WO2013157014A1 - Matériau semiconducteur en nitrure de groupe iii et procédé de fabrication dudit matériau - Google Patents

Matériau semiconducteur en nitrure de groupe iii et procédé de fabrication dudit matériau Download PDF

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WO2013157014A1
WO2013157014A1 PCT/IN2012/000287 IN2012000287W WO2013157014A1 WO 2013157014 A1 WO2013157014 A1 WO 2013157014A1 IN 2012000287 W IN2012000287 W IN 2012000287W WO 2013157014 A1 WO2013157014 A1 WO 2013157014A1
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nitride
nucleation
group ill
buffer layer
polar
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Priti Gupta
A. Azizur RAHMAN
Maheshwar Ramchandra GOKHALE
Lokeshwar BANDHU
Mandar Madhukar DESHMUKH
Arnab Bhattacharya
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Tata Institute of Fundamental Research
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    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
    • H10P14/3202—Materials thereof
    • H10P14/3204—Materials thereof being Group IVA semiconducting materials
    • H10P14/3206—Carbon, e.g. diamond-like carbon
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
    • H10P14/3202—Materials thereof
    • H10P14/3214—Materials thereof being Group IIIA-VA semiconductors
    • H10P14/3216—Nitrides
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    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
    • H10P14/3242—Structure
    • H10P14/3244—Layer structure
    • H10P14/3248—Layer structure consisting of two layers
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    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3414—Deposited materials, e.g. layers characterised by the chemical composition being group IIIA-VIA materials
    • H10P14/3416—Nitrides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3466—Crystal orientation
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/29—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by the substrates
    • H10P14/2901—Materials
    • H10P14/2902—Materials being Group IVA materials
    • H10P14/2903—Carbon, e.g. diamond-like carbon

Definitions

  • TITLE GROUP III-NITRIDE SEMICONDUCTING MATERIAL AND A METHOD OF MANUFACTURING THE SAME
  • the present invention relates to Group Ill-nitride semiconducting materials comprising a graphene based layer having thereon at least one nitride nucleation /buffer layer adapted for conformal coverage of entire graphene surface and atleast one group III- nitride semiconducting film selected from alloy family of (AI,Ga,In,B) N on said nitride nucleation/buffer layer, in orientations selected from polar, non-polar and semi-polar with or without a suitable underlying substrate.
  • group III- nitride semiconducting film selected from alloy family of (AI,Ga,In,B) N on said nitride nucleation/buffer layer, in orientations selected from polar, non-polar and semi-polar with or without a suitable underlying substrate.
  • the said Group Ill-nitride semiconducting film in the semiconducting material of the present invention comprises one or more layers of dissimilar compositions of the (Al, Ga, In, B) N alloy family selected from at least one or more of: binary GaN, AIN, InN compound semiconductors; ternary alloys of AIGaN, AIInN, InGaN ; or quaternary alloys of AIGalnN and the like, in said film.
  • the present invention more particularly relates to planar, free-standing said Group Ill-nitride semiconducting material comprising graphene as the selective intermediate layer having deposited thereon at least one Group Ill-nitride semiconducting film in semi-polar orientations such as (10-11), (11-22), (10-13), wherein said graphene as the selective intermediate layer having at least one nitride nucleation/ buffer layer allows the growth of said Group III nitride semiconducting film in said semi-polar orientations.
  • the present invention relates to an improved method of manufacturing said planar, group Ill-nitride semiconducting material scalable to large area preferably in semi-polar orientation, and more preferably, also relates to a method of providing free standing layers/ membrane of said group-Ill nitride semiconducting material that is advantageously transferable to a wide variety of substrates selected from glass or flexible plastic substrates and adapted for the fabrication of various optoelectronic devices including LEDs,' lasers, transistors.
  • Gallium nitride and related ternary and quaternary alloys are well-established as important materials for light emitting diodes and lasers in the UV/visible region.
  • the most stable crystal structure of group III nitrides is the hexagonal wurtzite form.
  • most single crystal thin films of the group III nitrides are grown on the basal plane, i.e. the c-plane or (0001) oriented plane. In this orientation, the alternating layers of Gallium and Nitrogen atoms lead to a spontaneous polarization that induces an internal electric field.
  • most nitrides are grown on sapphire, in which lattice mismatch results in strain, which further leads to piezoelectric polarization.
