CN1027204C - Method for preparing visible photoluminescent silicon quantum point - Google Patents

Method for preparing visible photoluminescent silicon quantum point Download PDF

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CN1027204C
CN1027204C CN92107762A CN92107762A CN1027204C CN 1027204 C CN1027204 C CN 1027204C CN 92107762 A CN92107762 A CN 92107762A CN 92107762 A CN92107762 A CN 92107762A CN 1027204 C CN1027204 C CN 1027204C
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陈坤基
黄信凡
徐骏
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Nanjing University
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Abstract

The present invention relates to a silicon quantum material for preparing photo visible luminescence and an application thereof. In the present invention, glass is used as a substrate material, and silane (SiH4) and ammonia gas (NH3) are used as gas sources; a-Si: H/a-SiNx: H multilayer films with various thicknesses are prepared by utilizing a plasma chemistry vapor deposition (PECVD) technology. Then, a continuous Ar<+> laser is used for carrying out scanning irradiation for a sample so as to crystallize the structure of an a-Si: H trap layer in the original sample. The material has a photo visible waveband luminescent property at a room temperature, and the peak energy of a luminescent spectrum of the photo visible waveband is about 2.1 eV. The peak energy not only greatly exceeds the band gap energy (1.1 eV) of crystalline silicon (C-Si), but also exceeds the band gap energy of non-crystalline silicon.

