line.
(6) sample room is evacuated to ultimate vacuum (3 × 10 -4pa).
(7) current-voltage characteristics curve is recorded before and after electron beam irradiation, as shown in Figure 2.The current-voltage curve of nanobelt predose is non-linear, defines non-ohmic contact between illustrative material and metal electrode; And when 1V bias voltage, electric current 10pA.Close electron beam perpendicular to CdSe nanobelt surface irradiation after 1 minute with 5keV, 133pA electron beam, after 20 hours, the I-V curve recorded is obvious ohmic contact characteristic, and when 1V bias voltage, electric current ~ 6 μ A, be before electron beam irradiation ~ 6 × 10 5doubly.After closing electron beam, under constant bias 1V condition, the electric current in 12-20 hours section is curve (voltage constant: 1V) over time, as shown in Figure 3.This result shows, the CdSe nano material after electron beam irradiation, and through right times, its conductivity is stable, but will increase substantially than before irradiation.Embodiment 2: the electrology characteristic being improved CdSe nanobelt field effect transistor by electron beam irradiation.
(1) CdSe nanobelt synthesis and based on the preparation of the field effect transistor (FET) of single CdSe nanobelt with reference to step (1)-(4) in embodiment 1.This FET for grid, is referred to as backgate FET with heavily doped p-type silicon.
(2) curve of output of FET and transfer curve in air ambient (humidity 50%RH), is recorded as shown in Figure 4.On-off ratio is about 15 times, carrier concentration ~ 1.1 × 10 14cm -3.
(3) this device is put into SEM sample room, be evacuated to 5 × 10 -4pa, closes electron beam perpendicular to nanobelt surface direction irradiation after 1 minute with the electron beam of 10keV, 128pA.
(4), after half an hour, the curve of output of this FET and transfer curve is recorded as shown in Figure 5.Compared with the FET test result before electron beam irradiation, the FET after electron beam irradiation has obviously more excellent switching characteristic and (is better than 10 7doubly).And electron beam irradiation changes the mode of operation of FET, become the depletion type after irradiation from the enhancement mode of predose.Electron beam irradiation also significantly improves carrier concentration (~ 1.3 × 10 16cm -3), be predose ~ 100 times.
Embodiment 3: electron beam irradiation improves conductivity and the photoelectric current of CdS nanobelt.
(1) CdS nanobelt is grown by CVD.
(2) preparation of CdS nanobelt device is as step (1)-(4) in embodiment 1, and the SEM photo of device as shown in Figure 6.
(3) similar in electronic transmission performance method of testing and embodiment 1, before electron beam irradiation, record current-voltage curve respectively, electron beam irradiation closed electron beam after 1 minute, recorded current-voltage curve again after 13 hours.
(4) test of photoelectric current, need introduce light source in SEM sample room, and the present invention introduces 532nm laser by optical fiber to vacuum chamber.During photoelectric current test, optical power density is constant is 0.81mW/cm 2, laser vertical is incident in nanobelt surface direction.
(5), before and after electron beam irradiation, light, dark current test result are as shown in Figure 7.Can find by figure, under bias voltage 1V condition, the electric current (11.6nA) after electron beam irradiation is before electron beam irradiation (~ 6.1 × 10 -5nA) ~ 1.9 × 10 5doubly; Under 1V bias condition, photoelectric current after electron beam irradiation (during illumination the difference of electric current and dark current, 47.8nA) is predose (9.6nA) ~ 5 times.

Claims (1)

1. improve a method for CdS or CdSe nano material conductivity and photoelectric current, it is characterized in that method is as follows:
CdS or CdSe nano wire, band or sheet are put into vacuum degree and is better than 1 × 10 -3in the vacuum system of Pa, CdS or the CdSe nano wire of electron beam to required process of 30pA, band or sheet irradiation more than 30 seconds is greater than with energy 0.2-30keV, line, close electron beam, being placed in vacuum system by material after irradiation makes material property tend towards stability in more than 3 hours, increases before the conductivity of now processed nano material and photocurrent ratio irradiation.
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CN1821083A (en) * 2006-03-07 2006-08-23 上海大学 Process for preparing nano cadmium sulfide

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A variable electron beam and its irradiation effect on optical and electrical properties of CdS thin films;M SINGH.et al;《Pramana-J.Phys》;20070930;第69卷(第4期);631-638 *

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