CN101775658A - Compound semiconductor material doped with rare-earth elements and growth method thereof - Google Patents
Compound semiconductor material doped with rare-earth elements and growth method thereof Download PDFInfo
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- CN101775658A CN101775658A CN200910247541A CN200910247541A CN101775658A CN 101775658 A CN101775658 A CN 101775658A CN 200910247541 A CN200910247541 A CN 200910247541A CN 200910247541 A CN200910247541 A CN 200910247541A CN 101775658 A CN101775658 A CN 101775658A
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Abstract
The invention discloses a compound semiconductor material doped with rare-earth elements, which is a crystal material being composed of III group elements and V group elements and doped with the rare-earth elements. The crystal material further comprises displacement adulterant which is an III group element or the combination of a plurality of III group elements, the atomic numbers of the III group elements contained in the displacement adulterant are smaller than those of the III group elements forming the crystal material, and the displacement adulterant substitutes original III group elements in crystal to form a displacement defect. The invention also provides a preparation method of the material. The invention has the advantages that the displacement defect is formed by doping elements with smaller atomic numbers in the material so as to improve the lattice deformation of the semiconductor material caused by doping the rare-earth element, thus improving the luminous efficiency of the material.
Description
[technical field]
The present invention relates to field of semiconductor materials, relate in particular to a kind of compound semiconductor materials and growth method thereof of doped with rare-earth elements.
[background technology]
Therefore third generation semiconductor material GaN and related device thereof are that the third generation semiconductor material of representative is described as the new engine of IT industry with GaN owing in fields such as light demonstration, optical storage, Laser Printing, optical illumination and medical treatment and military affairs wide application prospect is arranged.
GaN is a kind of wide bandgap semiconductor, and its energy gap reaches 3.4eV, therefore can mix various rare earth ions in GaN, and luminescence quenching can not take place.The luminous wave band of rare earth ion can cover from ultraviolet to infrared zone, and the luminescent transition of rare earth ion mainly results from transition between the 4f energy level that part fills up, and is subjected to the crystal field environmental influence less, and glow peak is sharp-pointed, and its purity of color is higher.The GaN material that mixes rare earth ion shows great application prospect in fields such as electroluminescent device, flat pannel display, laser diodes.The hot method of ammonia is a kind of important method for preparing the high-quality GaN crystalline material at present, and it is low that it has a cost, and therefore the advantage that the growing crystal dislocation desity is low has been subjected to investigator's attention.(" Nonpolar GaNsubstrates grown by ammonothermal method ", be published in APPLIED PHYSICSLETTERS 2009,95,131119), this GaN film shows great application prospect in fields such as electroluminescent device, flat pannel display, laser diodes.
Rare earth ion is after mixing GaN matrix, and that generally replace is Ga
3+Lattice site, and the radius of rare earth ion is generally than Ga
3+Radius want big, Ga
3+Radius be 62pm, and the rare earth ion radius is in 103.4pm (Ce
3+) and 84.8pm (Lu
3+) between.So the angle from the ionic radius coupling can cause bigger lattice distortion after rare earth ion mixes, undoubtedly, the generation of this lattice distortion can be introduced more point defect in crystal, thereby reduces GaN crystalline luminescent properties.
[summary of the invention]
Technical problem to be solved by this invention is, a kind of compound semiconductor materials and growth method thereof of doped with rare-earth elements are provided, can improve the lattice distortion that semiconductor material causes owing to doped with rare-earth elements, thereby improve the luminous efficiency of material photoluminescence.
In order to address the above problem, the invention provides a kind of compound semiconductor materials of doped with rare-earth elements, described semiconductor material is the crystalline material that is made of III family element and V group element, and be doped with rare earth element, further comprise the displacement hotchpotch in the described crystalline material, described displacement hotchpotch is the combination of a kind of III family's element or multiple III family element, and the III family Atom of Elements that is contained is less than the III family Atom of Elements that constitutes crystalline material, and described displacement hotchpotch substitutes original III family element and forms the displacement defective in crystal.
As optional technical scheme, the III family element in the described crystalline material is selected from one or more among B, Al, Ga and the In, and the element in the described displacement hotchpotch is selected from one or more among B, Al, Ga and the In.
As optional technical scheme, it is characterized in that the atom number of described displacement hotchpotch is not more than the atom number of rare earth element, and be not less than rare earth element atom number 1/10th.
The present invention further provides a kind of preparation method of above-mentioned semiconductor material, comprise the steps: to provide source material and displacement hotchpotch, described source material is to comprise one or more III family elements, and the mixture of one or more rare earth elements, described displacement hotchpotch is the mixture that comprises a kind of III family's element or multiple III family element, and the III family Atom of Elements that the displacement hotchpotch is contained is less than the III family Atom of Elements that is contained in the material of source; Described source material mixed being placed in the reactor with the displacement hotchpotch, and a seed crystal is placed reactor, and be separated from each other setting with the source material; In reactor, inject liquefied ammonia and mineralizer; Temperature in the conditioned reaction still, make the residing zone of described seed crystal have different temperature with the residing zone of displacement hotchpotch with described source material, so that enter into the source material of liquefied ammonia and displacement hotchpotch surperficial recrystallize at seed crystal, thereby obtain to contain the nitride of one or more III family elements in seed crystal face, and be doped with rare earth element and displacement hotchpotch.
