1. Field of the Invention
This invention relates to fabricating high power and high efficiency nitride Light Emitting Diodes (LEDs), especially in the range of wavelength from 560 nm to 680 nm, and nitride-based white LEDs.
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(s). 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.)
Current nitride technology for electronic and optoelectronic devices employs nitride films grown along the polar c-direction. However, conventional c-plane quantum well structures in III-nitride based optoelectronic and electronic devices suffer from the undesirable quantum-confined Stark effect (QCSE), due to the existence of strong piezoelectric and spontaneous polarizations. The strong built-in electric fields along the c-direction cause spatial separation of electrons and holes that in turn give rise to restricted carrier recombination efficiency, reduced oscillator strength, and red-shifted emission.
One approach to eliminating the spontaneous and piezoelectric polarization effects in GaN optoelectronic devices is to grow the devices on nonpolar planes of the crystal. Such planes contain equal numbers of Ga and N atoms and are charge-neutral. Furthermore, subsequent nonpolar layers are crystallographically equivalent to one another so the crystal will not be polarized along the growth direction. Two such families of symmetry-equivalent nonpolar planes in GaN are the {11-20} family, known collectively as a-planes, and the {1-100} family, known collectively as m-planes. Unfortunately, despite advances made by researchers at the University of California, growth of nonpolar nitrides remains challenging and has not yet been widely adopted in the III-nitride industry.
Another approach to reducing, or possibly eliminating, the polarization effects in GaN optoelectronic devices is to grow the devices on semipolar planes of the crystal. The term semipolar planes can be used to refer to a wide variety of planes that possess two nonzero h, i, or k Miller indices, and a nonzero l Miller index. Some commonly observed examples of semipolar planes in c-plane GaN heteroepitaxy include the {11-22}, {10-11}, and {10-13} planes, which are found in the facets of pits. These planes also happen to be the same planes that the authors have grown in the form of planar films. Other examples of semipolar planes in the wurtzite crystal structure include, but are not limited to, {10-12}, {20-21} and {10-14} planes. The nitride crystal's polarization vector lies neither within such planes or normal to such planes, but rather lies at some angle inclined relative to the plane's surface normal. For example, the {10-11} and {10-13} planes are at 62.98° and 32.06° to the c-plane, respectively.
In addition to spontaneous polarization, the second form of polarization present in nitrides is piezoelectric polarization. This occurs when the material experiences a compressive or tensile strain, as can occur when (Al, In, Ga, B)N layers of dissimilar composition (and therefore different lattice constants) are grown in a nitride hetero-structure. For example, a thin AlGaN layer on a GaN template will have in-plane tensile strain, and a thin InGaN layer on a GaN template will have in-plane compressive strain, both due to lattice matching to the GaN. Therefore, for an InGaN quantum well on GaN, the piezoelectric polarization will point in the opposite direction to the spontaneous polarization of the InGaN and GaN. For an AlGaN layer latticed matched to GaN, the piezoelectric polarization will point in the same direction as the spontaneous polarization of the AlGaN and GaN.
The advantage of using semipolar or nonpolar planes over c-plane nitrides is that the total polarization will be reduced. There may even be zero polarization for specific alloy compositions on specific planes. Such scenarios will be discussed in detail in future scientific papers. The important point is that the polarization will be reduced compared to the polarization of c-plane nitride structures. A reduced polarization field allows growth of a thicker quantum well. Hence higher Indium composition and thus longer wavelength emission can be realized by nitride LEDs. Many efforts have been made in order to fabricate semipolar/nonpolar based nitride LEDs in longer wavelength emission regimes [Refs. 1-4].
This disclosure describes an invention allowing for fabrication of blue, green, yellow, and amber LEDs on semipolar or nonpolar (Al, In, Ga, B)N semiconductor crystals. So far, no nitride LEDs have been successful at longer wavelength emission in the yellow and amber regions. However, the present invention, which will be discussed in more detail in the following sections, demonstrates promising results for commercialization of nitride-based yellow and amber LEDs.
