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WO1999036968A1 - Procedes servant a fabriquer des couches minces a semi-conducteur au moyen d'une synthese de faisceaux ioniques - Google Patents

Procedes servant a fabriquer des couches minces a semi-conducteur au moyen d'une synthese de faisceaux ioniques Download PDF

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Publication number
WO1999036968A1
WO1999036968A1 PCT/GB1999/000127 GB9900127W WO9936968A1 WO 1999036968 A1 WO1999036968 A1 WO 1999036968A1 GB 9900127 W GB9900127 W GB 9900127W WO 9936968 A1 WO9936968 A1 WO 9936968A1
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WO
WIPO (PCT)
Prior art keywords
thin film
layer
nitride
ions
disordered
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1999/000127
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English (en)
Inventor
Sembukuttiarachilage Ravi Pradip Silva
Serrita Avril Almeida
Brian John Sealy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Surrey
Original Assignee
University of Surrey
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Surrey filed Critical University of Surrey
Publication of WO1999036968A1 publication Critical patent/WO1999036968A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi

Definitions

  • This invention relates to methods for manufacturing semiconductor thin films and to thin films produced by such methods .
  • the invention relates to the manufacture of thin films of disordered R nitride (d-RN) , where R is at least one Group III metal; that is, at least one metal selected from Ga, Al and In.
  • R is at least one Group III metal; that is, at least one metal selected from Ga, Al and In.
  • the invention relates particularly, though not exclusively, to the manufacture of a thin film of disordered gallium nitride (d-GaN) .
  • d-GaN disordered gallium nitride
  • Crystalline gallium nitride (c-GaN) and its ternary alloys GalnN and GaAlN have proved to be excellent electroluminescent materials and have found particular application in the production of light emitting diodes and lasers.
  • the manufacture of these materials has presented serious technical problems which have been difficult to overcome. More specifically, the material needs to be grown on a lattice- matched substrate using a deposition technique such as metalorganic chemical vapour deposition (MOCVD) or molecular beam epitaxy. These techniques are not suited to the production of large-area thin films for use in applications such as flat panel displays.
  • MOCVD metalorganic chemical vapour deposition
  • molecular beam epitaxy molecular beam epitaxy
  • d-GaN Disordered GaN
  • a method for manufacturing a thin film of disordered R nitride (d-RN) , where R is at least one Group III metal the method including using an ion implantation process to combine atoms of said at least one metal R and atoms of nitrogen in a layer made from an amorphous, crystalline or polycrystalline material.
  • the thin film may be a continuous thin film; alternatively, the thin film may be a discontinuous thin film, such as a film containing colloids or precipitates.
  • the method of this invention obviates the need for use of a lattice-matched substrate, can be readily implemented on a commercial scale and is particularly, though not exclusively, suited to the manufacture of large-area thin films as may be used, for example, in the production of flat panel displays. More specifically, the method of this invention employs an ion implantation process, a process which is widely used in the semiconductor industry as an industrial standard.
  • the method includes implanting ions of said at least one metal R in a said layer made from amorphous silicon nitride (a-SiN) .
  • amorphous silicon nitride is preferably hydrogenated amorphous silicon nitride (a-SiN:H) .
  • Such a layer can be formed using existing deposition techniques which are already widely used for industrial -scale production and which are particularly suitable for the manufacture of large-area substrates.
  • Figures 1 (a) and 1 (b) illustrate Rutherford Back-Scattering (RBS) spectra obtained from a layer of hydrogenated amorphous silicon nitride before and after implantation with gallium ions , and
  • Figures 2 (a) and 2 (b) illustrate the variation of Ga Auger parameter as a function of depth obtained from a layer of hydrogenated amorphous silicon nitride which has been implanted with gallium ions respectively before and after annealing .
  • gallium ions are implanted in a layer of hydrogenated amorphous silicon nitride (a-SiN:H) .
  • One effect of the implantation process is to cause existing chemical bonds between atoms of silicon and nitrogen to break and to create new bonds between atoms of gallium and nitrogen whereby to form a thin film of disordered gallium nitride (d- GaN)
  • the ratio ⁇ of the number of nitrogen atoms to the number of silicon atoms should be greater than or equal to 1.5.
  • This can be accomplished by providing or forming a layer of nitrogen-rich a-SiN, that is a layer having the composition SiN x , where x > 1.5.
  • the layer may have the composition SiN x , where x ⁇ 1.5, and additional nitrogen ions are co-implanted with the gallium ions (with or without hydrogen ions) to give an overall value of ⁇ greater than or equal to 1.5.
  • the amorphous silicon nitride is preferably hydrogenated.
  • the layer of amorphous silicon nitride can conveniently be formed from a mixture of SiH 4 (silane) and NH 3 (ammonia) using a known plasma enhanced chemical vapour deposition (PECVD) technique .
  • PECVD plasma enhanced chemical vapour deposition
  • Ions and radicals produced in the plasma are deposited onto a substrate due to a small electrical self-bias developed between the substrate and the plasma.
