CN101712456B - Method for eliminating intrinsic electric field in ZnSe/BeTe II quantum well - Google Patents

Method for eliminating intrinsic electric field in ZnSe/BeTe II quantum well Download PDF

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CN101712456B
CN101712456B CN200910230077A CN200910230077A CN101712456B CN 101712456 B CN101712456 B CN 101712456B CN 200910230077 A CN200910230077 A CN 200910230077A CN 200910230077 A CN200910230077 A CN 200910230077A CN 101712456 B CN101712456 B CN 101712456B
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bete
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CN101712456A (en
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冀子武
郑雨军
赵雪琴
徐现刚
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Shandong University
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Abstract

The invention relates to a method for eliminating an intrinsic electric field in a ZnSe/BeTE II quantum well and belongs to the technical field of photoelectric material preparation. In the method, an II type quantum well material is prepared by the molecular beam epitaxy process; and a buffer layer, an isolation layer, a potential well-potential barrier-potential well layer and the like grow on a substrate. The quantum well material of the growth interface structure has the characteristics of high quality, good crystal lattice matching on interfaces and II type energy band structures. The material interface has large energy band head drop to make space separation easily happen on electrons and cavity void. Two heterojunction interfaces have a plurality of Zn-Te and Te-Zn chemical bond structures. Compared with the conventional II type energy band structure, the chemical bond structures have longer space indirect recombination luminescence service life, is more favorable for observing and researching high-density condensing phenomena, can weaken the intrinsic electric field in the structure, flattens conduction band and valence band structures, avoids tunneling effect, and is favorable for photoelectric devices to independently control positive and negative charges. The method can be used in the fields of observing the high-density phenomena, researching and manufacturing the photoelectric devices and the like.

Description

Grasp the method for electric field in eliminating in the ZnSe/BeTe II SQW
Technical field
Grasp the method for electric field in the present invention relates in a kind of ZnSe/BeTe of elimination II type quantum well structure, particularly a kind ofly prepare the method that a kind of special interfacial structure is grasped electric field in eliminating with molecular beam epitaxial growth.
Background technology
Because the electronics of being excited to produce in the II type quantum well structure is in respectively in the adjacent different SQWs with the hole, make people control their behavior more easily independently, so this structure have important use in the research and development of opto-electronic device and making.
The wide bandgap compound semiconductor ZnSe that covalency is stronger in the II-VI family (～2.8eV) and BeTe (～ZnSe/BeTe/ZnSe the SQW 4.2eV) formed has II type (type-II) and can be with structure, and there is a big energy drop (Δ E on conduction band (or valence band) limit CB:～2.3eV, Δ E VB:～0.8eV).The electronics that this design feature can cause being excited to produce separates with the hole generation space, and is in respectively in the different trap layers.Because so dark potential well makes the wave function in electronics and hole that a very little overlapping scope arranged, so this structure is considered to indirect (being the II type) the recombination luminescence life-span of very long space.Therefore, ZnSe/BeTe/ZnSeII type quantum well structure is considered to observe and study the important materials of high density phenomenon (like charged exciton, excitonic molecule, exciton polymer and Bose-Einstein condensation etc.) and making opto-electronic device.
II type quantum well structure is to observe and study the high density phenomenon (like charged exciton; Excitonic molecule, exciton polymer and Bose-Einstein condensation etc.) one of important means, just playing a part to become more and more important with origin for the luminous mechanism of understanding and verify the many two-phonon process that comprise spin state.Mainly contain II type quantum well structure of forming by the III-V compound semiconductor and the II type quantum well structure of forming by the II-VI compound semiconductor according to disclosed II type quantum well structure.U.S.'s academic journal magazine " Physical Review B " (2000; The 61st volume; The 10782nd page; " Theory of electronic and optical propertiesof bulk AlSb and InAs and InAs/AlSb superlattices ") experimental result (G.Theodorou, et al., 61 (2000) 10782) of the II type quantum well structure research luminescence generated by light of forming with the III-V compound semiconductor disclosed.(the conduction band drop is about Δ E but because this structure has less conduction band (or valence band) drop at the heterojunction boundary place C=1.35eV, the valence band drop is about Δ E V=0.13eV); Making the electronics of being excited to produce separate back (being that electronics is in different trap layers respectively with the hole) with the hole generation space is still having bigger wave function overlapping at the interface; Therefore its space combines (spatially indirectrecombination) has indirectly again had bigger increase though the life-span of the direct recombination radiation in space in luminous life-span and the I type quantum well structure is compared, and the condensed state phenomenon is undesirable for observing.Britain's academic journal magazine " Semiconductuor Science andTechnology " (2006; The 21st volume; The 87th page; " Electric-and magnetic-field effects on radiativerecombination in modulation n-doped ZnSe/BeTe type-II quantum wells ") to disclose the II type quantum well structure of forming with the II-VI compound semiconductor (be traditional I I type quantum well structure; Shown in accompanying drawing 3) research luminescence generated by light experimental result (Ziwu Ji, et al., 21 (2006) 87).Though this structure has bigger conduction band (Δ E CB:～2.3eV) and valence band (Δ E VBThe drop of :～0.8eV) helps observing and research high density coacervation.But grasp electric field in stronger owing to exist in its non-doped structure; The caused Stark effect of this electric field makes conduction band and valence band run-off the straight; Thereby cause photic carrier generation tunnel-effect, be unfavorable for the observation and the application aspect photoelectric device of high density phenomenon.