Description

Method for preparing visible photoluminescent silicon quantum point
The present invention relates to semiconductor quantum structure (also claiming low dimensional structures) preparation methods and be applied to quantum device preparation method and application.
Semiconductor quantum structure (as quantum well, quantum wire, quantum dot) is one of field with fastest developing speed in the current novel low dimension semiconductor device architecture.Wherein the earliest be the One-dimensional Quantum well structure, it is that semi-conducting material by the relative narrow band gap of one deck is clipped in the semi-conducting material of two layers of relative broad-band gap and constitutes, the thickness of typical quantum well layer is 1 to 10nm scope.In such structure, the Charge carrier in the quantum well layer has two-dimensional freedom in layer plane, and is restricted on the direction on perpendicular layers plane, has therefore produced many new physics phenomenons that can not occur in the body material.
Early stage semiconductor quantum well structures utilizes molecular beam epitaxy (MBE) technology to realize by GaAs/AlGaAs.For the quantum well structure of Si, nineteen eighty-three is at first by B.Abeles and T.Tiedje 1Prepare a-Si: the most sub-trap of H, and observe the One-dimensional Quantum restriction effect, if in a film, comprise many quantum well, then also be referred to as " Multiple Quantum Well " or " superlattice " structure, can be referring to K.J.Chen and H.Fritzsche, Bulletin of APS31(1986) 333. 2
People such as S.Furukawa were at report in 1989 3Utilizing sputtering technology to obtain size on low temperature (77K) substrate is the Si particulate of 2~5nm, is also referred to as quantum dot.And the surface of particulate is by H 2Passivation.The optical band gap of this material can reach 2.4eV, and at room temperature observed photoluminescence spectrum is at red spectral band.
People such as nineteen ninety L.Canham report 4Utilize electrochemical etching method on the Si sheet, can prepare the Si quantum wire array that diameter is equal to or less than 3nm, and at room temperature also observe photoluminescence spectrum at red spectral band.The method of Canham comprises that (1) obtains porous silicon layer by the anodic oxidation of Si sheet; (2) with chemical corrosion the hole in the porous silicon is enlarged until forming certain quantum wire.The characteristics of method are that technology is simple, are easy to realize.But because preparation process is the process of a chemical corrosion, so controllability, repeatability are relatively poor, and are subjected to the influence of surface state bigger, the mechanism of the visible photoluminescent of this material resulted from quantum limitation effect? different views is arranged.
Though a-Si: the H optical band gap of sub-well structure can increase to 2.1eV, because a-Si: the existence of magnetic tape trailer defect state in the H trap layer, only observe the near infrared light of 0.9 μ m(~1.37eV) in the photoluminescence spectrum.And,,, bring difficulty to practicality owing to controllability, repeated relatively poor though can observe strong photic as seen luminous (0.7~0.8 μ m) by the quantum wire array that electrochemical erosion method obtains.The objective of the invention is to seek the method for preparing the minor structure of Si beyond the electrochemical erosion method, improve control precision, realize artificial design Si visible photoluminescent.This has major application and is worth and scientific meaning.
In order to realize above-mentioned goal of the invention, the present technique solution is: (1) utilizes plasma chemical vapor deposition (PECVD) technology, select the a-SiNX of broad-band gap for use: H makes barrier layer, the a-Si of narrow band gap: H makes potential well layer, prepares the a-Si that adheres to specification: H/a-SiHX: the H multi-quantum pit structure.(2) utilize the laser scanning irradiation technique, make a-Si: H trap layer structure generation crystallization, acquisition has the crystallization a-Si of definite degree of crystallinity: H/a-SiNX: the H multi-quantum pit structure, and in this material, observe the photoluminescence spectrum that peak value is positioned at 0.6 μ m(~2.1eV).
By silane (SiH 4) decomposing gas acquisition a-Si: H layer, its optical band gap are 1.75eV.By silane (SiH 4)/ammonia (NH 3) mist decomposition acquisition a-SiNX: the H layer, wherein the component X of N can be by changing (SiH 4/ NH 3) ratio control.Along with the variation of X, a-SiNX: the optical band gap of H layer is controlled between 2.9~3.5eV, corresponding to (NH 3)/(SiH 4)=2~9.The a-Si of mqw material: H layer thickness Ls is 20~50
Figure 921077629_IMG4
, SiNX: H layer thickness LN is 50~100
Figure 921077629_IMG5
, trap layer gross thickness<1 μ m.
The key technology that obtains quantum well structure is planarization and the abruptness that guarantees each interface, sublayer.Its key is: (1) guarantees the time T that reacting gas is detained in reative cell when changing reative cell atmosphere component RFar be shorter than the time T of growth G, by formula T R-VP/F OP O, V=1000cm in our growth conditions 3, P=200-400mTorr, F O=120cm 3/ min, P OBe standard atmospheric pressure, the substitution following formula gets T R=0.1~0.2sec is less than the growth time T of individual layer G=10~20sec has guaranteed the abruptness at interface.(2) by artificial design, machine control as calculated, the fit quality flowmeter has accurately been controlled the variation of reaction atmosphere.Confirm the a-Si that we prepare: H/a-SiNX by cross section transmission electron microscopy mirror (TEM) photo (seeing accompanying drawing 1): the interface of H multi-quantum pit structure has atomic-level flatness.
At this a-Si: H/a-SiNX: in the H multi-quantum pit structure, work as a-Si: the thickness Ls of H trap layer is less than 40
Figure 921077629_IMG6
The time, observe the blue shift of the optical absorption edge that causes by quantum limitation effect, when Ls little of 20
Figure 921077629_IMG7
