1. Field of the Invention
The invention is related generally to the field of electronic and optoelectronic devices, and more particularly, to selective dry etching of nitrogen face (N-face) (Al,In,Ga)N heterostructures.
2. Description of the Related Art
(Note: This application references a number of different publications as indicated throughout the specification by one or more reference numbers within brackets, e.g., [Ref. X]. A list of these different publications ordered according to these reference numbers can be found below in the section entitled “References.” Each of these publications is incorporated by reference herein.)
Typical GaN-based light-emitting diodes (LEDs) are planar structures, where a several-micron-thick GaN template and InGaN/GaN quantum-well active region are grown on a lower index Sapphire substrate. The top air/GaN interface and the GaN/Sapphire interface serve as mirrors to form discrete bound states for photons, so called guided modes. As these guided modes propagate parallel to the planar geometry, the direct emission in the vertical direction is low, i.e., a few percent of the total emission. Therefore, the integration (packaging) of external optics is necessary to retain the vertical emission.
Submicron-thick micro-cavity light emitting diodes (MCLEDs) [Ref 1] and photonic-crystal-MCLEDs (PC-MCLEDs) [Ref 2] promise superior performance to conventional LEDs. Tailoring of the modal characteristics can lead to enhancement of spontaneous emission [Ref 3], spectral purity [Ref 4], and directionality [Refs. 5-6], which contribute to increased brightness and energy efficiency. This invention addresses critical challenges in the fabrication of such devices, enabling commercial realization of these LEDs with exceptional extraction efficiency.
In more conventional III-V materials, such as GaAs and InP, highly efficient microcavity optical devices with controlled light emission can be formed through the monolithic growth of high reflectivity mirrors, and a thin active region whose thickness and composition are controlled by the precision of the epitaxial growth technique. Such techniques are not practical, or easily implemented or accomplished, in GaN-based LEDs and lasers.
For GaN-based LEDs and lasers, a high quality underlying mirror is required to direct light away from the substrates, which serves as a loss channel for the generated light. Although AlGaN/GaN Distributed Bragg Reflectors (DBRs) have been formed, the low index contrast between AlGaN/GaN requires high Al composition and a large number of DBR periods for a highly reflective mirror [Ref 7]. The inherent strain in this heterostructure leads to the formation of cracks and other defects in the mirror structure [Ref. 8].
The lossy effects of the substrate may be addressed through removal of the active layer from the substrate, through techniques like laser lift-off (LLO) [Refs. 9-10]. The lift-off structure can then be bonded to a different substrate, and appropriate dielectric DBRs deposited [Ref 11]. However, a certain minimum thickness (several microns) between the active area and the original substrate is required to ensure the integrity of the active region during the lift-off process. Precision control of the post LLO etch in the vertical direction determines the thickness of the MCLED; uniformity of the etch in the lateral direction will ensure a high yield of devices. Such etch control is a critical factor in the fabrication and ultimate manufacturability of such devices.
Recently, T. Fujii et al. [Ref 1] have demonstrated submicron-thick MCLEDs by utilizing the LLO technique and the nonselective thinning process, i.e., reactive ion etching (RIE) and successive chemical mechanical polishing (CMP) [Ref. 12]. This processing scheme has further been a basis for exploring PC-MCLEDs [Ref 2]. However, the adopted thinning method lacks reproducibility, precision, and scalability in controlling the microcavity thickness.
The present invention proposes the incorporation of an etch-stop layer into the device structure, and a controlled, highly selective, etch process. Specifically, the present invention includes: (1) the incorporation of an easily formed, compatible etch-stop layer in the growth of the device structure, (2) the use of a laser-lift off or similar process to decouple the active layer from the original ‘growth’ substrate, and (3) the achievement of etch selectivity higher than 14:1 on N-face (Al,In,Ga)N.
For a GaN structure, InxGa1-xN or AlxGa1-yN layers can be epitaxially incorporated, generally with a thickness commensurate with a critical thickness [Ref. 13]. Generally, it is expected that the higher the chemical difference between etch stop layer and the surrounding material, the higher the achievable dry-etch or wet-etch selectivity.
The choices of selective wet etches are limited, although some high-temperature etches have been found for AlGaN and photoelectrochemical etching has been shown to be effective for a broad composition of (Al,Ga,In)N. There are a number of dry or gas-phase etches; in general, all such processes, e.g., RIE, inductively coupled plasma (ICP) etching, etc., contain a chemical component and an ion-assisted (physical) component.