Summary of the invention
To grasp the difficulty that electric field brings in order overcoming in above-mentioned, to the present invention proposes a kind of particular interface structure of utilizing and (comprise several Zn-Te or several Te-Zn chemical bond at the interface.Fig. 2 has shown the situation of three chemical bonds) replace the traditional interface structure and (only comprise Zn-Te or Te-Zn at the interface.Fig. 3 has shown the situation of a chemical bond) to grasp the method for electric field in eliminating.This invention is to prepare the ZnSe/BeTe/ZnSe II type SQW with particular interface structure through molecular beam epitaxy (MBE) growing method.In growth course, the switch number of times through the different solid source baffle plates of suitable adjusting and reach the purpose that preparation has the particular interface structure switch time.
A kind of have the method for the ZnSe/BeTe/ZnSe II type SQW of particular interface structure with the preparation of molecular beam epitaxy (MBE) growing method, and step is following:
1. the gallium arsenide substrate with (001) orientation is fixed in the holder of molybdenum (Mo) sample with indium (In);
2. logical cooled with liquid nitrogen growth room is confirming that III-V family growth room's vacuum is 1 * 10 -10After below the Torr, be sent to sample in the III-V family growth room through the magnetic force driven rod; With the sample holder, the K-cell container of As solid source is housed and the K-cell container heat temperature raising of Ga solid source is housed, the temperature that makes it to reach setting is respectively 300 ℃, 100 ℃ and 750 ℃;
3. adjust the temperature of As source K-cell container; After making it to begin to warm to 295 ℃ by 100 ℃, the temperature with sample holder and Ga source K-cell container is set at 550 ℃ and 915 ℃ respectively again, and begins to heat up; Open the baffle plate of As source K-cell container simultaneously; The As molecular beam is radiated on the substrate, the evaporation of the substrate surface As cause because of underlayer temperature raises with compensation, and make the evaporation of As on the substrate surface reach balance with adhering to;
4. after treating that Ga source K-cell container rises to 915 ℃; Again the sample holder is warming up to 620 ℃; Can on [110] direction, observe through reflected high energy electron diffraction (RHEED appearance) appearance between temperature raising period; Striped occurs if can observe clearly, the oxide of under this temperature, having removed substrate surface then is described and is obtained the orderly substrate surface of cleaning;
5.GaAs the generation of cushion: open the baffle plate that temperature has risen to 915 ℃ Ga source K-cell container, the Ga molecular beam is radiated on the substrate; This moment, the molecular beam of Ga and As was radiated at substrate surface simultaneously; The growth of GaAs cushion begins, and growth time is 24 ~ 120 minutes, and the thickness of GaAs cushion can reach 200 ~ 1000nm; Turn off the Ga source this moment; And the temperature of Ga source K-cell container reduced to 750 ℃ by 915 ℃, reduce to 300 ℃ afterwards again, and a cleaning, smooth and orderly surface are arranged through the substrate that the RHEED appearance can be observed this moment;
6. after stablizing 5 minutes, underlayer temperature is reduced to 580 ℃ gradually by 620 ℃, cool-down method is a staged, and promptly each cooling is set at falls 5 ℃, sets next time when reaching design temperature again, divides and accomplishes cooling 8 times; After the cooling beginning, when observing image and do not have what ANOMALOUS VARIATIONS, the As source is turned off, and the As source temperature is transferred to 100 ℃ by 295 ℃ through the RHEED appearance;
7. underlayer temperature is reduced to 500 ℃ gradually by 580 ℃, cool-down method is a staged, falls 10 ℃ at every turn; Afterwards, again underlayer temperature is reduced to 300 ℃ gradually by 500 ℃, whole temperature-fall period divides and carries out for 10 times, and each cooling is spaced apart 20 ℃;
8. observing RHEED appearance image does not have any ANOMALOUS VARIATIONS, and can turn off the RHEED appearance this moment, becomes 7.5 * 10 in the vacuum of confirming III-V family growth room -9After below the Torr, turn off being used for the power supply of heated substrate, and prepare substrate is passed to II-VI family growth room through the high vacuum transmission pipeline;
9. be 1 * 10 in the vacuum of confirming II-VI family growth room -10The temperature in Zn, Be, Te, Se and Mg source in below the Torr and the II-VI family growth room is heated to respectively after 150,820,150,50 and 200 ℃, is sent to II-VI family growth room to substrate by III-V family growth room through ultra-high vacuum transmission pipeline again; Substrate is warming up to 300 ℃ ~ 350 ℃, and the temperature in Zn, Be, Te, Se and Mg source is warming up to 307,1065,320,202 and 322.5 ℃ more respectively;
10.BeTe the generation of cushion: after the temperature in Be, Te source reaches 1065 and 320 ℃ respectively, stablized 30 minutes, open the baffle plate in Be, Te source, Be molecular beam and Te molecular beam are radiated at the surface of substrate, and the BeTe cushion begins to grow this moment; Monitor (perhaps, set, control, down together) in real time with the RHEED appearance with computer according to the growth rate of each solid source that records in advance before the growth; When the growth thickness of BeTe cushion is about 5ML; Growth ending is turned off the Be source then earlier, turns off the Te source subsequently again;
