CN106356280A - Method for orientation growth of ordered quantum dot array by template - Google Patents
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- CN106356280A CN106356280A CN201510408442.4A CN201510408442A CN106356280A CN 106356280 A CN106356280 A CN 106356280A CN 201510408442 A CN201510408442 A CN 201510408442A CN 106356280 A CN106356280 A CN 106356280A
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
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Abstract
The invention discloses a method for orientation growth of an ordered quantum dot array by a template. The method includes the steps of preparing an inorganic phase-change film material on the surface of a substrate, preparing an inorganic phase-change film material graphical template, epitaxially growing an InAs film in graphical holes of the graphical template, conducting thermal annealing, epitaxially growing a GaAs film and epitaxially growing InAs quantum dots on the surface of the GaAs film. Direct writing and scribing of graphs by maskless laser contribute to preparation of the complex graphical template, but the graphical template is prepared directly from a barrier material, so that damage of the substrate surface can be avoided and defects introduced in a quantum dot growth process can be reduced. The method has the advantages that a technological process is simplified, a preparation process of quantum dot materials is optimized, uniformity of the epitaxially prepared quantum dot materials is enhanced, the performance of a quantum-dot optoelectronic device is improved correspondingly, multiple structures of quantum dot materials can be prepared, and accordingly the method is beneficial to universality and diversified application of the quantum dot materials.
Description
Technical field
The present invention relates to a kind of epitaxial growth technology of semiconductor-quantum-point material, particularly to a kind of orderly using Template Location growth
The method of quantum dot array, belongs to nano material and structure preparation and application technical field.
Background technology
Quantum information research is one of the great research direction in physicss field forward position.Manipulated based on single-photon state and realize quantum meter
Calculate, quantum communications are current quantum information technology most important physics realization methods.But lack preferable emitter at present
Part, the experimental demonstration of quantum key communication all adopts laser attenuation light source analogy single photon emission, and this experiment needs extremely complex
Light path system, and single photon generation efficiency is very low, nor eliminate the presence of multi-photon it is impossible to avoid being attacked by multi-photon
Probability.This will bring potential safety hazard to quantum communications, and such as listener-in can enter commit theft by number of photons division (pns) method
Listen.Therefore how to obtain a kind of stable, efficient, reliable single-photon source, have become as quantum communications and quantum cryptography is practical
One bottleneck.Because it is in x, the size in tri- directions of y, z is between several nanometers to several tens of nanometers, so inciting somebody to action for Semiconductor Quantum Dot Structures
It is subject to the quantum limitation effect of very strong three-dimensional, energy level distribution is in hydrogen-like spectral like, be typical " class atom " structure.And also have
Standby tunable wave length scope big it is easy to the advantage such as integrated, so one of becoming ideal chose of preparation single photon emission device.
However, traditional s-k pattern quantum dot growth process is difficult to grow the controlled quantum-dot structure in density, size, position.
Content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of utilization Template Location grows the side of sequential quantum dot array
Method.
For realizing aforementioned invention purpose, the technical solution used in the present invention includes:
A kind of method that utilization Template Location grows sequential quantum dot array, comprising:
(1) inorganic-phase variable film material plies are prepared in clean substrate surface;
(2) laser direct-writing no mask on described inorganic-phase variable film material plies is utilized to inscribe figure, and by being developed in described substrate
Upper formation graphical template;
(3) epitaxial growth inas thin-film material in the figure hole of described graphical template;
(4) obtained sample final to step carries out thermal anneal process, so that described inas thin-film material is changed and is formed as Seed Layer amount
The ground floor inas quantum dot of son point, and remove the remaining nothing of described substrate surface before thermal anneal process or during thermal anneal process
Machine phase change film material;
(5) step (4) finally obtained sample surface epitaxial growth as sealing coat gaas thin film, afterwards described
The surface epitaxial growth second layer inas quantum dot of gaas thin film, forms the sequential quantum dot array of uniformly rule.
Further, described inorganic-phase variable thin-film material can include gesbte alloy, the gesbte alloy mixing bi or mix se's
Gesbte alloy, but not limited to this.
More preferred, the thickness of described inorganic-phase variable thin-film material is 40nm~100nm.
Further, the shape in described figure hole can be circle, rectangle, triangle, strip, annulus etc. various simple and
The complex geometry being combined by simple graph.
More preferred, the aperture≤200nm in described figure hole, preferably 50nm~200nm.
