CN103236648A - Method for realizing blue shift of band gap of semiconductor quantum well structure - Google Patents
Method for realizing blue shift of band gap of semiconductor quantum well structure Download PDFInfo
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- CN103236648A CN103236648A CN2013101543246A CN201310154324A CN103236648A CN 103236648 A CN103236648 A CN 103236648A CN 2013101543246 A CN2013101543246 A CN 2013101543246A CN 201310154324 A CN201310154324 A CN 201310154324A CN 103236648 A CN103236648 A CN 103236648A
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Abstract
The invention provides a method for realizing blue shift of a band gap of a semiconductor quantum well structure. The method comprises the steps of depositing a surface sacrificial layer on the quantum well structure; selecting a regional surface sacrificial layer through ultrashort pulse laser irradiation or scanning to realize chemical modification or introducing structure defects in the regional surface sacrificial layer to form a laser modified region; and conducting quick thermal annealing to a component comprising the quantum well structure and the surface sacrificial layer, transmitting the chemical modification of the laser modified region or the introduced structure defects into the quantum well structure through a thermal induction effect to enable well/barrier components of the quantum well structure to be mutually mixed to realize the wavelength blue shift of the band gap of the quantum well structure.
Description
Technical field
The present invention relates to optical semiconductor and photonic integrated circuits technology, particularly a kind of method of utilizing the ultra-short pulse laser technology to realize the semiconductor quantum well structures band gap blue shift.
Background technology
Continuous development along with optical-fibre communications, single chip integrated demand to all kinds of photonic devices continues to increase, the development situation of photonic integrated circuits will realize more massive application in future as the extensive electronic integrated circuit of nineteen seventies generation at present.
At present, different with the microelectronic integrated circuit maximum, photonic integrated circuits need form the material of various different band gap at same substrate, to satisfy the requirement of all kinds of different active and passive devices, need absorb light as the detector in the optic integrated circuit, and waveguide needs printing opacity, and the desired material band gap of these devices is different.For realizing this purpose, development has played multiple technologies, and wherein quantum well mixing technology (Quantum Well Intermixing:QWI) is a kind of feasible method of realizing the quantum-well materials band gap blue shift by aftertreatment technology.At present, QWI realizes in the semi-conducting material of III/V family, for example gallium aluminium arsenic and InGaAsP, and this material is grown on the binary semiconductor material substrate, as GaAs or indium phosphide.QWI has changed the band gap of institute's growth structure by quantum well and relevant phase counterdiffusion of building layer element, has formed the mixed zone of new component distributing, makes the band gap big (be band gap blue shift) of this mixed zone than the quantum well of original growth.At present, reported the accomplished in many ways quantum well mixing, for example:
(1) enter quantum well by other impurity of elevated temperature heat diffusion introducing and cause QWI, perhaps inject some element by ion and introduce point defect at the semiconductor of band quantum well structure, annealing realizes quantum well mixing then; This QWI technology has many pieces of bibliographical informations.Though this class depends on the band gap that the quantum well mixing of impurity induced can change semi-conducting material, residual diffusion or implanted dopant can be because the free carrier mechanism of absorption cause absorptivity to increase;
(2) free from admixture room diffusion technique is to have realized another important method of quantum well mixing.This method is by the cvd silicon oxide film, and high annealing realizes that gallium is diffused in the silica, then produce the room diffusion and cause quantum well mixing, but this method is temperature required too high, is difficult for constituency control;
(3) method by light has also realized quantum well mixing, and University of Glasgow has developed the mutual expansion that utilizes continuous Nd:YAG LASER HEATING to drive between the different bases of quantum well structure and the trap and realized quantum well mixing; Subsequently, adopt pulse duration also to realize quantum well mixing and device development for the Nd:YAG laser of number nanosecond, but this method exists point defect to produce simultaneously and the thermal induction diffusion, repeatability and stability all have much room for improvement.
Summary of the invention
(1) technical problem that will solve
In view of above-mentioned technical problem, the invention provides a kind of method that realizes the semiconductor quantum well structures band gap blue shift.
(2) technical scheme
According to an aspect of the present invention, provide a kind of method that realizes the semiconductor quantum well structures band gap blue shift.This method comprises: deposition surface sacrifice layer on quantum well structure; By the surperficial sacrifice layer of ultra-short pulse laser irradiation or scanning selection area, to realize chemical modification or to introduce fault of construction at the surperficial sacrifice layer in this zone, form laser modified district; The element that comprises quantum well structure and surperficial sacrifice layer is carried out rapid thermal annealing, by the thermal induction effect chemical modification in laser modified district or the fault of construction of introducing are delivered in the quantum well structure, trap/base the composition of quantum well structure is mixed mutually, realize the band gap wavelength blue shift of quantum well structure.