As optional technical scheme, III family element in the material of described source, the rare earth element in the material of source and the atom number proportioning between the displacement hotchpotch are (1-x-y): x: y, wherein the span of x and y is respectively 0.1%≤x≤10.0%, 0.1x≤y≤x.
As optional technical scheme, described mineralizer is alkaline mineralizer, contains material MNH in the described alkaline mineralizer
2, described M is selected from one or more among Li, Na and the K, and in the step of described conditioned reaction temperature in the kettle, the temperature in seed crystal zone of living in is higher than the temperature in described source material and displacement hotchpotch zone of living in.
As optional technical scheme, described mineralizer is an acidic mineralizer, contains material NH in the described acidic mineralizer
4X, described X is selected from one or more among Cl, Br and the I, and in the step of described conditioned reaction temperature in the kettle, the temperature in seed crystal zone of living in is lower than the temperature in described source material and displacement hotchpotch zone of living in.
As optional technical scheme, the mole number ratio range of described mineralizer and liquefied ammonia is 0.02: 1 to 0.05: 1.
The present invention further provides a kind of preparation method of above-mentioned semiconductor material, comprise the steps: to provide first, second and the 3rd source material, wherein the second source material is selected from one or more among Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and the Yb, the first source material is selected from one or more among B, Al, Ga and the In, the 3rd source material is selected from one or more among B, Al, Ga and the In, and in the 3rd source material ordination number of institute's containing element less than the ordination number of institute's containing element in the first source material; Make by N
2, H
2, and three kinds of mixed gass that gas constituted of HCl surface by first, second and the 3rd source material successively, same again NH
3Mix; Make mixed gas pass through the surface of growth substrates again, thereby obtain to contain the nitride of the first source material, and be doped with the first and the 3rd source material on the growth substrates surface.
As optional technical scheme, the atom number proportioning of described three provenance materials is (1-x-y): x: y, and wherein the span of x and y is respectively 0.1%≤x≤10.0%, 0.1x≤y≤x.
As optional technical scheme, pass through in the process of three provenance material surfaces at mixed gas, the surface temperature control of the first source material is between 850 ℃ to 900 ℃, the surface temperature control of the second source material is between 500 ℃ to 1000 ℃, and the surface temperature control of the 3rd source material is between 800 ℃ to 1000 ℃.
The invention has the advantages that,, form the displacement defective by foreign atom ordinal number smaller elements in material, improving the lattice distortion that semiconductor material causes owing to doped with rare-earth elements, thus the luminous efficiency of raising material.
[description of drawings]
It shown in the accompanying drawing 1 the implementation step synoptic diagram of first embodiment of the growth of compound semiconductor materials method of doped with rare-earth elements of the present invention;
It shown in the accompanying drawing 2 the implementation step synoptic diagram of second embodiment of the growth of compound semiconductor materials method of doped with rare-earth elements of the present invention.
[embodiment]
Below in conjunction with accompanying drawing the compound semiconductor materials of a kind of doped with rare-earth elements provided by the invention and the embodiment of growth method thereof are elaborated.
Provide the embodiment of the compound semiconductor materials of a kind of doped with rare-earth elements of the present invention at first in conjunction with the accompanying drawings.The described semiconductor material of this embodiment is the crystalline material that is made of III family element and V group element, and be doped with rare earth element, further comprise the displacement hotchpotch in the described crystalline material, described displacement hotchpotch is the combination of a kind of III family's element or multiple III family element, and the III family Atom of Elements that is contained is less than the III family Atom of Elements that constitutes crystalline material, and described displacement hotchpotch substitutes original III family element and forms the displacement defective in crystal.
Concrete institute, described semiconductor material is the III-V group iii v compound semiconductor material, for example GaN, GaAs, InGaN, InGaAs, AlGaN, AlGaAs or other similar binary or polybasic III-V compound semiconductor crystalline material.So-called rare earth element is the general name of Elements C e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.Can produce photoluminescence for III-V group iii v compound semiconductor material doped with rare-earth elements, important use all arranged in a lot of fields.But because mixing of rare earth element causes lattice distortion easily, this embodiment suppresses this lattice distortion by mix the displacement hotchpotch in semiconductor material.The displacement hotchpotch that this embodiment adopted also is III family element, but ordination number is less than the III family element that constitutes the semiconductor crystal material.If described semiconductor crystal material is simple binary compound, GaN for example, the displacement hotchpotch that is then adopted can be B, Al or the mixture of the two; If described semiconductor material is ternary or multi-element compounds, then each Atom of Elements all should be less than any one element in the original III of the compound semiconductor family element in the displacement hotchpotch, for example working as compound semiconductor is under the situation of AlGaN, hotchpotch should be B, and be under the situation of InGaN at compound semiconductor, hotchpotch just can be B, Al or the mixture of the two.