Etch selectivities for the Group-III face (III-face) III-nitride materials have been demonstrated by, e.g., S. A. Smith et al. [Ref 14] using an ICP process with Cl2 and Ar to etch GaN, AlGaN, and AlN. S. J. Pearton et al. [Ref 15] have utilized etch gases of Cl2, BCl3, SF6, and Ar for ICP etching of GaN, AlN, and InN. The maximum etch selectivity of 6:1 was obtained for GaN:AlN by the Cl2-based ICP.
The demonstration of selective etches for the III-face does not guarantee etch behavior of the N-face; differences in etch behavior of the two faces have already been suggested in Refs. 16-18. In fact, I. Waki et al. [Ref 19] have investigated the ICP etching of (0001) (-c) N-face GaN, which was obtained by LLO process. The etch rate of ˜7 nm/min was obtained with the flow rates of 20 sccm for BCl3 and 5 sccm for SF6, the chamber pressure of 4 Pa, and the source and bias powers of 250 W and 175 W, respectively. However, the etch selectivity was not achieved.
Thus, there is a need in the art for improved methods for nano-precision etching of GaN, AlGaN, InGaN, and AlInGaN, in the fabrication of electronic and optoelectronic devices. The present invention satisfies this need. Specifically, the present invention provides for selective dry etching of N-face (Al,In,Ga)N heterostructures.
To overcome the limitations in the prior art described above, and to overcome other limitations that will become apparent upon reading and understanding the present specification, the present invention discloses a method for selective dry etching of N-face (Al,In,Ga)N heterostructures through the incorporation of an etch-stop layer into the structure, and a controlled, highly selective, etch process. Specifically, the present invention includes: (1) the incorporation of an easily formed, compatible etch-stop layer in the growth of the device structure, (2) the use of a laser-lift off or similar process to decouple the active layer from the original growth substrate, and (3) the achievement of etch selectivity higher than 14:1 on N-face (Al,In,Ga)N. The present invention also encompasses devices fabricated according to this method.
Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
a) are simplified schematic diagrams showing the steps of a method of the present invention, used for a conventional GaN-based LED grown on a Sapphire substrate, including laser debonding of the Sapphire substrate, followed by selective etching of a GaN template utilizing an etch stop layer.
b) is a Scanning Electron Micrograph (SEM) of a test material with the Al0.30Ga0.70N etch stop layer grown by Molecular Beam Epitaxy (MBE).
a)-2(d) are simplified schematic diagrams showing the steps of a method of the present invention, used to verify the selective removal of N-face GaN by BCl3 and SF6 based ICP etching.
a) and 4(b) are SEM images taken after (
a)-5(d) are SEM images showing the correlation between the micro-cone density and the Al composition (x) in the AlxGa1-xN layer, wherein
a)-6(h) are simplified schematic diagrams showing the steps of a process, according to one embodiment of the present invention, used to fabricate MCLEDs and/or PC-MCLEDs for an epi-structure grown on a Sapphire substrate.
a)-7(i) are simplified schematic diagrams showing the steps of a process, according to one embodiment of the present invention, used to fabricate MCLEDs and/or PC-MCLEDs for an epi-structure grown on a free-standing GaN substrate.
In the following description of the preferred embodiment, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration a specific embodiment in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
Overview
This invention describes a method to utilize controllable and extremely high etch selectivities of (Al,In,Ga)N heterostructures for devices of those materials requiring fabrication with nano-scale precision. Specifically, this invention relates to a nano-precision etching method with reproducibility and scalability for GaN and its ternary and quaternary compounds incorporating aluminum and indium (AlGaN, InGaN, AlInGaN), which are essential for visible and ultraviolet optoelectronic devices and high-power electronic devices.
In one embodiment, the present invention discloses a method for dry etch selectivity in fabricating an opto-electronic device, by etching one or more nitride layers having an (Al,In,Ga)N etch-stop layer containing at least some Aluminum (Al), wherein the nitride layers and etch-stop layer comprise layers of dissimilar (Al,Ga,In)N composition and the nitride layers are etched at a higher rate than the etch-stop layer.
Other aspects of this embodiment include:
In another embodiment, the present invention discloses a method for dry etch selectivity in fabricating an opto-electronic device, by etching one or more nitride layers having an (Al,In,Ga)N etch-stop layer containing at least some Indium (In), wherein the nitride layers and etch-stop layer comprise layers of dissimilar (Al,Ga,In)N composition and the nitride layers are etched at a higher rate than the etch-stop layer.