(3) beneficial effect
From technique scheme as can be seen, the present invention realizes that the method for semiconductor quantum well structures band gap blue shift has following beneficial effect:
(1) because ultrashort pulse irradiation can reduce thermal effect, the uncertain band gap that the thermal diffusion effect when making owing to laser irradiation causes moves significantly and reduces;
(2) because the peak power of ultrashort pulse is very high, be lower than under the material ablation threshold value situation, even even also can excite at material surface even innerly cause a large amount of point defects owing to multiphoton ionization, various elementary excitation (local fields) or sound wave to 1/10th the laser flux that has only the laser fusion threshold value little, thereby improve efficient and the stability that produces point defect greatly;
(3) realized that modification is directly write in scanning and selection changes quantum well band gap regionally, and can have controlled blue shift amount by laser parameter, thereby can realize extensive industrialization.
Description of drawings
Fig. 1 realizes the flow chart of the method for semiconductor quantum well structures band gap blue shift for the embodiment of the invention;
Fig. 2 A～Fig. 2 C is the schematic diagram of each step of execution of method shown in Figure 1.
Fig. 2 A utilizes ultrashort pulse irradiation or scanning to have the schematic diagram of the sample surfaces of quantum well structure;
Fig. 2 B is the schematic diagram that utilizes the irradiated quantum well structure sample of quick thermal annealing process ultrashort pulse;
Fig. 2 C is the band gap schematic diagram through the quantum well structure sample zones of different after the quick thermal annealing process;
Fig. 3 has provided in the print the photoluminescence spectrum of zone after short annealing of being crossed by laser treatment zone and ultrashort pulse laser scan, and the variation of the excitation wavelength peak of correspondence has embodied the band gap blue shift that laser treatment causes.
[main element symbol description of the present invention]
The 1-quantum well structure layer; 2-ultra-short pulse laser bundle;
The quantum well structure surface sacrifice layer that 3-is not crossed by laser treatment;
The surperficial sacrifice layer that 4-is crossed by laser treatment;
5-need utilize the regional A of ultrashort pulse modification;
6-need utilize the regional B of ultrashort pulse modification;
The substrate material layer of 7-quantum well structure;
The 8-medium protective layer;
9-thermal annealing equipment;
E
0, E
1And E
2Be respectively and realized the A in quantum well mixing zone and the band gap width of B by laser treatment regional excessively band gap width and ultrashort pulse.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.Need to prove that in accompanying drawing or specification description, similar or identical part is all used identical figure number.The implementation that does not illustrate in the accompanying drawing or describe is the form known to the those of ordinary skill in the affiliated technical field.In addition, though this paper can provide the demonstration of the parameter that comprises particular value, should be appreciated that parameter need not definitely to equal corresponding value, but can in acceptable error margin or design constraint, be similar to corresponding value.In addition, the direction term of mentioning in following examples, for example " on ", D score, " preceding ", " back ", " left side ", " right side " etc., only be direction with reference to the accompanying drawings.Therefore, the direction term of use is to illustrate not to be to limit the present invention.
The invention provides a kind of method that realizes the semiconductor quantum well structures band gap blue shift.This method adopts ultra-short pulse laser constituency irradiation or scanning quantum well structure material, introduces point defect at surperficial sacrifice layer, subsequently by the induction of rapid thermal annealing, realizes the band gap wavelength blue shift of quantum well structure.
In one exemplary embodiment of the present invention, provide a kind of method that realizes the semiconductor quantum well structures band gap blue shift.Fig. 1 realizes the flow chart of the method for semiconductor quantum well structures band gap blue shift for the embodiment of the invention.As shown in Figure 1, present embodiment comprises:
Steps A: deposition surface sacrifice layer on quantum well structure;
Present embodiment, the substrate of quantum well structure are indium phosphide.The present invention is not as limit, and this substrate can also be selected the III-V family semi-conducting material of direct band gaps such as GaAs for use;
The quantum well structure 1 of present embodiment comprises 5 layers quantum well, and wherein 5 layers of indium gallium arsenic are isolated by 7 layers of InGaAsP respectively.Among the present invention, the semi-conducting material of quantum well structure is single quantum well or multi-quantum pit structure.And, it will be apparent to those skilled in the art that the inventive method is equally applicable to for example gallium aluminium arsenic/gallium arsenic, gallium aluminium arsenic/indium gallium arsenic, other quantum well structures such as AlGaInP/GaAs.