11.Zn 0.77Mg 0.15Be 0.08The growth of Se separation layer: open the baffle plate in Zn source earlier, the baffle plate of opening Se, Be and Mg source again carries out Zn 0.77Mg 0.15Be 0.08The growth of Se separation layer; There are this moment Zn molecular beam, Se molecular beam, Be molecular beam and Mg molecular beam to be radiated at the surface of substrate simultaneously respectively, when the separation layer growth thickness is 200 ~ 1000nm, finish growth; Close Se, Be, Mg source earlier, close the Zn source again after about 5 ~ 10 seconds;
12.ZnSe the growth of potential well layer: open Zn, Se source; The two is radiated on the substrate surface simultaneously, and the temperature of Zn, Se solid source remains on 307 and 202 ℃ respectively, when the thickness of ZnSe layer growth is 4 ~ 80ML; Growth ending; Close the Se source earlier, after about 5 ~ 10 seconds, close the Zn source again, so that form rich Zn superficial layer;
13.BeTe the temperature in the growth of barrier layer: Be, Te source remains on 1065 and 320 ℃ respectively, opens the Zn source earlier, after about 5 ~ 10 seconds, closes the Zn source, opens the Te source simultaneously, and after about 5 ~ 10 seconds, closes the Te source; Repeat the operation 1 ~ 3 time in above-mentioned Zn source and Te source; Open Te source and Be source afterwards again; Te source and Be source are radiated on the substrate surface simultaneously, and the BeTe barrier layer that begins to grow, when the thickness of BeTe barrier layer growth is about 10ML; Close the Be source earlier and close the Te source again, the growth ending of BeTe barrier layer; The special construction that above-mentioned growth course can obtaining at the interface between ZnSe and BeTe has 3,5 or 7 Zn-Te chemical bond forms;
14.ZnSe the growth of potential well layer: keep the temperature-resistant of above-mentioned Zn, Se, Te source, open the Te source earlier, after about 5 ~ 10 seconds, close the Te source, open the Zn source simultaneously, and after about 5 ~ 10 seconds, close the Zn source; Repeat the operation 1 ~ 3 time in above-mentioned Te source and Zn source, can reduce to 150 ℃ this moment with the temperature in Te source, opens Zn source and Se source afterwards simultaneously, and Zn source and Se source are radiated on the substrate surface simultaneously, and begin the growing ZnSe potential well layer; When the thickness of ZnSe potential well layer growth was about 4 ~ 80ML, the active layer growth ending was closed the Se source afterwards earlier and is closed the Zn source again; The special construction that above-mentioned growth course can obtaining at the interface between BeTe and ZnSe has 3,5 or 7 Te-Zn chemical bond forms;
15. the growth course of the separation layer of repeating step 11 can obtain the thick Zn of 200 ~ 1000nm 0.77Mg 0.15Be 0.08The Se separation layer; To close Se, Be, Mg source earlier during growth ending, close the Zn source again after about 10 seconds, can not corroded with the protection sample at grown on top one deck Zn of sample as cover layer like this; Behind the growth ending, underlayer temperature is made as 150 ℃ and make it cooling, simultaneously also the temperature in Zn, Se, Be and Mg source is set at 100,50,820 and 150 ℃ and make it cooling respectively; Reduce to after 150 ℃ and the temperature of confirming the Se source reduce to below 100 ℃ when underlayer temperature, sample is taken out from the growth room, can obtain the quantum-well materials of complete ZnSe/BeTe/ZnSe form.
Through above-mentioned growth course, we can obtain having the SQW (that is, two heterogeneous interface places in the active layer include the special construction of 3,5 or 7 Zn-Te and Te-Zn chemical bond form respectively) of the ZnSe/BeTe/ZnSe form of particular interface structure.
RHEED appearance used in the present invention is the refletcion high-energy electron diffraction appearance.
Above-mentioned ML is the abbreviation of english words monolayer, i.e. molecular layer.For BeTe or ZnSe, 1ML is about 0.28nm.
The present invention organizes the II type quantum well structure that compound semiconductor (ZnSe and BeTe) has the particular interface structure through the preparation of molecular beam epitaxy (MBE) growing method with II-VI, and used II-VI compound semiconductor ZnSe and BeTe have very wide forbidden band (being about 2.8eV and 4.2eV respectively) and stronger ionic associative key.ZnSe/BeTe/ZnSe quantum well structure by they are formed is compared with other traditional heterojunction structure, have II type (type-II) and can be with structure, and there is a big energy drop (Δ E on conduction band (or valence band) limit CB:～2.3eV, Δ E VB:～0.8eV).The electronics that this design feature can cause being excited to produce separates with the hole generation space, and is in respectively in the different trap layers.This structure so observe the high density coacervation more easily, also helps the effective control to photo-generated carrier owing to have particular chemical bond structure (being the special chemical bonding structure of a plurality of Zn-Te or Te-Zn form) at the interface simultaneously.Therefore this structure is more suitable in the application of theoretical research and photoelectric device.
The used growing system of the present invention has two growth rooms, is respectively applied for the epitaxial growth of III-V family and the epitaxial growth of II-VI family.During with molecular beam epitaxial method growing ZnSe/BeTe/ZnSe heterojunction structure,, can obtain having the particular interface structure of a plurality of Zn-Te or Te-Zn form through regulating the formation of heterojunction boundary place chemical bond.
