CN106328772A - Preparation method of high-quality nitride epitaxial wafer - Google Patents

Preparation method of high-quality nitride epitaxial wafer Download PDF

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Publication number
CN106328772A
CN106328772A CN201610739620.6A CN201610739620A CN106328772A CN 106328772 A CN106328772 A CN 106328772A CN 201610739620 A CN201610739620 A CN 201610739620A CN 106328772 A CN106328772 A CN 106328772A
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source
nitride
growth
buffer layer
nitride buffer
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CN106328772B (en
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王国宏
李志聪
王明洋
戴俊
闫其昂
孙军
孙一军
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YANGZHOU ZHONGKE SEMICONDUCTOR LIGHTING CO Ltd
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YANGZHOU ZHONGKE SEMICONDUCTOR LIGHTING CO Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/12—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Led Devices (AREA)

Abstract

The invention provides a preparation method of a high-quality nitride epitaxial wafer, relates to the technical field of growth of a light-emitting diode epitaxial wafer. A nitride buffer layer and a nitride layer are sequentially formed on a substrate through epitaxial growth; when the nitride buffer layer grows in an epitaxial manner, a V N source precursor and an III metal organic compound are introduced; and the V N source precursor is a mixture formed by an organic nitrogen source and NH3 with a low decomposition temperature. By simultaneously adopting the organic nitrogen source and the NH3 with the low decomposition temperature as an N source required for epitaxial growth and adjusting the ratio of the organic nitrogen source to the NH3, growth of the nitride buffer layer is improved, seed crystal with a relatively small number and relatively large grains is obtained and the enough active N source is obtained under the condition of an optimized V/III ratio, so that the quality of the nitride epitaxial wafer is improved.

Description

A kind of preparation method of high-quality nitride epitaxial sheet
Technical field
The present invention relates to the growing technology field of a kind of LED epitaxial slice.
Background technology
Group III-nitride (InN, GaN and AlN) and relevant multi-element compounds thereof are as very important broad-band gap half Conductor material, plays an important role in the semiconductor device, especially for photoelectric device.
LED growth technology, due to substrate used and extension interlayer lattice paprmeter and the difference of thermal coefficient of expansion, causes There is more dislocation defects in Material growth, affect device performance, report at present is main by patterned substrate technology or substrate The nitride buffer layer technology of upper growing AIN or GaN, obtains negligible amounts, nitride seed that crystal grain is bigger at nucleating layer, changes The crystal mass of kind GaN, AlGaN and InGaN epitaxial nitride layer.Improve nitride epitaxial layer crystal mass the most further to depend on Old is service workers's research emphasis.
Summary of the invention
The present invention seeks to propose the preparation method of a kind of high-quality nitride epitaxial sheet.
The present invention is epitaxially-formed nitride buffer layer and nitride layer on substrate successively, at epitaxial growth nitride During cushion, it is passed through V race N source predecessor and III metallo-organic compound；The invention have the characteristics that described V race N source forerunner Thing is the organic nitrogen source by low decomposition temperature and NH3The mixture of composition.
The present invention is by using organic nitrogen source and the NH of low decomposition temperature simultaneously3For the N source needed for epitaxial growth, allocate two Person's ratio, under the conditions of the V/III ratio optimized, improves the growth of nitride buffer layer, it is thus achieved that the crystalline substance that negligible amounts, crystal grain are bigger Kind, it is thus achieved that sufficient active N source, to improve the quality of nitride epitaxial sheet.
It addition, when nitride buffer layer described in epitaxial growth, described V race N source predecessor closes with III Organometallic The mixed volume ratio of thing is 50～200: 1, the organic nitrogen source of low decomposition temperature and NH in the predecessor of described V race N source3Mixture Long-pending ratio is 0.01～1: 1.
It is in the range of 50～200: 1 at V race N source predecessor mixed volume metal-organic with III ratio, than It is easier to regulation and control and grows the dividing potential drop of Shi Ge race source of the gas, and then growing environment is realized regulation and control, it is achieved AlN nitride buffer layer two dimension The switching that planar growth grows with three dimensional structure.
And the organic nitrogen source of low decomposition temperature and NH in the predecessor of V race N source3Mixed volume than the model in 0.01～1: 1 When enclosing interior, the organic nitrogen source of low decomposition temperature primarily serves the allotment effect of N source supply, because its decomposition temperature is on the low side, in temperature I.e. can reach the decomposition efficiency of more than 50% under conditions of being 400～600 DEG C, therefore during low-temperature epitaxy nitride buffer layer, regulate and control low The supply ratio of temperature organic nitrogen source, can control the delivery rate of N, and NH3Reach higher decomposition efficiency, its decomposition temperature Need more than 800 DEG C, therefore NH during low-temperature nitride buffer growth3Primarily serve maintenance V race N source predecessor and III gold Belong to the effect of the flow proportional of organic compound.
Preferably, the organic nitrogen source of low decomposition temperature of the present invention is uns-dimethylhydrazine or phenylhydrazine.
Use low decomposition temperature organic nitrogen source uns-dimethylhydrazine or phenylhydrazine and NH3Mixing, can basis as N source predecessor The ratio needing to allocate organic nitrogen source with NH3 of growth morphology, when needs planar growth, organic by strengthening low decomposition temperature The ratio in nitrogen source, at a low growth temperature, promotes that more N sources predecessor separates, and makes N source be easier to adsorb on substrate, in shape When becoming nitride film, III metal is prone to form two dimensional surface growth by the distribution of atom N, strengthens nitride film Nucleation probability, and then obtain more plane wider space.When needs three dimensional growth, by reducing low decomposition temperature organic nitrogen source Ratio, make N source be in under-supply state, at a low growth temperature, on the low side in conjunction with self mobility of III metallic atom Feature, the growth that easily occurs to reunite forms three dimensional structure.Nitride buffer layer grows through two dimensional surface growth and three dimensional structure The switching regulation and control of growth, promote Stress Release during subsequent nitride growth.
It addition, the epitaxial growth temperature of described nitride buffer layer is 400～600 DEG C, growth atmosphere is H2。
Nitride buffer layer growth temperature controls when 400～600 DEG C, is mostly derived from described low temperature organic nitrogen source at this point The decomposition efficiency of more than 50% is i.e. can reach at a temperature of solution.This decomposition efficiency favorably provides sufficient active N, promotes that N is at substrate Absorption, and then promote the two dimensional surface growth of nitride buffer layer.Additionally inclined because of III metallic atom mobility at low temperatures Low, therefore nitride buffer layer growth temperature controls, 400～600 DEG C of growths, favorably to realize the life of three dimensional structure by this feature Long, this growth temperature combines the allotment of both the above N source predecessor ratio and V race N source predecessor and III metallic compound The allotment of flow proportional, it is achieved the growth of nitride buffer layer two dimensional surface regulates and controls with the switching of three dimensional structure growth.
The growth atmosphere of nitride buffer layer is H2, utilize H2There is higher heat-conductive characteristic, can preferably transmit input Heat, keep being uniformly distributed of growing environment temperature, and then promote the homogeneity of Material growth.
Detailed description of the invention
Embodiment 1:
The present invention provides a kind of GaN base epitaxial growth method, it is adaptable to prepare high brightness GaN-based LED, the method step As follows:
1, growing one layer of nitride buffer layer on a sapphire substrate: growth temperature 400～600 DEG C, pressure is 65000Pa, raw Long N source is uns-dimethylhydrazine and NH3, uns-dimethylhydrazine and NH3Mixed volume ratio be 0.01～1: 1, and it is organic to be passed through III metal Compound.
V race N source mixed precursor (i.e. uns-dimethylhydrazine and NH3) mixed volume ratio metal-organic with III be 50～200: 1.
During growth, atmosphere is H2, and use mixed above than being passed through N source and III source metal, form nitride buffer layer Thickness is 30nm.
2, liter high-temperature is to 1000～1250 DEG C, grown nitride layer on nitride buffer layer: pressure is 40000Pa, Growth N source is uns-dimethylhydrazine and NH3Mixture, uns-dimethylhydrazine and NH3Mixed volume ratio be 0.01～1: 1, be passed through III simultaneously Race's metallo-organic compound.
V race N source mixed precursor (i.e. uns-dimethylhydrazine and NH3) mixed volume ratio metal-organic with III be 50～200: 1.
During growth, atmosphere is H2, and use mixed above than being passed through N source and III source metal, form nitride buffer layer Thickness is 3 μm.
Embodiment 2:
The present embodiment differs only in embodiment one: uns-dimethylhydrazine is replaced by phenylhydrazine.
Going out equally and can be formed epitaxially one after the other nitride buffer layer and nitride layer on a sapphire substrate, properties of product are suitable With upper example product.

