CN1075831A - A kind of blue-green semiconductor laser material and preparation method thereof - Google Patents
A kind of blue-green semiconductor laser material and preparation method thereof Download PDFInfo
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- CN1075831A CN1075831A CN92113809A CN92113809A CN1075831A CN 1075831 A CN1075831 A CN 1075831A CN 92113809 A CN92113809 A CN 92113809A CN 92113809 A CN92113809 A CN 92113809A CN 1075831 A CN1075831 A CN 1075831A
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Abstract
The invention provides a kind of blue-green semiconductor laser material and preparation method thereof.Adopt atom-layer-epitaxial method growth atomic layer superlattice (quantum well) at the laser active area.Wherein form with ZnSe and CdSe respectively as potential well in the atomic layer superlattice of potential well and potential barrier, its thickness is no more than its critical thickness, eliminates the misfit dislocation that lattice relaxation caused, and improves the crystal structure integrality, has improved the semiconductor laser performance.Zn in n district folder one deck 50 nanometers
1-xCd
zS
ySc
1-y, under the forward bias of laser, just can improve the barrier effect in hole, increase the laser quantum efficiency.And use atomic layer doping, improved the ohmic contact character of p type island region.
Description
The present invention relates to utilize the stimulated emission device field, belong to a kind of active medium of semi-conducting material, green semiconductor laser material of particularly a kind of orchid and preparation method thereof.
Sixties semiconductor laser has been heard since the generation, and the wavelength of laser rests on the infrared and red wave band always.Finally successively be developed into blue green laser in 91 years by Minnesota Mining and Manufacturing Company and Blang-release from sufferings cooperation group through the effort in 30 years based on ZnSe.Its related content can be consulted document M.A.Haase, J.Qiu, J.M.DePuydt and H.Cheng:Blue-green laser diodes, Appl.Phys.Lett.59(1991) 1272. and H.Jeon, J.Ding, W.Patterson, A.V.Nurmikko, W.Xie, D.C.Grillo, M.Kobayashi and Gunshor:Blue-green injection laser diodes in(Zn, Cd) Se/ZnSe quantum wells, Appl.Phys.Lett.59(1991) 3619.
Blue green laser and light-emitting diode (LED) have potential widely application background, and its appearance will make the memory space of laser-optical disk improve an order of magnitude.Highdensity optics reservoir will show bigger superiority.Also can be applicable to high brightness indicator, medical diagnosis, seawater and subglacial communication or the like.Yet present blue green laser and LED also exist some problems, at room temperature continuous operation.Mainly contain the problem of three aspects:
The first, the active area crystal structure in the laser.Active area all adopts quantum well structure at present, and the material of its potential well and potential barrier is used ZnSe respectively, and materials such as ZnCdSe and ZnSSe are formed, and the structural intergrity of molecular beam epitaxial growth ternary compound is generally than binary compound difference.Lattice mismatch is more much bigger than GaAlAs system between II-VI compounds of group, and the lattice mismatch between ZnSe and CdSe and the ZnS is respectively 6.6% and 4.7%.Therefore when the quantum well trap is wider than critical thickness, the crystal structure relaxation will take place and produce a large amount of misfit dislocations, make non-radiative compound increase, reduce the quantum efficiency of laser, until destruction laser stimulated emission.
The second, Valence band Discontinuity is minimum in the system of ZnSe/ZnCdSe, △ Ev=0, so hole effect without limits in quantum well.When laser injects at forward, a part of hole not with the conduction band quantum well in electron recombination just flowed out active area, obviously just reduced the quantum efficiency of laser.
The 3rd, ohm knot of electrode touches problem.Semiconductor diode laser is the device of the big current work of forward, and electrode part was divided heating when the electrode contact resistance will make work greatly, had reduced Laser emission efficient, shortens the working life of laser.The hole concentration 10 of special P type ZnSe
17Centimetre
-3The electrode contact resistance is just very big when not too high.
The object of the present invention is to provide green semiconductor laser material of a kind of orchid and preparation method thereof,, avoid the generation of misfit dislocation to improve the crystal structure integrality of active area in the blue green laser; With the restriction that increases the hole; And the reduction ohmic contact resistance, thereby improve the performance of blue green semiconductor laser.
