CN101748382B - Method of growing GaN-based luminescent crystalline membrane for molecular beam epitaxy - Google Patents

Method of growing GaN-based luminescent crystalline membrane for molecular beam epitaxy Download PDF

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CN101748382B
CN101748382B CN2010100171350A CN201010017135A CN101748382B CN 101748382 B CN101748382 B CN 101748382B CN 2010100171350 A CN2010100171350 A CN 2010100171350A CN 201010017135 A CN201010017135 A CN 201010017135A CN 101748382 B CN101748382 B CN 101748382B
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gan
rare earth
molecular beam
beam epitaxy
evaporation tank
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CN101748382A (en
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曾雄辉
徐科
王建峰
任国强
黄凯
包峰
张锦平
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Abstract

The invention discloses a method of growing GaN-based luminescent crystalline membrane for molecular beam epitaxy, which dopes rare earth ions in the growth process to replace part of lattice site of Ga3+ and is characterized by comprising the following steps: doping III group element boron or aluminum in the raw material formula of the GaN crystalline membrane according to a certain ratio, wherein the III group element boron or aluminum enters into GaN lattice site via a mode of trivalent ion in the growth process; preparing ion radius difference between the rare earth ion and the Ga3+, wherein the molar ratio of the raw material formula is as follows: Ga:Re:A=(1-x-y):x:y, x represents rare earth metal, A represents III group element boron or aluminum, x is more than or equal to 0.1% and less than or equal to 10.0%, and y is more than or equal to 0.1x and less than or equal to x. In the invention, III group element boron or aluminum is doped with rare earth metal together according to a certain ratio so as to greatly improve lattice deformation of the GaN crystalline membrane caused by larger radius mismatch of Re3+ and Ga3+, and increase luminescent performance of the GaN crystalline membrane.