Optical band gap can increase to 2.1eV during the left and right sides, than unmodulated a-Si: the band gap of H film (1.75eV) has improved 0.35eV, but at this a-Si: H/a-SiNX: in the H quantum well structure, the peak of photoluminescence spectrum is the near infrared region near 0.9 μ m(~1.37eV).The reason that luminous energy is lower than optical band gap is because at a-Si: have a large amount of magnetic tape trailer defect states in the H trap layer, the portions of electronics hole that illumination produces is non-radiative compound to being undertaken by the magnetic tape trailer defect state, be that effective optical band gap has narrowed down, the photon energy of radiation recombination is reduced.
In order to improve a-Si: the energy of the radiation recombination photon in the H trap layer, valid approach are the magnetic tape trailer defect state densities that reduces a-Si: H, have selected Ar for use for this reason +Laser scanning irradiation technique, purpose are by this treatment technology, have both improved a-Si: the crystallinity of H trap layer, reduced defect state density, and do not destroy the quantum well structure of this material again.Therefore the key problem in technology of laser scanning radiation is photon energy and a power density of selecting laser, is controlled in the solid-phase crystallization process.Select the principle of optical maser wavelength to be:
E Si<EL<ESiNX is the laser photon energy less than a-SiNX: the band gap of H layer (promptly allow its total transmissivity) is again greater than a-Si: the band gap of H layer (allow its hypersorption), EL is about between 2.3~2.8eV, so we select the Ar of 488nm for use +Laser.For making silicon trap layer material solid-phase crystallization, laser power is adjustable continuously at 0.8~2.2W, and beam spot diameter, is less than 150 μ m, and sweep speed 4.0~9.0cm/s scans overlapping greater than 50%, and laser irradiating device as shown in Figure 2.
Utilize material of the present invention can make opto-electronic device, the present invention also can be used for making the germanium quantum point material.
Be subjected to the restriction of potential well layer thickness with the size of the crystallization Si quantum dot (or longitudinal size of quantum well) of the inventive method preparation, therefore the quantum dot size distribution is even in whole material.Confirm that by Raman spectrum (seeing accompanying drawing 3) the Si quantum dot has good crystallinity, at room temperature we observe the photic visible light wave range glow peak of this material, peak 0.6 μ m(~2.1eV), the halfwidth at peak (FWHM)<0.25eV.(seeing accompanying drawing 4)
The present invention's advantage compared with prior art is: (1) quantum well layer thickness can manually design, can be easily by computer control, and precision can reach 5 , controllability is better than electrochemical erosion method greatly.(2) grain size behind the laser crystallization is evenly distributed, and its crystallite dimension is limited by the trap layer thickness.Therefore the halfwidth of the glow peak of this material (<0.25eV) less than the halfwidth (~0.32eV at the porous silicon luminescence peak of electrochemical erosion method preparation.The light luminous spectrum that gained of the present invention is described is pure.(3) the present invention can be used for preparing other semiconductor quantum wells, quantum-dot structure, for example the Ge quantum dot.(4) by Si quantum well, the quantum-dot structure of the present invention's preparation, help designs and development.
The invention will be further described below in conjunction with accompanying drawing and by embodiment:
Fig. 1: Ar +(b) a-Si: H/ behind (a) and the irradiation before the laser irradiation
A-SiN X: the TEM photo of H.
Multiplication factor: 100,000
Example interface is clear behind the irradiation, no apparent damage.
Fig. 2: Ar +Laser scanning irradiation devices schematic diagram:
1-Ar +Laser 2-Ar +Laser beam
3-condenser lens 4-speculum
5-sample 6-XY travelling carriage
Fig. 3: a-Si: H/a-SiNX: the H sample is at Ar +Before the laser irradiation
(1) Raman spectrum of (2) and behind the irradiation
Predose is at 480cm -1Present diffuse peaks
Behind the irradiation at 511cm -1~516cm -1The place presents spike
A-Si is described: the H film is crystallization.
Fig. 4: the a-Si of different trap layer thicknesses: H/a-SiNX: H sample
At Ar +Photoluminescence spectrum after the laser irradiation
(1)Ls=35
(2)Ls=40
Select silane (SiH for use 4) and ammonia (NH 3) make gas source, utilize the PECVD technology, deposit a-Si: H/a-SiNX on glass or quartz plate substrate: H multi-quantum-well film.Process conditions are as follows:
Power source frequency 13.5MHz
Deposit power demand density 0.2W/cm 2
Deposition chamber pressure 275mTOrr
250 ℃ of underlayer temperatures
Deposition rate 1.1/S
At a-Si: H/a-SiNX: in the H multi-quantum pit structure, potential well layer a-Si: H is by pure SiH 4Decompose deposit and form, its band gap width is 1.75eV; Barrier layer layer a-SiNX: H is by mist [NH 3]/[SiH 4]=3.6.Decompose deposit and form, its band gap width is 2.9eV.On the basis of known deposition speed, sublayer thickness is determined by deposition time.In the present embodiment, the thickness L of potential well layer a-Si: H s=35
Figure 921077629_IMG9
, barrier layer is at the thickness L of a-SiNX: H N=60
Figure 921077629_IMG10
, totally 72 cycles.The switching of two kinds of materials is realized by the open and-shut mode of computer control air intake valve in the deposition process.
A-Si by above-mentioned PECVD technology preparation: H/a-SiNX: the H Multiple Quantum Well is an amorphous structure, and we put into the device shown in the accompanying drawing 2 to the sample of original deposit, and it is carried out the laser scanning radiation treatment, and condition of work is as follows:
Laser beam spot diameter 100 μ m
Laser beam flying speed 4.5cm/s
Laser beam flying overlaps>50%
Laser beam power 2.0W
170 ℃ of underlayer temperatures
Sample behind laser crystallization, Si potential well layer structure is good crystallinity, is measured by Raman and determines about the about 4nm of its grain size (seeing accompanying drawing 3-(2)), do not have destroyed through sectional tem check (seeing Fig. 1 (b)) the most sub-original well structure.This proof has successfully prepared Si quantum-dot structure material with the inventive method.In this material we to observe wavelength be 0.6 μ m(2.1eV) photic visible waveband luminous.(seeing the spectral line 1 among Fig. 4)
When changing a-Si: H potential well layer L s=40, also can get intact Si quanta point material with above-mentioned same procedure; Its photoluminescence spectrum is shown in (2) among Fig. 4.