The operation principle of the inventive method is following:
Choose II-VI compound semiconductor ZnSe and BeTe with broad stopband; Utilize they on the conduction band limit (or valence-band edge) locate can be with discontinuous and the characteristics than the macro-energy drop are arranged; Particularly utilize at the bottom of the conduction band of ZnSe not only low at the bottom of the conduction band than BeTe; Simultaneously also low characteristics at the bottom of the valence band than BeTe at the bottom of the valence band of ZnSe form the ZnSe/BeTe/ZnSe SQW with II type band structure characteristics.Such design feature makes the electronics of being excited to produce in the ZnSe layer can generation space separate with the hole, and promptly electronics is still stayed in the original ZnSe layer, and the hole is transferred in the adjacent BeTe layer.Owing to grown into a plurality of Zn-Te or Te-Zn chemical bonding structure (this has three Zn-Te or Te-Zn chemical bond at the interface shown in accompanying drawing 2) at the interface; Make the distance between the carrier of both sides, interface strengthen; So not only weakened widely inside configuration in grasp electric field; Make that also the life-span of space indirect transition is elongated, thus this structure be observe, research condensed state phenomenon, and the ideal structure of development photoelectric device.
A kind of equipment that is used for above-mentioned preparation method; Promptly two growth rooms molecular beam epitaxy system; Comprise two growth rooms of III-V family and II-VI family, it is characterized in that each growth room all has solid source evaporimeter, five dimension adjustable specimen holder, QMS and reflection high energy electron diffractions etc.; Wherein two solid source evaporimeters in the III-V family growth room are Ga evaporimeter and As evaporimeter, and five solid source evaporimeters in the II-VI family growth room are Te, Zn, Se, Mg and Be source evaporimeter; Connect so that the transmission of sample with ultra-high vacuum transmission pipeline between two growth rooms; Ultra-high vacuum transmission pipeline has air extractor, and two growth rooms that are connected with two ends separate with push-pull valve respectively; Specimen holder and solid source evaporimeter all are connected to heater strip respectively, to satisfy the requirement of temperature adjustment; All be furnished with the cooled with liquid nitrogen device near growth room's inwall and solid source evaporimeter and the substrate, so that absorption indoor showy atom in growth room and molecule, thereby reduce the indoor air pressure in growth room and guarantee sample cleannes on every side.
The ZnSe/BeTe/ZnSe SQW with particular interface structure that the inventive method is grown has crystal mass height, the characteristics of good, the II type band structure of lattice matched at the interface.ZnSe and BeTe very big can be with drop having at the interface, can make electronics and hole be easy to generation space and separate.Simultaneously because two heterojunction interfaces have a plurality of Zn-Te and Te-Zn chemical bonding structure; Compare with traditional I I type band structure; Has the indirect recombination luminescence life-span of longer space; More help observing, research high density coacervation, like charged exciton, Bose-Einstein condensation, and Fermi can hold unusually (Fermi-nergyedge sigularity) phenomenon etc.In addition, this particular interface structure can also weaken in the structure in grasp electric field, make conduction band and valence band structure become smooth, thereby avoided tunnel-effect, help photoelectric device to the control of the independence of positive and negative charge.
Description of drawings
Fig. 1 is the crystal structure of zinc selenide/zinc selenide of the present invention (ZnSe/BeTe/ZnSe) whole sample and can be with sketch map.Figure below wherein is the sectional view that comprises the whole sample structure of active layer ZnSe/BeTe/ZnSe, and last figure is the band structure corresponding to active layer and cushion.C.B and V.B represent conduction band and valence band respectively, and DT represents the direct transition in the space in the ZnSe layer (being the transition of I type), and IT represents the space indirect transition (being the transition of II type) between ZnSe layer and the BeTe layer.
Wherein: 1, GaAs substrate, 2, the GaAs cushion, 3, the BeTe cushion, 4, Zn 0.77Mg 0.15Be 0.08The Se separation layer, 5, the ZnSe potential well layer, 6, the BeTe barrier layer, 7, the ZnSe potential well layer, 8, Zn 0.77Mg 0.15Be 0.08The Se separation layer, 9, the Zn cover layer.
In addition: E S=3.0eV (Zn 0.77Mg 0.15Be 0.08The energy gap of Se), E B=4.2eV (energy gap of BeTe), E W=2.8eV (energy gap of ZnSe), Δ E C=2.3eV (conduction band of BeTe and ZnSe is poor), Δ E V=0.8eV (valence band of BeTe and ZnSe is poor), Δ E C1=0.2eV (Zn 0.77Mg 0.15Be 0.08The conduction band of Se and ZnSe is poor), Δ E V1=0.1eV (ZnSe and Zn 0.77Mg 0.15Be 0.08The valence band of Se is poor).
Fig. 2 is zinc selenide/zinc selenide (ZnSe/BeTe/ZnSe) active layer crystal structure sketch map partly that the present invention has the particular interface structure.
Fig. 3 is zinc selenide/zinc selenide (ZnSe/BeTe/ZnSe) active layer crystal structure sketch map partly with traditional interface structure.
The specific embodiment
Below in conjunction with accompanying drawing 1 and accompanying drawing 2 and embodiment the present invention's (especially manufacturing process of particular interface) is further specified, but be not limited thereto.
