CN101736400B - Method for growing GaN-based luminous crystal film by metal organic chemical vapor deposition - Google Patents
Method for growing GaN-based luminous crystal film by metal organic chemical vapor deposition Download PDFInfo
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- CN101736400B CN101736400B CN2010100171346A CN201010017134A CN101736400B CN 101736400 B CN101736400 B CN 101736400B CN 2010100171346 A CN2010100171346 A CN 2010100171346A CN 201010017134 A CN201010017134 A CN 201010017134A CN 101736400 B CN101736400 B CN 101736400B
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Abstract
The invention discloses a method for growing a GaN-based luminous crystal film by metal organic chemical vapor deposition. The method is characterized in that: trimethylborine or trimethylaluminium are doped in a raw material formula of the GaN crystal film in proportion, and boron or aluminum enter a GaN crystal lattice in a mode of trivalent ion in a growing process to regulate the ionic radius difference between rare-earth ions and Ga3+; the molar ratio of the raw material formula is that: Ga (CH3)3 to rare-earth organic complex to A(CH3)3 is (1-x-y):x:y, wherein the rare-earth organic complex is Re(TMHD)3 or Re (i-PrCp)3 taking rare-earth element Re as a core; A represents III group element boron or aluminum; x is more than or equal to 0.1 percent and less than or equal to 10.0 percent; and y is more than or equal to 0.1 time of the x and less than or equal to x. Because the organic complex of the III group element boron or aluminum and the rare-earth organic complex are co-doped in a certain proportion, the method can improve lattice distortion of the GaN crystal film caused by larger radius mismatch between Re3+ and Ga3+ to a large extent so as to improve the luminous performance of the GaN crystal film.
Description
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 MOCVD.
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 luminous crystal film by metal organic chemical vapor deposition, 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 luminous crystal film by metal organic chemical vapor deposition, 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 trimethyl-boron or trimethylaluminium in proportion, get into the GaN lattice, allotment rare earth ion and Ga with the form of trivalent ion at boron described in the process of growth or aluminium
3+Between ionic radius poor; Said composition of raw materials molar ratio is: Ga (CH
3)
3: rare earth organic complex: A (CH
3)
3=(1-x-y): x: y, wherein rare earth organic complex is meant with the rare earth element Re to be the Re (TMHD) of core
3Or Re (i-PrCp)
3, Re refers to is any one or multiple using with 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; A representes III family element boron or aluminium; 0.1%≤x≤10.0%, 0.1x≤y≤x.
Specifically: the method for growing GaN-based luminous crystal film by metal organic chemical vapor deposition is characterized in that comprising step: I, Ga (CH in molar ratio
3)
3: rare earth organic complex: A (CH
3)
3=(1-x-y): x: y, 0.1%≤x≤10.0%, 0.1x≤y≤x raw materials weighing Ga (CH
3)
3, rare earth organic complex and trimethyl-boron or trimethylaluminium, be positioned over respectively in each bubbler in the device; II, GaN base substrate is placed the reactor drum of metal organic chemical vapor deposition, with H
2For carrier, with NH
3Be nitrogenous source, and GaN base substrate is heat-treated, maintain the temperature at 1020 ℃-1060 ℃; III, regulate and control each bubbler temperature, control growing speed is at 1-3 μ m/h; IV, naturally cooling substrate promptly get rare earth ion and B to room temperature
3+Or Al
3+The GaN crystal film of mixing altogether.
Further, the method for aforesaid electron beam evaporation growing GaN-based luminous crystal film, 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 luminous crystal film by metal organic chemical vapor deposition of the present invention, its advantage is:
Owing to adopted the organic coordination compound and the rare earth organic complex of III family element boron or aluminium 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, and then 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.
Therefore, the present invention proposes a kind of method of growing GaN-based luminous crystal film by metal organic chemical vapor deposition, doping with rare-earth ions in process of growth replaces part Ga
3+Lattice site, in the composition of raw materials of said GaN crystal film, mix especially trimethyl-boron or trimethylaluminium in proportion, get into the GaN lattice, allotment rare earth ion and Ga at boron described in the process of growth or aluminium with the form of trivalent ion
3+Between ionic radius poor.Wherein said composition of raw materials molar ratio is: Ga (CH
3)
3: rare earth organic complex: A (CH
3)
3=(1-x-y): x: y, wherein rare earth organic complex is meant with the rare earth element Re to be the Re (TMHD) of core
3Or Re (i-PrCp)
3, Re refers to is any one or multiple using with 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; A representes III family element boron or aluminium; 0.1%≤x≤10.0%, 0.1x≤y≤x.