Description

The method of growing GaN-based luminescent crystalline membrane for molecular beam epitaxy
Technical field
The present invention relates to a kind of growth method of GaN mould material, relate in particular to the grow method of rare-earth-ion-doped GaN crystal film of a kind of MBE.
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 mover 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 in GaN, can mix various rare earth ions, 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 receives the crystal field environmental influence less, and glow peak is sharp-pointed, and its purity of color is higher.Adopting at present MBE to prepare rare-earth-ion-doped GaN film has received investigator's generally attention (" Rare-Earth-Doped GaN:Growth; Properties; and Fabrication of Electroluminescent Devices " has been published in IEEEJournal of Selected Topics In Quantum Electronics, 2002; 8 (4): 749), this GaN film shows great application prospect in fields such as electroluminescent device, FPD, laser diodes.
Rare earth ion is after mixing GaN matrix, and general substituted 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 film, thereby reduces the luminescent properties of GaN crystal film.
Summary of the invention
In view of the deficiency of above-mentioned prior art, the object of the invention aims to provide a kind of method of growing GaN-based luminescent crystalline membrane for molecular beam epitaxy, solves formerly in the technology because the rare earth ion and the Ga that mix 3+Between bigger ionic radius mismatch and the lattice distortion problem that causes, thereby improve the luminescent properties of rare-earth-ion-doped GaN base crystal film.
For realizing above-mentioned purpose, technical solution of the present invention is:
On the whole: the method for growing GaN-based luminescent crystalline membrane for molecular beam epitaxy, doping with rare-earth ions in process of growth replaces part Ga 3+Lattice site, it is characterized in that: in the composition of raw materials of said GaN crystal film, mix III family element boron or aluminium in proportion, get into the GaN lattice, allotment rare earth ion and Ga with the form of trivalent ion at the family's element boron of III described in the process of growth or aluminium 3+Between ionic radius poor; Said composition of raw materials molar ratio is: Ga: Re: A=(1-x-y): x: y; Wherein Re representes rare earth metal, comprises among cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, the lutetium Lu any one or multiple using with; A representes III family element boron or aluminium; 0.1%≤x≤10.0%, 0.1x≤y≤x.
Specifically: the method for growing GaN-based luminescent crystalline membrane for molecular beam epitaxy; It is characterized in that comprising step: I, Ga: Re: A=(1-x-y) in molar ratio: x: y; 0.1%≤x≤10.0%; 0.1x≤y≤x raw materials weighing Ga, Re and A are positioned over respectively in each evaporation tank in the device, wherein A representes III family element boron or aluminium; II, GaN base substrate is placed the molecular beam epitaxy chamber, vacuumize and GaN base substrate is heat-treated, maintain the temperature at 550 ℃-600 ℃; III, regulate and control each evaporation tank temperature, each raw material element is evaporated in proportion, control growing speed is at 0.5-1 μ m/h; And through radio-frequency plasma generation Nitrogen Atom; IV, naturally cooling substrate and each evaporation tank with the emptying of molecular beam epitaxy chamber, promptly get rare earth ion and B again 3+Or Al 3+The GaN crystal film of mixing altogether.
Further; The method of aforesaid growing GaN-based luminescent crystalline membrane for molecular beam epitaxy; Ga evaporation tank temperature is controlled at 850 ℃-945 ℃ among the Step II I, and Re evaporation tank temperature is controlled at 500 ℃-1100 ℃, and the evaporation tank temperature of III family element boron or aluminium is controlled at 800 ℃-1100 ℃; GaN described in Step II base substrate comprises that growth has in the silicon of GaN film, sapphire that growth has the GaN film or the GaN block any one.
The method of growing GaN-based luminescent crystalline membrane for molecular beam epitaxy of the present invention, its remarkable advantage is:
Owing to adopted III family element boron or aluminium and rare earth metal to mix altogether according to a certain ratio, thereby can improve to a great extent because Re 3+And Ga 3+Between bigger radius mismatch and the GaN crystal film lattice distortion that causes, thereby improve the luminescent properties of GaN crystal film.
Embodiment
B 3+And Al 3+Radius be respectively 20pm and 50pm, so if in the GaN crystal film, mix the B of III family element altogether according to suitable proportioning 3+Or Al 3+And rare earth ion, can improve the crystal film lattice distortion to a certain extent; And because B 3+Or Al 3+Be a kind of neutral component, so mix a spot of B 3+Or Al 3+Can spinoff not arranged to the luminescent properties of GaN crystal film.
Embodiment 1:
In this example, x=0.1%, y=0.01%, Re are rare earth metal erbium Er, and A is boron (B).Above-mentioned load weighted raw material is packed in the different evaporation tanks in molecular beam epitaxy (hereinafter to be referred as the MBE) device separately; Substrate selects growth that the sapphire of GaN film is arranged; Ga evaporation tank temperature is controlled at 900 ℃, and the Er evaporation tank is controlled at 850 ℃, and the evaporation tank temperature of crystal B is controlled at 900 ℃.And through radio-frequency plasma generation Nitrogen Atom.After obtaining the film of 5 μ m thickness, naturally cooling substrate and each evaporation tank can take out Er after the MBE emptying 3+And B 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 erbium Er, and A is metallic aluminium (Al).Above-mentioned load weighted raw material is packed in the different evaporation tanks in the MBE device separately, and substrate selects growth that the silicon of GaN film is arranged, and Ga evaporation tank temperature is controlled at 900 ℃, and the Er evaporation tank is controlled at 1000 ℃, and the evaporation tank temperature of metal A l is controlled at 980 ℃.And through radio-frequency plasma generation Nitrogen Atom.After obtaining the film of 5 μ m thickness, naturally cooling substrate and each evaporation tank can take out Er after the MBE emptying 3+And Al 3+The GaN crystal film of mixing altogether.Than not mixing Al 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 erbium Er, and A is metallic aluminium (Al).Above-mentioned load weighted raw material is packed in the different evaporation tanks in the MBE device separately, and substrate is selected HVPE Grown GaN block, and Ga evaporation tank temperature is controlled at 900 ℃, and the Er evaporation tank is controlled at 950 ℃, and the evaporation tank temperature of metal A l is controlled at 930 ℃.And through radio-frequency plasma generation Nitrogen Atom.After obtaining the film of 5 μ m thickness, naturally cooling substrate and each evaporation tank can take out Er after the MBE emptying 3+And Al 3+The GaN crystal film of mixing altogether.Than not mixing Al 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 thulium Tm, and A is metallic aluminium (Al).Above-mentioned load weighted raw material is packed in the different evaporation tanks in the MBE device separately, and substrate is selected HVPE Grown GaN block, and Ga evaporation tank temperature is controlled at 900 ℃, and the Tm evaporation tank is controlled at 600 ℃, and the evaporation tank temperature of metal A l is controlled at 930 ℃.And through radio-frequency plasma generation Nitrogen Atom.After obtaining the film of 5 μ m thickness, naturally cooling substrate and each evaporation tank can take out Tm after the MBE emptying 3+And Al 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 praseodymium Pr, and A is metallic aluminium (Al).In the different evaporation tanks in each self-chambering people MBE device of above-mentioned load weighted raw material, substrate is selected HVPE Grown GaN block, and Ga evaporation tank temperature is controlled at 900 ℃, and the Pr evaporation tank is controlled at 1200 ℃, and the evaporation tank temperature of metal A l is controlled at 900 ℃.And through radio-frequency plasma generation Nitrogen Atom.After obtaining the film of 5 μ m thickness, naturally cooling substrate and each evaporation tank can take out pr after the MBE emptying 3+And Al 3+The GaN crystal film of mixing altogether.Than not mixing Al altogether 3+Same concentration mix pr 3+The GaN crystal film, fluorescence intensity strengthens 5%-20%.
Embodiment 6:
In this example, x=5%, y=0.5%, Re are rare earth metal europium Eu, and A is metallic aluminium (Al).Above-mentioned load weighted raw material is loaded in the different evaporation tanks in the MBE device separately, and substrate is selected HVPE Grown GaN block, and Ga evaporation tank temperature is controlled at 900 ℃, and the Eu evaporation tank is controlled at 570 ℃, and the evaporation tank temperature of metal A l is controlled at 900 ℃.And through radio-frequency plasma generation Nitrogen Atom.After obtaining the film of 5 μ m thickness, naturally cooling substrate and each evaporation tank can take out Eu after the MBE emptying 3+And Al 3+The GaN crystal film of mixing altogether.Than not mixing Al altogether 3+Same concentration mix Eu 3+The GaN crystal film, though fluorescence intensity increases 5%-20%.