  • the substrate is typically held at a temperature in the range 250°C to 350°C during the deposition process, and suitable substrate 5 materials include silicon, quartz and glass.
  • the proportion of ammonia in the gas mixture will be higher than that used to produce stoichiometric amorphous silicon nitride, the proportion of ammonia being suitably adjusted according to the required composition.
  • regions of unconverted a-SiN may remain in the layer following implantation of gallium ions. At least some of these regions may subsequently be converted to d-GaN by implanting additional nitrogen, and possibly hydrogen ions following the implantation of gallium ions.
  • Formation of d-GaN may be assisted by heating the layer of amorphous silicon nitride during the implantation process, typically at a temperature in the range from 20° to 350°C, but preferably at about 200°C.
  • the quality of the resultant thin film can be improved by subjecting it to thermal annealing, again typically at a temperature in the range 20°C to 350°C.
  • the resultant thin film may be subjected to rapid thermal annealing or laser thermal processing.
  • a layer of nitrogen-rich hydrogenated amorphous silicon nitride approximately 0.2 ⁇ m thick having the composition SiN x 6 was deposited on a silicon substrate and implanted with gallium ions having a relatively high flux density ( ⁇ 5x10 16 ions/cm 2 ) and a relatively low ion energy (50keV) . Following implantation the layer was annealed at 200°C for 20 mins .
  • Figures 1(a) and 1(b) show Rutherford Back-Scattering (RBS) spectra obtained from the layer respectively before and after implantation with gallium ions, and illustrate the relative proportions, as a function of depth, of silicon and nitrogen atoms and of silicon, nitrogen and gallium atoms (prior to annealing) .
  • RBS Rutherford Back-Scattering
  • Figures 2 (a) and 2 (b) illustrate the variation of Ga Auger parameter with respect to a GaN standard obtained from samples prepared by the described process respectively before and after annealing, as the samples are progressively etched.
  • these Figures represent the variation of Ga Auger parameter as a function of sample depth.
  • the Ga Auger parameter derived from a sample before etching is close to that for GaN, but only in a relatively thin surface region of the layer. At greater depths the Ga Auger parameter approaches that for elemental Ga.
  • the Ga Auger parameter derived from the sample after annealing is close to that for GaN over a much greater range of depths, but approaches that for elemental Ga just below the surface of the layer.
  • gallium ions can be implanted at greater depths using a higher ion energy, and a range of different ion energies may be used with a view to obtaining a desired gallium profile as a function of depth.
  • the thickness of thin films produced by these processes will be dependent upon the chosen operational parameters, particularly ion energy and annealing temperature, but may typically be in the range 0. l ⁇ m to l.O ⁇ m.
  • gallium ions need not necessarily be implanted into a layer made from a nitrogen- containing material such as hydrogenated amorphous silicon nitride .
  • gallium ions and nitrogen ions and optionally hydrogen ions are co-implanted in a layer made from an amorphous, crystalline or polycrystalline material which contains no nitrogen.
  • Suitable amorphous materials include glass, polymers and quartz.
  • a relatively high dose e.g. >10 16 ion cm "2
  • nitrogen ions was implanted in the substrate to make the substrate nitrogen rich, followed by a comparable dose of gallium and optionally hydrogen ions.
  • the order of implantation could be reversed.
  • the implantation energies need to be tailored to ensure that the implantation depth is the same for both kinds of ion. Therefore, because gallium ions are larger than 8 nitrogen and hydrogen ions and penetrate less deeply into the substrate, the ion energy of the gallium ions needs to be correspondingly higher than that of the nitrogen and hydrogen ions .
  • the layer is made from a rigid, self-supporting amorphous material a separate support substrate may not be needed.
  • the layer is subjected to heating and/or annealing the operating temperature used would need to be well below the melting temperature of the amorphous material and of the substrate, if provided.
  • the invention is not restricted to the implantation of gallium ions; in general, the implanted ions may be of at least one Group III metal; that is, at least one metal selected from Ga, In and Al . Accordingly, the invention can be used to synthesise a thin film of disordered R nitride, where R is at least one metal selected from Ga, In and Al ; including the other binary alloys AlN and InN, the ternary alloys GalnN, GaAlN and InAlN and nitrides containing mixed doses of Ga,In and Al .
  • Dopant atoms e.g. Si,Mg, may also be included in the structure to modify and control the electrical properties of the disordered semiconductor thin film material .
  • d-GaN shows promise as an electronic grade thin film having low electron affinity. Accordingly it is believed that material according to the invention can be used, inter alia, as an electron field emitter, or as a thin film conductor for use in smart devices, for example.
  • material manufactured according to the invention can be used as a "seed" substrate for the growth/deposition of the corresponding polycrystalline materials.
  • the film finds application as an electroluminescent, phosphorescent or cathodoluminescent material .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Led Devices (AREA)