The objective of the invention is to reach by following technical proposals: the first adopts atom-layer-epitaxial method growth superlattice.Potential well and potential barrier are formed with two kinds of binary compounds respectively in the superlattice, for example ZnSe and CdSe etc., and its thickness is no more than its critical thickness, and the potential well of this superlattice replacement ternary compound as quantum well.This quantum well is made its lattice structure of laser active area material and is better than the quantum well that ternary compound is formed.It two is to adopt the atomic layer doping technology to improve doping content, solves the ohmic contact problem of P type.It three is to adopt Zn
1-xCd
xS
ySe
1-yQuaternary material is made the hole potential well, increases the restriction in hole, improves quantum efficiency.
The present invention is further elaborated below in conjunction with accompanying drawing.
Fig. 1 is the band structure figure of the present invention at the laser of the Multiple Quantum Well of active area employing atom-layer-epitaxial method growth superlattice.
Fig. 2 is that the present invention is at the folder one deck Zn of the ZnSe place in n district
1-xCd
xS
ySe
1-ySet up the band structure figure of the laser of hole potential well.
Consult Fig. 1, adopting n type carrier concentration is 1 * 10
18Centimetre
-3(100) GaAs substrate, the GaAs transition zone of the same electron concentration of first extension one deck, regrowth 2.0-2.5 micron thickness carrier concentration is 5 * 10
17Centimetre
-3N type resilient coating.Resilient coating is growth like this, and growth 2 micron thickness are mixed the n type ZnSxSel-x(x=0.06 of ZnCl earlier) epitaxial loayer, carrier concentration is 5 * 10
17Centimetre
-3The n type ZnSe of 0.2～0.5 micron of extension one deck then, carrier concentration is 5 * 10
17Centimetre
-3Then with atom-layer-epitaxial method growth atomic layer superlattice [(ZnSe) m(CdSe) n] j; Wherein m and n are for being not more than the 4 monatomic numbers of plies, and j is atomic layer superlattice (ZnSe) m(CdSe less than 15) periodicity of n.Its growth temperature is 220～250 ℃, and the baffle plate of opening the Se beam source earlier is at epitaxial loayer deposit one deck Se of ZnSe atom, and the line of Se is 1.87 * 10
-4Pa evaporates 3～6 atomic layers, forms excessive Se face on the surface of ZnSe.Close Se electron gun fender plate again, pause and grew for 2 seconds, at this moment the upward excessive Se of ZnSe just evaporates at an easy rate again, because the Se-Se key is very weak.The ZnSe surface that stays is the stable Se surface of one deck.Open Zn electron gun baffle plate then, the line of Zn is 1.07 * 10
-4Pa evaporated for 5～6 seconds, quite evaporated 2～5 layers of Zn atom on the steady face of the Se of ZnSe.Se on the steady face of Zn atom and Se forms firm chemisorbed.And unnecessary Zn atom just spreads on the ZnSe surface, and perhaps evaporation more again is up to the whole surperficial layer overlay Zn atomic layer of ZnSe.When closing Zn electron gun fender plate again, unnecessary Zn atom is all evaporated.A monoatomic layer growth circulation is formed in two layers of atomic layer chemical absorption of Se and Zn like this.If this growth circulation growth conditions is suitable, its growth thickness is adjusted to a monoatomic layer automatically.We are total to m circulation by growing ZnSe, promptly are m monoatomic layers.CdSe is total to n atomic layer with the quadrat method growth.N layer CdSe atomic layer level thickness can not surpass critical thickness, and CdSe is thinner good certainly, more difficult generation lattice mismatch relaxation.If ZnSe is as resilient coating, the ZnSem layer thickness does not have the restriction of critical thickness so.(ZNSe) m(CdSe) the n superlattice period is counted j can not unrestrictedly increase, and it also has a critical thickness.We are used in j less than 15.The atomic layer superlattice are as the potential well of quantum well, and 20 nanometer ZnS e are as potential barrier.Such quantum well repeats M time, and general M is 5～7 times, composed atom layer superlattice Multiple Quantum Well active area.Regulate different m, n and j number can be made the blue green semiconductor laser of different wave length.Its wavelength control repeated fine.