In order to obtain good effect, should the number of described hotchpotch be optimized.Experiment shows that the optimization dosage of hotchpotch should be that the atom number of displacement hotchpotch is not more than the atom number of rare earth element, and be not less than rare earth element atom number 1/10th.The meaning that the displacement hotchpotch exists is to improve rare earth element and mixes the lattice distortion that takes place afterwards, therefore the doping ratio of displacement hotchpotch can not be too little, preferable ratio is to be not less than 1/10th of rare earth element atom number, otherwise with the number of comparing between the rare earth element very little, reduced it and improved the effect of lattice distortion effect.Further, the doping meeting of displacement hotchpotch excites the luminous efficiency of photoluminescence to play certain side effect to crystal, therefore the adulterated preferable ratio of reaching the standard grade is the atom number that is not more than rare earth element, otherwise the displacement hotchpotch will become apparent in view to the influence of fluorescence radiation efficient.
Next provide first embodiment of the growth of compound semiconductor materials method of doped with rare-earth elements of the present invention in conjunction with the accompanying drawings.
Accompanying drawing 1 is depicted as the implementation step synoptic diagram of this embodiment, comprising: step S10 provides source material and displacement hotchpotch; Step S11 mixes described source material to be placed in the reactor, and a seed crystal is placed reactor, and is separated from each other setting with the source material with the displacement hotchpotch; Step S12 injects liquefied ammonia and mineralizer in reactor; Temperature in the step S13, conditioned reaction still makes the residing zone of described seed crystal have different temperature with described source material with the residing zone of displacement hotchpotch.
Refer step S10 at first, source material and displacement hotchpotch are provided, described source material is one or more III family elements, and the mixture of one or more rare earth elements, described displacement hotchpotch is the mixture of a kind of III family's element or multiple III family element, and the III family Atom of Elements that the displacement hotchpotch is contained is less than the III family Atom of Elements that is contained in the material of source.
Specifically, so-called rare earth element is the general designation of element periodic table Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.Described source material contains one or more among B, Al, Ga and the In, and contains rare earth element.
The displacement hotchpotch is selected from one or more among B, Al, Ga and the In, and ordination number is less than should be less than the III Atom of Elements that is contained in the material of source.
For example, if only contain Ga in the material of described source, the displacement hotchpotch that is then adopted can be B, Al or the mixture of the two; If contain two kinds or two or more III family elements in the material of described source, then each Atom of Elements all should be less than any one element in the III family element that is had in the material of source in the displacement hotchpotch, for example in the material of described source, contain under the situation of Al and Ga, hotchpotch should be B, and in the material of described source, containing under the situation of In and Ga, the displacement hotchpotch just can be B, Al or the mixture of the two.
In order to obtain good effect, should the number of described hotchpotch be optimized.III family element in the material of described source, the rare earth element in the material of source and the atom number proportioning between the displacement hotchpotch are (1-x-y): x: y.Experiment shows, the optimization dosage of hotchpotch should be the atom number that the atom number of displacement hotchpotch is not more than rare earth element, and be not less than rare earth element atom number 1/10th, promptly the span of x and y should be respectively 0.1%≤x≤10.0%, 0.1x≤y≤x.The meaning that the displacement hotchpotch exists is to improve rare earth element and mixes the lattice distortion that takes place afterwards, therefore the doping ratio of displacement hotchpotch can not be too little, preferable ratio is to be not less than 1/10th of rare earth element atom number, otherwise with the number of comparing between the rare earth element very little, reduced it and improved the effect of lattice distortion effect.Further, the doping meeting of displacement hotchpotch excites the luminous efficiency of photoluminescence to play certain side effect to crystal, therefore the adulterated preferable ratio of reaching the standard grade is the atom number that is not more than rare earth element, otherwise the displacement hotchpotch will become apparent in view to the influence of fluorescence radiation efficient.
III family element is Ga in the source material that this embodiment adopts, and the displacement hotchpotch that is adopted is the mixture of B and Al.
Continue refer step S11, described source material is mixed being placed in the reactor with the displacement hotchpotch, and a seed crystal is placed reactor, and be separated from each other setting with the source material.
Described reactor is the reactor of liquid ammonia process for caustic soda purification special use, can bear acid and alkali corrosion, and can tolerate high pressure.
The mole number ratio range of optimizing between mineralizer and the liquefied ammonia is 0.02: 1 to 0.05: 1.
Continue refer step S12, in reactor, inject liquefied ammonia and mineralizer.