Claims (5)

1. the method for growing GaN-based luminescent crystalline membrane for molecular beam epitaxy, doping with rare-earth ions in process of growth replaces part Ga 3+Lattice site, it is characterized in that: in the composition of raw materials of said GaN crystal film, mix III family element boron or aluminium in proportion, get into the GaN lattice, allotment rare earth ion and Ga with the form of trivalent ion at the family's element boron of III described in the process of growth or aluminium 3+Between ionic radius poor; Said composition of raw materials molar ratio is: Ga: Re: A=(1-x-y): x: y, and wherein Re representes rare earth metal, A representes III family element boron or aluminium, 0.1%≤x≤10.0%, 0.1x≤y≤x.
2. the method for growing GaN-based luminescent crystalline membrane for molecular beam epitaxy according to claim 1 is characterized in that: said rare earth metal comprises among cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, the lutetium Lu any one or multiple using with.
3. the method for growing GaN-based luminescent crystalline membrane for molecular beam epitaxy is characterized in that comprising step:
I, Ga: Re: A=(1-x-y) in molar ratio: x: y, 0.1%≤x≤10.0%, 0.1x≤y≤x raw materials weighing Ga, Re and A are positioned over respectively in each evaporation tank in the device, and wherein A representes III family element boron or aluminium;
II, GaN base substrate is placed the molecular beam epitaxy chamber, vacuumize and GaN base substrate is heat-treated, maintain the temperature at 550 ℃-600 ℃;
III, regulate and control each evaporation tank temperature, each raw material element is evaporated in proportion, control growing speed is at 0.5-1 μ m/h; And through radio-frequency plasma generation Nitrogen Atom;
IV, naturally cooling substrate and each evaporation tank with the emptying of molecular beam epitaxy chamber, promptly get rare earth ion and B again 3+Or Al 3+The GaN crystal film of mixing altogether.
4. the method for growing GaN-based luminescent crystalline membrane for molecular beam epitaxy according to claim 3; It is characterized in that: Ga evaporation tank temperature is controlled at 850 ℃-945 ℃ among the Step II I; Re evaporation tank temperature is controlled at 500 ℃-1100 ℃, and the evaporation tank temperature of III family element boron or aluminium is controlled at 800 ℃-1100 ℃.
5. the method for growing GaN-based luminescent crystalline membrane for molecular beam epitaxy according to claim 3 is characterized in that: the base of GaN described in Step II substrate comprises that growth has in the silicon of GaN film, sapphire that growth has the GaN film or the GaN block any one.
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CN1316783A (en) * 2000-03-24 2001-10-10 日本碍子株式会社 Semiconductor device and manufacturing method thereof and its used semconductor device substrate

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CN1316783A (en) * 2000-03-24 2001-10-10 日本碍子株式会社 Semiconductor device and manufacturing method thereof and its used semconductor device substrate

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