Behind the active area growth ending, the P type ZnSe that regrowth one deck is about 1 micron, dopant are that its carrier concentration is 4 * 10 with the N atom of plasma ionization
17Centimetre
-3But such P type concentration is unfavorable to the electrode ohmic contact, therefore must improve P type concentration at the contact-making surface place.
The present invention adopts the atomic layer doping technology to improve doping content.Because II-when the VI compounds of group mixes compensation very serious, for example during As doped ZnS e, As accounts for the Se position and then shows acceptor impurity, As falls into the Zn position and then shows alms giver's characteristic on the contrary.And general ZnSe molecular beam epitaxy promptly uses cracking As to make doped source when mixing As, and the concentration of As is mixed to 1 * 10
21Centimetre
-3, do not show strong P-type conduction yet, illustrate that self compensation is very serious.For As or N atom are correctly mixed on the Se position, can overcome self-compensating shortcoming with atomic layer doping.
Atomic layer doping method is as follows: open Zn electron gun fender plate earlier, make epi-layer surface form rich Zn face, close the Zn electron gun fender plate several seconds, allow unnecessary Zn atom evaporate again, make epi-layer surface form monoatomic layer Zn surface.Open pyrolysis furnace As baffle plate then or open plasma ionization N atomic generator, make a part of As of deposition or N atom on the Zn surface.Open the Se stove after closing the dopant baffle plate, allow deposition one deck Se on the Zn surface.The lattice position of some Se is captured by As or N atom on this layer Se face.Obviously at this moment As and N are typical acceptor states.If there is 0.3% Se position to be captured by As or N on the Se face, then its acceptor concentration is 1 * 10
20Centimetre
-3Atomic layer doping also can be when mixing As or N source open simultaneously with the Se source, adjusting Se electron gun can obtain different acceptor concentrations with the ratio of As or N electron gun.When extremely can not surveying, can decide according to As electron gun furnace temperature as if the As line is little.If can obtain 1 * 10
20Centimetre
-3P type ZnSe layer, at this moment steam and electrically contact character behind the gold and can significantly improve.
ZnSe-[(ZnSe) and m(CdSe) n]
j MAll there are same problem in the Multiple Quantum Well of atomic layer superlattice and ZnCdSe-ZnSe Multiple Quantum Well, promptly are that these quantum well can only constitute electron trap, and do not form hole trap, and the hole is not produced restriction.Because the valence band energy potential difference △ Ev of CdSe and ZnSe is almost nil.Even the ZnS of growth one deck and GaAs coupling on the GaAs substrate
0.06Se
0.94, the △ Ev between its ZnSe has only 30 milli electron-volts, and is smaller to the restriction in hole.If increase the component of S the lattice mismatch between ZnSSe and GaAs and the ZnSe is increased.The present invention adopts Zn for this reason
1-xCd
xS
ySe
1-y, can be both increase the potential difference △ Ev of valence band, again with the ZnSe lattice match with ZnSe.
Fig. 2 is at the Zn of the ZnSe place in n district folder one deck 50 nanometers
1-xCd
xS
ySe
1-y(x=0.15 y=0.25), just can improve the barrier effect in hole under the forward bias of laser, increase the quantum efficiency of laser.If Zn
1-xCd
xS
ySe
1-yCrystalline structure growth get finely, can partly all make all ZnSe and ZnSSe into Zn
1-xCd
xS
ySe
1-y, have only the atomic layer superlattice partly constant.Can set up the hole potential well like this, wavelength also has shortening.
Good effect of the present invention is as follows:
1. make quantum-well materials with the atomic layer superlattices and replace ternary compound, eliminate the misfit dislocation that lattice relax causes, improve the integrality of crystal structure. The half-peak breadth at the exciton transition peak of photoluminescence spectrum is reduced. And then the performance of raising semiconductor laser.
2. use quaternary system Zn1-xCd
xS
ySe
1-yMaterial is made the hole potential well, increases the restriction in hole, improves quantum efficiency.
3. improve doping content with atomic layer doping method, reach P type carrier concentration 1 * 10
20Centimetre
-3, solve P type ohmic contact problem.
