CN105006427B - A kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer - Google Patents

A kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer Download PDF

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CN105006427B
CN105006427B CN201510470018.2A CN201510470018A CN105006427B CN 105006427 B CN105006427 B CN 105006427B CN 201510470018 A CN201510470018 A CN 201510470018A CN 105006427 B CN105006427 B CN 105006427B
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gallium nitride
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gallium
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CN105006427A (en
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张志荣
尹甲运
房玉龙
芦伟立
冯志红
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CETC 13 Research Institute
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02455—Group 13/15 materials
    • H01L21/02458—Nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H01L21/205—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy using reduction or decomposition of a gaseous compound yielding a solid condensate, i.e. chemical deposition
    • H01L21/2056—Epitaxial deposition of AIIIBV compounds

Abstract

The invention discloses a kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer, it is related to technical field of semiconductors.This method comprises the following steps：1）Using MOCVD technologies, after being heat-treated at high temperature to substrate, cooling；2）In one layer of low-temperature nitride forming core layer of Grown；3）Annealing, realize that forming core layer crystallizes；4）Temperature is raised, grows one layer of gallium nitride on forming core layer after annealing；5）Stopping is passed through gallium source, and stop growing gallium nitride, cooling；6）Continue to be passed through gallium source growing gallium nitride, and raise temperature；7）Grow insert layer, channel layer, cap and passivation layer successively on that gallium nitride layer, the epitaxial structure completed.The present invention effectively reduces epitaxial layer of gallium nitride dislocation density using low temperature buffer layer, improves gallium nitride quality, and then improve the service life and efficiency of gallium-nitride-based devices.