Other aspects of this embodiment include:
A particular embodiment of the present invention involves the formation of an AlGaN etch-stop layer. The device fabrication process and the role of the etch-stop layer are shown in
An alternative embodiment of the present invention involves the formation of an InGaN etch-stop layer in a similar structure and using a similar process to perform selective etching of the GaN template utilizing the etch stop layer. In this embodiment, the etch gas used must (1) etch GaN at a fairly substantial rate, (2) much higher than the rate of etching of the InGaN. Similar to Al, the choice of etch gas is a fluorine-containing gas, wherein In is known to form the nonvolatile InF3 layer during fluorine-based dry etching, and another choice of etch gas is a chlorine-containing gas, wherein In is known to form the nonvolatile InCl3 layer during chlorine-based dry etching.
The inventors have specifically investigated the etch selectivity between N-face GaN and an AlxGa1-xN etch stop layer. For a detailed characterization of etch selectivity, the inventors have grown samples with AlxGa1-xN etch stop layers of various Al compositions (e.g., x=15%, 30%, and 51%) by MBE on a freestanding GaN substrate. The target thicknesses of AlxGa1-xN layers were 60 nm, 30 nm, and 10 nm, respectively. Because of the lattice mismatch, there is an inverse relationship between the percentage of Al and achievable etch-stop thickness. In particular, N-face GaN is grown to mimic the thinning process of [Ref. 1]; the GaN template obtained by the LLO process is N-face.
The experimental procedure is illustrated in
(1) Growth on a GaN substrate 200, including a GaN layer 202, an AlxGa1-xN layer 204 and an N-face GaN layer 206, followed by patterning photoresist mesas 208 on the N-face GaN 206 using optical lithography, as shown in
(2) Introducing a 200 nm-thick SrF2 mask layer 210 by e-beam deposition and a lift-off technique to remove the photoresist 208, as shown in
(3) Pre-cleaning of the exposed N-face GaN 206 with BCl3 based dry etching using an ICP etching system (Panasonic ICP Model E640), as shown in
(4) Selective removal of the exposed N-face GaN 206 using BCl3 and SF6 based ICP etching, as shown in
(5) Inspection of the etch rate and etch damage on the surface by scanning electron microscopy (SEM) and atomic force microscopy (AFM).
To investigate the etch damage on the Al0.30Ga0.70N surface, the inventors carried out an extended 20 minutes of ICP etching for another sample at the same ICP condition. The surface quality of the Al0.30Ga0.70N etch stop layer seems to be similar to that from 15 minutes of ICP etching, as shown in
The correlation between the etch selectivity and the sample structure, i.e., the Al composition (x) in the AlxGa1-xN layer, was also investigated by the inventors.
All the AlxGa1-xN layers demonstrate very robust etch-stopping behavior, as shown in
Embodiments of the present invention may involve the fabrication of MCLEDs or PC-MCLEDs. The fabrication procedures for the epi-structures grown on two types of substrates, i.e., Sapphire and GaN, are described below.
a)-6(h) are simplified schematic diagrams showing the steps of a process, according to one embodiment of the present invention, used to fabricate MCLEDs and/or PC-MCLEDs for an epi-structure grown on a Sapphire substrate 600. The steps of this first fabrication procedure are described as follows:
(1) Growth of the epi-structure with a GaN layer 602, an AlxGa1-xN etch stop layer 604 and a GaN/InGaN/GaN active region 606 on the Sapphire substrate 600 by metalorganic chemical vapor deposition (MOCVD), as shown in
(2) Metal wafer bonding to a submount 608 using bonding metals 610 such as Tin (Sn) and Gold (Au), as shown in
(3) Laser debonding of the Sapphire substrate 600, as shown in
(4) Initial thinning process utilizing a chemical mechanical polishing or non-selective (Cl and Ar-based) dry-etch process with the ICP system (Panasonic ICP Model E640), as shown in
(5) Pre-cleaning of the N-face GaN 602 surface with BCl3 based dry etching with the ICP system (not shown).
(6) Selective thinning of the N-face GaN 602 with BCl3 and SF6-based ICP etching, as shown in
(7) Post-cleaning of GaN microcones on the surface of AlxGa1-xN layer 604 with SF6 based ICP etching, as shown in
(8) Rinse with HCl, de-ionized water, acetone, and isopropanol, as shown in
(9) Cathode 612 deposition to form an MCLED, as shown in
(10) Photonic-crystal (PC) formation in the etch stop layer 604 and cathode 612 deposition to form a PC-MCLED, also as shown in
a)-7(h) are simplified schematic diagrams showing the steps of a process, according to one embodiment of the present invention, used to fabricate MCLEDs and/or PC-MCLEDs for an epi-structure grown on a free-standing GaN substrate 700. The steps of this second fabrication procedure are described as follows:
(1) Growth of the epi-structure with a GaN layer 702, an AlxGa1-xN etch stop layer 704 and a GaN/InGaN/GaN active region 706 on the GaN substrate 700 by MOCVD, as shown in
(2) Wafer bonding to a temporary glass submount 708 using an epoxy glue 710, which is soluble by acetone, as shown in
(3) An initial thinning process utilizing a chemical mechanical polishing or non-selective (Cl and Ar-based) dry-etch process with the ICP system (Panasonic ICP Model E640), as shown in
(4) Pre-cleaning of the N-face GaN 702 surface with BCl3 based dry etching with the ICP system (not shown).