More preferred, step (3) includes: epitaxial growth temperature≤300 DEG C of described inas thin-film material, preferably smaller than
300 DEG C, more preferably 150 DEG C~300 DEG C, more preferably 180 DEG C~300 DEG C, growth thickness is 2ml~5ml.
More preferred, step (4) includes:
By step (3), finally obtained sample is sent in thermal annealing stove and carries out high-temperature vacuum annealing, under vacuum conditions simultaneously,
When 400 DEG C of temperature t >, inorganic-phase variable thin-film material is made to completely remove from substrate surface desorption;
Or, first with wet method or dry etch process by the remaining inorganic-phase variable thin film of the final substrate surface of obtained sample of step (3)
Material removes, then carries out high-temperature vacuum annealing.
It is more highly preferred to, the sample thermal annealing temperatures adopting in step (4) are 400 DEG C -500 DEG C.
Further, concentration is mainly adopted to be the koh solution of 1wt% or the reactive ion beam of argon gas atmosphere in step (4)
Etching removes described substrate surface remaining inorganic-phase variable thin-film material.
More preferred, the thickness of described gaas thin film is 5nm~20nm.
More preferred, step (5) includes: the growth temperature of described second layer inas quantum dot is 480 DEG C~520 DEG C, growth
Thickness is 2ml~5ml.
Further, the material of described substrate preferably from but be not limited to iii-v race semi-conducting material, such as gaas, gasb or
Inp etc..
Further, the epitaxial growth method adopting among the method includes molecular beam epitaxial process but it is also possible to be known to industry
Alternate manner, such as mocvd, vpe, lpe etc..
Compared with prior art, the invention has the advantages that
(1) simplification of flowsheet, optimizes the preparation process of quanta point material.The method of the present invention is carved using the laser direct-writing of no mask
Write figure, it is to avoid traditional complicated photoetching process, then directly prepared using the inorganic-phase variable thin-film material as barrier material and scheme
Shape template, can avoid the damage on the surface of gaas substrate, and during complete substrate surface advantageously reduces Quantum Dots Growth
The defect introducing, improves the performance of quanta point material.
(2) the controlled quanta point material of stand density, and then improve corresponding quantum dot device performance, such as using low-density quantum dot
The single photon device of material.The method of the present invention utilizes uniform template graphics, is conducive to growing the quantum dot of homogeneous texture, carries
The performance of high quantum dot device, such as quantum dot laser etc..
(3) quantum-dot structure of various structures, is conducive to the variation application of quanta point material.The present invention is inscribed by laser direct-writing
Figure is easy to prepare the graphical template of various complexity, thus growing the quantum-dot structure of structure diversification.
Brief description
Fig. 1 is the structural representation of gaas substrate among the present invention one typical embodiments;
Fig. 2 is the schematic diagram preparing inorganic-phase variable thin layer among the present invention one typical embodiments in gaas substrate surface;
Fig. 3 is the schematic diagram inscribing figure among the present invention one typical embodiments in inorganic-phase variable thin-film material surface no mask;
Fig. 4 is the schematic diagram forming graphical template on substrate after development among the present invention one typical embodiments;
Fig. 5 is that among the present invention one typical embodiments, in the figure hole of graphical template, epitaxial growth inas thin-film material obtains institute
State the schematic diagram of sample a;
Fig. 6 is the schematic diagram removing the obtained sample b of remaining inorganic-phase variable thin-film material among the present invention one typical embodiments;
Fig. 7 is the signal among the present invention one typical embodiments in described sample b one layer of gaas sealing coat of surface epitaxial growth
Figure;
Fig. 8 is the schematic diagram of last epitaxial growth second layer sequential quantum dot array among the present invention one typical embodiments;
Description of reference numerals: 110 substrates;120 inorganic-phase variable thin-film materials;121 no masks inscribe figure;122 figures
Hole;123 inas thin-film materials;124 ground floor inas quantum dots;130 gaas thin film;131 second layer inas quantum
Point.
Specific embodiment
In view of deficiency of the prior art, inventor, through studying for a long period of time and putting into practice in a large number, is proposed the technical side of the present invention
Case.This technical scheme, its implementation process and principle etc. will be further explained as follows.
Refer to Fig. 1-Fig. 8, the one kind providing among an embodiment of the present invention utilizes Template Location to grow sequential quantum dot matrix
The method of row, comprises the following steps:
(1) prepare one layer of inorganic-phase variable thin-film material 120 on substrate 110 surface cleaning up;
(2) using laser direct-writing, no mask is carried out on described inorganic-phase variable thin-film material 120 and inscribe figure 121, and by development
Inorganic-phase variable thin-film material 120 graphical template is formed on described substrate 110;
(3) the described substrate 110 with graphical template is put into molecular beam epitaxy system, in the figure hole 122 of described template
Low-temperature epitaxy growth inas thin-film material 123, obtains sample a;
(4) described sample a is carried out with thermal anneal process, removes the inorganic-phase variable thin-film material of sample a substrate 110 surface residual
120, and because the inas thin-film material 123 that thermal anneal process makes low-temperature epitaxy defines ground floor inas quantum dot 124, will
124 as Seed Layer quantum dot, obtains sample b.Again described sample b is put into molecular beam epitaxy system, in the table of described sample b
One layer of gaas thin film 130 of face epitaxial growth as sealing coat, then, in the surface of the described sealing coat epitaxial growth second layer again
Inas quantum dot 131 forms the sequential quantum dot array of uniformly rule.