Embodiment 1:
A kind of have the method for the ZnSe/BeTe/ZnSe II type SQW of particular interface structure with the preparation of molecular beam epitaxy (MBE) growing method, and shown in Fig. 1-2, step is following:
1. the gallium arsenide substrate with (001) orientation is fixed in the holder of molybdenum (Mo) sample with indium (In);
2. logical cooled with liquid nitrogen growth room is confirming that III-V family growth room's vacuum is 1 * 10 -10After below the Torr, be sent to sample in the III-V family growth room through the magnetic force driven rod; With the sample holder, the K-cell container of As solid source is housed and the K-cell container heat temperature raising of Ga solid source is housed, the temperature that makes it to reach setting is respectively 300 ℃, 100 ℃ and 750 ℃;
3. adjust the temperature of As source K-cell container; After making it to begin to warm to 295 ℃ by 100 ℃, the temperature with sample holder and Ga source K-cell container is set at 550 ℃ and 915 ℃ respectively again, and begins to heat up; Open the baffle plate of As source K-cell container simultaneously; The As molecular beam is radiated on the substrate, the evaporation of the substrate surface As cause because of underlayer temperature raises with compensation, and make the evaporation of As on the substrate surface reach balance with adhering to;
4. after treating that Ga source K-cell container rises to 915 ℃; Again the sample holder is warming up to 620 ℃; Can on [110] direction, observe through reflected high energy electron diffraction (RHEED appearance) appearance between temperature raising period; Striped occurs if can observe clearly, the oxide of under this temperature, having removed substrate surface then is described and is obtained the orderly substrate surface of cleaning;
5.GaAs the generation of cushion: open the baffle plate that temperature has risen to 915 ℃ Ga source K-cell container, the Ga molecular beam is radiated on the substrate; This moment, the molecular beam of Ga and As was radiated at substrate surface simultaneously; The growth of GaAs cushion begins, and growth time is about 30 minutes, and growth thickness is about the GaAs buffer layer of 250nm; Turn off the Ga source this moment; And the temperature of Ga source K-cell container reduced to 750 ℃ by 915 ℃, reduce to 300 ℃ afterwards again, and a cleaning, smooth and orderly surface are arranged through the substrate that the RHEED appearance can be observed this moment;
6. after stablizing 5 minutes, underlayer temperature is reduced to 580 ℃ gradually by 620 ℃, cool-down method is a staged, and promptly each cooling is set at falls 5 ℃, sets next time when reaching design temperature again, divides and accomplishes cooling 8 times; After the cooling beginning, when observing image and do not have what ANOMALOUS VARIATIONS, the As source is turned off, and the As source temperature is transferred to 100 ℃ by 295 ℃ through the RHEED appearance;
7. underlayer temperature is reduced to 500 ℃ gradually by 580 ℃, cool-down method is a staged, falls 10 ℃ at every turn; Afterwards, again underlayer temperature is reduced to 300 ℃ gradually by 500 ℃, whole temperature-fall period divides and carries out for 10 times, and each cooling is spaced apart 20 ℃;
8. observing RHEED appearance image does not have any ANOMALOUS VARIATIONS, and can turn off the RHEED appearance this moment, becomes 7.5 * 10 in the vacuum of confirming III-V family growth room -9After below the Torr, turn off being used for the power supply of heated substrate, and prepare substrate is passed to II-VI family growth room through the high vacuum transmission pipeline;
9. be 1 * 10 in the vacuum of confirming II-VI family growth room -10The temperature in Zn, Be, Te, Se and Mg source in below the Torr and the II-VI family growth room is heated to respectively after 150,820,150,50 and 200 ℃, is sent to II-VI family growth room to substrate by III-V family growth room through ultra-high vacuum transmission pipeline again; Substrate is warming up to 320 ℃, and the temperature in Zn, Be, Te, Se and Mg source is warming up to 307,1065,320,202 and 322.5 ℃ more respectively;
10.BeTe the generation of cushion: after the temperature in Be, Te source reaches 1065 and 320 ℃ respectively, stablized 30 minutes, open the baffle plate in Be, Te source, Be molecular beam and Te molecular beam are radiated at the surface of substrate, and the BeTe cushion begins to grow this moment; Monitor (perhaps, set, control, down together) in real time with the RHEED appearance with computer according to the growth rate of each solid source that records in advance before the growth; When the growth thickness of BeTe cushion is about 5ML; Growth ending is turned off the Be source then earlier, turns off the Te source subsequently again;
11.Zn 0.77Mg 0.15Be 0.08The growth of Se separation layer: open the baffle plate in Zn source earlier, the baffle plate of opening Se, Be and Mg source again carries out Zn 0.77Mg 0.15Be 0.08The growth of Se separation layer; There are this moment Zn molecular beam, Se molecular beam, Be molecular beam and Mg molecular beam to be radiated at the surface of substrate simultaneously respectively, when the separation layer growth thickness is about 200nm, finish growth; Close Se, Be, Mg source earlier, close the Zn source again after about 5 seconds;
12.ZnSe the growth of potential well layer: open Zn, Se source; The two is radiated on the substrate surface simultaneously, and the temperature of Zn, Se solid source remains on 307 and 202 ℃ respectively, when the thickness of ZnSe layer growth is 14ML; Growth ending; Close the Se source earlier, after about 5 seconds, close the Zn source again, so that form rich Zn superficial layer;