Described mineralizer can be acidic mineralizer or alkaline mineralizer.If described mineralizer is alkaline mineralizer, then should should contain material MNH in the alkalescence mineralizer
2, described M is selected from one or more among Li, Na and the K; If described mineralizer is an acidic mineralizer, then contain material NH4X in this acidic mineralizer, described X is selected from one or more among Cl, Br and the I.
No matter be acidic mineralizer or alkaline mineralizer, the effect of being played all is to make the simple substance element in source material and the displacement hotchpotch become ion by chemical reaction, enter into liquefied ammonia, and at the seed crystal face recrystallize, in order to promote the generation of above-mentioned chemical reaction, thermograde in should the conditioned reaction still in follow-up step, and for acid and alkaline mineralizer, the method for attemperation is diverse.
In order to guarantee that successful reaction carries out, the cumulative volume that injects liquefied ammonia and mineralizer should be that the autoclave volumetrical is more than 60% at least.
Continue refer step S13, the temperature in the conditioned reaction still makes the residing zone of described seed crystal have different temperature with described source material with the residing zone of displacement hotchpotch.
In this step, if the mineralizer that is adopted is alkaline mineralizer, then the temperature in seed crystal zone of living in should be higher than the temperature in described source material and displacement hotchpotch zone of living in; If instead the mineralizer that is adopted is an acidic mineralizer, then the temperature in seed crystal zone of living in should be lower than the temperature in described source material and displacement hotchpotch zone of living in.
No matter adopt which kind of mineralizer, the preferred temperature of control growing should be between 400 ℃ to 600 ℃, and promptly the temperature of the high-temperature zone of reactor and cold zone all should be controlled within this scope.
Keep the said temperature condition, so that enter into the source material of liquefied ammonia and displacement hotchpotch surperficial recrystallize at seed crystal, thus obtain to contain the nitride of one or more III family elements in seed crystal face, and be doped with rare earth element and displacement hotchpotch.The hold-time of the described temperature condition of step S13 is determined by needed crystal geometrical dimension, needs to implement the time in 3 to 8 weeks usually.After enforcement finishes, promptly obtain to be doped with the GaN crystal of rare earth element, boron and aluminium.Owing to be doped with boron and aluminium in the crystal, can improve the lattice distortion that causes owing to rear-earth-doped, improve the luminous efficiency of photoluminescence.
Next provide second embodiment of the growth of compound semiconductor materials method of doped with rare-earth elements of the present invention in conjunction with the accompanying drawings.
Accompanying drawing 2 is depicted as the implementation step synoptic diagram of this embodiment, comprising: step S20 provides first, second and the 3rd source material; Step S21 makes the mixed gas surface by first, second and the 3rd source material successively; Step S22 makes mixed gas pass through the surface of growth substrates.
Refer step S20 at first, first, second and the 3rd source material are provided, wherein the second source material is selected from one or more among Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and the Yb, the first source material is selected from one or more among B, Al, Ga and the In, the 3rd source material is selected from one or more among B, Al, Ga and the In, and in the 3rd source material ordination number of institute's containing element less than the ordination number of institute's containing element in the first source material;
The effect of described the 3rd source material is as crystalline displacement hotchpotch.The described second source material comes down to rare earth element.
For example, if the described first source material is Ga, the 3rd source material that is then adopted can be B, Al or the mixture of the two; If contain two kinds or two or more III family elements in the described first source material, then each Atom of Elements all should be less than any one element in the III family element that is had in the first source material in the 3rd source material, for example in the described first source material, contain under the situation of Al and Ga, the 3rd source material as the displacement hotchpotch should be B, and containing under the situation of In and Ga in the described first source material, just can be B, Al or the mixture of the two as the 3rd source material of displacement hotchpotch.
In the first source material that this embodiment adopts is Ga, and the 3rd source material that is adopted is the mixture of B and Al.
Continue refer step S21, make mixed gas successively by the surface of first, second and the 3rd source material, described mixed gas is by N
2, H
2, and three kinds of gases of HCl constitute, the mixed gas of above-mentioned three kinds of gases is successively by first, second and the surface of the 3rd source material same again NH afterwards
3Mix.
HCl as with first, second and the reactant gases of the 3rd source material, above-mentioned source transport of substances is arrived growth substrates surface, N
2And H
2As the carrier gas of above-mentioned source transport of substances, and NH
3As nitrogenous source, thereby obtain nitride on the growth substrates surface.
In order to improve the speed of reaction between HCl and the source material, by in the process of three provenance material surfaces, can heat above-mentioned three provenance materials at mixed gas.The surface temperature control of the first source material is between 850 ℃ to 900 ℃, the surface temperature control of the second source material is between 500 ℃ to 1000 ℃, the surface temperature control of the 3rd source material can effectively improve the speed of response of source material and HCl between 800 ℃ to 1000 ℃.
Continue refer step S22, make mixed gas pass through the surface of growth substrates.