Present embodiment surface sacrifice layer 3 is for being coated with the phosphorization phosphide indium layer (i-InP) of 200nm thickness Intrinsical.Among the present invention, the surface sacrifice layer can also be that for example gallium aluminium arsenic material etc. utilizes the metal organic chemical vapor deposition way directly to grow at its surperficial semi-conducting material when quantum well structure grow or utilizes deielectric-coating such as silicon dioxide that the way of vapour deposition grows up, silicon nitride, can also be the composite film of these materials.The thickness of surface sacrifice layer 3 is generally between the 50nm to 500nm.If be lower than 50nm, then the laser in later stage may see through this surface sacrifice layer, damages quantum well structure; If be higher than 500nm, then the transmission of defective is comparatively difficult.
Step B: by the surperficial sacrifice layer on ultra-short pulse laser irradiation or the scanning quantum well structure, to realize chemical modification or to introduce fault of construction at the surperficial sacrifice layer of selection area, form laser modified district;
In the present embodiment, utilize pulsewidth 30ps, surperficial sacrifice layer on the laser beam 2 scanning quantum well structure materials that the semiconductor pumped solid state laser of wavelength 532nm produces, owing to exist the phosphorus in the chemical breakdown effect indium phosphide can reduce and form point defect, so just formed by laser modified surperficial sacrifice layer 4 in the zone of laser scanning.
Ultra-short pulse laser refer to the pulse duration be pulsewidth less than the pulse laser of 100ps, its wavelength is that 400nm is to 1300nm.Ultrashort pulse laser comprises all kinds of laser that can export femtosecond or picosecond magnitude.This type of laser is solid-state laser, semiconductor laser, fiber laser, ti sapphire laser, dye laser etc. for example, also comprises parametric amplifier or the laser group zoarium of two kinds of pulsewidths, and wherein having at least a kind of is ultrashort pulse.
The environment of ultra-short pulse laser irradiation or scanning can be in the atmospheres such as air, vacuum, oxygen, nitrogen, argon gas or in liquid phase environments such as deionized water, liquid nitrogen, ethanol.
In addition, in this step, can be by changing the laser irradiation parameter to form different laser modified districts, the laser irradiation parameter of available change is average power, optical maser wavelength, pulse flux, pulsewidth, umber of pulse, incident angle, polarization mode etc.Please refer to Fig. 2 A, by different laser parameters such as average power, formed laser modified district 5 and laser modified district 6.Difference was that laser flux is different when the a-quadrant was with the B sector scanning in the example, and the laser power flux that handle in A and B zone is respectively 0.25J/cm
2And 0.15J/cm
2
Step C: comprising on the surperficial sacrifice layer in laser modified district at deposition medium protective layer 8;
In the present embodiment, utilize the plasma enhanced vapor deposition method to cover the thick silicon oxide layer 8 of last layer 200nm.This silicon oxide layer 8 can completely cut off quantum well structure and external environment, avoids quantum well structure to be polluted, and is beneficial to the later stage preparation of devices.This silica can also be media protection layer materials such as silicon nitride, indium gallium arsenic.The thickness of medium protective layer 8 is generally between 50nm～500nm.
Need to prove that this step can be carried out, and perhaps all carried out before step B and afterwards before or after step B.When this step was carried out before step B, ultra-short pulse laser can also be on this medium protective layer manufacturing defect.
Step D, element to this quantum well structure and surface media composition carries out rapid thermal annealing, by the thermal induction effect chemical modification or the fault of construction in the laser modified district of surperficial sacrifice layer is delivered to quantum well structure, trap/base the composition of quantum well structure is mixed mutually, realize the band gap wavelength blue shift of quantum well structure.
In the present embodiment, with the sample after the laser treatment, in thermal annealing equipment 9, carry out rapid thermal annealing, continue 120s down at 725 ℃, shown in Fig. 2 B.The present invention is to the mode of rapid thermal annealing, temperature and time all without limits: rapid thermal annealing comprises electric heating annealing, infra-red heat annealing and LASER HEAT annealing, annealing temperature between 500 ℃ to 850 ℃, annealing time at 20s between the 3min.
Mix speed because the diffusion of the corresponding quantum well area under it has been accelerated in the existence of surperficial sacrifice layer point defect greatly, realized different band gap blue shift.Shown in Fig. 2 C, be not E by the regional band gap width of laser treatment
0, band gap width and the ultrashort pulse in zone do not realize that the A in quantum well mixing zone and the band gap width of B are respectively E excessively by laser treatment
1And E
2Fig. 3 has provided the photoluminescence spectrum of three different band gap correspondence, can see E
1And E
2Than E
0Wavelength blue shift has largely appearred.
So far, by reference to the accompanying drawings the method for present embodiment realization semiconductor quantum well structures band gap blue shift is described in detail.According to above description, those skilled in the art should have clear, complete understanding to the present invention.In addition, need to prove also that above-mentioned definition to each step is not limited in the various concrete mode of mentioning in the execution mode, those of ordinary skill in the art can replace simply to it with knowing.