  • Polarization-related issues are a major cause of concern in the performance of these devices, especially in the widely used crystal orientation-the standard basal plane (0001) of the wurtzite crystal structure.
  • crystal orientation-the standard basal plane (0001) of the wurtzite crystal structure Recent experimental evidence suggests that the use of "semi-polar" planes (wurtzite crystal planes such as ⁇ 11-22 ⁇ , ⁇ 10-11 ⁇ , ⁇ 10-13 ⁇ etc.) are advantageous for optoelectronic devices, and such semi-polar layers have been used to demonstrate the best green LEDs and lasers.
  • US Patents including US 7,687,293, US 7,575,947, US 7,790,584 and US 7,704,324 disclose methods for growing a semi-polar nitride semiconductor thin film on a substrate, all of which require either a complicated multi-step etch, or re-growth processes, or achieve the semi-polar surface only in certain regions of the wafer, or require miscut /(Disoriented substrates.
  • Graphene has been a material of contemporary research interest as it can serve as a transparent conducting electrode for use in various optoelectronic devices.
  • Ill-Nitride materials such as GaN on graphene has not received much attention possibly due to the chemical inertness of the graphene surface.
  • a recent publication by Chung et al. claims that GaN nucleation does not occur on the basal plane of pristine graphene, and some GaN islands grow on roughened graphene surfaces subjected to Oxygen-plasma treatment. They say that even the typical two-temperature growth process using a low-temperature GaN buffer layer does not improve the film properties. Hence they use zinc oxide as an intermediate layer for GaN growth.
  • group Ill-nitride semiconducting (Al, Ga, In, B)N material to enable fabrication of wide range of optoelectronic devices including LEDs, lasers, transistors involving said free-standing layers/ membrane and a method to achieve the same involving the steps of lifting off the group Ill-nitride material from the substrate on which it is deposited so as to transfer it to another substrate.
  • a Group III- nitride semiconducting material comprising of graphene based layer having thereon atleast one nitride nucleation /buffer layer adapted for conformal coverage of entire graphene surface and atleast one group Ill-nitride semiconducting film selected from alloy family of (AI,Ga,In,B)N on said nitride nucleation /buffer layer.
  • nitride nucleation/buffer layer adapted for conformal coverage of entire graphene based layer and thereon providing for atleast one group Ill-nitride semiconducting film selected from alloy family of (AI,Ga,In,B)N on sa jd nitride nucleation /buffer layer, that enabled the provision of the much desired single phase semiconducting material and preferably even in semi-polar orientations.
  • the single phase semiconducting material of the present invention which involves a graphene based layer is also advantageous in that the same is easily scalable to large area and also advantageously transferable to a wide variety of substrates selected from glass or flexible plastic substrates adapted as free standing layers/ membrane of said Group Ill-nitride semiconducting material favouring fabrication of various optoelectronic devices.
  • said Group Ill-nitride semiconducting material wherein said group Ill-nitride semiconducting films of (Al, Ga, In, B) N comprise at least one or more layers of dissimilar compositions within the alloy family of (AI,Ga,In,B)N.
  • Group Ill-nitride semiconducting material wherein graphene based group Ill-nitride semiconducting film is planar with one or more orientations selected from polar, non- polar and semi-polar and selected from the group comprising of GaN, AIN, InN, AIGaN, AIInN, InGaN and AIGalnN.
  • said Group Ill-nitride semiconducting material wherein said graphene based group Ill-nitride semiconducting films comprise one or more layers of dissimilar compositions of the (Al, Ga, In, B) N alloy family selected from at least one or more of: GaN, AIN, InN alloys; ternary alloys of AIGaN, AIInN, InGaN; or quaternary alloys of AIGalnN and the like, in said film.
  • Group Ill-nitride semiconducting material wherein said graphene based group Ill-nitride semiconducting films comprise free standing graphene based films with one or more orientations selected from polar, non-polar and semi-polar preferably with semi-polar orientations selected from (10-11), (11-22), (10-13) as a single phase material.
  • said Group Ill-nitride semiconducting material wherein said graphene based group Ill-nitride semiconducting free standing films shaped and configured for variety of applications.
  • suitable substrates include rigid substrates preferably including glass or transparent conducting oxide (TCO) coated glass, and/or flexible substrates preferably including plastics or metal foils.