13.BeTe the temperature in the growth of barrier layer: Be, Te source remains on 1065 and 320 ℃ respectively, opens the Zn source earlier, after about 5 seconds, closes the Zn source, opens the Te source simultaneously, and after about 5 seconds, closes the Te source; Repeat the operation 1 time in above-mentioned Zn source and Te source, open Te source and Be source afterwards again, make Te source and Be source be radiated on the substrate surface simultaneously; And the BeTe barrier layer that begins to grow; When the thickness of BeTe barrier layer growth is about 10ML, closes the Be source earlier and close the Te source again, the growth ending of BeTe barrier layer; The special construction that above-mentioned growth course can obtaining at the interface between ZnSe and BeTe has 3 Zn-Te chemical bond forms;
14.ZnSe the growth of potential well layer: keep the temperature-resistant of above-mentioned Zn, Se, Te source, open the Te source earlier, after about 5 seconds, close the Te source, open the Zn source simultaneously, and after about 5 seconds, close the Zn source; Repeat the operation 1 time in above-mentioned Te source and Zn source, can reduce to 150 ℃ this moment with the temperature in Te source, opens Zn source and Se source afterwards simultaneously, makes Zn source and Se source be radiated on the substrate surface simultaneously and begin the growing ZnSe potential well layer; When the thickness of ZnSe potential well layer growth was about 14ML, the active layer growth ending was closed the Se source afterwards earlier and is closed the Zn source again; The special construction that above-mentioned growth course can obtaining at the interface between BeTe and ZnSe has 3 Te-Zn chemical bond forms;
15. the growth course of the separation layer of repeating step 11 can obtain that 200nm is thick, energy gap is the Zn of 3.0eV 0.77Mg 0.15Be 0.08The Se separation layer; To close Se, Be, Mg source earlier during growth ending, close the Zn source again after about 10 seconds, can not corroded with the protection sample at grown on top one deck Zn of sample as cover layer like this; Behind the growth ending, underlayer temperature is made as 150 ℃ and make it cooling, simultaneously also the temperature in Zn, Se, Be and Mg source is set at 100,50,820 and 150 ℃ and make it cooling respectively; Reduce to after 150 ℃ and the temperature of confirming the Se source reduce to below 100 ℃ when underlayer temperature, sample is taken out from the growth room, can obtain the quantum-well materials of complete ZnSe/BeTe/ZnSe form.
Embodiment 2:
The embodiment of the invention 2 is identical with embodiment 1, just:
The growth time of the GaAs buffer layer in the step 5 is 38 minutes, and growth thickness is about 320nm;
Substrate in the step 9 is warming up to 330 ℃;
When the separation layer growth thickness in the step 11 is 300nm, finish growth, close Se, Be, Mg source earlier, close the Zn source again after about 7 seconds;
When the thickness of the ZnSe layer growth in the step 12 was about 20ML, growth ending was closed the Se source earlier, after about 7 seconds, closes the Zn source again, so that form rich Zn superficial layer;
Before the BeTe layer growth in the step 13, open the Zn source earlier, after about 7 seconds, close the Zn source, open the Te source simultaneously, and after about 7 seconds, close the Te source.Repeat the operation 2 times in above-mentioned Zn source and Te source.The growth ending when thickness of BeTe barrier layer growth is about 10ML is closed the Be source earlier, after about 7 seconds, closes the Te source again; The special construction that above-mentioned growth course can obtaining at the interface between ZnSe and BeTe has 5 Zn-Te chemical bond forms.
Before the ZnSe potential well layer growth in the step 14, open the Te source earlier, after about 7 seconds, close the Te source, open the Zn source simultaneously, and after about 7 seconds, close the Zn source.Repeat the operation 2 times in above-mentioned Te source and Zn source.The thickness of ZnSe potential well layer growth is about 20ML, and ZnSe potential well layer growth ending is closed the Se source afterwards earlier and closed the Zn source again; The special construction that above-mentioned growth course can obtaining at the interface between BeTe and ZnSe has 5 Te-Zn chemical bond forms.
Separation layer thickness in the step 15 is 300nm.
Embodiment 3:
The embodiment of the invention 3 is identical with embodiment 1, just:
The growth time of the GaAs buffer layer in the step 5 is 43 minutes, and growth thickness is about 360nm;
Substrate in the step 9 is warming up to 340 ℃;
When the separation layer growth thickness in the step 11 is 330nm, finish growth, close Se, Be, Mg source earlier, close the Zn source again after about 9 seconds;
When the thickness of the ZnSe layer growth in the step 12 was about 28ML, growth ending was closed the Se source earlier, after about 9 seconds, closes the Zn source again, so that form rich Zn superficial layer;
Before the BeTe layer growth in the step 13, open the Zn source earlier, after about 9 seconds, close the Zn source, open the Te source simultaneously, and after about 9 seconds, close the Te source.Repeat the operation 3 times in above-mentioned Zn source and Te source.The growth ending when thickness of BeTe barrier layer growth is about 10ML is closed the Be source earlier, after about 6 seconds, closes the Te source again; The special construction that above-mentioned growth course can obtaining at the interface between ZnSe and BeTe has 7 Zn-Te chemical bond forms.
Before the ZnSe potential well layer growth in the step 14, open the Te source earlier, process is closed after about 9 seconds and is opened the Zn source simultaneously, and after about 9 seconds, closes the Zn source.Repeat the operation 3 times in above-mentioned Te source and Zn source.The thickness of ZnSe potential well layer growth is about 28ML, and ZnSe potential well layer growth ending is closed the Se source afterwards earlier and closed the Zn source again; The special construction that above-mentioned growth course can obtaining at the interface between BeTe and ZnSe has 7 Te-Zn chemical bond forms.