Further, remove remaining inorganic-phase variable thin-film material 120 technique and annealing process in step (4), following two can be selected
Kind technological process:
(1) sample a is sent in thermal annealing stove and carries out high-temperature vacuum annealing, meanwhile, under vacuum conditions, temperature t >
When 400 DEG C, inorganic-phase variable thin-film material 120 from substrate surface desorption, finally completely removes effectively.
Or, the koh solution that (2) are first 1% with mass percent or the reactive ion beam etching (RIBE) with argon (ar) atmosphere
The remaining inorganic-phase variable thin-film material 120 of sample a substrate surface is removed, then carries out high-temperature vacuum annealing.
The present invention adopts laser writing technology, prepares nano-patterned substrate using phase-change material as mask, and using outside molecular beam
In graph substrate Epitaxial growth quantum-dot structure, wherein, the selection of phase-change material can improve prepared nanometer figure to epitaxial growth technology
The precision of shape substrate, and be easy to remove, thus simplifying technological process;And the selection of quantum dot Seed Layer can regulate and control upper strata effectively
The density of quantum dot, position, and then improve quality of materials and the optical quality of locating growth quantum point structure.
With reference to embodiments technical scheme is further described.
Embodiment 1
(1) prepare one layer of inorganic-phase variable thin-film material 120 on substrate 110 surface cleaning up, the material of substrate 110 is
The iii-v such as gaas, gasb, inp race semi-conducting material, its surface is the area preparing inorganic-phase variable thin-film material 120 and quantum dot
Domain.Prepared inorganic-phase variable thin-film material 120 be gesbte alloy, mix bi gesbte alloy or the gesbte mixing se
Alloy etc., its thickness is 40nm~100nm.
(2) using laser direct-writing, no mask is carried out on described inorganic-phase variable thin-film material 120 and inscribe figure 121, the figure of inscription
Can be the complex geometry that circle, rectangle, triangle, strip, annulus etc. are various simple and are combined by simple graph,
Its size≤200nm, and by being developed in formation inorganic-phase variable thin-film material 120 graphical template on described substrate 110.
(3) substrate 110 with described graphical template is put into molecular beam epitaxy system, in the figure hole 122 of described template
Low-temperature epitaxy growth ground floor inas thin-film material 123, obtains sample a, the temperature of epitaxial growth ground floor inas thin-film material 123
About < 300 DEG C, thickness is 2ml~5ml (ml:monolayer, monoatomic layer) to degree.
(4) described sample a is made annealing treatment, annealing temperature is about 400 DEG C -500 DEG C, and removes described sample a substrate table
Face remaining inorganic-phase variable thin-film material 120, and because thermal anneal process makes ground floor inas thin-film material 123 shape of low-temperature epitaxy
Become ground floor inas quantum dot 124, as Seed Layer quantum dot, obtained sample b, wherein, annealing process and removal are surplus
The technique of remaining inorganic-phase variable thin-film material 120 comprises two kinds of technological processes:
One kind is sample a to be sent in vacuum annealing furnace carry out high-temperature vacuum annealing, meanwhile, under vacuum conditions, temperature
During 400 DEG C of t >, inorganic-phase variable thin-film material 120 is attached from substrate 110 surface desorption in a large number, finally completely removes, and forms quantum dot
While also been removed unnecessary inorganic-phase variable thin-film material;
Koh solution that another kind is is first 1% with mass percent or with the reactive ion beam etching (RIBE) of argon (ar) atmosphere by sample
The remaining inorganic-phase variable thin-film material 120 on product a substrate 110 surface removes, then carries out high-temperature vacuum annealing.
Afterwards, described sample b is put into molecular beam epitaxy system, in one layer of gaas thin film of surface epitaxial growth of described sample b
130 as sealing coat, and the thickness of sealing coat is 5nm~20nm, in the surface of described sealing coat epitaxial growth second layer inas amount again
Son point 131 forms the sequential quantum dot array of uniformly rule, and the temperature of epitaxial growth second layer inas quantum dot 131 is about
520 DEG C, its thickness is about 2ml~5ml.
It should be noted that the accompanying drawing of the present embodiment is all in the form of very simplification and all using non-accurately ratio, the side of being only used for
Just, embodiments of the invention are lucidly aided in illustrating.