  • TCO transparent conducting oxide
  • said Group Ill-nitride semiconducting material wherein said nitride nucleation/buffer layer adapted for conformal coverage of entire graphene surface comprise is an alloy selected from combinations of alloy family (Al, In, Ga)N preferably AIN.
  • said Group III- nitride semiconducting material comprising said graphene based group Ill-nitride semiconducting films on suitable substrates including sapphire, patterned sapphire, silicon, silicon oxide /dioxide coated silicon, silicon nitride coated silicon, silicon carbide and glass.
  • said graphene based group Ill-nitride semiconducting films adapted as free standing films on releasable sacrificial substrate layers including silicon oxide/dioxide, silicon nitride, spin-on-glass, polyimides.
  • said graphene Group Ill-nitride semiconducting films scalable to a large area from 10s to about 100s of cm 2 adapted for various optoelectronic devices.
  • a Group Ill-nitride semiconducting material comprising of graphene based layer having thereon at least one AIN nucleation /buffer layer having conformal coverage of entire graphene surface and atleast one group Ill-nitride semiconducting film selected from alloy family of (Al, Ga, In, B)N on said nitride nucleation /buffer layer with semi-polar orientations selected from (10-11), (11-22), (10-13).
  • a method of manufacture of Group Ill-nitride semiconducting material comprising a) providing a graphene based layer on a substrate;
  • a method of manufacture of Group Ill-nitride semiconducting material comprising a) providing a graphene based layer on a substrate;
  • the single phase semiconducting material of the present invention could avoid the limitations of achieving graphene based semiconducting materials with planar large area films by the above control of process parameters whereby even in the absence of specially miscut or mis-oriented sapphire or spinel substrates allows attainment of said Group Ill-nitride semiconducting material as a single phase material of high material quality with preferred semi-polar orientations that is advantageously both scalable to large area and also transferable to a wide variety of substrates adapted as free standing layers/ membrane of planar large-area films of said Group Ill-nitride semiconductors.
  • said nitride nucleation /buffer layer is grown on said graphene layer such as to achieve said conformai coverage on entire graphene based layer followed by growing thereon said nitride nucleation /buffer layer the said nitride semiconducting film involving a semiconductor deposition system and following one or more of techniques selected from metal organic chemical vapor deposition ( OCVD), metal organic vapour phase epitaxy (OVPE), solid or gas source molecular beam epitaxy (MBE), and hydride vapor phase epitaxy (HVPE). More preferably, said nitride semiconducting film is grown in one or more orientations selected from polar, non-polar and semi-polar. According to another aspect of the present invention said step (b) of providing a nucieation /buffer layer having conformal coverage on entire graphene based layer comprises the steps of
  • said step of providing AIN as nucieation /buffer layer comprises growing said nucieation /buffer layer involving precursors for nucieation involving low pressure in the range of 20 to 100 Torr following stepwise growth preferably involving either (A) two stage growth comprising (i) following a first stage growth for thickness in the range of 10 to 20 nm at temperature in the range of 700 to 800°C followed by (ii) second stage growth for thickness in the range of 25 to 40 nm at temperature in the range of 1000 to 1100 °C or (B) three stage growth (i) following a first stage growth for thickness in the range of 10 to 20 nm at temperature in the range of 600 to 700 °C (ii) second stage growth for thickness in the range of 10 to 20 nm at temperature in the range of 800 to 950 °C and (Mi) third stage growth for thickness in the range of 20 to 30 nm at temperature in the range of 1000 to 1100 °C .
  • said step (c) of providing thereon said nitride nucieation /buffer layer, the group III nitride semiconducting film comprises the steps of providing required metalorganic and hydride precursors in the pressure ranging from 20 to 760 Torr, temperature ranging from 530 to 1100 °C, depending on the particular Ill-Nitride film deposited.
  • said AIN as nucleation /buffer layer is grown in said semipolar orientation (10-11) involving precursors for nucleation and growth involving trimethylaluminium, ammonia and hydrogen carrier gas in the preferred temperature range of 600 to 1100 °C preferably about 1000 °C and pressure in the range of 20 to 100 Torr, preferably 50 Torr and with selective V/III ratio in the range of 2500 to 10000 preferably above 3500.