The present invention describes a method for growing planar blue, green, yellow, white, and other color Light Emitting Diodes (LEDs) with a bulk semipolar and nonpolar GaN substrate such as {10-1-1}, {11-22}, {1100}, and other planes. Semipolar and nonpolar (Al, In, Ga, B)N semiconductor crystals allow the fabrication of a multilayer structure with zero, or reduced, internal electric fields resulting from internal polarization discontinuities within the structure, as described in previous disclosures. This invention describes high quality crystal growth of LED or laser diode structures using an intentional interruption time introduced between Indium containing well layer growth and barrier layer growth of a multi-quantum well (MQW) or a single quantum well (SQW), by a Metal Organic Chemical Vapor Deposition (MOCVD) technique. This allows controllability over Indium incorporation into the well layer of indium containing layer(s) of the semipolar or nonpolar based planar LEDs or laser diodes. The use of a semipolar or nonpolar (Al, In, Ga, B)N semiconductor orientation results in reduced internal electric field and thus thicker quantum well and higher indium composition for longer wavelength emissions relative to [0001] nitride semiconductors.
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 III-nitride based optoelectronic device grown on a nonpolar or semipolar plane substrate, comprising an LED or laser diode with an indium containing III-nitride quantum well layer (e.g., InGaN), a peak emission wavelength longer than 500 nm (e.g., longer than 550 nm), and a dislocation density, originating from interfaces between the quantum well layer and barrier layers, less than 9×109 cm2 (e.g., less than 1×106 cm−2).
Alternatively, the dislocation density is sufficiently low to obtain an output power of the light of at least 3.5 mW at an operating current of 20 mA.
The LED may be grown on a nonpolar or semipolar plane of the substrate that enables an indium composition and/or thickness of the quantum well layer such that the quantum well layer is capable of emitting the light having the peak emission wavelength longer than 500 nm.
The LED or laser diode may have a semipolar orientation, for example. If the quantum well layer is semipolar (or nonpolar), then an amount of piezoelectric and spontaneous polarization of the well layer may be reduced as compared to a piezoelectric and spontaneous polarization of a c-plane indium containing quantum well layer. Alternatively, the indium containing quantum well layer's piezoelectric and spontaneous polarization vector lies in the plane of the interface(s), or at an angle less than 90 degrees inclined relative to interface(s) of the indium containing well layer with barrier layer(s), or in a direction that causes a QCSE that is reduced as compared a QCSE created by a piezoelectric and spontaneous polarization vector aligned with a c-axis, thereby enabling the light having a wavelength longer than 500 nm.
The LED or laser diode may be grown on the substrate that is a miscut nonpolar or semipolar plane substrate. For example, the optoelectronic device may be grown on a surface of the substrate, wherein the surface is at an angle with respect to a nonpolar or semipolar plane that maintains a semipolar or nonpolar property of the quantum well layer. For example, the surface is a miscut surface and the angle is a miscut angle.
As noted above, more generally, the present invention discloses a semipolar or nonpolar light emitting device, comprising a III-nitride quantum well layer with a reduced internal electric field and higher indium composition for longer wavelength emissions, relative to [0001] III-nitride semiconductors.
The present invention further discloses a light emitting device, comprising a first cladding layer material having a first cladding layer energy band; a second cladding layer material having a second cladding layer energy band; an active layer material for emitting light having a wavelength longer than 500 nm and having an active layer energy band, wherein the active layer material is between the first cladding layer material and the second cladding layer, and the first cladding material, second cladding material, and active layer material are such that the optical output power decreases, as a temperature of the light emitting device increases, to a lesser degree than the optical output power from the AlInGaP light emitting device.
The present invention further discloses a method of fabricating a III-nitride optoelectronic device, comprising growing the nonpolar or semipolar device with a period of interruption time of more than 5 seconds (e.g., more than 1 minute) between a well layer and barrier layers. A carrier gas may be nitrogen (N2) or hydrogen (H2), for example, during the period of interruption time.
Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
a) and 2(b) are graphs of interruption time dependence of emission wavelength of LEDs grown on c-plane (c-LED) and semipolar plane GaN substrates ((11-22) LED), wherein both
a) and 3(b) are cross-section Transmission Electron Micrograph (TEM) images of semipolar LED samples S071212 DB (left,
a) is a graph of output power (mW) vs. operating current (mA) for an InGaN based LED (S071020DE No. 2) and an AlInGaP based 5 millimeter (mm) lamp, and
a) is a schematic illustrating polar, nonpolar, and semipolar planes.
b) illustrates polarization discontinuity calculated for InGaN coherently strained to GaN, after [Ref. 5], wherein the curves (1), (2), (3), and (4) are for Indium compositions in the InGaN of 0.05, 0.10, 0.15, and 0.20, respectively.
a) is a schematic of c-plane GaN and InGaN,
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
The present invention allows the growth of planar LEDs with longer wavelength emission (500 nm or higher) by incorporating more Indium in the well layer (InxGa1-xN) of a MQW or SQW, using MOCVD or MBE growth techniques. This will be an important method for fabricating and commercializing high power and high efficient nitride LEDs, especially in the range of wavelength from 560 nm to 680 nm, and nitride-based white LEDs.
Current AlInGaP-based yellow and amber LEDs are not suitable for high temperature and high injection current operations due to carrier overflow due to the small conduction band offset between the active region and the cladding layer. Temperature dependence of the output power of InGaN-based LEDs is less sensitive and hence it operates more efficiently and with more stability.
Technical Description
Process Steps
The present invention describes a method for growth of planar LED structures on semipolar {10-1-1} and/or {11-22} GaN via MOCVD.
Block 100 represents loading the substrate. For the growth of a semipolar LED structure, a bulk {10-1-1} or {11-22} GaN substrate is loaded into an MOCVD reactor.
Block 102 represents the step of heating the substrate under hydrogen and/or nitrogen and/or ammonia. The reactor's heater is then turned on and ramped to a set point temperature under hydrogen and/or nitrogen. Generally, nitrogen and/or hydrogen flow over the substrate at atmospheric pressure.
Block 104 represents depositing a n-type nitride semiconductor film (e.g., n-type GaN) on the substrate. After the heating step of block 102, the temperature is set to 1100° C. and 54 μmol/minute of Trimethylgallium (TMGa) is introduced into the reactor with DiSilane for 30 minutes to initiate the growth of n-type GaN. 4 slm of Ammonia (NH3) is also introduced at this stage and the ammonia level is kept at the constant level until the end of the growth.
Block 106 represents depositing the nitride active layer. Once the desired n-type GaN thickness is achieved in block 104, the reactor's temperature set point is decreased to 815° C., and 6.9 μmol/minute of Triethylgallium (TEGa) is introduced into the reactor and a 20 nm thick GaN barrier layer is grown. Once the desired thickness of GaN barrier is achieved, 10.9 μmol/minute of TMIn is introduced into the reactor to deposit a 3 nm thick quantum well. After the deposition of the InGaN layer, 6.9 μμmol/minute of TEGa is again introduced into the reactor for growth of a GaN barrier to finalize the quantum well structure. Between the InGaN well growth and GaN barrier growth, intentional interruption is introduced and the duration varies from 1 minute to 10 minutes depending on the desired Indium composition. This step can be repeated several times to form MQWs. Thus, the present invention discloses a method of fabricating a III-nitride optoelectronic device, comprising growing the nonpolar or semipolar device with a period of interruption time of more than 5 seconds between a well layer and barrier layers. The period of interruption time may be more than 1 minute, and use a carrier gas such as Nitrogen (N2) or hydrogen (H2) during the period of interruption time.
Block 108 represents depositing an electron blocking layer on the active layer of block 106. Once the SQW/MQW is deposited, 3.6 μmol/minute of TMGa, 0.7 μmol/minute of Trimethylaluminum (TMAl), and 2.36×10−2 μmol/minute of Cp2Mg are introduced into the reactor in order to form a 10 nm-thick AlGaN electron blocking layer which is slightly doped with Mg.
Block 110 represents depositing low temperature nitride p-type semiconductor (e.g., p-type GaN, or p-GaN) on the blocking layer. Once a desired AlGaN thickness is achieved in block 108, the reactor's set point temperature is maintained at 820° C. for 10 minutes. For the first 3 minutes of this interval, 12.6 μmol/minute of TMGa and 9.8×10−2 μmol/minute of Cp2Mg are introduced into the reactor. For the last 7 minutes, the flow of Cp2Mg is doubled. Then the temperature is ramped to 875° C. in 1 minute, and TMGa flow is kept at the same constant level and Cp2Mg is reduced back to 9.8×10−2 μmol/minute during this ramp time. The growth of p-GaN is continued at 875° C. for another 1 minute. The end result is a nitride diode with longer wavelength emission.