Additionally, inventor also instead of the corresponding composition in embodiment 1 with the other iii-v races semi-conducting material addressed above,
And using close mode, the performance of obtained product is tested, find that it is respectively provided with similar excellent ability.
It should be appreciated that above-described embodiment technology design only to illustrate the invention and feature, its object is to allow and be familiar with technique
Personage will appreciate that present disclosure and implements according to this, can not be limited the scope of the invention with this.All smart according to the present invention
Equivalence changes or modification that god's essence is made, all should be included within the scope of the present invention.
Claims (13)
1. a kind of utilization Template Location grows the method for sequential quantum dot array it is characterised in that including:
(1) prepare inorganic-phase variable thin-film material (120) on clean substrate (110) surface;
(2) laser direct-writing no mask on described inorganic-phase variable thin-film material (120) is utilized to inscribe figure (121), and by aobvious
Shadow is in described substrate (110) upper formation graphical template;
(3) epitaxial growth inas thin-film material (123) in the figure hole (122) of described graphical template;
(4) to step (3), finally obtained sample carries out thermal anneal process, so that described inas thin-film material (123) is changed and is formed
Ground floor inas quantum dot (124) as Seed Layer quantum dot, and remove before thermal anneal process or during thermal anneal process
The inorganic-phase variable thin-film material of described substrate (110) surface residual;
(5) final the obtained sample of step (4) surface epitaxial growth as the gaas thin film (130) of sealing coat, exist afterwards
Surface epitaxial growth second layer inas quantum dot (131) of described gaas thin film (130), forms the sequential quantum of uniformly rule
Lattice array.
2. utilization Template Location according to claim 1 grows the method for sequential quantum dot array it is characterised in that described nothing
Machine phase change film material includes gesbte alloy, mixes the gesbte alloy of bi or mix the gesbte alloy of se.
3. utilization Template Location according to claim 1 and 2 grows the method for sequential quantum dot array it is characterised in that described
The thickness of inorganic-phase variable thin-film material is 40nm~100nm.
4. utilization Template Location according to claim 1 grows the method for sequential quantum dot array it is characterised in that described figure
The shape in hole (122) includes circle, rectangle, triangle, any one or two or more combinations in rectangle.
5. utilization Template Location according to claim 1 or 4 grows the method for sequential quantum dot array it is characterised in that described
The aperture in figure hole (122) is 50nm~200nm.
6. utilization Template Location according to claim 1 grows the method for sequential quantum dot array it is characterised in that step (3)
Including: the epitaxial growth temperature of described inas thin-film material (123) is 150 DEG C~300 DEG C, and growth thickness is 2ml~5ml.
7. utilization Template Location according to claim 1 grows the method for sequential quantum dot array it is characterised in that step (4)
Including:
By step (3), finally obtained sample is sent in thermal annealing stove and carries out high-temperature vacuum annealing, under vacuum conditions simultaneously,
When 400 DEG C of temperature t >, surface desorption is attached and completely removes from substrate (110) to make inorganic-phase variable thin-film material;
Or, first will be inorganic for the residue on final substrate (110) surface of obtained sample of step (3) with wet method or dry etch process
Phase change film material removes, then carries out high-temperature vacuum annealing.
8. utilization Template Location according to claim 1 or 7 grows the method for sequential quantum dot array it is characterised in that step
(4) the sample thermal annealing temperatures adopting in are 400 DEG C -500 DEG C.
9. utilization Template Location according to claim 7 grows the method for sequential quantum dot array it is characterised in that step (4)
In mainly adopt the koh solution that concentration is 1wt% or the reactive ion beam etching (RIBE) of argon gas atmosphere to remove described substrate (110)
The inorganic-phase variable thin-film material of surface residual.
10. utilization Template Location according to claim 1 grows the method for sequential quantum dot array it is characterised in that described
The thickness of gaas thin film (130) is 5nm~20nm.
11. utilization Template Location according to claim 1 grow the method for sequential quantum dot arrays it is characterised in that step
(5) include: the growth temperature of described second layer inas quantum dot (131) be 480 DEG C~520 DEG C, growth thickness be 2ml~
5ml.
12. utilization Template Location according to claim 1 grow the method for sequential quantum dot arrays it is characterised in that described substrate
(110) material includes iii-v race semi-conducting material, and described iii-v race semi-conducting material includes gaas, gasb or inp.
13. utilization Template Location according to claim 1 grow sequential quantum dot arrays method it is characterised in that the method it
The epitaxial growth method of middle employing includes molecular beam epitaxial process.
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CN112038882A (en) * | 2020-08-21 | 2020-12-04 | 北京大学 | Integrated structure of single photon emitter and metal waveguide, preparation method thereof and quantum loop |
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