Claims (4)

1. a preparation method for high-quality nitride epitaxial sheet, substrate is epitaxially-formed successively nitride buffer layer and Nitride layer, when epitaxial growth nitride buffer layer, is passed through V race N source predecessor and III metallo-organic compound；It is special Levy and be: described V race N source predecessor is the organic nitrogen source by low decomposition temperature and NH3The mixture of composition.
Preparation method the most according to claim 1 and 2, it is characterised in that: when nitride buffer layer described in epitaxial growth, Described V race N source predecessor mixed volume metal-organic with III ratio is 50～200: 1, described V race N source predecessor In the organic nitrogen source of low decomposition temperature and NH3Mixed volume ratio be 0.01～1: 1.
Preparation method the most according to claim 1 and 2, it is characterised in that: the organic nitrogen source of described low decomposition temperature is inclined Dimethylhydrazine or phenylhydrazine.
Preparation method the most according to claim 3, it is characterised in that: the epitaxial growth temperature of described nitride buffer layer is 400～600 DEG C, growth atmosphere is H2。
CN201610739620.6A 2016-08-29 2016-08-29 A kind of preparation method of high quality nitride epitaxial piece Active CN106328772B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023092717A1 (en) * 2021-11-26 2023-06-01 江苏第三代半导体研究院有限公司 Semiconductor epitaxial wafer and manufacturing method therefor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020136932A1 (en) * 2001-03-21 2002-09-26 Seikoh Yoshida GaN-based light emitting device
CN101340058A (en) * 2007-07-02 2009-01-07 三菱电机株式会社 Nitride semiconductor stacked structure and semiconductor optical device, and methods for manufacturing the same
CN102903615A (en) * 2012-10-18 2013-01-30 中山大学 Preparation method of p type GaN and AlGaN semiconductor material
CN105023829A (en) * 2014-04-25 2015-11-04 三星电子株式会社 Method of growing nitride single crystal and method of manufacturing nitride semiconductor device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020136932A1 (en) * 2001-03-21 2002-09-26 Seikoh Yoshida GaN-based light emitting device
CN101340058A (en) * 2007-07-02 2009-01-07 三菱电机株式会社 Nitride semiconductor stacked structure and semiconductor optical device, and methods for manufacturing the same
CN102903615A (en) * 2012-10-18 2013-01-30 中山大学 Preparation method of p type GaN and AlGaN semiconductor material
CN105023829A (en) * 2014-04-25 2015-11-04 三星电子株式会社 Method of growing nitride single crystal and method of manufacturing nitride semiconductor device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023092717A1 (en) * 2021-11-26 2023-06-01 江苏第三代半导体研究院有限公司 Semiconductor epitaxial wafer and manufacturing method therefor

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