Claims (7)
1, the green semiconductor laser material of a kind of orchid, adopting n type carrier concentration is 1 * 10
18Centimetre
-3(100) GaAs substrate, on substrate successively the growth have:
(1.1) 1 micron thickness electron concentrations are 1 * 10
18Centimetre
-3The GaAs transition zone,
(1.2) 2.0～2.5 micron thickness carrier concentrations are 5 * 10
17Centimetre
-3N type resilient coating, it is characterized in that:
Atomic layer superlattice Multiple Quantum Well active area { ZnSe (20 nanometer)--[(ZnSe) m (CdSe) n] of (1.3) atomic layer epitaxy method growth
j}
M, wherein m and n are not more than 4 the monatomic number of plies, and j is the atomic layer superlattice period number less than 15, and M is the number of 5～7 Multiple Quantum Well,
The carrier concentration of (1.4) 1 micron thickness is 4 * 10
17Centimetre
-3P type ZnSe layer,
(1.5) carrier concentration of 20-30 nanometer thickness is 1 * 10
20Centimetre
-3The contact layer of P type ZnSe layer.
2, the preparation method of the green semiconductor laser material of a kind of orchid comprises:
(2.1) adopting n type carrier concentration is 1 * 10
18Centimetre
-3(100) GaAs substrate,
(2.2) extension one deck 1 * 10 on substrate
18Centimetre
-3The GaAs transition zone of electron concentration,
(2.3) grow the then carrier concentration of 2.0～2.5 microns of one decks is 5 * 10
17Centimetre
-3N type resilient coating,
It is characterized in that:
(2.4) the ZnSe potential barrier of usefulness atomic-layer epitaxial growth 20 nanometers
(2.5) then grow superlattice [(ZnSe) with atom-layer-epitaxial method
m(CdSe)
n]
j, wherein m and n are the monatomic number of plies greater than 4, and j is the periodicity less than 15 atom superlattice, and its growth temperature is 220～250 ℃,
(2.5.1) open the Se beam source earlier, deposit one deck Se atom on n type epitaxial loayer, the line of Se is 1.87 * 10
-4Pa evaporates 3-6 atomic layer, forms excessive Se face on the surface of ZnSe, closes the Se source, pauses and grows for 2 seconds, and at this moment excessive Se evaporates again on the n type epitaxial loayer, and staying in n type epi-layer surface is the stable Se surface of one deck,
(2.5.2) open the Zn electron gun, the line of Zn is 1.07 * 10
-4Pa, evaporate 5-6 second, quite on the steady face of the Se of ZnSe, evaporate 2～5 layers of Zn atom, Se on the steady face of Zn atom and Se forms firm chemisorbed, close the Zn electron gun, a monoatomic layer growth circulation is formed in two layers of atomic layer chemical absorption of Se and Zn like this, the automatic transfer to of its a growth thickness monoatomic layer
(2.5.3) repeating step (2.5.1), (2.5.2) m circulation altogether, i.e. m monoatomic layer,
(2.5.4) continue to be no more than n atomic layer of critical thickness with the same atom-layer-epitaxial method CdSe that grows,
(2.5.5) repeating step (2.5.1), (2.5.2), (2.5.3) and (2.5.4) j circulation altogether, growth j layer superlattice,
(2.6) altogether M circulation of repeating step (2.4) and (2.5), M the atomic layer superlattice Multiple Quantum Well of growing be as active area,
(2.7) behind the active area growth ending, the P type ZnSe of regrowth one deck 1 micron thickness, dopant are that its carrier concentration is 4 * 10 with the N atom of plasma ionization
17Centimetre
-8,
(2.8) adopt the atomic layer doping technology to improve the doping content of contact-making surface, improve ohmic contact,
(2.8.1) open the Zn electron gun, make epi-layer surface form rich Zn face, close the Zn electron gun, allow unnecessary Zn atom evaporate again, make epi-layer surface form atomic layer Zn surface,
(2.8.2) open pyrolysis furnace As source or open plasma ionization N atomic generator, make a part of As of deposition or N atom on the Zn surface, close doped source,
(2.8.3) open the Se source, allow deposition one deck Se on the Zn surface, the lattice position of some Se is captured by As or N atom on this layer Se face, with obtain steaming behind the gold to electrically contact the carrier concentration that character can obviously improve be 1 * 10
20Centimetre
-3P type ZnSe layer.