Block 112 represents annealing the p-type film of block 110 in a hydrogen deficient ambient gas. Once the reactor has cooled, the epitaxial wafer of nitride diode grown in blocks 100-110 is removed and annealed in a hydrogen deficient ambient for 15 minutes at a temperature of 700° C. in order to activate Mg doped GaN.
Block 114 represents the end result, a nitride (Al, In, Ga, B)N diode with longer wavelength emission, e.g., a semipolar or nonpolar light emitting device, comprising a III-nitride quantum well layer with a reduced internal electric field, increased thickness, and/or higher indium composition for longer wavelength emissions, relative to [0001] III-nitride semiconductors. In one example, the device is a III-nitride based optoelectronic device grown on a nonpolar or semipolar substrate, comprising an LED or laser diode with an indium containing III-nitride quantum well layer, a peak emission wavelength longer than 500 nm, and a dislocation density, originating from interfaces between the indium containing III-nitride quantum well layer and III-nitride barrier layers, less than 9×109 cm−2.
Experimental Results
In order to observe the effect of the interruption time, LEDs were grown on two bulk GaN substrates with different orientations—c-plane and semipolar plane—in the same MOCVD reactor.
Possible Modifications and Variations
Images shown in
The output powers of the yellow and amber LED (S071216DA) and the red LED (S071212 DB) were measured, and are illustrated in
Advantages and Improvements
The existing practice has not been able to produce nitride-based planar high-power LEDs emitting light at longer wavelength (500 nm or above). The only commercially available LEDs at longer wavelength are AlInGaP-based LEDs in the amber region. However, the disadvantage of AlInGaP-based LEDs is their temperature-sensitive operation due to carrier overflow from the active regions, illustrated in
Another disadvantage of AlInGaP technology is that (Al, In, Ga)P alloys cannot produce shorter wavelength LEDs in the blue and near ultraviolet regions, while InGaN quantum well can cover from near ultraviolet to microwave regions. Therefore, having controllability of Indium composition for nitride LEDs can broaden the spectrum of semipolar and nonpolar-based Nitride LEDs and replace current AlInGaP based LEDs in the longer wavelength region.
As described in previous sections, interruption time between the growth of the well layer (InGaN) and the barrier layer (GaN) has shown promising results, with a lower dislocation density, for making high-power semipolar-based nitride LEDs in the yellow and amber regions. By engineering the bandgap of active layers, combinations of more than two layers with different bandgaps can produce multi-color LEDs, including a white LED on a single chip, without having to combine many chips together. Hence, it will be possible to fabricate high-power and high efficiency planar white LEDs, and other colors, solely based on nitride LEDs grown on semipolar GaN substrates.
LED Structure
In one embodiment, the LED 600 or laser diode has a semipolar orientation 616, for example, by growing the LED 600 epitaxially in the semipolar direction 616 on the top surface 618, which is a semipolar plane 602, of the substrate 604. If the well layer 606 is semipolar, the well can have an amount of piezoelectric and spontaneous polarization reduced as compared to a piezoelectric and spontaneous polarization of a c-plane indium containing III-nitride quantum well layer.
The LED or laser diode 600 may be grown on the substrate that is a miscut nonpolar or semipolar plane substrate 604. For example, the optoelectronic device 600 may be grown on a surface 618 of the substrate 604, wherein the surface 618 is at an angle 620 with respect to a nonpolar or semipolar plane 622 and the surface 618 maintains a semipolar or nonpolar property of the quantum well 606. In this case the surface 618 is a miscut surface and the angle 620 is a miscut angle. However, the surface 618 is not limited to miscut surfaces, and can include angled surfaces obtained by other means.