Abstract

On fabrique une couche mince de GaN désordonné (d-Gan) au moyen d'un procédé d'implantation d'ions afin de combiner des atomes de Ga et de N dans une couche constituée par un matériau amorphe. Dans un mode de réalisation, on implante des ions gallium dans une couche constituée par du nitrure de silicium amorphe hydrogéné (a-SiN:H). Dans un autre mode de réalisation, on implante conjointement des ions gallium, des ions azote et des ions hydrogène dans une couche constituée par un matériau amorphe ne contenant pas d'azote, tel qu'un matériau de silicium amorphe ou un matériau plastique. On peut, de façon générale, mettre en application un procédé d'implantation d'ions afin de fabriquer une couche mince de RN désordonné dans laquelle R représente au moins un métal sélectionné dans Ga, Al et In.
PCT/GB1999/000127 1998-01-19 1999-01-15 Procedes servant a fabriquer des couches minces a semi-conducteur au moyen d'une synthese de faisceaux ioniques Ceased WO1999036968A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9801066.3 1998-01-19
GBGB9801066.3A GB9801066D0 (en) 1998-01-19 1998-01-19 Methods for manufacturing semiconductor thin films

Publications (1)

Publication Number Publication Date
WO1999036968A1 true WO1999036968A1 (fr) 1999-07-22

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PCT/GB1999/000127 Ceased WO1999036968A1 (fr) 1998-01-19 1999-01-15 Procedes servant a fabriquer des couches minces a semi-conducteur au moyen d'une synthese de faisceaux ioniques

Country Status (2)

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GB (1) GB9801066D0 (fr)
WO (1) WO1999036968A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001033643A1 (fr) * 1999-10-29 2001-05-10 Ohio University Formation de bande interdite d'alliages al-ga-n amorphes
US6689630B2 (en) 2000-05-23 2004-02-10 Ohio University Method of forming an amorphous aluminum nitride emitter including a rare earth or transition metal element
RU2699606C1 (ru) * 2016-11-28 2019-09-06 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Нижегородский государственный университет им. Н.И. Лобачевского" Способ ионно-лучевого синтеза нитрида галлия в кремнии

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2287825A (en) * 1994-03-24 1995-09-27 Univ Surrey Forming luminescent silicon material and luminescent device containing the material
US5464991A (en) * 1990-04-13 1995-11-07 Matsushita Electric Industrial Co., Ltd. Nonlinear optical materials and their manufacturing method
US5536193A (en) * 1991-11-07 1996-07-16 Microelectronics And Computer Technology Corporation Method of making wide band gap field emitter

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464991A (en) * 1990-04-13 1995-11-07 Matsushita Electric Industrial Co., Ltd. Nonlinear optical materials and their manufacturing method
US5536193A (en) * 1991-11-07 1996-07-16 Microelectronics And Computer Technology Corporation Method of making wide band gap field emitter
GB2287825A (en) * 1994-03-24 1995-09-27 Univ Surrey Forming luminescent silicon material and luminescent device containing the material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WOLK J A ET AL: "SYNTHESIS OF GAN NANOCRYSTALS BY SEQUENTIAL ION IMPLANTATION", APPLIED PHYSICS LETTERS, vol. 70, no. 17, 28 April 1997 (1997-04-28), pages 2268 - 2270, XP000690568 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001033643A1 (fr) * 1999-10-29 2001-05-10 Ohio University Formation de bande interdite d'alliages al-ga-n amorphes
US6486044B2 (en) 1999-10-29 2002-11-26 Ohio University Band gap engineering of amorphous Al-Ga-N alloys
US6689630B2 (en) 2000-05-23 2004-02-10 Ohio University Method of forming an amorphous aluminum nitride emitter including a rare earth or transition metal element
RU2699606C1 (ru) * 2016-11-28 2019-09-06 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Нижегородский государственный университет им. Н.И. Лобачевского" Способ ионно-лучевого синтеза нитрида галлия в кремнии

Also Published As

Publication number Publication date
GB9801066D0 (en) 1998-03-18

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