3,, it is characterized in that said n type resilient coating is the n type ZnS that mixes ZnCl of 2 micron thickness according to the green semiconductor laser material of a kind of orchid of claim 1 defined
0.08Se
0.98The n type epitaxial loayer of the ZnSe of epitaxial loayer and 0.2～0.5 micron thickness.
4, according to a kind of blue green laser material of claim 1 regulation, it is characterized in that said n type resilient coating is a ZnSe layer, and in ZnSe layer, sandwich the Zn that sets up the hole potential well of one deck 50 nanometers
0.85Cd
0.15S
0.25Se
0.75Layer.
5,, it is characterized in that n type resilient coating in the said step (2.3) is that growth 2 micron thickness are mixed the n type ZnS of ZnCe earlier according to the preparation method of the green semiconductor laser material of a kind of orchid of claim 2 regulation
0.08Se
0.98N type ZnSe layer with regrowth one deck 0.2-0.5 micron thickness.
6,, it is characterized in that n type resilient coating in the said step (2.3) is that the carrier concentration of 2.0～2.5 microns of extension one decks is 5 * 10 according to the preparation method of the green semiconductor laser material of a kind of orchid of claim 2 regulation
17Centimetre
-3N type ZnSe layer, and in ZnSe layer the Zn that sets up the hole potential well of growth one deck 50 nanometers
0.85Cd
0.15S
0.25Se
0.75Layer.
7,, it is characterized in that said step (2.8.2), when (2.8.3) mixes As or N source and Se source are opened simultaneously, to obtain 1 * 10 according to the preparation method of the green semiconductor laser material of a kind of orchid of claim 2 regulation
20Centimetre
-3P type ZnSe layer.
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|---|---|---|---|
| CN92113809A CN1025526C (en) | 1992-12-15 | 1992-12-15 | Blue-green semiconductor laser material and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92113809A CN1025526C (en) | 1992-12-15 | 1992-12-15 | Blue-green semiconductor laser material and its preparation method |
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| CN1075831A true CN1075831A (en) | 1993-09-01 |
| CN1025526C CN1025526C (en) | 1994-07-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623595A (en) * | 2012-04-23 | 2012-08-01 | 中国科学院物理研究所 | Epitaxial material structure of light-emitting diode |
| CN103275723A (en) * | 2013-05-30 | 2013-09-04 | 中国科学院上海光学精密机械研究所 | Chrome iron ion double-doped complex selenium zinc sulfide laser material and preparation method thereof |
| CN108183391A (en) * | 2018-01-04 | 2018-06-19 | 长春理工大学 | A kind of method for improving the material doped concentration of N-shaped GaSb base semiconductor lasers |
| CN109980105A (en) * | 2017-12-28 | 2019-07-05 | Tcl集团股份有限公司 | A kind of QLED device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7253452B2 (en) * | 2004-03-08 | 2007-08-07 | Massachusetts Institute Of Technology | Blue light emitting semiconductor nanocrystal materials |
-
1992
- 1992-12-15 CN CN92113809A patent/CN1025526C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623595A (en) * | 2012-04-23 | 2012-08-01 | 中国科学院物理研究所 | Epitaxial material structure of light-emitting diode |
| CN102623595B (en) * | 2012-04-23 | 2014-09-24 | 中国科学院物理研究所 | Epitaxial material structure of light-emitting diode |
| CN103275723A (en) * | 2013-05-30 | 2013-09-04 | 中国科学院上海光学精密机械研究所 | Chrome iron ion double-doped complex selenium zinc sulfide laser material and preparation method thereof |
| CN103275723B (en) * | 2013-05-30 | 2015-09-16 | 中国科学院上海光学精密机械研究所 | Ferrochrome ion is two mixes composite selenium zinc sulphide laserable material and preparation method thereof |
| CN109980105A (en) * | 2017-12-28 | 2019-07-05 | Tcl集团股份有限公司 | A kind of QLED device |
| CN108183391A (en) * | 2018-01-04 | 2018-06-19 | 长春理工大学 | A kind of method for improving the material doped concentration of N-shaped GaSb base semiconductor lasers |
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| Publication number | Publication date |
|---|---|
| CN1025526C (en) | 1994-07-20 |
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