  • nitride nucleation /buffer layer comprises growing the GaN film involving trimethylgallium, ammonia and hydrogen carrier gas, at 50 to 200 Torr preferably 50 Torr reactor pressure at temperature 1000 to 1100°C preferably of 1040°C to thereby obtain semi-polar oriented said GaN group III nitride semiconducting film as a single phase material.
  • AIN nitride nucleation /buffer layer preferably AIGaN as the group III nitride semiconducting film
  • providing thereon said AIN nitride nucleation /buffer layer, preferably AIGaN as the group III nitride semiconducting film comprises growing said Group Ill-nitride film involving selective precursor involving trimethylgallium, trimethylaluminium and ammonia and hydrogen carrier gas, at 50 to 100 Torr preferably 50 Torr reactor pressure at temperature 1000 to 1100°C preferably of 1040°C to thereby obtain semi-polar oriented said group III nitride semiconducting film comprising AIGaN semi-polar (10-11) layer adapted as a single phase material.
  • providing thereon said AIN nitride nucleation /buffer layer, InN or InGaN or as the group III nitride semiconducting film comprises growing the Group Ill-nitride film involving selective precursor involving trimethylindium, trimethylgallium, and ammonia and nitrogen carrier gas, at 200 to 500 Torr reactor pressure at temperature 530 to 800°C to thereby obtain semi-polar oriented said group III nitride semiconducting film comprising InN semi-polar (10-11) layer or InGaN semi-polar (10-11) layer adapted as a single phase material.
  • said substrate is selected from a group comprising of Sapphire, patterned Sapphire, Silicon, Silicon Oxide/Dioxide coated Silicon, Silicon Nitride coated Silicon, Silicon Carbide and Glass also comprising releasable sacrificial substrate layers including silicon oxide/dioxide, silicon nitride, spin-on-glass, polyimides.
  • said substrate is surface conditioned prior to deposition of said nitride semiconducting film by exposure to oxygen plasma after which thermal cleaning of the substrate is preferably achieved by heating under hydrogen flow just prior to growth in the semiconductor deposition system.
  • nucleation /buffer layer having conformal coverage, atleast one group Ill-nitride semiconducting film selected from alloy family of (Al, Ga, In, B)N to obtain therefrom graphene based group III nitride semiconducting films of desired thickness; and d) removing the sacrificial layer to thereby obtain free standing Group Ill-nitride semiconducting material.
  • a method comprising obtaining free standing graphene based group III nitride semiconducting films wherein said sacrificial substrate is selected from silicon oxide/ dioxide, silicon nitride, spin-on-glass, polyimides which is removed preferably by chemical etching of the said sacrificial layer, e.g. the silicon dioxide layer below said graphene layer is etched using HF/buffered HF.
  • an optoelectronic device comprising Group Ill-nitride semiconducting material comprising of graphene based layer having thereon atleast one nitride nucleation /buffer layer adapted for conformal coverage of entire graphene surface and atleast one group Ill-nitride semiconducting film selected from alloy family of (AI,Ga,In,B)N on said nitride nucleation /buffer layer with or without a suitable substrate.
  • Group Ill-nitride semiconducting material comprising of graphene based layer having thereon atleast one nitride nucleation /buffer layer adapted for conformal coverage of entire graphene surface and atleast one group Ill-nitride semiconducting film selected from alloy family of (AI,Ga,In,B)N on said nitride nucleation /buffer layer with or without a suitable substrate.
  • a semiconducting material adapted for facilitating epitaxial growth of semiconducting films as epilayer thereon comprising of graphene based layer and atleast one nitride nucleation /buffer layer comprising an alloy selected from combinations of alloy family (Al, In, Ga)N having conformal coverage of entire graphene surface with or without a suitable substrate.