Separation layer thickness in the step 15 is 330nm.
Embodiment 4:
The embodiment of the invention 4 is identical with embodiment 1, just:
The growth time of the GaAs buffer layer in the step 5 is 50 minutes, and growth thickness is about 420nm;
Substrate in the step 9 is warming up to 310 ℃;
When the separation layer growth thickness in the step 11 is 350nm, finish growth, close Se, Be, Mg source earlier, close the Zn source again after about 10 seconds;
When the thickness of the ZnSe layer growth in the step 12 was about 40ML, growth ending was closed the Se source earlier, after about 10 seconds, closes the Zn source again, so that form rich Zn superficial layer;
Before the BeTe layer growth in the step 13, open the Zn source earlier, after about 10 seconds, close the Zn source, open the Te source simultaneously, and after about 10 seconds, close the Te source.Repeat the operation 1 time in above-mentioned Zn source and Te source.The growth ending when thickness of BeTe barrier layer growth is about 10ML is closed the Be source earlier, after about 10 seconds, closes the Te source again; The special construction that above-mentioned growth course can obtaining at the interface between ZnSe and BeTe has 3 Zn-Te chemical bond forms.
Before the ZnSe potential well layer growth in the step 14, open the Te source earlier, process is closed after about 10 seconds and is opened the Zn source simultaneously, and after about 10 seconds, closes the Zn source.Repeat the operation 1 time in above-mentioned Te source and Zn source.The thickness of ZnSe potential well layer growth is about 40ML, and ZnSe potential well layer growth ending is closed the Se source afterwards earlier and closed the Zn source again; The special construction that above-mentioned growth course can obtaining at the interface between BeTe and ZnSe has 3 Te-Zn chemical bond forms.
Separation layer thickness in the step 15 is 350nm.

Claims (1)

1. one kind has the method for the II type SQW of particular interface with molecular beam epitaxial process preparation, and step is following:
1) gallium arsenide substrate with (001) orientation is fixed in the holder of molybdenum sample with indium;
2) logical cooled with liquid nitrogen growth room is confirming that III-V family growth room's vacuum is 1 * 10 -10After below the Torr, be sent to sample in the III-V family growth room through the magnetic force driven rod; With the sample holder, the K-cell container of As solid source is housed and the K-cell container heat temperature raising of Ga solid source is housed, the temperature that makes it to reach setting is respectively 300 ℃, 100 ℃ and 750 ℃;
3) temperature of adjustment As source K-cell container; After making it to begin to warm to 295 ℃ by 100 ℃, the temperature with sample holder and Ga source K-cell container is set at 550 ℃ and 915 ℃ respectively again, and begins to heat up; Open the baffle plate of As source K-cell container simultaneously; The As molecular beam is radiated on the substrate, the evaporation of the substrate surface As cause because of underlayer temperature raises with compensation, and make the evaporation of As on the substrate surface reach balance with adhering to;
4) treat that Ga source K-cell container rises to 915 ℃ after; Again the sample holder is warming up to 620 ℃; Can on [110] direction, observe through reflection high energy electron diffraction between temperature raising period; Striped occurs if can observe clearly, the oxide of under this temperature, having removed substrate surface then is described and is obtained the orderly substrate surface of cleaning;
5) generation of GaAs cushion: open the baffle plate that temperature has risen to 915 ℃ Ga source K-cell container, the Ga molecular beam is radiated on the substrate; This moment, the molecular beam of Ga and As was radiated at substrate surface simultaneously; The growth of GaAs cushion begins, and growth time is 24 ~ 120 minutes, and the thickness of GaAs cushion can reach 200 ~ 1000nm; Turn off the Ga source this moment; And the temperature of Ga source K-cell container reduced to 750 ℃ by 915 ℃, reduce to 300 ℃ afterwards again, and a cleaning, smooth and orderly surface are arranged through the substrate that the RHEED appearance can be observed this moment;
6) stablize 5 minutes after, underlayer temperature is reduced to 580 ℃ gradually by 620 ℃, cool-down method is a staged, promptly each cooling is set at falls 5 ℃, sets next time when reaching design temperature again, divides to accomplish for 8 times and lowers the temperature; After the cooling beginning, when observing image and do not have what ANOMALOUS VARIATIONS, the As source is turned off, and the As source temperature is transferred to 100 ℃ by 295 ℃ through the RHEED appearance;
7) underlayer temperature is reduced to 500 ℃ gradually by 580 ℃, cool-down method is a staged, falls 10 ℃ at every turn; Afterwards, again underlayer temperature is reduced to 300 ℃ gradually by 500 ℃, whole temperature-fall period divides and carries out for 10 times, and each cooling is spaced apart 20 ℃;
8) observing RHEED appearance image does not have any ANOMALOUS VARIATIONS, and can turn off the RHEED appearance this moment, becomes 7.5 * 10 in the vacuum of confirming III-V family growth room -9After below the Torr, turn off being used for the power supply of heated substrate, and prepare substrate is passed to II-VI family growth room through the high vacuum transmission pipeline;