Above-mentioned mixed gas by after the surface of three provenance materials, has become the gas that carries three kinds of substance ions successively.Make this gas again by the surface of growth substrates, the source material will promptly obtain to be doped with the GaN crystal of rare earth element, boron and aluminium at the surperficial recrystallize of growth substrates.Owing to be doped with boron and aluminium in the crystal, can improve the lattice distortion that causes owing to rear-earth-doped, improve the luminous efficiency of photoluminescence.
More than about the growth method described in first and second embodiments of growth method be respectively typical hot ammonia process and HVPE growth technique, concrete growing principle can be with reference to the technical information of relevant hot ammonia process and HVPE growth with processing parameter, unlike the prior art be, comprised the element of hotchpotch as an alternative in the source material that described hot ammonia process of present method and HVPE technology are adopted, the element of hotchpotch as an alternative, its ordination number is less than the III family element that forms in the III-V group iii v compound semiconductor material, and in compound semiconductor, form the displacement defective, therefore can improve the III-V compound semiconductor owing to the lattice distortion that rare earth element produces of having mixed, thereby improve the luminous efficiency of crystalline photoluminescence.
First embodiment of the growth of compound semiconductor materials method of above-mentioned doped with rare-earth elements and the prepared crystal of second embodiment are the crystalline material described in the embodiment of compound semiconductor materials of above-mentioned doped with rare-earth elements.The preparation method who should be pointed out that crystalline material of the present invention should be not limited to the method described in above-mentioned first and second embodiment, also can adopt MOCVD common in this area or MBE to grow.For example in organic source of MOCVD, add one the tunnel or the organic chelate of a few road displacement doped elements, perhaps in the molecular beam generating unit of MBE, add the source of corresponding element, also can obtain the above-mentioned crystal that is doped with displacement element and rare earth element.The aforesaid method those skilled in that art can be implemented according to the particular case of the equipment that adopts separately, repeat no more herein.
Next provide the embodiment of the growth of compound semiconductor materials method of doped with rare-earth elements of the present invention.
Embodiment 1:
In this example, x=0.1%, y=0.01%, Re are rare earth metal Er, A is the metal boron.Above-mentioned load weighted raw material is loaded on evaporation tank in the HVPE device separately, and substrate selects growth that the sapphire of GaN film is arranged, and Ga evaporation tank temperature is controlled at 850 ℃,, the Er evaporation tank is controlled at 850 ℃, and the evaporation tank temperature of metal B is controlled at 900 ℃.With N
2/ H
2Mixed gas as carrier gas, with NH
3As nitrogenous source, HCl flows through respectively as reactant gases Ga is housed, rare earth metal Er, three evaporation tanks of metal boron.Obtain 50
After the crystal film of um thickness, cooling substrate and each evaporation tank can take out rare earth ion and B to room temperature
3+The GaN crystal film of mixing altogether.Than not mixing B altogether
3+Same concentration mix Er
3+The GaN crystal film, fluorescence intensity strengthens 5%-20%.
Embodiment 2:
In this example, x=10%, y=1%, Re are rare earth metal Er, A is the metal boron.Above-mentioned load weighted raw material is loaded on evaporation tank in the HVPE device separately, and substrate selects growth that the sapphire of GaN film is arranged, and Ga evaporation tank temperature is controlled at 850 ℃,, the Er evaporation tank is controlled at 900 ℃, and the evaporation tank temperature of metal B is controlled at 950 ℃.With N
2/ H
2Mixed gas as carrier gas, with NH
3As nitrogenous source, HCl flows through respectively as reactant gases Ga is housed, rare earth metal Er, three evaporation tanks of metal boron.After obtaining the crystal film of 50um thickness, cooling substrate and each evaporation tank can take out rare earth ion and B to room temperature
3+The GaN crystal film of mixing altogether.Than not mixing B altogether
3+Same concentration mix Er
3+The GaN crystal film, fluorescence intensity strengthens 5%-20%.
Embodiment 3:
In this example, x=5%, y=0.5%, Re are rare earth metal Er, A is the metal boron.Above-mentioned load weighted raw material is loaded on evaporation tank in the HVPE device separately, and substrate selects growth that the sapphire of GaN film is arranged, and Ga evaporation tank temperature is controlled at 850 ℃,, the Er evaporation tank is controlled at 870 ℃, and the evaporation tank temperature of metal B is controlled at 920 ℃.With N
2/ H
2Mixed gas as carrier gas, with NH
3As nitrogenous source, HCl flows through respectively as reactant gases Ga is housed, rare earth metal Er, three evaporation tanks of metal boron.After obtaining the crystal film of 50um thickness, cooling substrate and each evaporation tank can take out rare earth ion and B to room temperature
3The GaN crystal film of mixing altogether.Than not mixing B altogether
3+Same concentration mix Er
3+The GaN crystal film, fluorescence intensity strengthens 5%-20%.