  • Fig. 1 depicts scanning electron microscope image showing conformal coverage of entire surface with AIN buffer layer on graphene
  • Fig. 3 depicts X-ray diffraction (XRD) profiles of the ⁇ -2 ⁇ scan for on-axis reflections for AIN layers grown on graphene at (a) different substrate temperatures and (b) different V/III ratios;
  • XRD X-ray diffraction
  • Fig. 4 depicts X-ray diffraction (XRD) profiles of the ⁇ -2 ⁇ scan for on-axis reflections showing AIN buffer layer and GaN semi-polar layer (10-11) grown on graphene;
  • Fig. 5 depicts room temperature photoluminescence emission spectra from the semi- polar (10-11) oriented GaN and AIGaN layers showing high material quality;
  • Fig. 6 depicts X-ray diffraction (XRD) profiles of the ⁇ -2 ⁇ scan for on-axis reflections showing patterns of GaN on AIN on graphene grown under different conditions showing mixed phases at low temperature
  • Fig. 7 depicts X-ray diffraction (XRD) profiles of the ⁇ -2 ⁇ scan for on-axis reflections of AIGaN alloy samples of varying aluminium content
  • Fig. 8(a) depicts a process of lift off of free standing GaN layer, after etching the underlying silicon dioxide layer in buffered HF (Fig.8 b), the nitride layer floats up on to the surface (Fig. 8 c), Fig. 8 (d) depicts free-standing GaN layer transferred to a glass slide, and Fig. 8 (e) is a x-ray diffraction pattern of the free-standing GaN showing a semi-polar orientation (10-11). Fig 8 (f) shows room temperature photoluminescence from the free-standing GaN layer, pointing to the high material quality.
  • the present invention provides for Group Ill-nitride semiconducting material comprising graphene based layer having thereon atleast one nitride nucleation /buffer layer adapted for conformal coverage of entire graphene surface and at least one group Ill-nitride semiconducting film selected from alloy family of (Al, Ga, In, B)N on said nitride nucleation /buffer layer, in orientations selected from polar, non-polar and semi-polar with or without a suitable substrate.
  • the said Group Ill- nitride semiconducting film of the semiconducting material of the present invention comprises one or more layers of dissimilar compositions of the (Al, Ga, In, B) N alloy family selected from at least one or more of: GaN, AIN, InN alloys; ternary alloys of AIGaN, AIInN, InGaN; or quaternary alloys of AIGalnN and the like.
  • the present invention provides for planar free standing semiconducting material scalable to large area and advantageously transferable to a wide variety of substrates selected from glass or flexible plastic substrates thereby favouring fabrication of various optoelectronic devices including LEDs, lasers, transistors wherein said III- nitride semiconducting film preferably involves semi-polar orientation such as (10-11), (11-22), (10-13).
  • the present invention relates to a method of growing planar group Ill-nitride semiconducting film (AI,Ga,In,B)N on a substrate comprising steps of:
  • the nitride semiconducting film grown by the present method can be deposited more of orientations selected from polar, non-polar and semi-polar orientations. By appropriate choice of growth conditions semi-polar orientations such as (10-11), (11- 22), (10-13) etc. can be obtained.
  • the planar group III nitride semiconducting film that is grown may contain one or more layers of dissimilar compositions of the (AI,Ga,In,B)N alloy family.
  • films which can be grown by the present method can be one or more of GaN, AIN, InN; ternary alloys like AIGaN, AIInN, InGaN; or quaternary alloys like AIGalnN and the like.
  • the planar group III nitride semiconducting film can be grown using one or more techniques selected from metal organic chemical vapor deposition (MOCVD), metalorganic vapour phase epitaxy (MOVPE), solid and gas source molecular beam epitaxy (MBE), or hydride vapor phase epitaxy (HVPE).
  • MOCVD metal organic chemical vapor deposition
  • MOVPE metalorganic vapour phase epitaxy
  • MBE solid and gas source molecular beam epitaxy
  • HVPE hydride vapor phase epitaxy
  • the group Ill-nitride semiconducting film is grown in a semi-polar orientation which is selected from (10-11), (10-13) and (11-22).
  • semi-polar group Ill-nitride semiconducting film can be grown on substrates such as Silicon, Sapphire, Silicon Carbide, or Silicon-dioxide/Silicon-nitride coated Silicon substrates using a graphene interlayer.
  • substrates such as Silicon, Sapphire, Silicon Carbide, or Silicon-dioxide/Silicon-nitride coated Silicon substrates using a graphene interlayer.
  • the present method does not require specially miscut or mis-oriented sapphire or spinel substrates.
  • Large area graphene layers used in the present invention can be synthesized using standard Chemical Vapor Deposition (CVD) techniques as disclosed in the literature, for example, through deposition by cracking of methane at high temperature on copper (or nickel) foils, followed by etching and lift-off.