Description

A kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer
Technical field
The present invention relates to technical field of semiconductors, more particularly to one kind to be grown outside high-quality gallium nitride using low temperature buffer layer Prolong the method for structure.
Background technology
As the Typical Representative of third generation semiconductor, gallium nitride material is due to wide energy gap, high velocity of electrons The features such as, gallium-nitride-based devices are widely used in the electronic systems such as radio communication, radar in microwave, millimeter wave frequency band, in photoelectricity Son and microelectronic development prospect are very wide.
At present, the main method for obtaining gallium nitride epitaxial materialses is by including nitridation in substrate Epitaxial growth, substrate Gallium, sapphire, carborundum, aluminium nitride and silicon-based substrate etc..It is but larger due to existing between gallium nitride material and substrate Lattice mismatch and thermal expansion mismatch,（It is 16% such as with sapphire mismatch, is 3.4% with carborundum mismatch, is with silicon substrate mismatch 17%）So that the gallium nitride epitaxial materialses of growth introduce substantial amounts of dislocation and defect, and defect concentration is up to 108~1010 cm-2, And then it have impact on the service life and service efficiency of gallium-nitride-based devices.
The method of traditional growing gallium nitride epitaxial material is, first in one layer of nitride forming core layer of Grown, so Continuous high temperature growing gallium nitride epitaxial material on forming core layer after annealing crystallization afterwards.Due to the nitride forming core layer of low-temperature epitaxy In the presence of substantial amounts of dislocation and defect, nucleus is second-rate, on this basis during high growth temperature gallium nitride epitaxial materialses, due to lattice Mismatch dislocation and defect caused by mismatching with thermal expansion to continue to extend, the dislocation and defect of gallium nitride epitaxial materialses are still very More, epitaxial material crystal mass is still very poor.
The content of the invention
The technical problems to be solved by the invention are to provide one kind using low temperature buffer layer growth high-quality gallium nitride extension The method of structure, it is by during growing gallium nitride, insertion one layer of low temperature buffer layer of growth, further lifting gallium nitride Crystal mass, improve the efficiency and service life of device.
In order to solve the above technical problems, the technical solution used in the present invention is：One kind is high using low temperature buffer layer growth The method of quality gallium nitride epitaxial structure, this method comprise the following steps：
1）Using MOCVD technologies, after being heat-treated at high temperature to substrate, cooling；
2）In one layer of low-temperature nitride forming core layer of Grown；
3）Annealing, realize that forming core layer crystallizes；
4）Temperature is raised, grows one layer of gallium nitride on forming core layer after annealing；
5）Stopping is passed through gallium source, and stop growing gallium nitride, cooling；
6）Continue to be passed through gallium source growing gallium nitride, and raise temperature；
7）Grow insert layer, channel layer, cap and passivation layer successively on that gallium nitride layer, the epitaxy junction completed Structure.
Preferably, the step 1）In substrate for gallium nitride, sapphire, SiC, Si, AlN, SiO2, diamond, graphite Any one in alkene.
Preferably, the step 1）The MOCVD technologies of middle use, made by the use of ammonia as nitrogen source, nitrogen or hydrogen For carrier gas, trimethyl gallium or triethyl-gallium, trimethyl aluminium, trimethyl indium are respectively as gallium source, silicon source and indium source, and silane is as silicon Source.
Preferably, the step 2）The temperature of middle growing nitride forming core layer is 20 DEG C~1000 DEG C of room temperature, forming core thickness Spend for 0~100nm.
Preferably, the step 3）Middle annealing temperature is 600 DEG C~1200 DEG C, and annealing time is 0~1000s.
Preferably, the step 4）On forming core layer after annealing grow one layer of gallium nitride growth temperature for 800 DEG C~ 1300 DEG C, thickness is 0~1 μm；
Preferably, the step 5）Middle rate of temperature fall is 0~1000 DEG C/s, and temperature is 20 DEG C~1000 DEG C.
It is using beneficial effect caused by above-mentioned technical proposal：The present invention is in sapphire or carborundum or silicon substrate etc. In foreign substrate, one layer of nitride forming core layer of low-temperature epitaxy, then after to forming core layer annealing crystallization, high growth temperature layer Gallium nitride, then stop be passed through gallium source and cool, formed low temperature buffer layer, i.e., " dead level ", then rise temperature continued growth Gallium nitride epitaxial materialses；The presence of " dead level ", releases stress, blocks a part of dislocation and continues to extend, reduces gallium nitride The dislocation density of epitaxial material, improve the crystal mass of gallium nitride epitaxial materialses.The present invention can utilize low temperature " dead level " effective Reduce epitaxial layer of gallium nitride dislocation density, improve gallium nitride quality, and then improve gallium-nitride-based devices service life and Efficiency, while the present invention has wider growth technique window.
Brief description of the drawings
Fig. 1 is flow chart of the present invention；
Fig. 2 is the temperature curve of traditional Grown on Sapphire Substrates epitaxy of gallium nitride；
Fig. 3 is the temperature curve of growing gallium nitride extension on a sapphire substrate of the invention；
Fig. 4 is the gallium nitride sample of this example（102）X ray double crystal diffraction curve, abscissa are ω scanning direction angles （Arc s）, ordinate is relative intensity.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made Embodiment, belong to the scope of protection of the invention.
As shown in figure 1, the present invention provides a kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer, By taking Sapphire Substrate as an example, comprise the following steps：
1）Using MOCVD technologies, Sapphire Substrate is heat-treated in MOCVD reative cells：In a hydrogen atmosphere, temperature is tieed up Hold at 800 DEG C~1300 DEG C, continue 300 s to 2000s；Then cool, MOCVD technologies therein, be by the use of ammonia as Nitrogen source, nitrogen or hydrogen are as carrier gas, and trimethyl gallium or triethyl-gallium, trimethyl aluminium, trimethyl indium are respectively as gallium source, aluminium Source and indium source, silane is as silicon source.
2）In one layer of low-temperature nitride forming core layer of Grown：Wherein the growth temperature of forming core layer is 20 DEG C~1000 DEG C, chamber pressure is 50~500mbar, V/III about 300~3000, forming core thickness degree is 0~100nm.
3）Annealing, realize that forming core layer crystallizes：Reaction chamber temperature is increased to annealing temperature：600 DEG C~1200 DEG C, annealing time For 0~1000s, make nitride forming core layer remaining a small amount of nucleus after annealing.
4）Raise and grow one layer of gallium nitride on the forming core layer of temperature after annealing：Wherein growth temperature is 800 DEG C~1300 DEG C, chamber pressure is the mbar of 100 mbar~1000, V/III about 300~400.
5）Stop growing gallium nitride, cooling：Under NH3 atmosphere protections, stopping is passed through trimethyl gallium, and rate of temperature fall is 0~ 1000 DEG C/s, temperature is 20 DEG C~1000 DEG C, and chamber pressure is constant, as shown in Figure 3.
6）Heating, continued growth gallium nitride：Trimethyl gallium source is passed through, is heated up, wherein growth temperature is 800 DEG C~1300 DEG C, chamber pressure is the mbar of 100 mbar~1000, V/III about 300~400.
7）Insert layer, channel layer, cap and passivation layer are grown successively in gallium nitride layer, obtain complete epitaxial structure.
As shown in figure 4, the gallium nitride sample of case study on implementation of the present invention（102）X-ray diffraction twin crystal curve, wherein horizontal seat It is designated as ω scanning direction angles（Second of arc）, ordinate is relative intensity；X-ray diffraction twin crystal curve halfwidth degree very little, about 300 Second of arc, illustrate that the gallium nitride quality that the present invention obtains is improved, and then improve the service life and efficiency of device, simultaneously should Method growing gallium nitride epitaxial structure has very wide growth technique window.