Embodiment 4:
In this example, x=5%, y=0.5%, Re are rare earth metal Tm, A is metallic aluminium Al.Above-mentioned load weighted raw material is loaded on evaporation tank in the HVPE device separately, and substrate selects growth that the sapphire of GaN film is arranged, and Ga evaporation tank temperature is controlled at 850 ℃,, the Tm evaporation tank is controlled at 580 ℃, and the evaporation tank temperature of metal A l is controlled at 985 ℃.With N
2/ H
2Mixed gas as carrier gas, with NH
3As nitrogenous source, HCl flows through respectively as reactant gases Ga is housed, rare earth metal Tm, three evaporation tanks of metallic aluminium.After obtaining the crystal film of 50um thickness, cooling substrate and each evaporation tank can take out rare earth ion and Al to room temperature
3+The GaN crystal film of mixing altogether.Than not mixing Al altogether
3+Same concentration mix Tm
3+The GaN crystal film, fluorescence intensity strengthens 5%-20%.
Embodiment 5:
In this example, x=5%, y=0.5%, Re are rare earth metal Eu, A is metallic aluminium Al.Above-mentioned load weighted raw material is loaded on evaporation tank in the HVPE device separately, and substrate selects growth that the sapphire of GaN film is arranged, and Ga evaporation tank temperature is controlled at 850 ℃,, the Eu evaporation tank is controlled at 570 ℃, and the evaporation tank temperature of metal A l is controlled at 985 ℃.With N
2/ H
2Mixed gas as carrier gas, with NH
3As nitrogenous source, HCl flows through respectively as reactant gases Ga is housed, rare earth metal Eu, three evaporation tanks of metallic aluminium.Obtain 50
After the crystal film of um thickness, cooling substrate and each evaporation tank can take out rare earth ion and Al to room temperature
3+The GaN crystal film of mixing altogether.Than not mixing Al altogether
3+Same concentration mix Eu
3+The GaN crystal film, fluorescence intensity strengthens 5%-20%.
Embodiment 6:
In this example, x=1%, y=0.1%, Re are rare earth metal Eu, A is metallic aluminium Al.Above-mentioned load weighted raw material is loaded on evaporation tank in the HVPE device separately, and substrate selects growth that the sapphire of GaN film is arranged, and Ga evaporation tank temperature is controlled at 850 ℃,, the Eu evaporation tank is controlled at 550 ℃, and the evaporation tank temperature of metal A l is controlled at 950 ℃.With N
2/ H
2Mixed gas as carrier gas, with NH
3As nitrogenous source, HCl flows through respectively as reactant gases Ga is housed, rare earth metal Eu, three evaporation tanks of metallic aluminium.Obtain 50
After the crystal film of um thickness, cooling substrate and each evaporation tank can take out rare earth ion and Al to room temperature
3+The GaN crystal film of mixing altogether.Than not mixing Al altogether
3+Same concentration mix Eu
3+The GaN crystal film, fluorescence intensity strengthens 5%-20%.
Embodiment 7:
In this example, x=0.1%, y=0.01%, Re are rare earth element er, A is the metallic element boron.Above-mentioned load weighted raw material is loaded in the autoclave body of ammonia thermal growth together, selects alkaline mineralizer NaNH
2, mineralizer also packed into go up in the autoclave body in step, inject liquefied ammonia then to autoclave 65% volume, the molar ratio of control mineralizer and liquefied ammonia is 0.02.The cold zone core temperature of reactor is 400 ℃, and the high-temperature zone core temperature is 430 ℃, and seed crystal is put in the high-temperature zone.Grow after about 8 weeks, programmed cooling can take out rare earth ion and and B to room temperature
3+The GaN crystal of mixing altogether.Than not mixing B altogether
3+Same concentration mix Er
3+The GaN crystal, fluorescence intensity strengthens 5%-20%.
Embodiment 8:
In this example, x=10%, y=1%, Re are rare earth element er, A is the metallic element boron.Above-mentioned load weighted raw material is loaded in the autoclave body of ammonia thermal growth together, selects alkaline mineralizer NaNH
2, mineralizer also packed into go up in the autoclave body in step, inject liquefied ammonia then to autoclave 65% volume, the molar ratio of control mineralizer and liquefied ammonia is 0.04.The cold zone core temperature of reactor is 400 ℃, and the high-temperature zone core temperature is 430 ℃, and seed crystal is put in the high-temperature zone.Grow after about 6 weeks, programmed cooling can take out rare earth ion and and B to room temperature
3+The GaN crystal of mixing altogether.Than not mixing B altogether
3+Same concentration mix Er
3+The GaN crystal, fluorescence intensity strengthens 5%-20%.