Claims (4)

1, the silicon quantum dot preparation method of visible photoluminescent, utilize plasma chemical vapor deposition (PECVD) method growth a-Si: H/a-SiNX earlier: H multi-quantum pit structure material, it is characterized in that with laser scanning irradiation a-Si: H/a-SiNX: H multi-quantum pit structure material, make the power of silicon trap layer material solid-state crystal laser be selected in 0.8~2.2W, Wavelength of Laser is selected for use in following ranges, and promptly its photon energy is less than a-SiNX: the band gap of H layer is again greater than a-Si: the band gap of H layer.
2, by the described method of claim 1, it is characterized in that a-Si: H/a-SiNX: the a-Si of the multi-quantum pit structure material of H: the thickness Ls of H trap layer is 20~50
Figure 921077629_IMG2
, SiNX: the thickness LN of H trap layer is 50~100 , trap layer gross thickness<1 μ m.
3, by claim 1 or 2 described methods, it is characterized in that scanning after the laser line focus, beam spot diameter, is less than 150 μ m, and sweep speed 4.0~9.0cm/s scans overlapping greater than 50%.
4, by claim 1 or 2 described methods, the silicon quantum dot material that it is characterized in that visible photoluminescent is in order to make opto-electronic device.
CN92107762A 1992-09-19 1992-09-19 Method for preparing visible photoluminescent silicon quantum point Expired - Fee Related CN1027204C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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CN100401337C (en) * 2000-02-15 2008-07-09 史蒂夫·马格鲁 Quantum point safety device and method
CN100446290C (en) * 2007-02-09 2008-12-24 南京大学 Oxygen silicon base doped nitride film yellow green wave band LED and its preparing method
CN102064470A (en) * 2010-12-17 2011-05-18 贵州大学 Full silicon quantum dot nano laser and manufacturing method thereof

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JP3469337B2 (en) * 1994-12-16 2003-11-25 株式会社半導体エネルギー研究所 Method for manufacturing semiconductor device
CN1326209C (en) * 2004-06-24 2007-07-11 复旦大学 Method for doping of Si quantum dot
CN101172607B (en) * 2007-10-10 2010-06-02 南京大学 Method of producing amorphous silicon nanoparticles
DE102008036400B3 (en) * 2008-08-01 2010-01-21 Technische Universität Berlin Photon pair source and process for their preparation
CN101570312B (en) * 2009-06-11 2011-04-20 南京大学 Method for realizing controlled doping of nano silicon quantum dots
CN103852951B (en) * 2014-02-19 2016-11-16 南京大学 Utilize nano-silicon and silicon dioxide interface state to the method improving non-linear optical property

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100401337C (en) * 2000-02-15 2008-07-09 史蒂夫·马格鲁 Quantum point safety device and method
CN100446290C (en) * 2007-02-09 2008-12-24 南京大学 Oxygen silicon base doped nitride film yellow green wave band LED and its preparing method
CN102064470A (en) * 2010-12-17 2011-05-18 贵州大学 Full silicon quantum dot nano laser and manufacturing method thereof

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