Claims (6)

  1. A kind of 1. method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer, it is characterised in that：This method includes Following steps：
    1）Using MOCVD technologies, after being heat-treated at high temperature to substrate, cooling；
    2）In one layer of low-temperature nitride forming core layer of Grown；
    3）Annealing, realize that forming core layer crystallizes；
    4）Temperature is raised, grows one layer of gallium nitride on forming core layer after annealing；
    5）Stopping is passed through gallium source, and stop growing gallium nitride, cooling；
    6）Continue to be passed through gallium source growing gallium nitride, and raise temperature；
    7）Grow insert layer, channel layer, cap and passivation layer successively on that gallium nitride layer, the epitaxial structure completed；
    The step 5）Middle rate of temperature fall is 0~1000 DEG C/s, and temperature is 20 DEG C~1000 DEG C.
  2. 2. a kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer according to claim 1, its It is characterised by：The step 1）In substrate for gallium nitride, sapphire, SiC, Si, AlN, SiO2, diamond, in graphene Any one.
  3. 3. a kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer according to claim 1, its It is characterised by：The step 1）The MOCVD technologies of middle use, be by the use of ammonia as nitrogen source, nitrogen or hydrogen as carrier gas, Trimethyl gallium or triethyl-gallium, trimethyl aluminium, trimethyl indium are respectively as gallium source, silicon source and indium source, and silane is as silicon source.
  4. 4. a kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer according to claim 1, its It is characterised by：The step 2）The temperature of middle growing nitride forming core layer is 20 DEG C~1000 DEG C of room temperature, forming core thickness degree is 0~ 100nm。
  5. 5. a kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer according to claim 1, its It is characterised by：The step 3）Middle annealing temperature is 600 DEG C~1200 DEG C, and annealing time is 0~1000s.
  6. 6. a kind of method that high-quality gallium nitride epitaxial structure is grown using low temperature buffer layer according to claim 1, its It is characterised by：The step 4）The growth temperature that one layer of gallium nitride is grown on forming core layer after annealing is 800 DEG C~1300 DEG C, Thickness is 0~1 μm.
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CN110517950B (en) * 2019-07-29 2021-06-18 太原理工大学 Method for preparing sphalerite GaN film on diamond substrate
CN111681953B (en) * 2020-05-20 2022-08-16 中国电子科技集团公司第五十五研究所 Growth method for improving interface quality of gallium nitride heteroepitaxy
CN112687525B (en) * 2020-12-24 2022-07-22 中国电子科技集团公司第五十五研究所 Epitaxial method for improving quality of ultrathin gallium nitride field effect transistor

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