Embodiment 9:
In this example, x=5%, y=0.5%, Re are rare earth element er, A is the metallic element boron.Above-mentioned load weighted raw material is loaded in the autoclave body of ammonia thermal growth together, selects alkaline mineralizer NaNH
2, mineralizer also packed into go up in the autoclave body in step, inject liquefied ammonia then to autoclave 65% volume, the molar ratio of control mineralizer and liquefied ammonia is 0.05.The cold zone core temperature of reactor is 600 ℃, and the high-temperature zone core temperature is 630 ℃, and seed crystal is put in the high-temperature zone.Grow after about 5 weeks, programmed cooling can take out rare earth ion and and B to room temperature
3+The GaN crystal of mixing altogether.Than not mixing B altogether
3+Same concentration mix Er
3+The GaN crystal, fluorescence intensity strengthens 5%-20%.
Embodiment 10:
In this example, x=5%, y=0.5%, Re are rare earth element Tm, A is metal element A l.Above-mentioned load weighted raw material is loaded in the autoclave body of ammonia thermal growth together, selects acidic mineralizer NH
4Cl also packs mineralizer into and to go up in the autoclave body in step, injects liquefied ammonia then to autoclave 65% volume, and the molar ratio of control mineralizer and liquefied ammonia is 0.03.The cold zone core temperature of reactor is 450 ℃, and the high-temperature zone core temperature is 480 ℃, and seed crystal is put in cold zone.Grow after about 6 weeks, programmed cooling can take out rare earth ion and and Al to room temperature
3+The GaN crystal of mixing altogether.Than not mixing B altogether
3+Same concentration mix Tm
3+The GaN crystal, fluorescence intensity strengthens 5%-20%.
Embodiment 11:
In this example, x=2%, y=0.2%, Re are rare earth element Eu, A is metal element A l.Above-mentioned load weighted raw material is loaded in the autoclave body of ammonia thermal growth together, selects acidic mineralizer NH
4Br also packs mineralizer into and to go up in the autoclave body in step, injects liquefied ammonia then to autoclave 65% volume, and the molar ratio of control mineralizer and liquefied ammonia is 0.03.The cold zone core temperature of reactor is 450 ℃, and the high-temperature zone core temperature is 480 ℃, and seed crystal is put in cold zone.Grow after about 6 weeks, programmed cooling can take out rare earth ion and and Al to room temperature
3+The GaN crystal of mixing altogether.Than not mixing B altogether
3+Same concentration mix Eu
3+The GaN crystal, fluorescence intensity strengthens 5%-20%.
Embodiment 12:
In this example, x=2%, y=0.2%, Re are rare earth element tb, A is metal element A l.Above-mentioned load weighted raw material is loaded in the autoclave body of ammonia thermal growth together, select acidic mineralizer NH4I, mineralizer also packed into go up in the autoclave body in step, inject liquefied ammonia then to autoclave 65% volume, the molar ratio of control mineralizer and liquefied ammonia is 0.03.The cold zone core temperature of reactor is 500 ℃, and the high-temperature zone core temperature is 530 ℃, and seed crystal is put in cold zone.Grow after about 7 weeks, programmed cooling can take out rare earth ion and and Al to room temperature
3+The GaN crystal of mixing altogether.Than not mixing B altogether
3+Same concentration mix Tb
3+The GaN crystal, fluorescence intensity strengthens 5%-20%.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (13)
1. the compound semiconductor materials of a doped with rare-earth elements, described semiconductor material is the crystalline material that is made of III family element and V group element, and be doped with rare earth element, it is characterized in that, further comprise the displacement hotchpotch in the described crystalline material, described displacement hotchpotch is the combination of a kind of III family's element or multiple III family element, and the III family Atom of Elements that is contained is less than the III family Atom of Elements that constitutes crystalline material, and described displacement hotchpotch substitutes original III family element and forms the displacement defective in crystal.
2. the compound semiconductor materials of doped with rare-earth elements according to claim 1, it is characterized in that, III family element in the described crystalline material is selected from one or more among B, Al, Ga and the In, and the element in the described displacement hotchpotch is selected from one or more among B, Al, Ga and the In.
3. the compound semiconductor materials of doped with rare-earth elements according to claim 1 and 2 is characterized in that, the atom number of described displacement hotchpotch is not more than the atom number of rare earth element, and be not less than rare earth element atom number 1/10th.
4. the preparation method of the described semiconductor material of claim 1, it is characterized in that, comprise the steps: to provide source material and displacement hotchpotch, described source material is to comprise one or more III family elements, and the mixture of one or more rare earth elements, described displacement hotchpotch is the mixture that comprises a kind of III family's element or multiple III family element, and the III family Atom of Elements that the displacement hotchpotch is contained is less than the III family Atom of Elements that is contained in the material of source;
Described source material mixed being placed in the reactor with the displacement hotchpotch, and a seed crystal is placed reactor, and be separated from each other setting with the source material;
In reactor, inject liquefied ammonia and mineralizer;
Temperature in the conditioned reaction still, make the residing zone of described seed crystal have different temperature with the residing zone of displacement hotchpotch with described source material, so that enter into the source material of liquefied ammonia and displacement hotchpotch surperficial recrystallize at seed crystal, thereby obtain to contain the nitride of one or more III family elements in seed crystal face, and be doped with rare earth element and displacement hotchpotch.