9) be 1 * 10 in the vacuum of confirming II-VI family growth room -10The temperature in Zn, Be, Te, Se and Mg source in below the Torr and the II-VI family growth room is heated to respectively after 150,820,150,50 and 200 ℃, is sent to II-VI family growth room to substrate by III-V family growth room through ultra-high vacuum transmission pipeline again; Substrate is warming up to 300 ℃ ~ 350 ℃, and the temperature in Zn, Be, Te, Se and Mg source is warming up to 307,1065,320,202 and 322.5 ℃ more respectively;
10) generation of BeTe cushion: after the temperature in Be, Te source reaches 1065 and 320 ℃ respectively, stablized 30 minutes, open the baffle plate in Be, Te source, Be molecular beam and Te molecular beam are radiated at the surface of substrate, and the BeTe cushion begins to grow this moment; Monitor in real time with the RHEED appearance, when the growth thickness of BeTe cushion was about 5ML, growth ending was turned off the Be source then earlier, turns off the Te source subsequently again;
11) Zn 0.77Mg 0.15Be 0.08The growth of Se separation layer: open the baffle plate in Zn source earlier, the baffle plate of opening Se, Be and Mg source again carries out Zn 0.77Mg 0.15Be 0.08The growth of Se separation layer; There are this moment Zn molecular beam, Se molecular beam, Be molecular beam and Mg molecular beam to be radiated at the surface of substrate simultaneously respectively, when the separation layer growth thickness is 200 ~ 1000nm, finish growth; Close Se, Be, Mg source earlier, close the Zn source again after about 5 ~ 10 seconds;
12) growth of ZnSe potential well layer: open Zn, Se source; The two is radiated on the substrate surface simultaneously, and the temperature of Zn, Se solid source remains on 307 and 202 ℃ respectively, when the thickness of ZnSe layer growth is 4 ~ 80ML; Growth ending; Close the Se source earlier, after about 5 ~ 10 seconds, close the Zn source again, so that form rich Zn superficial layer;
13) temperature in the growth of BeTe barrier layer: Be, Te source remains on 1065 and 320 ℃ respectively, opens the Zn source earlier, after about 5 ~ 10 seconds, closes the Zn source, opens the Te source simultaneously, and after about 5 ~ 10 seconds, closes the Te source; Repeat the operation 1 ~ 3 time in above-mentioned Zn source and Te source; Open Te source and Be source afterwards again; Te source and Be source are radiated on the substrate surface simultaneously, and the BeTe barrier layer that begins to grow, when the thickness of BeTe barrier layer growth is about 10ML; Close the Be source earlier and close the Te source again, the growth ending of BeTe barrier layer; The special construction that above-mentioned growth course can obtaining at the interface between ZnSe and BeTe has 3,5 or 7 Zn-Te chemical bond forms;
14) growth of ZnSe potential well layer: keep the temperature-resistant of above-mentioned Zn, Se, Te source, open the Te source earlier, after about 5 ~ 10 seconds, close the Te source, open the Zn source simultaneously, and after about 5 ~ 10 seconds, close the Zn source; Repeat the operation 1 ~ 3 time in above-mentioned Te source and Zn source, can reduce to 150 ℃ this moment with the temperature in Te source, opens Zn source and Se source afterwards simultaneously, and Zn source and Se source are radiated on the substrate surface simultaneously, and begin the growing ZnSe potential well layer; When the thickness of ZnSe potential well layer growth was about 4 ~ 80ML, the active layer growth ending was closed the Se source afterwards earlier and is closed the Zn source again; The special construction that above-mentioned growth course can obtaining at the interface between BeTe and ZnSe has 3,5 or 7 Te-Zn chemical bond forms;
15) growth course of the separation layer of repeating step 11 can obtain the thick Zn of 200 ~ 1000nm 0.77Mg 0.15Be 0.08The Se separation layer; To close Se, Be, Mg source earlier during growth ending, close the Zn source again after about 10 seconds, can not corroded with the protection sample at grown on top one deck Zn of sample as cover layer like this; Behind the growth ending, underlayer temperature is made as 150 ℃ and make it cooling, simultaneously also the temperature in Zn, Se, Be and Mg source is set at 100,50,820 and 150 ℃ and make it cooling respectively; Reduce to after 150 ℃ and the temperature of confirming the Se source reduce to below 100 ℃ when underlayer temperature, sample is taken out from the growth room, can obtain the quantum-well materials of complete ZnSe/BeTe/ZnSe form.
CN200910230077A 2009-11-13 2009-11-13 Method for eliminating intrinsic electric field in ZnSe/BeTe II quantum well Expired - Fee Related CN101712456B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1081027A (en) * 1992-05-22 1994-01-19 明尼苏达州采矿制造公司 The method of quantum well in the growth II-VI family laser diode
CN101236905A (en) * 2008-03-05 2008-08-06 浙江大学 A method for making IV-VI sector semiconductor single crystal film on CdZnTe underlay
CN101538700A (en) * 2009-04-21 2009-09-23 山东大学 Method and equipment for preparing II type quantum well with molecular beam epitaxial process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1081027A (en) * 1992-05-22 1994-01-19 明尼苏达州采矿制造公司 The method of quantum well in the growth II-VI family laser diode
CN101236905A (en) * 2008-03-05 2008-08-06 浙江大学 A method for making IV-VI sector semiconductor single crystal film on CdZnTe underlay
CN101538700A (en) * 2009-04-21 2009-09-23 山东大学 Method and equipment for preparing II type quantum well with molecular beam epitaxial process

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