(5) Selective thinning of the N-face GaN 702 with BCl3 and SF6-based ICP etching, as shown in
(6) Post-cleaning of GaN microcones on the surface of the AlxIn1-xN etch stop layer 704 with a SF6 based ICP etching, as shown in
(7) Rinse with HCl, de-ionized water (not shown).
(8) Introducing a thick metal submount 712, which serves as a cathode and a mirror, by electron-beam deposition or electroplating, as shown in
(9) Debonding the sample from the submount 708 using a solvent, such as acetone, as shown in
(10) Anode 714 deposition, such as a transparent Pd/Au metal or indium-tin-oxide (ITO) contact, to form an MCLED, as shown in
(11) Photonic crystal formation in the active region 706 and anode 714 deposition, such as a transparent Pd/Au metal or indium-tin-oxide (ITO) contact, to form a PC-MCLED, also as shown in
Another embodiment is the fabrication of a thin nitride-based film for efficient thermal management combined with a submount made of good thermal conductors. This can be integrated with a passive temperature control unit (e.g., heat dissipater) as well as an active temperature control unit (e.g., thermoelectric temperature controller), as shown in
Other embodiments would include nitride semiconductor lasers as well as electronic devices that require the etch selectivity between N-face nitride layers and an AlxIn1-xN etch stop layer.
Some examples of the many products that would benefit from the present invention include III-nitride-based MCLEDs, PC-MCLEDs, and High-Electron Mobility Transistors (HEMTs).
Other are areas that would benefit from the present invention include:
(1) Optimization of MOCVD growth for (Al,In,Ga)N heterostructures with a thin (400 nm) AlxGa1-xN etch stop layer where 0.1<x<0.5.
(2) Optimization of Hydride Vapor Phase Epitaxy (HVPE) growth for (Al,In,Ga)N heterostructures with a thin (400 nm) AlxGa1-xN etch stop layer where 0.1<x<0.5.
(3) Optimization of ICP conditions to maximize etch selectivity between (Al,In,Ga)N heterostructures.
(4) Optimization of ICP conditions to minimize etch damage to a (Al,In,Ga)N hetero structures.
(5) Optimization of ICP conditions to minimize the roughness of the etch surface. Nomenclature
The terms “(Al,In,Ga)N”, “III-nitride”, “Group-III nitride”, or “nitride,” or GaN, AlGaN, InGaN or AlInGaN, as used herein refer to any alloy composition of the (Al,In,Ga)N semiconductors having the formula AlxInyGazN where 0≦x≦1, 0≦y≦1, 0≦z≦1, and x+y+z=1. These terms are intended to be broadly construed to include respective nitrides of the single species, Al, In and Ga, as well as binary, ternary and quaternary compositions of such Group III metal species. Accordingly, it will be appreciated that the discussion of the invention hereinafter in reference to GaN, AlGaN and InGaN materials is applicable to the formation of various other (Al,In,Ga)N material species. Further, (Al,In,Ga)N materials within the scope of the invention may further include minor quantities of dopants and/or other impurity or inclusional materials.
The following references are incorporated by reference herein:
This concludes the description of the preferred embodiments of the present invention. The foregoing description of one or more embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 61/551,181, filed on Oct. 25, 2011, by James S. Speck, Evelyn L. Hu, Claude C. A. Weisbuch, Yong Seok Choi, Gregor Koblmuller, Michael Iza, and Christophe Hurni, and entitled “SELECTIVE DRY ETCHING OF N-FACE (Al,In,Ga)N HETEROSTRUCTURES,” attorneys' docket number 30794.413-US-P1 (2007-460-1), which application is hereby incorporated by reference herein.
This invention was made with Government support under Grant No. DE-FC26-06NT42857 awarded by the U.S. Department of Energy. The Government has certain rights in this invention.
Number | Date | Country | |
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61551181 | Oct 2011 | US |