The barrier layer 612 is typically also an n-type III-nitride (e.g., n-type GaN) layer. Also shown is a p-type III-nitride layer (e.g., Mg doped GaN) 624, electron blocking layer 626 (e.g., Mg doped AlGaN), p-type contact layer (e.g., ITO) 628, n-type contacts (e.g., Ti/Al/Ni/Au) 630, and metallization 632, 634 (e.g., Au). The top or growth surface 636a of the n-type layer 612, or top surface 636b of the quantum well 606, and/or interfaces 608, 610, may a semipolar plane, or be angled with respect to a semipolar plane so long as the quantum well 606 maintains a semipolar or nonpolar property. Also shown are an additional quantum well (e.g., InGaN) 638 and barrier layer 640 (e.g., GaN), thereby forming a MQW.
The LED may emit light (from the well layer 606), having a peak emission wavelength longer than 550 nm. The nonpolar or semipolar plane 602, or orientation 618, or orientation of the polarization vector 642, enables an indium composition of, thickness 646 of, and/or QCSE (or polarization field) within, the indium containing well layer 606 such that the indium containing quantum well layer 606 is capable of emitting the light having the peak emission wavelength longer than 500 nm, or even longer than 550 nm.
Furthermore, the first cladding material 714, second cladding material 716, and active layer material 710 may be such a first energy band offset 720 between the active layer energy band and the first cladding layer energy band, and a second energy band offset 722 between the active layer energy band and the second cladding layer energy band, may be smaller than an AlInGaP energy band offset between an AlInGaP active layer energy band and an AlInGaP cladding layer energy band in an AlInGaP light emitting device. Typically the first energy band offset 720 and second energy band offset 722 are the same.
a) illustrates polar, nonpolar and semipolar planes in a wurtzite III-nitride crystal, and
a) shows the position or orientation of group III atoms and nitrogen atoms relative to one another within the quantum well layer (InGaN 900) and barrier layers (GaN 902, 904), wherein the InGaN 900 and GaN 902, 904 are grown on a c-plane or Ga face orientation (as indicated by the [0001] direction in
b) shows the valence band Ev and conduction band Ec across the GaN/InGaN/GaN structure of
c) shows the position or orientation of group III atoms and nitrogen atoms relative to one another within the quantum well layer (InGaN 914) and barrier layers (GaN 916, 918), wherein the InGaN 914 and GaN 916, 918 are grown on an a-plane (nonpolar plane, as indicated by the 11-20 direction). Positive ionic charge 906 on the group III atoms and negative charge 908 on the nitrogen atoms is shown.
d) shows the valence band Ev and conduction band Ec across the GaN/InGaN/GaN structure of
The following references are incorporated by reference herein.
This concludes the description of the preferred embodiment 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. Section 119(e) of co-pending and commonly-assigned U.S. Provisional Patent Application Ser. No. 61/042,639, filed on Apr. 4, 2008, by Hitoshi Sato, Roy B. Chung, Feng Wu, James S. Speck, Steven P. DenBaars and Shuji Nakamura, entitled “MOCVD GROWTH TECHNIQUE FOR PLANAR SEMIPOLAR (Al, In, Ga, B)N BASED LIGHT EMITTING DIODES,” attorney's docket number 30794.274-US-P1 (2008-534), which application is incorporated by reference herein. This application is related to co-pending and commonly-assigned U.S. Utility patent application Ser. No. ______, filed on same date herewith, by Hitoshi Sato, Hirohiko Hirasawa, Roy B. Chung, Steven P. DenBaars, James S. Speck and Shuji Nakamura, entitled “METHOD FOR FABRICATION OF SEMIPOLAR (Al,In,Ga,B)N BASED LIGHT EMITTING DIODES,” attorneys' docket number 30794.264-US-P1 (2008-415-1), which which application claims the benefit under 35 U.S.C. Section 119(e) of U.S. Provisional Application Ser. No. 61/042,644, filed on Apr. 4, 2008, by Hitoshi Sato, Hirohiko Hirasawa, Roy B. Chung, Steven P. DenBaars, James S. Speck and Shuji Nakamura, entitled “METHOD FOR FABRICATION OF SEMIPOLAR (Al,In,Ga,B)N BASED LIGHT EMITTING DIODES,” attorneys' docket number 30794.264-US-P1 (2008-415-1); which applications are incorporated by reference herein.
Number | Date | Country | |
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61042639 | Apr 2008 | US |