In sum, the invention provides a kind of ultra-short pulse laser irradiation technique that utilizes in surperficial sacrifice layer manufacturing place defective or vacancy defect, and by rapid thermal annealing point defect or the vacancy defect of surperficial sacrifice layer is passed to quantum well structure, thereby accurately control the method for band gap blue shift amount, and can realize different band gap by control laser parameter constituency.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a method that realizes the semiconductor quantum well structures band gap blue shift is characterized in that, comprising:
Steps A, deposition surface sacrifice layer on quantum well structure;
Step B by the surperficial sacrifice layer of ultra-short pulse laser irradiation or scanning selection area, to realize chemical modification or to introduce fault of construction at the surperficial sacrifice layer in this zone, forms laser modified district;
Step D, the element that comprises quantum well structure and surperficial sacrifice layer is carried out rapid thermal annealing, by the thermal induction effect chemical modification in laser modified district or the fault of construction of introducing are delivered in the quantum well structure, trap/base the composition of quantum well structure is mixed mutually, realize the band gap wavelength blue shift of quantum well structure.
2. method according to claim 1 is characterized in that, the ultra-short pulse laser among the described step B be pulsewidth less than the pulse laser of 100ps, its wavelength is between 400nm～1300nm.
3. method according to claim 2 is characterized in that, described step B also comprises:
By changing the laser irradiation parameter to form different laser modified districts, this laser irradiation parameter is average power, optical maser wavelength, pulse flux, pulsewidth, umber of pulse, incident angle or polarization mode.
4. method according to claim 1 is characterized in that, among the described step D in the rapid thermal anneal process: annealing time is between 20s～3min, and annealing temperature is between 500 ℃～850 ℃.
5. method according to claim 4 is characterized in that, realizes described rapid thermal anneal process by electric heating annealing, infra-red heat annealing or LASER HEAT annealing.
6. method according to claim 1 is characterized in that, the thickness of the surperficial sacrifice layer in the described steps A is between 50nm～500nm, and its material is selected from a kind of in the following material: indium phosphide, gallium aluminium arsenic, silicon dioxide and silicon nitride.
7. method according to claim 6, it is characterized in that, described quantum well structure is single quantum or multi-quantum pit structure, and this quantum well structure is a kind of in the following structure: indium gallium arsenic/InGaAsP, gallium aluminium arsenic/gallium arsenic, gallium aluminium arsenic/indium gallium arsenic and AlGaInP/GaAs.
8. method according to claim 6 is characterized in that, the backing material at described quantum well structure place is selected from the III-V family semi-conducting material of direct band gap.
9. according to each described method in the claim 1 to 8, it is characterized in that, before the described step B and/or also comprise afterwards:
Step C, on described surperficial sacrifice layer at the deposition medium protective layer.
10. method according to claim 9 is characterized in that, the thickness of described medium protective layer is between 50nm～500nm, and its material is selected from a kind of in the following material: silica, silicon nitride and indium gallium arsenic.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108054379A (en) * | 2017-12-29 | 2018-05-18 | 潍坊学院 | A kind of preparation method of nano-silicon graphene composite lithium ion battery negative material |
| CN111312928A (en) * | 2020-03-12 | 2020-06-19 | 昆明理工大学 | Semiconductor device for changing band gap through thermal induction |
| CN114122914A (en) * | 2021-11-11 | 2022-03-01 | 中国科学院半导体研究所 | Laser and preparation method thereof |
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| CA2331567A1 (en) * | 2000-09-01 | 2002-03-01 | National Research Council Of Canada | Laser-induced bandgap shifting for photonic device integration |
| US20040175852A1 (en) * | 2001-07-26 | 2004-09-09 | Phosistor Technologies, Inc. | Method for quantum well intermixing using pre-annealing enhanced defects diffusion |
| CN101774540A (en) * | 2010-02-09 | 2010-07-14 | 浙江大学 | Quantum well mixing method |
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| CA2331567A1 (en) * | 2000-09-01 | 2002-03-01 | National Research Council Of Canada | Laser-induced bandgap shifting for photonic device integration |
| US20040175852A1 (en) * | 2001-07-26 | 2004-09-09 | Phosistor Technologies, Inc. | Method for quantum well intermixing using pre-annealing enhanced defects diffusion |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108054379A (en) * | 2017-12-29 | 2018-05-18 | 潍坊学院 | A kind of preparation method of nano-silicon graphene composite lithium ion battery negative material |
| CN111312928A (en) * | 2020-03-12 | 2020-06-19 | 昆明理工大学 | Semiconductor device for changing band gap through thermal induction |
| CN114122914A (en) * | 2021-11-11 | 2022-03-01 | 中国科学院半导体研究所 | Laser and preparation method thereof |
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Application publication date: 20130807 |