Below, specify procedure of the present invention through some concrete embodiment:
Embodiment 1:
In this example, x=0.1%, y=0.01%, Re are rare earth element er Er, A is element boron (B).Above-mentioned load weighted raw material is loaded on respectively in the bubbler in the MOCVD device (following all refer to Bubbler), with H
2As carrier gas, with NH
3As nitrogenous source, substrate selects growth that the sapphire of GaN film is arranged, and underlayer temperature is 1020 ℃, and growth velocity is controlled at 3 μ m/h, finally obtain the crystal film of 5 μ m thickness after, the cooling substrate 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 element er Er, A is element boron (B).Above-mentioned load weighted raw material is loaded on respectively in the Bubbler in the MOCVD device, with H
2As carrier gas, with NH
3As nitrogenous source, substrate selects growth that the silicon of GaN film is arranged, and underlayer temperature is 1040 ℃, and growth velocity is controlled at 2 μ m/h, finally obtain the crystal film of 5 μ m thickness after, the cooling substrate 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 element er Er, A is element boron (B).Above-mentioned load weighted raw material is loaded on respectively in the Bubbler in the MOCVD device, with H
2As carrier gas, with NH
3As nitrogenous source, substrate selects growth that the sapphire of GaN film is arranged, and underlayer temperature is 1060 ℃, and growth velocity is controlled at 1 μ m/h, finally obtain the crystal film of 5 μ m thickness after, the cooling substrate 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 4:
In this example, x=5%, y=0.5%, Re are REE thulium Tm, and A is metallic element aluminium (Al).Above-mentioned load weighted raw material is loaded on respectively in the Bubbler in the MOCVD device, with H
2As carrier gas, with NH
3As nitrogenous source, substrate selects growth that the sapphire of GaN film is arranged, and underlayer temperature is 1040 ℃, and growth velocity is controlled at 2 μ m/h, finally obtain the crystal film of 5 μ m thickness after, the cooling substrate 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=2%, y=0.2%, Re are rare earth elements europium Eu, A is metallic element aluminium (Al).Above-mentioned load weighted raw material is loaded on respectively in the Bubbler in the MOCVD device, with H
2As carrier gas, with NH
3As nitrogenous source, substrate is selected HVPE Grown GaN block, and underlayer temperature is 1040 ℃, and growth velocity is controlled at 2 μ m/h, finally obtain the crystal film of 5 μ m thickness after, the cooling substrate 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=2%, y=0.2%, Re are REE terbium Tb, and A is metallic element aluminium (Al).Above-mentioned load weighted raw material is loaded on respectively in the Bubbler in the MOCVD device, with H
2As carrier gas, with NH
3As nitrogenous source, substrate is selected HVPE Grown GaN block, and underlayer temperature is 1040 ℃, and growth velocity is controlled at 2 μ m/h, finally obtain the crystal film of 5 μ m thickness after, the cooling substrate 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 Tb
3+The GaN crystal film, fluorescence intensity strengthens 5%-20%.
Claims (4)
1. the method for growing GaN-based luminous crystal film by metal organic chemical vapor deposition, 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 trimethyl-boron or trimethylaluminium in proportion, get into the GaN lattice, allotment rare earth ion and Ga with the form of trivalent ion at boron described in the process of growth or aluminium
3+Between ionic radius poor; Said composition of raw materials molar ratio is: Ga (CH
3)
3: rare earth organic complex: A (CH
3)
3=(1-x-y): x: y, wherein rare earth organic complex is meant with the rare earth element Re to be the Re (TMHD) of core
3Or Re (i-PrCp)
3, A representes III family element boron or aluminium, 0.1%≤x≤10.0%, 0.1x≤y≤x.
2. the method for growing GaN-based luminous crystal film by metal organic chemical vapor deposition according to claim 1 is characterized in that: said REE 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 luminous crystal film by metal organic chemical vapor deposition is characterized in that comprising step:
I, Ga (CH in molar ratio
3)
3: rare earth organic complex: A (CH
3)
3=(1-x-y): x: y, A represent III family element boron or aluminium, 0.1%≤x≤10.0%, 0.1x≤y≤x, raw materials weighing Ga (CH
3)
3, rare earth organic complex and trimethyl-boron or trimethylaluminium, be positioned over respectively in each bubbler in the device, wherein said rare earth organic complex is for being the Re (TMHD) of core with the rare earth element Re
3Or Re (i-PrCp)
3
II, GaN base substrate is placed the reactor drum of metal organic chemical vapor deposition, with H
2For carrier, with NH
3Be nitrogenous source, and GaN base substrate is heat-treated, maintain the temperature at 1020 ℃-1060 ℃;
III, regulate and control each bubbler temperature, control growing speed is at 1-3 μ m/h;
IV, naturally cooling substrate promptly get rare earth ion and B to room temperature
3+Or Al
3+The GaN crystal film of mixing altogether.
4. the method for growing GaN-based luminous crystal film by metal organic chemical vapor deposition 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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| KR20110093856A (en) * | 2008-11-07 | 2011-08-18 | 더 리전츠 오브 더 유니버시티 오브 캘리포니아 | Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-iii nitride crystals |
| CN103173221B (en) * | 2013-03-20 | 2014-12-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Upconversion fluorescent material and preparation method thereof |
| DE102019212821A1 (en) * | 2019-08-27 | 2021-03-04 | Albert-Ludwigs-Universität Freiburg | Method and device for the production of a layer, the substrate provided therewith and the use thereof |
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