  • CVD Chemical Vapor Deposition
  • Graphene Synthesis by CVD on Copper Substrates The 2009 NNIN REU Research Accomplishments, p. 71 to 74 and Matthew O'Brien et al, "CVD Synthesis and Characterization of Graphene Thin Films", Army Research Laboratory, 2010, p. 1 to 15, http: //www.arl.army.mil/arlreports/2010/ARL-TR-5047.pdf.
  • nickel see for example, K-S. Kim, et al, Nature 457, 706-710 (2009).
  • surface conditioning of the graphene layer prior to deposition of nitride layer was done by exposure to oxygen plasma.
  • the wafer was loaded into an MOVPE reactor and heated under hydrogen flow and thermally cleaned, typically at 1040°C for 5 min before cooling down for deposition of the nucleation or buffer layer.
  • the nitride nucleation or buffer layer used was AIN, which was grown conformally as detailed below on the graphene layer (Fig. 1), hence permitting the growth of smooth layers of GaN on top of it (Fig 2a), whereas direct deposition of GaN on the graphene layer (at 1040 °C 50 Torr) results in isolated island growth (Fig. 2b).
  • the AIN nucleation layer was grown at a low reactor pressure, for example, 50 Torr, and either as a two step growth - for example, low temperature nucleation step of 15 nm at 600°C, followed by a high temperature grown layer 35 nm at 1040°C, or as a 3-step growth with a low temperature nucleation step of 15 nm at 600°C, followed by 15 nm growth at 900°C, and a high temperature grown buffer layer 35 nm at 1040°C.
  • a low reactor pressure for example, 50 Torr
  • the reactor temperature was further ramped to an appropriate temperature for growth of desired group Ill-nitride semiconducting epilayer.
  • the reactor temperature ranged from 1040°C for GaN to 530°C for InN.
  • Example III Under this example, in accordance with the present invention, the desired group III- nitride semiconducting epilayer was grown on top of an AIN buffer layer by admitting the appropriate metalorganic and hydride precursors at a specific pressure, temperature, V/III ratio, and growth rate to favour a preferential surface orientation of the epilayer. It was noted that typically high temperature and low pressure conditions favored the growth of semi-polar oriented layers while low temperature and high pressure conditions lead to mixed phases with polar and semi-polar oriented domains.
  • Example IV Under this example, AIN layers were grown using trimethylaluminium and ammonia and hydrogen carrier gas, at growth temperatures ranging from 800°C to 1100°C and V/III ratios from 500 to 5000.
  • Fig. 3 (a) shows the X-ray diffraction (XRD) of the ⁇ -2 ⁇ scan for on-axis reflections for a series of AIN layers grown at different growth temperatures in the range 900 to 1040°C keeping other parameters fixed. From the accompanying figure it can been seen at lower temperatures mixed phases are obtained, as the temperature increases the intensity of the (0002) peak drops, and reached a minimum at an optimum temperature of 1000°C.
  • Fig. 3 shows the X-ray diffraction (XRD) of the ⁇ -2 ⁇ scan for on-axis reflections for a series of AIN layers grown at different growth temperatures in the range 900 to 1040°C keeping other parameters fixed. From the accompanying figure it can been seen at lower temperatures mixed phases are obtained, as the temperature increases the intensity of the (0002)
  • 3(b) shows a series of AIN layers growth at different V/III ratios from 500 to 4500 keeping other parameters fixed. From the figure it can be seen that for growth at low V/III ratio other parasitic phases such as the (0002), (10-12) and (11-20) are seen. These phases reduce on increasing the V/III ratio, and almost single phase (10-11) semipolar AIN is obtained at V/III ratios above 3500.
  • GaN and AIGaN layers were grown using trimethylgallium, trimethylaluminium and ammonia and hydrogen carrier gas, growth at 1040°C and 50 Torr reactor pressure leading to layers with a preferential (10-11) orientation (Fig. 4)
  • Fig. 4 shows the X-ray diffraction (XRD) profile of the ⁇ -2 ⁇ scan for on-axis reflections showing AIN buffer layer, GaN semi-polar (10-11) layer and AIGaN semi-polar (lO-l l)layer grown on graphene. A single phase material was thus obtained.
  • Fig. 5 shows the room temperature photoluminescence from these GaN and AIGaN layers pointing to the high quality of the material.
  • Fig. 6 shows the X-ray diffraction (XRD) profile of the ⁇ -2 ⁇ scan for on-axis reflections showing patterns of GaN on AIN on graphene grown under different conditions showing mixed phases at low temperature.