5. preparation method according to claim 4 is characterized in that, the III family element in the material of described source, the rare earth element in the material of source and the atom number proportioning between the displacement hotchpotch are (1-x-y): x: y,
Wherein the span of x and y is respectively 0.1%≤x≤10.0%, 0.1x≤y≤x.
6. according to claim 4 or 5 described preparation methods, it is characterized in that described mineralizer is alkaline mineralizer, contain material MNH in the described alkaline mineralizer
2, described M is selected from one or more among Li, Na and the K.
7. preparation method according to claim 6 is characterized in that, in the step of described conditioned reaction temperature in the kettle, the temperature in seed crystal zone of living in is higher than the temperature in described source material and displacement hotchpotch zone of living in.
8. according to claim 4 or 5 described preparation methods, it is characterized in that described mineralizer is an acidic mineralizer, contains material NH in the described acidic mineralizer
4X, described X is selected from one or more among Cl, Br and the I.
9. preparation method according to claim 8 is characterized in that, in the step of described conditioned reaction temperature in the kettle, the temperature in seed crystal zone of living in is lower than the temperature in described source material and displacement hotchpotch zone of living in.
10. according to claim 4 or 5 described preparation methods, it is characterized in that the mole number ratio range of described mineralizer and liquefied ammonia is 0.02: 1 to 0.05: 1.
11. the preparation method of the described semiconductor material of claim 1, it is characterized in that, comprise the steps: to provide first, second and the 3rd source material, wherein the second source material is selected from one or more among Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and the Yb, the first source material is selected from one or more among B, Al, Ga and the In, the 3rd source material is selected from one or more among B, Al, Ga and the In, and in the 3rd source material ordination number of institute's containing element less than the ordination number of institute's containing element in the first source material;
Make by N
2, H
2, and three kinds of mixed gass that gas constituted of HCl surface by first, second and the 3rd source material successively, same again NH
3Mix;
Make mixed gas pass through the surface of growth substrates again, thereby obtain to contain the nitride of the first source material, and be doped with the first and the 3rd source material on the growth substrates surface.
12. preparation method according to claim 11 is characterized in that, the atom number proportioning of described three provenance materials is (1-x-y): x: y, and wherein the span of x and y is respectively 0.1%≤x≤10.0%, 0.1x≤y≤x.
13. according to claim 11 or 12 described preparation methods, it is characterized in that, pass through in the process of three provenance material surfaces at mixed gas, the surface temperature control of the first source material is between 850 ℃ to 900 ℃, the surface temperature control of the second source material is between 500 ℃ to 1000 ℃, and the surface temperature control of the 3rd source material is between 800 ℃ to 1000 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108866629A (en) * | 2017-05-11 | 2018-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | III group-III nitride monocrystalline of rare earth doped element and its preparation method and application |
| CN110036144A (en) * | 2016-11-25 | 2019-07-19 | 国立大学法人大阪大学 | Nitride semiconductor base plate and its manufacturing method and semiconductor devices |
| CN110195258A (en) * | 2019-07-10 | 2019-09-03 | 上海玺唐半导体科技有限公司 | Gallium nitride crystal growth device and its growing method |
| CN113196448A (en) * | 2018-11-20 | 2021-07-30 | Iqe公开有限公司 | III-N to rare earth transition in semiconductor structures |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080008855A1 (en) * | 2002-12-27 | 2008-01-10 | General Electric Company | Crystalline composition, wafer, and semi-conductor structure |
-
2009
- 2009-12-30 CN CN200910247541A patent/CN101775658A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080008855A1 (en) * | 2002-12-27 | 2008-01-10 | General Electric Company | Crystalline composition, wafer, and semi-conductor structure |
Non-Patent Citations (1)
| Title |
|---|
| A.WAKAHARA ET AL: ""Energy-Back-Transfer Process in Rare-Earth Doped AlGaN"", 《MATER.RES.SOC.SYMP.PROC.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110036144A (en) * | 2016-11-25 | 2019-07-19 | 国立大学法人大阪大学 | Nitride semiconductor base plate and its manufacturing method and semiconductor devices |
| CN108866629A (en) * | 2017-05-11 | 2018-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | III group-III nitride monocrystalline of rare earth doped element and its preparation method and application |
| CN113196448A (en) * | 2018-11-20 | 2021-07-30 | Iqe公开有限公司 | III-N to rare earth transition in semiconductor structures |
| CN110195258A (en) * | 2019-07-10 | 2019-09-03 | 上海玺唐半导体科技有限公司 | Gallium nitride crystal growth device and its growing method |
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