  • XRD X-ray diffraction
  • InN and In-containing alloys were grown in a similar manner as described herein, but by using nitrogen carrier gas instead of hydrogen. After a group III nitride semiconducting layer of a desired thickness was grown, the supply of reagents was switched off and the reactor cooled to room temperature and the sample removed.
  • planar group III nitride films obtained by the present method are found to be advantageously of a large area, limited only by the size of the graphene layer transferred onto the substrate. Since CVD graphene can be grown over large areas (10s to 100s of cm 2 ), semi-polar nitride films of large area can thus be obtained by the method of the present invention.
  • Example VI
  • the graphene layer was transferred to a silicon dioxide or silicon nitride coated substrate (wafer).
  • the silicon dioxide/nitride served as a sacrificial layer in a process for the fabrication of free standing semiconductor layers.
  • the method of the present invention provides for fabrication of free-standing layers of the semi-polar nitride semiconductor film.
  • the free-standing nitride film was obtained by chemical etching of the silicon oxide layer below the graphene layer by using HF/buffered HF etchants. This separated the nitride layer on the graphene from the substrate and releases the nitride layer as a free standing membrane, which was then transferred to other materials, such as glass or flexible plastic substrates.
  • the group III nitride semiconducting material manufactured by the method of the present invention can thus be used advantageously as substrates for a range of optoelectronic device applications such as LEDs, lasers, transistors and the like.
  • a device preferably an optoelectronic device was fabricated comprising Group Ill-nitride semiconducting material comprising of graphene based layer having thereon atleast one nitride nucleation /buffer layer adapted for conformal coverage of entire graphene surface and atleast one group Ill-nitride semiconducting film selected from alloy family of (AI,Ga,In,B)N on said nitride nucleation /buffer layer with or without a suitable substrate.
  • Group Ill-nitride semiconducting material comprising of graphene based layer having thereon atleast one nitride nucleation /buffer layer adapted for conformal coverage of entire graphene surface and atleast one group Ill-nitride semiconducting film selected from alloy family of (AI,Ga,In,B)N on said nitride nucleation /buffer layer with or without a suitable substrate.
  • Group Ill-nitride semiconducting material comprising of graphene based layer having thereon atleast one nitride nucleation /buffer layer adapted for conformal coverage of entire graphene surface and atleast one group Ill-nitride semiconducting film selected from alloy family of (AI,Ga,In,B)N on said nitride nucleation /buffer layer with orientations selected from polar, non-polar and semi-polar comprises one or more layers of dissimilar compositions of the (Al, Ga, In, B) N alloy family selected from the group comprising at least one or more of GaN, AIN, InN, AIGaN, AIInN, InGaN or AIGaInN. :GaN, AIN, InN alloys.
  • the present invention provides for planar free standing layers/ membrane of said Group Ill-nitride semiconducting material scalable to large area and advantageously transferable to a wide variety of substrates selected from glass or flexible plastic substrates thereby favouring fabrication of various optoelectronic devices including LEDs, lasers, transistors, wherein said graphene based group Ill-nitride semiconducting film involves semi-polar orientation selected from (10-11), (11-22), (10- 13) as a single phase material.

Abstract

La présente invention concerne des matériaux semiconducteurs en nitrure de groupe III comprenant une couche à base de graphène recouverte d'au moins une couche de nucléation/tampon de nitrure conçue pour recouvrir de manière conforme l'ensemble de la surface de graphène et au moins un film semiconducteur en nitrure de groupe III sélectionné parmi la famille d'alliages de N (Al, Ga, In, B) sur ladite couche de nucléation/tampon en nitrure, dans des orientations sélectionnées parmi des orientations polaires, non-polaires et semi-polaires avec ou sans substrat sous-jacent adapté, et un matériau semiconducteur en nitrure dudit groupe III planaire et libre qui peut être transféré de façon avantageuse sur une grande variété de substrats sélectionnés parmi des substrats de verre ou de plastique flexible et conçu pour la fabrication de divers dispositifs optoélectroniques comprenant des diodes électroluminescentes, des lasers, des transistors.
PCT/IN2012/000287 2012-04-20 2012-04-20 Matériau semiconducteur en nitrure de groupe iii et procédé de fabrication dudit matériau Ceased WO2013157014A1 (fr)

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